Anal. Chem.

1994, 66, 360R-427R

Dynamic Electrochemistry: Methodology and Application

Michael D. Ryan
Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53233

Edmond F. Bowden
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695

James Q. Chambers'
Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996

Review Contents Miscellaneous Bioelectrochemical Studies

Books and Reviews 360R Characterization of Redox Reactions 404R
Mass Transport 363R Electron-Transfer Mechanisms
Microelectrodes Organic Electrochemistry
Hydrodynamic Methods Organometallic Electrochemistry
Analytical Voltammetry 368R Inorganic Electrochemistry
Methodologies Activation of Small Molecules
Stripping Voltammetry Electrosynthesis
Catalytic Methods Micelles and Surfactants
Derivatization Methods Spectroelectrochemistry 407R
.Analytical Use of Micelles Instrumentation 410R
Pulse and Sweep Methods
Metal/Ligand Complexation Studies This article reviews the literature of electroanalytical
Chemometric Approaches chemistry in the period between December 1991 and the end
Heterogeneous/Homogeneous Kinetics 371R of November 1993. An attempt was made to minimize the
Electron-Transfer Theories gap in the coverage between this and the previous Dynamic
Heterogeneous Kinetics Electrochemistry review in Analytical Chemistry ( A I ) .
Homogeneous Kinetics The focus of this review is on fundamental advances and
Double-Layer Studies practical applications of electrochemistry that pertain to
Adsorption Studies electroanalytical chemistry. Topics covered include ultra-
Surface Electrochemistry 374R
microelectrodes, analytical voltammetry, electrode kinetics,
Theoretical Aspects
Mercury Electrodes
surface electrode phenomena, modified electrodes, bioelec-
Carbon Electrodes
trochemistry, characterization of inorganic, organic, and
Single Crystal Surfaces organometallic redox couples, spectroelectrochemistry, and
Surface Imaging Techniques instrumentation. The subject is of course quite broad and the
Polycrystalline Electrodes divisions overlap. It is perhaps easier to indicate topics not
Miscellaneous Electrodes covered in detail. Applications where there is no net current
Modified Electrodes 383R flow, e.g., potentiometric sensors, have traditionally been
Charge Transport in Polymer Films covered elsewhere in this review issue. There is not a separate
Electrocatalysis at Modified Electrodes section on photoelectrochemistry in the present review,
Ion-Exchange Polymer Film Electrodes although citations to articles relating to this topic can be found
Ionophore Films
throughout the review. For the most part, articles were
Redox Polymer Films
excluded that dealt with exotic electrode materials or media
Electrochromism and Pattern Formation in
Polymer Electrodes where the emphasis was not electroanalytical in nature.
Conducting Polymer Electrodes Industrial electrochemistry, fuel cells, and battery applications
Self-Assembled Monolayers were also omitted from the coverage.
Other Modified Electrodes The literature cited below was selected by scanning Citation
Bioelectrochemistry 392R Index, C A Selects: Electrochemical Reactions, C A Selects:
Books and Reviews Analytical Electrochemistry, and our personal reading of the
Small Molecules of Biological Importance literature. The coverage is not exhaustive, but is intended to
Protein Electrochemistry
highlight important developments and activity.
Enzyme Electrodes
Polynucleotides and Nucleic Acids
In Vivo and Cellular Electrochemistry A. BOOKS AND REVIEWS
Immunological and Recognition-Based Three accounts of a historical nature on square-wave and
Electrochemistry pulse voltammetry have appeared, in part commemorating
360R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994 0003-2700/94/0366-0360$14.00/0
0 1994 American Chemical Society
Mlchael D. Ryan is Associate Professor of
Chemistry at Marquette University. I n
1969 he receivedhis B.S. degree from the
University of Notre Dame and in 1973 he
was awarded a Ph.D. from the University
of Wisconsin, Madison. Beforejoining the
faculty of Marquette University in 1974, he
served as Lecturer at the University of
Arizona. His current interests include the
study of indirect reduction of nitrite, nitric
oxide, and sulfite reductases and the
kinetics of electron-transfer reactions of
biological compounds.
Edmond F. Bowden is currently an as-
sociate professor in the Department of
Chemistry at North Carolina State Univer-
sity and a member of the Biotechnology
Faculty. After earning a B.S. degree in
aerospace engineering at Syracuse Uni-
versity in 1970, he spent several years
working in the aerospace and chemical
industries before returning to school. He
obtained his Ph.D. at Virginia Common-
wealth University in 1982 under the guid-
ance of Fred M. Hawkridge and then held
a postdoctoralappointment at the Univer-
sity of Minnesotawith John F. Evansbefore
moving to NCSU. His. research interests
include interfacialbioelectrochemistry,biologicalelectron transfer and
bioenergetics, enzyme electrodes for bioanalysis, and electroactive
monolayers.
James Q. Chambers earned his A.B.
degree in chemistry from Princeton Uni-
versity in 1959. His graduate work under
the direction of Ralph N. Adams was
conducted at the University of Kansas,
where he received the Ph.D. degree in
1964. The research interests of Prof.
Chambers are in the general area of
electroanalyticalchemistryandare focused
primarily on understanding and character-
izingelectrodereactionsinvolvingorganic,
polymeric, and biologically importantcom-
pounds.
the original publication of Barker 40 years ago (A2-A4).
Osteryoung also makes a passionate case for the advantages
and virtues of pulse voltammetry in an Accounts of Chemical
Research article (A5). Of practical value is the IUPAC
commission on electroanalyticalchemistry review on the effects
that arise in pulse voltammetry when adsorptionof the reactant
is significant (A6).
Several monographs or reviews have appeared recently that
would make suitable reading for beginning students at various
levels. Koryta has written a short introduction to ionic
solutions, electrochemistry, and membrane phenomena that
emphasizes concepts and is nonmathematical in nature (A7).
A practical treatment of classical polarography also avoids
mathematical detail (A8). Run0 and Peters have written an
undergraduate level introduction to concepts involving elec-
trode potentials (A9). At the graduate level, the monograph
by Gileadi on electrodekinetics is especially noteworthy (AZO).
This text does a remarkable job of covering the fundamental
concepts of electrode kinetics as well as presenting clear
introductory descriptionsof modern techniques, experimental
details, and applications to batteries, fuel cells, corrosion, and
electroplating.
A number of impressiveedited compilations of chapters on
topics related to some aspect of electrochemical science have
been published in the last two years. Before detailing these,
we will note the extensive, multiauthor review on the current
state of understanding and research on the electrode/
electrolyte interface by Bard et al. (A2 2). This report focuses
on new experimental capabilities and outstanding issues in
three areas: structural characterization, dynamics, and
materials aspects of the electrode/electrolyte interface.
Elsewhere, Bard has speculated on future directions of
electrochemistry in a provocative article (A22). Areas
mentioned included UMEs and unusual media, scanning probe
microscopies, and molecular biology.
Three volumes of Modern Aspects of Electrochemistry
have appeared ( A 2 3 4 2 5 ) . Volume 25 has chapters on
hydrogen ingress in metals, charge transfer across liquid/
liquid interfaces, dc techniques for measurement of corrosion
rates, ellipsometry, and electrical breakdown in liquids.
Volume 23 contains chapters on ion and electron transfer
across monolayers of organic surfactants, determination of
current distributions by Laplace transformation, cathodic
protection engineering,semiconductor/metal cluster surfaces,
and electrical breakdown in anodic oxide films. Continuing
with the eclectic nature of this series, Volume 24 treats nerve
excitation, membrane energy transduction, the chlor-alkali
process, bioelectrochemical field effects, electronic factors in
charge-transfer reactions, and electrodeposition of metal
powders with controlled particle grain size and morphology.
In similar manner, a compilation with a high-sounding title
(A26) contains chapters on the double layer, in situ spectro-
scopic examination of electrodes, electrode kinetics, organic
electrochemistry, high-temperature electrochemistry, corro-
sion, and others.
The most recent volume of Advances in Electrochemical
Science and Engineering (A2 7) contains four chapters:
Trasatti on electrocatalysis of the HER, Hammou on solid
oxide fuel cells, Richmond on second harmonic generation at
single crystal electrodes, and Deslouis and Tribollet on flow
modulation techniques. Lipkowski and Ross have edited two
volumes of generally high caliber reviews relating to funda-
mental surface science at electrode interfaces (A28, A29).
The first, which deals with adsorption of molecules, contains
several chapters on radiochemical and spectroscopic char-
acterization of adsorbed layers. The second, which is a
collection of major reviews on the structure of the metal/
electrolyte interface, includes chapters by vacuum surface
experimentalists, theorists, and electrochemists. Among the
latter are reports by Ross on surface crystallography, Kolb on
surface reconstruction, and Soriaga on molecular adsorption
a t single crystal electrodes. Omitted from the previous
Analytical Chemistry review ( AI ) was mention of a compila-
tion that contained chapters on the structure of halides and
small organic molecules on metal surfaces by Hubbard, on
heterogeneous catalysis of substitution reactions by Spiro, on
the kinetics of crystallization of solids from aqueous solution
by House, and a general introduction to corrosion of metals
by Hammond (A20). In yet another volume one can learn
about the semiconductor/electrolyte interface, electrode
potentials, and energy scales, the application of STM to
electrochemistry, adsorption and electron transfer at interfaces,
and various electrochemical aspects of biomembranes (A22).
Two reviews of solvent effects on electron-transferreactions
have appeared (A22, A23). Weaver’s article is mostly
Analytical Chemistry, Vol. 66, No. 12, June 15, 1994 361R
 nonmathematical and emphasizes concepts. Galus sum-
marizes theoretical treatments of the reaction rates for both
soluble couples and amalgam-forming reactions such as Zn2+/
Zn(Hg). In a review by Saveant of his contributions to our
understanding of dissociative electron-transfer reactions, he
outlines criteria for distinguishing between stepwise and
concerted mechanisms in electrode reactions ( A 2 4 ) .
Trasatti has reviewed recent theory on the adsorption of
organics on electrode surfaces (A25), and Parsons and
Ritzoulis critically compare experimental results for adsorption
on stepped surfaces of Pt and Au single crystal electrodes
(A26). In the latter article, the evidence for the assignment
of voltammetric peaks in the hydrogen region to hydrogen
atom adsorption on steps of surface unit cells was clearly
summarized. A thorough review of UHV techniques as applied
toobtain atomic level information about the electrode interface
at single crystal electrodes has been provided by Soriaga (A27).
This treatment is suitable for a graduate student level
introduction to the area.
A substantial analysis of the kinetics of oxygen reduction
at solid electrodes in aqueous solution has been written by
Appleby (A28), and a book has appeared on the electro-
chemistry of surfaces from the critical perspective of Professor
J. O’M. Bockris (A29). Catalysis of the hydrogen ion
reduction by metal surfaces has been briefly reviewed (A30).
An IUPAC Commission report has appeared that compiles
kinetic parameters on the C12/C1- electrode reaction (A31).
Also the IUPAC Commission report dealing with the
measurement of real surface areas has been published a second
time (A32). This report describes 15 methods, 11 in situ and
4 ex situ, in detail.
A variety of ancillary techniques for the study of electrode
processes are treated in a recent volume; included are chapters
on ellipsometry, inferometric methods, SERS, Mossbauer
spectroscopy, photothermal deflection spectroscopy, X-ray
absorption and neutron scattering, impedance spectroscopy,
and others ( A 3 3 ) . An introduction to STM and AFM with
emphasis on basic theory and practicalities has appeared that
discusses the application of these techniques to in situ
electrochemistry (A34). Scanning tunneling spectroscopy,
which can map the surface electronic structure with atomic
resolution in the best scenario, was also addressed.
Buttry and Ward have written perhaps the most authori-
tative of several recent reviews on electrochemical quartz
crystal microscopy (EQCM) (A35). Hillman et al. also
reviewed the QCM technique with emphasis on the detection
of mobile species transferred during the redox switching of
polymer films (A36). A review of electrochemical mass
spectroscopy (ECMS) contains some excellent examples of
the use of a thermospray LC/MS interface with an electro-
chemical cell (A37). Solution IR spectroelectrochemistry has
also been briefly reviewed (A38). Recent applications of
spectroelectrochemistry have been described in a report that
focuses on the redox chemistry of thin-film interfaces, e.g.,
inorganic semiconductors, oxide and chalcogenide films on
native metals, dye-modified electrodes, conducting polymer
films, and others (A39).
Volume 18 of the Bard series, Electroanalytical Chemistry,
contains reviews on electrochemistry in microheterogeneous
fluids by Rusling, charge transport in polymer-modified
362R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
electrodes by Inzelt, and SECM by Bard et al. ( A 4 0 ) . Inzelt
has also reviewed polymer film electrodes elsewhere ( A 4 1 ) .
Microelectrodes have been covered thoroughly in a pub-
lication of the proceedings of a NATO advanced study institute
that contains articles from most of the laboratories which
have contributed to the development of this area (A42). The
authoritative review by Heinze on this subject is also
recommended ( A 4 3 ) .
The latest in the Techniques in Chemistry series deals with
the molecular design of electrode surfaces. Nine individual
chapters written by active mod squad researchers cover subjects
such as adsorption on single crystal electrodes, various aspects
of redox polymer electrodes, and self-assembled monolayers.
The volume, which includes more than 1400 references, is
tightly edited by Royce Murray, who contributed a highly
recommended overview chapter (A44). Reviews in this area
have appeared elsewhere (A45-A49). The articles by Forster
and Vos on the theory and applications of modified electrodes
(A45) and by Zagal on electrocatalytic processes at metal-
lophthalocyanine surfaces (A46) are nicely done.
Several reviews treat subjects that strongly overlap elec-
trochemistry and the amorphous, but fashionable, area of
materials science. The chapter on processable conducting
polymers in a compilation containing five chapters on nonlinear
optics and conducting polymers is especiallynoteworthy (A50).
Mirkin and Ratner have produced a provocative treatise on
molecular electronics (A.71) and electrochemistry at high-T,
superconducting working electrodes, an area where electro-
chemistry can contribute to both fabrication and character-
ization, is the subject of a report (A52). Other reviews treated
the structure and physical properties of PEO-type polymer
electrolytes (A53) and the electrochemical synthesis and
properties of conducting polymers ( A 5 4 ) . The article by
Curran et ai. narrowly focused on the various methods by
which polypyrrole can be employed as a support for electro-
catalytic materials or substituent groups ( A 5 5 ) .
Recent work toward the development of practical biosensors
has been reviewed from several different viewpoints (A56-
A62). These devices are generally based around a redox
enzyme coupled with a molecular mediating species entrapped
in an interfacial matrix of some kind. Both amperometric
and potentiometric detection can be employed. The review
of Alvarez-Icaza and Bilitewski gave a good summary of design
parameters and their optimization (A56). Thearticleof Wring
and Hart (A61) concentrated on the chemistry of the
modification of carbon-based substrates for these devices,while
that of Hilditch and Green had a practical bent describing
disposable electrochemical biosensors in or near to commercial
production (A62).
Ewing et al. have reviewed progress on the difficult problem
of analyzing the contents of single nerve cells with emphasis
on in vivo electrochemistry and EC detection for capillary
electrophoresis where the Penn State group has made major
contributions (A63).
Several works have appeared that concern more classical
analytical voltammetry. These include a little monograph by
Smyth on the voltammetry of biologically important molecules
(A64)and reviews of analytical voltammetry theory by Cassidy
(A65),adsorptive cathodic stripping voltammetry by van den
Berg (A66), the reduction of metal complexes on Hg by
Tur’yan (A67), and instrumentation for voltammetry by
Barisci et al. (A68). In addition, a bookon cyclicvoltammetry
has been recently advertized (A69).
In the realm of organic electrochemistry, several important
books or reviews have been published in recent years. A revised
and expanded third edition of the Manual Baizer opus has
appeared (A70). To complement this work, a book based on
a symposium in honor of Manny Baizer contains 48 chapters
organized under the following headings: Mechanism; Reduc-
tion; Oxidation; Mediated Reactions; Biochemical, Biomass
and Natural Products; Modified, Sacrificial/Consumable
Electrodes; Electrogenerated Bases; Film-Forming Electro-
polymerization; and Ion-Exchange (A71). Professor Shono
has written a brief text that features experimental details for
150 electrochemical transformations of specific compounds
(A72). Niyazymbetov and Evans have summarized the use
of carbanions and heteroatom anions in electroorganic
synthesis (A73). Recent examples of in situ generation of
anions and anodic oxidation of anions are given. Commercial
applications are emphasized in a brief review of the use of
sacrificial anodes in synthetic electrochemical processes
involving C 0 2 (A74). The problem of C 0 2 reduction has also
been treated from several different angles in a collection of
chapters by different authors (A75). Other reviews have
appeared on the electrosynthesis of polymers with emphasis
on intermediates (A76) and on the electrochemistry of
chlorophyll (A77).
Two excellent treatments of important topics have been
produced by authorities in their respective fields. Wayner
and Parker have provided an Accounts of Chemical Research
article on the thermodynamic relationships between bond
dissociation energies and redox potentials of the derived
radicals and their corresponding ions (A78). A clear descrip-
tion is given here of the way to incorporate voltammetric peak
potential data into the thermodynamic cycles. Koval and
Howard have presented a thorough review of electron transfer
at semiconductor electrode/liquid electrolyte interfaces (A79).
While the emphasis of this review is on research advances
since 1985, it also serves well as a lucid introduction to the
terms and fundamental concepts of a complex subject. Gratzel
has given an account of his research on photoelectrochemical
energy conversion using a “molecular machine” based on thin
films of colloidal Ti02 particles that are sintered together to
allow for charge carrier transport (A80, ,481). The phe-
nomenon of room-temperature photoluminescence from porous
Si was reviewed in comprehensive fashion (A82),and a review
of photoemission at metal/electrolyte interfaces includes a
discussion of the cathodic generation of solvated electrons
(A83). An issue of Electrochimica Acta was devoted to new
trends in photoelectrochemistry (A84).
Finally, two issues of the Journal of Electroanalytical
Chemistry have accounts of the scientific careers and useful
complete lists of their publications for two stalwarts of physical
electrochemistry: Professors Brian Conway and John O’Mara
Bockris in Vols. 355 and 357, respectively (A85, A86).
6. MASS TRANSPORT
Microelectrodes. Theory. The intense activity in the area
of microelectrode theory has lessened in the last few years.
Applications of UMEs have mushroomed, however, and there
have been some important and useful papers published that
deserve mention here.
In the latter category, Mirkin and Bard have presented a
theoretical analysis of quasi-reversible steady-state voltam-
mograms that allows extraction of the kinetic parameters (ko
and a ) from a single i-E curve without independent deter-
mination of the Eo’value ( B I ) . They gave extensive tables
for the wave shape parameters, E114 - E112 and E112 - E3149
that correlate with given sets of kinetic parameters. Cor-
relation tables were given both for the case of uniformly
accessible electrodes, such as a RDE and an U M E hemisphere,
and for a U M E disk. Another procedure that appears to be
easy to implement for the determination of heterogeneous
rate constants from CV peak separation data is that of
Lavagnini et al., which only requires intermediate diffusion
control such that peak currents are evident in the CVs (B2).
Exact formalism for the ac impedance of spherical,
cylindrical disk, and ring UMEs was developed (B3). Real
and imaginary components of the impedance, assuming
uniform flux at the electrode surface, were tabulated as a
function a2w/D, a dimensionless quantity where a is the
characteristic dimension of the UME, w is the frequency, and
D is the diffusion coefficient of the Ox/R couple. Linear
sweep voltammograms obtained at ring electrodes were
calculated over 9 orders of magnitude sweep rate and compared
to experimental results (B4). Calculation of the theoretical
voltammograms required the value of a dimensionless pa-
rameter, y = (R2 + R1)/2(R2 - Rl), where R2 and R1 are the
outer and inner ring radii, respectively.
Oldham has continued his penetrating theoretical exami-
nation of microelectrode behavior in a very general treatment
of steady-state voltammetry at UMEs of arbitrary shape (B5).
H e showed that the steady-state current depends on three
factors: the electrode area, an accessibility factor, and a
heterogeneity function. A universal equation is given for the
i-E relationship.
A sophisticated integral equation approach was used by
Bender and Stone to treat steady-state mass transport to
microelectrodes (B6). They gave a numerical solution
procedure for calculation of the surface flux that is applicable
to the general case of an arbitrarily shaped planar electrode,
including both surface and bulk catalytic regeneration reac-
tions. Multidimensional integral equations were used in
another mathematically sophisticated approach to UME
diffusion problems (B7, B8). The approach was stated to
have considerable advantage over the conceptually simpler
finite difference and finite element digital simulations in terms
of computer requirements and execution time. UME con-
figurations considered were microdisks embedded in an
insulating plane of infinite or finite extent, microbands, the
SECM problem, and an array of inlaid planar electrodes of
arbitrary shape.
Brodsky et al. presented closed-form solutions of the
diffusion kinetic equation for individual or arrays of UMEs
that were based on a “zero range approximation” (B9). They
achieved excellent agreement between calculated and experi-
mental collection efficienciesusing literature data. Conformal
mapping procedures for the digital simulation of diffusion at
a microdisk have been optimized and improved (BI0, SI]).
Analytical Chemistry, Vol. 66,No. 12, June 15, 1994 363R
 Oldham has also generalized his treatment of steady-state
voltammetry in the absence of supporting electrolyte (SE) in
two important papers (B12, B13). In the first, theory was
developed for three classes of voltammograms: “sign-retention
voltammograms”,where Ox and R have the same sign; “charge
neutralization voltammograms”, where a neutral product is
generated; and “sign reversal voltammograms”, where Ox and
R have opposite signs. In the first two situations, plateaus
will exist in the limiting current region, while in the latter the
current was predicted to increase in a linear fashion with
potential. For the charge reversal CVs, there is a marked
dependence on trace amounts of supporting electrolyte (B12).
The second paper gave steady-state voltammetry theory at a
hemisphere UME for any degree of supporting electrolyte
excess relative to the concentration of the reactant. Reversible,
quasi-reversible, and irreversible i-E curves can be calculated
from the equations given and representative examples of
different cases are worked out. The criteria presented by
Myland and Oldham should give theexperimentalist new tools
for characterizing electrode reactions by variation of the S E
concentration. The theory, however, is developed by assuming
that there is no adsorption of Ox or Ron the electrode surface.
Myland and Oldham also derived the support ratio, [SEI/
[reactant], needed to ensure that thelimiting current is within
2% of iIimfor infinite excess SE, and to ensure that E1p is
likewise displaced by less than 1 mV. Convective mass
transport at macroelectrodes, i.e., RDEs, may be treated in
a way that exactly parallels the general theory of this paper
with simple algebraic replacements (B13).
Two important papers address problems that will arise for
so-called nanodes, electrodes with characteristic dimensions
on the order of nanometers. Smith and White calculated i-E
curves for very small electrodes based on a numerical solution
of the Nernst-Planck and Poisson equations (814). They
showed that the double-layer electrical field can markedly
affect the currents, even in the presence of a large excess of
S E and even for neutral reactants. Under conditions where
the double layer and the depletion layer have similar
dimensions, and where charge separation in the depletion
region occurs due to ionic flux, the assumption of electro-
neutrality is not generally valid. Another possible artifact for
very small electrodes is the problem of incomplete adhesion
or cracks between the electrode surface and the insulating
sheath. This can create a “lagoon” of electrolyte solution
behind a pinhole. Oldham modeled this situation with a
geometrically well-defined lagoon and solved Fick’s equation
in elegant style (B15). The limiting currents, the time to
reach steady state, and the kinetic parameters extracted from
the CVs all are significantly altered. These lagooned
electrodes, however, do behave as UMEs and can have some
analytical virtues, e.g., more reversible behavior phenomeno-
logically.
Several articles have considered coupled homogeneous
chemical reactions at UMEs (B16-B21). The EC, EC’, ECE,
and DISPl reaction schemes were incorporated into simple
theory using a steady-state reaction/diffusion layer concept
( 8 1 7 ) . Bond et al. have applied UMEs for the determination
of Eo’values and kinetic parameters for a Cr carbonyl complex
that participates in a square scheme (B22). This paper also
described a neat procedure for correction of the iR, drop
364R Analytical Chemistry, Vol. 66,No. 12, June 15, 1994
involving the simultaneous measurement of the difference
current between electrolyte solution in the presence and
absence of analyte.
Other miscellaneous applications include the chrono-
amperometric determination of the absolute concentration of
a well-behaved electroactive species at a microwire UME
(B23). The procedure rested on the Aoki equation, whereby
the concentration is a function of the intercept and slope of
the it112/area vs t ’ I 2 curve (and the electrode radius and n
value). A procedure was given by Wikiel et al. for measure-
ment of the stability constants of metal complexes by analysis
of the anodic dissolution reaction of a metal UME operating
in a normal pulsevoltammetry mode ( 8 2 4 ) . Pulse techniques
applied to dissolving metal UMEs such as Cu render the entire
voltammetric wave accessible due to the reduced iR drop and
double-layer capacity of the UME ( 8 2 5 ) . A Monte Carlo
method of modeling the random motion of particles was
employed to simulate diffusion noise at a UME (B26).
Experimental Aspects. Procedures for the fabrication of
UMEs have been pretty well worked out in recent years.
Nonetheless, useful tidbits can be gleaned by perusal of
experimental sections of the myriad of articles on UME
applications. The reader is to be warned that surveying the
literature in this manner is hit and miss.
A careful study was carried out on methods to maximize
the S / N ratio for the detection of dopamine using Nafion-
coated carbon fiber UMEs (B27). Sources of noiseconsidered
included Johnson noise from the feedback resistor in the current
follower, waveform generator noise, line noise, and physi-
ological noise in in vivo measurements. In this study dopamine
was readily detected at a 100 nM concentration with a S/N
ratio of 25 using fast-sweep voltammetry.
Reasonable CVs of dopamine were obtained using very
small carbon fiber UMEs (overall dimensions of 400 nm) that
had been insulated with a phenol-allylphenol copolymer (B28).
A simple procedure of sealing UME carbon fibers or wires in
polypropylene has been published (B29). On-line iR, com-
pensation was employed to perform CV at sweep rates up to
11 kV/s using 7-pm carbon fibers (830). Peng et al. have
described fabrication and electrochemical activation of carbon
fiber UMEs for the in vivo determination of neurotransmitters
(B31).
Photolithographic methods were used to make carbon IDAs
with 3-pm-wide fingers separated by 2 pm of Si3N4 insulation
(B32). The carbon, which was vapor deposited by pyrolysis
of a perylenetetracarboxylic dianhydride, exhibited an elec-
trochemical behavior similar to that of glassy carbon.
Wrighton’s group, which has pioneered the use of photo-
lithography to make UME arrays, has used surface spec-
troscopy to characterize an array consisting of six or eight
individually addressable Au or Pt UMEs on a Si3N4 substrate
(B33).
The experimental details for carbon-based enzyme elec-
trodes often involve state-of-the-art fabrication techniques.
For example, amperometric enzyme electrodes were prepared
using extremely thin (35-50 nm thick) carbon films prepared
by the pyrolysis of spin-cast polyacrylonitrile (B34). The
enzymes were entrapped on the nanobands by electropoly-
merization of 1,2-diaminobenzene in the presence of the
enzyme. Mention is also made of the elegant surface
 modifications of carbon fiber UMEs by Kuhr and co-workers
(B35,B36). Enzyme electrodes were made using TTF-TCNQ
salt deposited in the recessed tips of 7-pm carbon-fiber UMEs.
The conducting salt mediated the redox chemistry of fla-
voenzymes attached to the surface via the glutaraldehyde
method (837).
Platinum and gold UMEs were prepared by the direct
electroreduction of Au(II1) and Pt(IV/II) onto the tips of
carbon fiber electrodes that had been coated with an insulating
polymer (B38). Also, Ewing’s group has used Au ring UMEs
prepared by electrodeposition of Au onto carbon rings (B39).
A little paper on the measurement of k” values for the
Fe(CN)63-/4- couple has some interesting details (B40). The
presence of millimolar amounts of cyanide in 1 M KCl solution
was found to stabilize the response. Pretreatment by either
polishing with an alumina slurry containing KCN or by laser
activation yielded k” values in the range of 0.5 cm/s.
Particulars were given for construction of U M E arrays
using Buckbee-Mears minigrids (B41). The epoxy-potted
electrodes were polishable and had relatively regular spacings
(which were the cross sections of the minigrid wires). The
morphology of micropit arrays formed by electrochemical
etching of carbon fiberlepoxy electrodes was characterized
by bullet-shaped tips (B42). A proof-of-principle sub-
micrometer galvanic cell consisting of STM-deposited Cu and
Ag pillars on a HOPG surface was demonstrated (B43).
Atomic microscopy showed that the 70-nm cell discharged
when immersed in a plating solution.
Martin and his troops have been busy making and
characterizing arrays of metal cylinders deposited in the pores
of alumina microporous template membranes. They have
prepared recessed gold disk array electrodes, for example,
with very deep 200-nm-diameter microholes (B44). In another
study, they showed that the color of arrays of Au cylinders
with nanometer dimensions could be changed by variation of
the aspect ratio of the nanocylinders (B45). Properly prepared
arrays were transparent in the infrared region (2000-4000
cm-I) (B46). Also, arrays of CdSe and CdTe microfibrils
were fabricated in this manner (B47).
Iridium is known to be a good substrate for mercury
electrodes. A nice application of anodic stripping square wave
voltammetry employed an iridium substrate-based Hg UME
where the Ir was etched to a radius of 5-10 pm prior to Hg
deposition (B48). Metal ions were determined without
deoxygenation, without added SE, and without controlled
stirring during the deposition step. The diffusion coefficient
of T1” in T1 amalgams was determined by UME chrono-
amperometric methods (B49).
Applications. Even a cursory survey of the current
literature reveals that U M E methodology and theory have
widened considerably the playing field of electroanalytical
chemistry. Several accounts have described UME voltam-
metry in the absence, or at low ratios, of the SE to analyte
concentration where agreement was sought with Oldham’s
theory (B50). Drew et al. reported agreement for ratios greater
than 0.1, but found that natural convection and the tendency
of the generated ions to scavenge ions into the diffusion layer
vitiated the theory (B51). For inorganic redox couples of
varying charge and Elf2 values, Cooper et al. also reported
anomalous behavior in several instances (B52). Lee and Anson
found that the electroreduction of Fe(CN)a3- at carbon and
Pt UMEs was markedly suppressed in the complete absence
of S E (B53). Reduction of this species, however, could be
efficiently mediated by the positively charged M V W + couple.
Comproportionation kinetics of the latter system were studied
by steady-state voltammetry in solutions of low S E concen-
tration (B54).In an interesting study, Cooper and Bond found
adsorption of neutral cobaltocene and passivation of the
electrode surface for the (Cp)2C0+/~f-system in CHsCN
(B55). At UMEs this gave rise to stochastic processes at
negative potentials where cathodic dissolution of the film, as
(Cp)2-, is possible.
Homogeneous electron-transfer kinetics in monomeric
organic liquids such as nitrobenzene were studied by Norten
et al. (B56). At Pt UMEs, the second wave for the formation
of the NB2- dianion was depressed relative the first wave due
to the combined effects of the comproportionation reaction
and electrostatic repulsion of the NB’- away from the
negatively charged depletion layer surrounding the electrode.
Others have looked at the UME voltammetry of nitrobenzenes
in low ionic strength aprotic media (B57), and Ciszkowska
and Stojek obtained well-defined anodic waves, with a 0.5 n
value, for the oxidation of solvent in neat alcohol solution with
LiC104 SE (B58).
Several studies have employed UMEs at low or wide
temperature ranges. Attention is drawn to the low-tempera-
ture CVs of the (Cp)2M2+f+f0/-f2-cobaltocene and nickelocene
systems in liquid SO2 (B59), the careful kinetic study of the
ferrocene couple over the 200-300 K temperature range (BbO),
and the temperature-dependent phase transitions and diffusive
electron and solute transport seen in polyether “solid-state”
solvents (B61). CVs of the Fe3+f2+couple in ice featured
surface or thin-layer behavior, indicating the existence of liquid
water microphases in contact with the UME surface at
temperatures below the freezing point (B62). Modestly fast
CVs and chronoamperometry of polyaniline films in contact
with H C 1 0 ~ 5 . 5 H z Oat temperatures down to 220 K suggested
that the oxidation process involved electrocrystallization
phenomena (B63).
Voltammetry and chronoamperometry has been performed
at pressures up to 8000 bar using Pt microcylinder wire
electrodes (B64, B65). A two-electrode cell with a UME
coated with redox polymer/enzyme functioned remarkably
well in a CO2-based fluid near its critical point (B66).
Several more strictly analytical applications of UMEs
included studies of the reduction of acids in the presence and
absence of S E (B67, B68), ASV of heavy metals in natural
waters at Hg UMEs (B69),and a method for thedetermination
of the total acidity of various wines (B70). Good results were
obtained for analysis of Hg in the absence of S E by ex situ
plating of a U M E Pt disk followed by transfer of the electrode
to an electrolyte solution for ASV (B71). Very nice CVs of
solid-state vanadyl sulfate hydrate were obtained at a carbon
disk U M E (B72).
U M E voltammetry was carried out in a single drop of
solution by Unwin and Bard, who measured the adsorption
and ion exchange of H+ on a silicate mineral surface and of
methylene blue on HOPG and polycrystalline graphite surfaces
(B73). Likewise, Bowyer et al. did electrochemistry involumes
as small as 0.05 pL using a three-band array consisting of a
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 365R
4-pm Pt working electrode, a 100-pm Ag reference electrode,
and a 100-pm Pt counter electrode separated by heat-sealing
film (B74).
In continuing publications, mostly from the Texas labora-
tory of Bard and co-workers, the versatility of the scanning
electrochemical microscopy (SECM) technique has been
demonstrated. Wipf and Bard made significant improvement
in the technique by employing small-amplitude tip-position
modulation in combination with lock-in detection of the signal
( B 7 5 ) . This gave unambiguous indication of whether a surface
was conducting or insulating and markedly improved the
contrast between those surfaces. In another study, it was
shown that information on the tip shape could be obtained
from the SECM response at a well-defined flat surface (B76).
This is important for very small UMEs where conical-shaped
electrodes are much more easily fabricated than insulated
UME disks. SECM theory was developed for the determina-
tion of fast heterogeneous kinetics from steady-state currents
(B77, B78). The method, which involves determining the
current as a function of potential for fixed values of d / a ,
where d is the separation between the scanning tip of radius
a and the conductive surface, should permit rate constants up
to 10-20 cm/s to be measured. The technique was applied
to the measurement of the rate constants for the ferrocene+/O
and C& couples (B78,B79). Also SECM, operating in the
feedbackand generation/collection modes, was applied to the
measurement of rates of chemical reactions coupled to electron-
transfer steps for the electrodimerization of activated olefins
(B80). Simulation of the redox kinetics in the tipsubstrate
gap was performed in conjunction with SECM to image the
redox enzyme glucose oxidase immobilized on nonconducting
substrates such as nylon, hydrogel membranes, or a L-B film
(B81).
An antimony UME was used with the SECM apparatus
as a potentiometric sensor for hydrogen ion activity (B82).
General theory was developed and applied to give pH images
around a Pt electrode during the reduction of water, a corroding
AgI disk in cyanide solution, a disk of immobilized urease
hydrolyzing urea, and other systems. The SECM technique
was used to characterize solid films of AgBr (B83). The
diffusion coefficient of bromide ion in the AgBr matrix was
deduced from the tip current transients produced when the
tip/substrate pair was pulsed in a thin-layer electrochemical
mode. SECM has also been employed to map ionic fluxes of
electroactive species at various porous membranes including
mica and mouse skins (B84), to detect proton motion at
polyaniline film electrodes (B85),to monitor ion release from
protonated poly(viny1pyridine) films (B86),and to characterize
a 200-nm-thick polymer film (B87). Surface diffusion and
desorption processes are readily handled by SECM. In this
application, the probing tip, biased at a potential where the
adsorbate is electroactive, yields a current that is a function
of the rate of diffusion through solution, the adsorption/
desorption kinetics, and the rate of surface diffusion (B88).
The approach was illustrated by detection of H+adsat rutile-
(001) and aluminosilicate surfaces.
In vivo electrochemistry under physiological conditions,
which was the original motivation for U M E voltammetry,
has provided some of the most impressive applications of UMEs
in analytical chemistry. The detection of the release of
386R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
catecholamines at the femtomole level from individual adrenal
medullary chromaffin cells continues this tradition (B89).
Interestingly, both cells that released only epinephrine and
cells that released a mixture of epinephrine and norepinephrine
were identified. Wightman’s group have used UMEs to
monitor the flux of catecholamines from other biological cells
during exocytosis (B90). The process was analyzed in terms
of diffusive mass transport from a point source. Ewing’sgroup
has used platinized carbon microring electrodes to monitor
0 2 concentrations and to perform multiple pulsevoltammetry
in single neuron cells of their favorite pond snails (B91,B92).
Oxidation currents have also been measured due to generation
of superoxide anions at a carbon UME in contact with a single
biological cell (B93),and a Pt on graphite UME was used to
monitor oxygen efflux from illuminated algae protoplasts
(B94). The release of NO from a single cell was detected
with a carbon fiber UME coated with a polymeric porphyrin/
Nafion composite film (B95). Adams and co-workers used
Nafion-coated carbon fibers to detect norepinephrine release
and to profile glutamate-evoked ascorbic acid release in the
brains of freely moving rats (B96,B97). Impedance analysis
of 100-pm Pt electrodes covered with biological cell cultures
indicated the formation of pores in the cell membranes upon
application of small applied voltages (B98).
UME arrays have been employed in innovative fashion.
Electrochemical luminescence, generated by a radical cation
plus radical anion annihilation reaction, was examined at
double-band UME arrays both experimentally and theoreti-
cally using conformal mapping transformations (B99). For
reversible systems the depletion effect in differential pulse
voltammetry is minimized for an interdigitated array (IDA)
working electrode operating in the feedback mode (BIOO).
An IDA electrode, also operating in the collection mode, was
shown to be a sensitive detector under conditions compatible
with an enzyme immunoassay (BIOI). Volumes as small as
800 nL were successfully handled in this study. A clever
application of an IDA incorporated an electrochemical
coulometer in series with an IDA in a solution of a reversible
redox couple. The coulometric process employed was elec-
trodeposition of a metal, which was followed by ASV analysis
allowing determination of the redox couple at the M level
(B102). IDAs have been used to measure apparent electron
diffusion coefficients in polymeric matrices: good examples
are the study by Nishihara et al. of poly(ethy1eneoxide) (8103)
and the redox switching of poly(pyrro1e) films (B104).
Several papers have addressed theoretical aspects of various
array geometries. These include a treatment of the overlap
of diffusion layers at microband arrays (B105),cylinder arrays
closely aligned parallel to a planar electrode (B106),and dual-
cylinder UMEs in parallel operating in a biamperometric mode
with a small imposed voltage difference (B107). The latter
theory was applied to the titration of ascorbic acid with
ferricyanide.
Frequencies as high as 20-30 kHz were used for the
generation of electrochemical luminescence by square-wave
generation of the radical ions at UMEs (B108). A lower limit
on the ion-annihilation rate constant for diphenylanthracene
of 2 X 1O9 M-’ s-l was determined. Double-band UME arrays
have also been used to generate ECL in a steady-state mode
of operation (B109).
 Hydrodynamic Methods. Rotated Electrodes. Verbrugge
has given a theoretical analysis of the RDE convectivediffusion
problem for an Ox/R couple that is valid for a wide range of
Schmidt numbers and Reynoldsnumbers (BIIO).Thecurrent
response was found to be bounded by the Levich equation for
large Schmidt and Reynolds numbers and by the stationary
disk response for zero Schmidt or Reynolds numbers. Vieil
developed a general mathematical treatment of mass transfer
that quantifies the transition between stationary convective
mass transport and time-dependent accumulation at an
electrode surface (BI 11). A mass-transfer rate expression is
given that can accommodate a variety of experimental
conditions such as fractal geometries and transient behavior
at RDEs. Simulation of transient diffusion and migration to
a RDE during deposition of a metal film gave information on
the current distribution, the effect of inert electrolyte, and the
role of disk size (B112).
Bartlett and Eastwick-Field have written a particularly
cogent analysis of limiting currents at a RDE for a generalized
ECE reaction scheme (B113).
The effect of rotation rate on U M E array composite RDEs
was studied using composite electrodes of gold and graphite
particles embedded in Kel-F (BI 14). As expected, significant
enhancement of true current density was seen at the array
electrode in comparison to solid electrodes; Le., [(i/area),,,,,/
(i/area),,~id] > 1, where the active area is used to calculate
the current density.
Several researchers have used rotation rate modulation
techniques in various studies. The rotation rate step method
of Blauch and Anson (B115)was applied to a silver electrode
to determine the diffusion coefficients of electroinactive ligands
(BI 16). Anodic 0-transfer reactions at several electrodes
(Pt, Au, Pd, Ir, and glassy carbon) were studied using a current
difference RDE method that diminished the contribution of
0 2 evolution to the observed response (BI 17). A key role for
adsorbed hydroxyl radicals was deduced in this study.
Engelhardt et al. have presented theory for hydrodynamic
square-wave modulation of a rotating ring disk electrode
(B118-B120). The method is useful when there are parallel
reactions and the ring current of interest is masked by large
background currents. In the experiments of Schwartz (B121),
the rotation rate of a commercial RDE was modulated by a
sinusoidal or by a square root waveform. Fourier transfor-
mation then gave the frequency response of the system in a
single experiment. Hydrodynamic impedance has also been
employed by Deslouis and Tribollet (B122).
Papers continue to be published that exploit the power of
rotating electrodes in mechanistic studies. Rotating ring disk
techniques were used to study the MV2+l+Iosystem (MV is
methyl viologen) in aqueous solution, where surface blocking
by adsorbed neutral species had to be taken into account
(8123). Likewise, Kokkinidis et al. found that electrodepo-
sition of neutral benzyl viologen onto Pt or Hg proceeded by
direct nucleation and 3-D growth under mass transport control
(B124). Other studies include chronocoulometric measure-
ment of adsorbed intermediates in the oxidation of iodide at
a Pt RDE (B125),voltammetry of adsorbed intermediates in
the HER (B126), the electrocatalytic oxidation of CN- at a
glassy carbon RDE (B127), the mediated reduction of an
alkyl halide (BI 28), the detection of the anaesthetic halothane
via oxidation of released B r a t the ring electrode (B129),and
measurement of enhanced D values due to homogeneous
electron exchange in the RDE voltammetry of Ru-EDTA-
poly(viny1pyridine) complexes (B130).
On the more applied side, the photographic fixation process
at a AgCl emulsion disk electrode was followed by monitoring
the flux at a ring electrode (B131),and a novel RRDE method
was described for the detection of COz expired in breath from
a human subject (B132).
Compton and Brown have proposed a RDE method to
monitor particle size in solution that is based on the
enhancement of mass transport in the presence of suspended
particles (B133). Others have studied mass-transfer en-
hancement in a dilute suspension of rotating particles under
the influence of shear flow (B134),and Gabrielli et al. treated
the ac impedance of fluidized-bed electrodes, both theoretically
and experimentally for gold beads in NaOH solution (B135).
In the miscellaneous category are papers on the rotating
ring cone electrode (B136),mass transfer at the entire surface
of a vertical cylinder electrode (B137),the use of an inverted
RDE for the study of gas-evolving reactions (B138),and mass
transfer at a RDE with external forced convection (B139).
Wall Jet and Channel Electrodes. R. G. Compton and his
colleagues have continued their sophisticated analysis of wall
jet and channel electrodes. As will be noted below in the
section on electrochemical detectors for FIA or chromato-
graphic columns, these configurations have real practical
significance.
The Compton group has presented theory for the transient
current response for a simple E step at a WJE (B140) and at
the ring in a wall jet ring disk electrode (8141). The theory
was experimentally verified in a later study (B142). They
also developed theory for CV at a WJE where the electrode
is substantially larger than the jet. The theory predicts
transitions from steady-state CVs at slow sweep rates to peak-
shaped response at fast sweep rates (B143). The roleof radial
diffusion in the WJE response has been considered in a more
recent paper (B144).
Compton et al. have presented a general computational
approach to calculation of i-E curves at channel electrodes
(B145)and, in a related paper, calculated limiting currents
for UME band electrodes in a rectangular flow channel under
conditions where convection is the predominant mode of mass
transport (B146). Tait et al. have also tackled the difficult
problem of a U M E disk electrode in a flow channel using
finite difference simulation (B147). The effect of electrode
size, solution velocity, and channel thickness on the magnitude
of the near-steady-state currents and the time required to
reach this condition were determined in the latter paper. A
treatment of the catalytic EC’ reaction at a flow channel
electrode is representative of several articles on coupled
chemical reactions under these conditions (B148).
A four-element carbon paste array detector, which consisted
of different graphite/metal oxide composite surfaces in a wall
jet configuration, displayed different electrocatalytic sensitivi-
ties toward carbohydrates and amino acids (B149). In another
study, the performance of an array W J E assembly was
optimized (B150).
Flow- Through Electrochemical Detectors. Electrochemi-
cal detectors for chromatographic or FIA columns (LCEC)
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 367R
 are routinely employed. Only a fraction of the recent papers
that present possible advancements in the methodology will
be cited here.
The WJE configuration is wellsuited to theLCEC problem.
Stojanovic et al. evaluated cylindrical wire, thin-layer, and
WJEdetectors with constant and pulsed amperometric (PAD)
modes of operation for the determination of inorganic arsenic
(B151). In their hands, the WJE had the best LOD. Other
recent examples of WJE LCEC detection can be mentioned
(B152, B153). It can be noted, however, that the impressive
sensitivity of carbon-fiber detectors, which has been exploited
in the determination of catecholamines in single bovine
adrenomedullary cells (B154),is difficult to match.
Electrochemical detection has been applied to capillary
electrophoresis with much success. Sloss and Ewing, for
example, have improved their methods by enlarging the end
of the capillary to accommodate a larger UME. Problems
with variation of the capillary/electrode alignment were also
minimized with their new design, which gave detection limits
as low as 11 amol for catechol (B155).Lunte and co-workers
have given details on the construction of a complete capillary
electrophoresis system with electrochemical detection (B156).
They found that a 50-pm-diameter Au(Hg) amalgam UME
functioned well as a C E detector for free thiols (B157). Lu
and Cassidy evaluated several UMEs in a WJE configuration
as detectors for capillary electrophoresis columns. Not
unexpectedly, mercury amalgam electrodes gave the best
performance for 14 test metal ions (8158) and PAD at a Au
UME worked well on the anodic side (B159).
Mahoney et al. modified a commercial stationary mercury
drop electrode apparatus so that square-wave voltammograms
could be obtained under stopped-flow conditions (B160).
Rapid-scan voltammetry at a UME detector was shown to
give theoretical steady-state CVs under chromatographic
conditions (B161). Trade-offs in sweep rate, UME diameter,
and flow rate were evaluated.
Two groups have put 16-element LCEC amperometric
detectors to good use. In the study of Sparks and Geng,
detection over a potential window of 0.75 V greatly increased
the information content of a single chromatogram (B162).In
the impressive work of Aoki et al., 80-channel detection was
achieved by application of a five-step E-staircase waveform
with 10-mV step heights to the 16 elements oft he array (8163).
IDAs operated in the dual-electrode mode were shown to have
good sensitivities as flow detectors: 100 pM dopamine was
detected under HPLC conditions (B164). An advantage of
this mode of detection is that the component of the current
due to redox cycling is flow rate independent.
Descriptions of several novel spectroelectrochemical flow
detectors have appeared. Brown et al. used anodic photo-
currents at Ti02 to detect species with redox potentials more
negative than the valence band edge of the semiconductor at
the 100-pmol concentration level (B165). Another flow cell
was based on indirect detection of eluents by the decrease in
the intensity of electrogenerated luminol chemiluminescence
(B166). Also, a pulsed flash photolysis amperometric detector
was described that appears to have some promise as a general
purpose LCEC detector (B167).
Several papers have proposed various surface modifications
to improve LCEC response. The dual-electrode sensor of
368R AnalyticalChemistry, Vol. 66,No. 12,June 15, 1994
Doherty et al., which is based on redox polymer-modified
electrodes, nicely performs speciation analysis of Fe(I1) and
Fe(II1) (B168). One electrode was coated with a Ru-bpy
polymer (E1p = 0.75 V vs SCE), which mediated the oxidation
of Fe(II), and the other was coated with an Os-bpy polymer
(E1p = 0.25 Vvs SCE), which mediated the Fe(II1) reduction.
The latter electrode was also used for the FIA of nitrite ion
with excellent sensitivity and stability of response (B169).
Wang et al. employed self-assembled monolayers (SAMs) of
n-alkanethiols on Au electrodes to vary the response of LCEC
detectors to analytes such as chlorpromazine in urine samples
(BZ70). The SAM-modified electrodes discriminated against
small ionic electroactive species and were stable under the
hydrodynamic conditions of the flow cells. Mark and
colleagues (B171), and others (B172), have found that
conducting polymer film electrodes show improved perfor-
mance in terms of sensitivity and antifouling properties for
the detection of ionic species.
Numerous examples of chromatographic analyses employ-
ing electrochemical detection can be found in the forests of
chromatography literature. Examples of pulse amperometric
detection include a study of the sulfur compounds cysteine,
cystine, methionine, and glutathione, all of which were detected
in human blood samples using simple LC PAD procedures
(8173). PAD and HPLC/MS were employed in comple-
mentary fashion for the analysis of aminoglyoside antibiotics
(B174); SO2 has been analyzed in beer by IC with PAD
detection (B175);and HPLC of amino acids using PAD had
excellent sensitivity and required little to no sample preparation
(BI 7 6 ) . Johnson and co-workers have published two papers
refining their PAD methodology. In one, pulsed voltammetry
at a RDE was used to optimize the potential and time
parameters for the PAD waveforms (B177), and the second
gives construction details for a simple low-cost LCEC detector
employing a gold working electrode (B178).
Other examples of LCEC that caught your reviewer’s eye
were a fast-scan voltammetric detection of fullerenes (BI 7 9 ) ,
detection of underivatized polypeptidesusing constant potential
amperometry (B180), and the coulometric detection of
neurotransmitters and respiratory metabolites in brain tissue
(B181).
Zhu and Curran considered porous flow-through ampero-
metric detectors under conditions of low conversion efficiencies
(B182). RVC electrodes were used to test the theory which
predicted that the limiting currents were proportional to the
2 / 3 power of the pore diameter. A UME biamperometric GC
detector was evaluated (B183).
C. ANALYTICAL VOLTAMMETRY
Methodologies. The year 1992 marked the 40th an-
niversary of the publication of the seminal article by Barker
and Jenkins on square-wave polarography. This paper was
reprinted by the Analyst in honor of the event (C1), along
with a retrospective by Barker and Gardner (C2). The
development of square-wave voltammetry (SWV), as well as
other electroanalytical techniques, has continued over the past
two years. For example, Chin et al. ( C 3 ) reported on the
mathematicalenhancement ofSWV. Lovricet al. (C4)treated
theoretically the use of SWV in cathodic stripping, while
Komorsky-Lovric et al. (C5)looked at peakcurrent/frequency
relationships in adsorptive stripping. The theory and experi-
mental verification of pseudopolarography at the mercury
hemisphere ultramicroelectrode was examined for use in anodic
stripping voltammetry and metal speciation studies (C6).A
reference element (internal standard) method was examined
for the analysis of natural waters by stripping voltammetry
(C7).
As in the past review, adsorptive stripping voltammetry
has been the most dominant approach that has been reported.
Jin et al. (C8) studied the amount adsorbed in the adsorptive
accumulation at a symmetric spherical electrode in a stirred
solution. Li, James, and Magee(C9) examined the effect of
the accumulation potential in the adsorptive stripping vol-
tammetry of organochlorine compounds. As will be seen
below, the analysis of metals by an adsorbed metal complex
has been quite productive. The induced reactant adsorption
in pulse polarography was examined by Puy et al. in a series
ofarticles ( C I e C 1 2 ) . Jin et al. (C13)compared conventional
and derivative measuring techniques for linear potential sweep
adsorption stripping voltammetry.
Stripping Voltammetry. The scope and selectivity of
adsorptive stripping voltammetry has been greatly extended
by the use of complexing agents either in solution or attached
to the electrode. This has enabled adsorptive stripping
voltammetry to beextended to a wide range of metals. Carbon
paste electrodes are excellent candidates in that a wide variety
of reagents can be incorporated into the paste. For example,
the incorporation of salicylideneamino-2-thiophenolallowed
for the accumulation and adsorptivestripping of copper (C14).
A functionalized silica gel was incorporated into carbon paste
for the adsorptive stripping of mercury(I1) (C15). Mercury
(C16) and thallium (C17) were concentrated with anion
exchangers which were present in the carbon paste. A
diphenylcarbazide-modified carbon paste electrode was used
for the determination of chromium(V1) and chromium(II1)
(C18). Gold was selectively extracted with triisooctylamine-
modified carbon paste (C19) or with thiobenzanilide (C20).
A long alkyl chain amine was used for the selective deter-
mination of pyridoxal in nonfat dry milk (C21). A moss-
modified carbon paste electrode was found to efficiently
bioaccumulate lead (C22). Organic cations such as paraquat
were determined by adsorptive stripping voltammetry with
Amberlite resin in carbon paste electrodes (C23) or an ion
pair at a hanging mercury drop electrode (C24). Silica-
modified carbon paste electrodes were used for the determi-
nation of todralazine in biological fluids (C25). OV-17
silicone-modified carbon paste electrodes selectively concen-
trated organic compounds such as benomyl prior to analysis
(C26). A diphenyl ether graphite paste electrode was used
in the analysis of vanillin (C27). While carbon paste has
been the most popular electrode material, other electrodes
have been derivatized or modified in some manner so as to
provide for preconcentration prior to the stripping analysis.
Nafion mercury film-modified electrodes were used for the
anodic stripping voltammetry of bismuth (C28). A glassy
carbon electrode coated with a Nafion film was used to
preconcentrate a nitrosoamine ((229). Gold(II1) was deter-
mined by anodic stripping voltammetry using a glassy carbon
electrode with an aza crown ether (C30).
While significant sensitivity and selectivity enhancement
can be obtained by covalently bonding or mechanically
entrapping an agent near the electrode, similar results can be
obtained by forming strongly adsorbable complexes in solution.
Some examples are the use of Beryllon I11 to form complexes
with beryllium (C31) or copper (C32) prior to adsorptive
stripping analysis. The same technique was used to determine
aluminum (C33)or uranium (C34)with cupferron. Vanadium
(C35)was determined by cathodic stripping voltammetry after
deposition as the Solochrome Violet R S complex, while this
same ligand can be used to determine aluminum by adsorptive
stripping voltammetry (C36). Cathodic stripping voltammetry
was used to determine tripeptides by the formation of the
copper complex at a mercury electrode (C37, C38). Fulvic
acid enhanced the adsorption of the Mo(V1)-phenanthroline
complex in cathodic stripping analysis (C39).
A wide variety of organic compounds can be adsorbed on
electrode surfaces and are ideal candidates for adsorptive
stripping voltammetry. This is especially true of pharma-
ceutical compounds. Some examples of the drugs, elec-
troanalytical techniques, and sample matrices that have been
examined in the past two years are summarized below in order
to give the reader a flavor for the scope of the technique.
Villar et al. (C40) determined mitoxantrone using phase-
selective ac adsorptive stripping voltammetry in a flow system.
Phase-selective ac adsorptive stripping voltammetry was also
used in the analysis of folic acid on a mercury thin-film
electrode (C41)and aminopterin on a mercury thin-filmcarbon
fiber microelectrode (C42). Mercury-coated carbon fiber
microelectrodes were also used in the adsorptive stripping
voltammetry of folic acid and mitoxantrone (C43). Fluni-
trazepam (a psychotropic drug) (C44) and lormetazepam
(C11) were determined in urine by adsorptive stripping.
Ranitidine in stomach tissue was determined by the same
technique (C45),as was metronidazole in human serum (C46).
Cholesterol (C47)in blood serum and testosterone propionate
in pharmaceutical preparations (C48) was determined fol-
lowing adsorptive preconcentration. Multispecies analysis was
obtained for the determination of riboflavin and folic acid in
multivitamin preparations (C49) and nickel(I1) and cobalt-
(11) on a rotating disk mercury film electrode (C50).
Economou and Fielden (C51),though, investigated the effect
of surfactants on adsorptive stripping voltammetry and found
that interferences can occur on the milligram per liter level.
They examined the use of fumed silica gel and Nafion films
to alleviate these problems.
A more forceful way of applying the sample to the surface
was utilized in abrasive stripping voltammetry, where the
sample is physically deposited unto the surface. Komorsky-
Lovric et al. compared the use of electrochemical and abrasive
deposition onto a paraffin-impregnated graphite electrode for
the analysis of lead and mercury (C52). Scholz et al. (C53)
examined the anodic dissolution of dental amalgams by
abrasive stripping voltammetry. This same stripping technique
was also used to study the thermodynamics of solid-phase
transitions (C54).
There were several reports over the past two years on the
use of new electrodes for anodic stripping voltammetry.
Mercury films on conducting poly(3-methylthiophene) (C55)
or poly-N-ethyltyramine (C56) on carbon surfaces were
Analytical Chemistty, Voi. 66, No. 12, June 15, 1994 389R
 reported. Wang et al. investigated the use of mercury-coated
carbon foam composite electrodes (C57), vitreous carbon
aerogel electrodes (C58), and screen-printed stripping elec-
trodes (C59). Frenzel (C60) discussed the attributes and
problems of using mercury films on a glassy carbon support.
Ultramicroelectrodes have also been applied to anodic stripping
analysis. A mercury ultramicroelectrode electrode was used
by Peng and Jin (C61) to determine lead in a sample-limited
analysis (e.g., 1 mg of hair). Gold fiber microelectrodes were
used to determine mercury in high-purity gallium arsenide
(C62)or waters and fertilizers (C63),mushrooms (C64),and
selenium( IV) in blood serum (C65). Copper (C66)and lead/
cadmium (C67) were determined in the absence or presence
of low concentrations of supporting electrolyte. Kouvanes
and Deng (C68)examined the use of an iridium-based mercury
ultramicroelectrode with square-wave anodic stripping vol-
tammetry.
The effectiveness of various methods to remove interfer-
ences in anodic stripping voltammetry was examined. The
influence of complexing agents on the effectiveness of
electrochemical masking with anionic surfactants was ex-
amined by Opydo (C69). The detection of Ga-Zn interme-
tallic compounds and its removal with antimony was reported
by Cofre and Brinck (C70). Surfactants were used to suppress
the indium peak in the determination of lead in samples that
contained large concentrations of indium (C71). A photo-
chemical process was reported by Barisci and Wallace (C72)
for the removal of oxygen in flowing solutions. Photochemistry
was also used in sample preparation of heavy metals in peat
(C73),while a digestion method for soil samples was reported
by Fernando and Plambeck (C74). Systematic errors due to
adsorption of metal complexes onto cell components were
investigated (C75). Sodium and other impurities in alkoxy-
silanes were determined by anodic stripping square-wave
voltammetry (C76).
Metals are generally the most likely candidates for
determination by anodic stripping voltammetry, but there are
several reports on the determination of organic compounds,
either directly or indirectly. Cholesterol in blood serum was
found to be amenable to anodic stripping voltammetry (C77),
as were ionic alkyllead compounds in natural waters (C78).
An indirect method for the analysis of NTA and EDTA in
natural water by means of a bismuth complex was reported
(C79)*
The bulk of the reports on cathodic stripping voltammetry
has involved the determination of halides and chalcogens. For
example, total inorganic iodine in seawater (C80) or a variety
of sulfur species such as thiols, sulfides, cysteine, and cystine
(C81) were also determined. Wang and Lu (C82) reported
on the ultratrace measurement of selenium in the presence of
rhodium. A mercury-coated carbon-fiber electrode was used
for the determination of selenium(1V) in blood serum (C83).
Smyth et al. (C84) reported on the determination of organic
and inorganic selenium compounds, while Kotoucek et al.
(C85) determined arsenic. Organic compounds such as
cytosine 3’-phosphate (C86), thiamine (C87), pentamidine
isethionate (C88), and glutathione in natural waters (C89)
were amenable to cathodic stripping voltammetry. The
adsorption of “reduced COZ”on platinum was the basis of a
new technique for the determination of carbon dioxide (C90).
370R Analytical Chemistry, Vol. 66,No. 12, June 15, 1994
Wang and Tian (C91) developed a mercury-free disposal
lead sensor based on potentiometric stripping voltammetry
using gold-coated screen-printed electrodes. Xie and Huber
(C92)used constant-current enhanced potentiometric stripping
voltammetry for the analysis of cadmium. Potentiometric
stripping voltammetric techniques were also developed for
the determination of cadmium and lead in whole blood (C93),
copper and lead in tap water (C94), and manganese (C95).
Komorsky-Lovric and Branica (C96)compared potentiometric
stripping voltammetry and square-wave voltammetry with
respect to the influence of Triton X- 100. Aldstadt and Dewald
(C97) studied the effect of model organic compounds on
potentiometric stripping voltammetry with a cellulose acetate
membrane covered electrode.
Catalytic Methods. The combination of preconcentration
of the analyte in stripping analysis and enhancement of the
signal by use of a catalytic reaction (dual amplification)
provides for a very attractive approach to develop extremely
sensitive electroanalytical methods. Some examples of this
methodology have been recently reported. One elegant
approach is to use a complexing agent that is, itself, an oxidizing
or reducing agent in the stripping step. This technique was
used in the analysis of chromium (C98),molybdenum (C99),
and thorium (C100) using cupferron as the ligand for
adsorptive stripping voltammetry as well as the catalytic
oxidizer in the stripping step. In addition to cupferron, organic
hydroxy acids (CIOI) and chlorate (mandelate as the ligand)
(C102)were used to determine molybdenum. Iron in seawater
was determined by cathodic stripping with 2-nitroso-2-
naphthol and the use of hydrogen peroxide as the oxidizing
agent in the stripping step (C10.3). Bobrowski and Bond
(C104) combined adsorptive stripping voltammetry of a cobalt
complex with the catalytic effect of nitrite on the stripping
wave to enhance the sensitivity of the cobalt analysis. The
catalytic reaction, alone, without prior accumulation, was used
by Hsieh and Ong to determine molybdenum by differential
pulse polarography (C105), and by Jiang et al. (C106) to
determine nitrite.
Derivatization Methods. The efficient conversion of
electroinactive compounds to eiectroactive materials or to
change the redox potential of electroactive materials can be
exploited to develop new electroanalytical methods. For
example, reactive organic halides can be determined at low
levels via in situ generation of S-alkylisothiouronium salts
(C107) with differential pulse polarography. Similarly,
ethanol (CI08),amines ( C I 0 9 ) ,and amino acids (CIIO)can
be determined via in situ generation of dithiocarbamates.
Oxalate can be determined by differential pulse polarography
after derivatization with o-phenylenediamine (C11I ) . Sul-
fanilic acid was converted into an azo compound prior to
differential pulse polarographic measurement (CI 12). Somer
and Kocak developed a method for the differential pulse
polarographic determination of sulfur dioxide using selenite
(C113). The reaction of ammonia with formaldehyde was
used as the basis for the analysis of ammonia in seawater
(CI 1 4 ) . The formation of nickel complexes with ampicillin
and amoxycillin led to a selective differential pulse polaro-
graphic method (CI15).
Analytical Use of Micelles. Micellar and emulsified media
provide an efficient method for solubilization and transport
of the analyte to the electrode surface. Emulsified media
were used to determine pesticides by differential pulse
polarography (CI 1 6 4 1 18). The combination of micellar
media and a surfactant-modified carbon paste electrode was
used for the adsorptive stripping analysis of piroxicam (C119).
Zinc in lubricating oils was determined in emulsified media
(C120).
Pulse and Sweep Methods. While prior accumulation of
analyte can greatly lower the limit of detection, such sensitivity
is often not required, and an accurate, direct method is
appropriate. In this section, recent applications of direct
voltammetric analysis will be reviewed. A number of articles
addressed themselves to the determination of acidity in a
variety of matrices. For example, steady-state voltammetry
of simple and polyelectrolyte strong acids, as well as weak
acids, with and without supporting electrolyte was examined
(C121, C122). Ultramicroelectrodes were used to determine
the total acidity in wines (C123)and the "in situ" acid number
of fluid lubricants (phosphate esters) (C124). An ultra-
microdisk electrode was used for the solid-state electroanalysis
of silicotungstic acid single crystals (C125). The determination
of elemental sulfur and sulfide was obtained by the use of ac
voltammetry (CZ 26).
Many examples of the use of differential pulse voltammetry
to measure a substrate or impurity were reported. For
example, furaltadone (CI 27) in milk and urine was determined
by differential pulse polarography. Trace levels of selenium
in Chinese herbal drugs (CI28) and total pyrethroid residues
in stored cereals (CI29) were determined by differential pulse
polarography. Impurities in several pharmaceutical prepara-
tions were determined by differential pulse polarography
(C130, C131). Pulse methods were also found to be useful
in the analysis of solid materials such as the determination of
iron in Y Ba2(Cul,Fex)30, superconducting compounds (CI 32)
or the analysis of additives such as iron, sulfur, or chromium
oxide in soda lime silica glass (C133). The oxygen-to-uranium
ratio in uranium dioxide was determined by differential pulse
polarography (CI 34). A lichen-modified carbon paste elec-
trode was found to be useful for the analysis of lead, copper,
and mercury (C135).
Mathematical methods to enhance the signal and resolution
have been applied to various pulse techniques. The Kalman
filter approach was used for curve resolution and quantification
of pyrazines by differential pulse polarography (C136).
Reverse differential pulse voltammetry was used by Matysik
et al. (C137) to improve the resolution between various
catechols such as norepinephrine and 3,4-dihydroxyphen-
ylacetic acid. Engblom et al. (C138) studied mechanically
generated noise in static mercury drop electrodes.
Metal/Ligand Complexation Studies. The complexing
ability of natural waters can significantly affect the bioavail-
ability of metals. Electrochemical methods are ideal to probe
these effects and give them a significant advantage over atomic
methods. The derivation and application of steady-state
(C139) or normal pulse (C140) voltammetry for the deter-
mination of formation constants were examined. An anodic
stripping voltammetry titration technique was developed for
estimating the complexation capacity of natural waters (C141).
Anion coordination chemistry was studied by the application
of the molar ratio method to competitive cyclic voltammetry
(C142). Esteban and Diaz-Cruz (C143) reported on a general
voltammetric method for studying metal complexation in
macromolecular systems. Zelic and Branica (C144)examined
the influence of anion-induced adsorption on the voltammetric
determination of stability constants. Van den Berg and Donat
(C145) found that there was a linear relationship between the
detection windowsof the analytical techniques and the detected
metal complexation. They investigated the effect of multiple
ligands on speciation studies as well as the presence of slow
metal/ligand dissociation kinetics. The effect of deposition
potential on the voltammetric determination of complexing
ligand concentrations in seawater was also examined (C146).
Equilibria that involved metal-humate complexes, as
models for natural water and seawater studies, were examined
using anodic stripping voltammetry. A modified carbon paste
electrode was reported for the study of the metal humic
complexation reaction (C147). A procedure for metal
speciation studies in the natural environment was reported
which involved ultrafiltration of the sample and the study of
the complexation dissociation kinetics using anodic stripping
voltammetry and ion exchange (C148). This approach allowed
the study of dissociation kinetics that could be varied between
2 ms to 8 days. The effect of competitive kinetics between
a solution copper complex and an iminodiacetate group, which
was incorporated into a carbon paste electrode, was the basis
for a copper speciation analysis (C149). A solution ligand
competition technique was proposed for the voltammetric
measurement of the labile metal fraction (C150). The basis
of this technique is that the natural copper complex dissociates
too slowly for the copper to be deposited while the ethylene-
diamine complex is labile and can be detected by anodic
stripping voltammetry. The effect of sodium dodecyl sulfate
on the measurement of labile copper(I1) in the presence of
humic acid was examined (CIS]).
Chemometric Approaches. The chemometric approach
to linear calibration was used by Allus and Brereton (C152)
to determine thallium in cement dust and sediment samples
using anodic stripping voltammetry. Ni et al. (C153)
developed a method for the analysis of mixtures of pyrazines,
which are flavor components of cocoa. The severe overlap of
the peaks would preclude normal voltammetric analysis, but
the use of chemometric methods with differential pulse
voltammetry made it possible to carry out the analysis. An
expert system for the determination of trace metals was
reported by Esteban et al. (C154, C155). The expert system
guided the user through appropriate methods, data analysis,
and interference problems.
D. HETEROGENEOUS/HOMOGENEOUS KINETICS
Electron-TransferTheories. The solution and molecular
factors that affect the electron-transfer process is a question
of fundamental importance in electrochemistry and continues
to be the focus of considerable research. Fawcett and Opallo
( D J ) examined the question of why activation enthalpies for
anions were larger than for cations. They proposed that the
differences may be due to outer-sphere contributions to the
Gibb's energy of activation. They also examined 18 hetero-
geneous redox reactions and found that the degree of
dependence bfthe rate constant on the longitudinal relaxation
time of the solvent decreases with the heterogeneous rate
Analytical Chemistty, Vol. 66,No. 12,June 15, 1994 371R
constant ( 0 2 ) . The results were discussed in light of
contemporary electron-transfer theory. Phelps et al. ( 0 3 )
studied solvent dynamical effects in electron transfer with a
series of sesquibicyclic hydrazines as a probe of coupled
vibrational activation. These systems provide an interesting
opportunity to assess the manner and extent in which
overdamped solvent relaxation may limit the electron-transfer
dynamics. Fawcett and Fedurco ( 0 4 ) examined medium
effects on the electroreduction of benzophenone in aprotic
solvents. The solvation of the activated complex was based
on three contiguous spheres corresponding to the two phenyl
rings and the carbonyl group and was used to assess the outer-
sphere contribution to the Gibb’s activation energy. It has
been found that the heterogeneous electron-transfer rate
constant decreased as the size of the tetraalkylammonium
cation in the supporting electrolyte increased. But Fawcett
et al. ( 0 5 )found that the activation enthalpy was independent
of the cation size and that the slow electron transfer was due
to an adsorbed layer of cations at the electrode surface.
Pressure was used by Cruanes et al. ( 0 6 ) to study solute/
solvent interaction in electron-transfer processes. Increases
in pressure (up to 10 kbar) led to shifts in the redox potentials
which were attributed to the effect of the metal cluster’s
electronic structure on the overall size of the complex and on
its ability to interact with the solvent. Fawcett et al. ( 0 7 )
reported on the use of buckminsterfullerene as a model reactant
for testing electron-transfer theories. McDermott et al. ( 0 8 )
examined electron-transfer kinetics of aquated iron, europium,
and vanadium couples at carbon electrodes and found inner-
sphere catalysis by surface oxides. Straus and Voth ( 0 9 )
presented a computer simulation study of free energy curves
in heterogeneous electron transfer.
Dissociative electron-transfer reactions were studied ex-
tensively by Saveant and co-workers. As with the simpler
heterogeneous electron-transfer reactions reported above, the
role of the solvent was an important focus of these studies.
The role of the solvent was examined by an ab initio study of
the carbon halogen bond reductive cleavage in methyl and
perfluoromethyl halides (010). New tests of the electron-
transfer theory were examined using data derived from outer-
sphere electron-transfer data gathered in the same solvent
( 0 1 1 ) . They also reported examples of passage from a
sequential to a concerted mechanism in the electrochemical
reductive cleavage of arylmethyl halides ( 0 1 2). Jaworski et
al. ( 0 1 3 ) used the Hammett reaction constant for the two-
electron irreversible reductive cleavage of substituted chlo-
robenzenes and bromobenzenes to show the role of solvent
relaxation dynamics in irreversible electrode processes ac-
companied by bond cleavage. Concurrent metal-ligand bond
dissociation was reported by Carlin et al. ( 0 1 4 ) to lead to
asymmetric electrode kinetics.
Heterogeneous Kinetics. Methods to measure faster
electron-transfer rates continue to be pursued. Karpinski and
Osteryoung ( 0 1 5 ) used pulse times of 5 ps in normal and
reverse pulse voltammetry to measure the electron-transfer
rates of ferrocene (1.2 cm/s) and anthracene (0.73 cm/s) at
5-pm platinum electrodes. Safford and Weaver ( 0 1 6 ) used
lower temperatures to determine rate constants for rapid
electrode reactions using microelectrode voltammetry. U1-
tramicroelectrodes allow the charging current to decay rapidly,
372R Analytical Chemistry, Vol. 66,No. 12,June 15, 1994
and as a result, the voltammograms could be obtained with
little of the charging current present. Lavagnini et al. ( 0 1 7 )
developed the theory for the measurement of electron-transfer
rates under mixed spherical/semiinfinite linear diffusion at
microdisk electrodes. Birke and Huang ( 0 1 8 ) investigated
steady-state voltammetry for quasi-reversible heterogeneous
electron transfer on a mercury oblate spheroidal micro-
electrode. Mirkin and Bard ( 0 1 9 )presented a simpleanalysis
of quasi-reversible steady-state voltammograms using the E1/4,
E , / * ,and E314 potentials. Kim et al. ( 0 2 0 ) examined the use
of derivatives to analyze voltammograms for reversible, quasi-
reversible, and irreversible electrode processes. Munoz et al.
( 0 2 1 ) found that electron-transfer processes with very low
transfer coefficients led to a splitting of the differential pulse
polarographic wave, even though there was only a single
electron transfer. Engstrom et al. ( 0 2 2 ) used scanning
electrochemical microscopy to observe microscopically local
electron-transfer kinetics. Cassidy et al. ( 0 2 3 )extended cyclic
voltammetric theory to a quasi-reversible system with a
Gaussian distribution of heterogeneous rate constants. Mirkin
et al. ( 0 2 4 ) used scanning electrochemical microscopy to
measure fast heterogeneous kinetics. The heterogeneous rate
constant for ferrocene in acetonitrile, which was measured at
steady state with solution resistance and charging current,
was found to be 3.7 cm/s, 2-4 times the values determined
by fast-scan cyclic voltammetry.
Accurate measurement of peak potentials and currents in
transient signals are usually imperative in order to obtain
good kinetics information. Andrieux et al. ( 0 2 5 ) examined
methods to improve the kinetically relevant data in cyclic
voltammetry and showed that filtering caused significant
increases in systematic error which negated any advantage in
the reduction of random error. Smith and White ( 0 2 6 )
cautioned that the use of ultramicroelectrodes with dimensions
less than 0.1 pm will lead to violation of electroneutrality due
to the high electric fields, even in the presence of excess
supporting electrolytes. This can result in significantly
enhanced or depressed values of the heterogeneous rate
constant. Two reports, which take different approaches to
the removal of iR drop in cyclic voltammetry, have appeared.
Eichhorn et al. ( 0 2 7 ) used a numerical method to correct iR
drop errors for (quasi-)reversible electrode processes, while
Hsueh and Brajter-Toth ( 0 2 8 ) used on-line iR compensation
at carbon fiber ultramicroelectrodes.
Homogeneous Kinetics. The development of much more
efficient numerical methods for solving diffusion/kinetic
problems has continued unabated. Most electrochemical
mechanisms are a combination of several kinetic steps that
must be considered if a complete fit of the data over a wide
time window is to be attempted. This can only be accomplished
by fast and accurate algorithms. Bieniasz (D29) proposed a
dynamically adaptive grid technique for the solution of finite
difference equations with a fast homogeneous reaction. While
the approach is not entirely satisfactory at present, this strategy
does permit the simulation of homogeneous rate constants
that are as much as 20 orders of magnitude faster than the
maximum possible in corresponding fixed-grid calculations
with the same number of space grid points. Horno et al.
( 0 3 0 ) presented a network approach to the simulation of
electrochemical processes where space was discretized but
time was continuous, This allowed a mathematical model to
be described by a network model and its simulation could
then be carried out by a suitable electric simulation routine
without having to deal explicitly with thedifferential equations.
Rudolph (031)reported an improved treatment of electro-
chemical mechanisms with second-order reactions using the
fast implicit finite difference (FIFD) algorithm. Britz (032)
incorporated the Crank-Nicolson scheme and N-point bound-
ary expression into the Rudolph algorithm. Storzbach and
Heinze (033)simulated electrode processes at macro- and
microelectrodes using the Crank-Nicolson technique. The
simulations included iR effects and double-layer capacitance
as well as the heterogeneous/homogeneous reactions. Bieniasz
and Britz (034) presented electrochemical simulations of
mixed diffusion/ homogeneous reaction problems by the
Saul’yev finite difference algorithm. They also compared the
efficiency of electrochemical simulations by orthogonal col-
location and finite difference methods (035). A very
interesting and valuable report on the von Neumann stability
of finite difference algorithm was published by Bieniasz (036).
The stability of the explicit, second-order Runge-Kutta,
DuFort-Frankel, fully implicit, Crank-Nicolson, and Saul’yev
methods was examined. It was found that the stability depends
notonlyon the DAt/h2(A) factor but alsoon therateconstant.
In examining the error growth as time goes to infinity, the
criterion of h < 0.5 is insufficient for stability when
homogeneous reaction kinetics are involved.
Mirkin and Bard (037, 038) used multidimensional
integral equations to solve microelectrode diffusion problems
with application to microband electrodes and scanning
electrochemical microscopy. Second-order homogeneous
chemical reactions were also studied by scanning electro-
chemical microscopy (039).Che and Dong published a series
of papers on the theory for the use of ultramicroelectrodes to
study first- and second-order homogeneous catalytic reactions
(040-042). Lavagnini et al. (043)carried out the digital
simulation of steady-state and non-steady-state voltammetric
responses for electrochemical reactions occurring at an inlaid
microdisk electrode. In this work, they examined the ECi,
catalytic, and C E first-order reactions. Evans (044)examined
the two-component diffusion (involving cyclodextrin equi-
libria) with reaction in chronoamperometry. Andrieux et al.
(045) studied the response of an irreversible system to
repetitive cyclic voltammetry. Maestre et al. (046)applied
Matsuda’s pulse polarographic theory to the study of the C E
mechanism by differential pulse polarography. Mellado et
al. (047) derived the theory for electrochemical processes
preceded by concurrent first-order chemical reactions in dc
polarography. Laviron and Meunier-Prest (048)examined
the cubic scheme with electrochemical reactions and proto-
nations at equilibrium. Vincent and Peters (049)carried out
the computer simulation of large-scale controlled-potential
electrolysis involving father, son and grandfather, grandson
self-protonation systems. Kumar and Birke (050)used global
analysis of current/potential time data to study an EC reaction.
Bieniasz presented a PC program, ELSIM, which can
simulate a variety of electrochemical mechanisms by finite
difference or orthogonal collocation methods (051). A very
attractive approach for the construction of digital simulation
programs was reported where the equations which describe
the electrochemical kinetic initial and boundary value problems
are treated as text input data for a special formula translator
(052). The use of a knowledge-based system for automatic
polarographic elucidation of the ECE, EE, and adsorption
mechanisms was reported by Palys et al. (053).
Hydrodynamic methods are quite attractive for kinetics
studies becauseone does not need to measure a transient signal.
Compton et al. examined thin-layer effects and the shape of
quasi-reversible current/voltage curve (054)and the catalytic
mechanism (055,056) for channel electrode voltammetry.
It was also found that radial diffusion must be considered at
the wall jet electrode in order to have a full quantitative
description of the steady state or transient current (057).The
authors reported that this additional computational complexity
may limit this technique for use in kinetic studies. Benderskii
and Mairanovskii (058) described numerical/analytical
methods to study ECE processes at the rotating disk electrode.
Daasbjerg (059)reported on a new method for studying the
competition between coupling or further reduction of elec-
trogenerated material using a rotating disk or ultramicro-
electrode.
Double-Layer Studies. There was considerable interest
in the electrical double layer that extended well beyond
electroanalytical considerations. While beyond the scope of
this review, there were many studies on electrical double layers
at nonconducting surfaces, in colloids, and in chromatography.
For electrochemists, an understanding of the electrical double
layer is tightly connected to an understanding of the electron-
transfer process, which occurs within that region. Murphy
et al. (060)presented a numerical study of the equilibrium
and nonequilibrium diffuse double layer applying the finite
difference method to the Nernst-Planck and Poisson equations.
Karasevskii et al. (061)developed a self-consistent theory of
the metal/solvent boundary using a jellium model of the metal
and a continuum solvent model. They found the existence of
a quasi-metal layer in the near electrode region which provides
a novel explanation of the large width (3-5 A) for the area
of adiabatic reaction, the independence of the heterogeneous
rate constant on the nature of the metal, and the capacitance
properties of the boundary. Damaskin and Safonov (062)
studied the mercury/water interface using a model which
separates the diffusion layer region with a reduced value of
the dielectric constant that is inaccessible for some electrolyte
ions. Izotov and Kuznetsov (063)examined changes in the
electron-transfer coefficient caused by the rearrangement of
the compact double layer following changes in electrode
potential. Hsu and Kuo (064)derived approximate analytical
expressions for the properties of an electrical double layer
with asymmetric electrolytes. Daghetti et al. (065)calculated
single ion activities based on the electrical double-layer model.
Hamelin et al. (066)tested the Gouy-Chapman theory at a
(1 11) silver single crystal electrode.
Fawcett et al. examined the double layer in ethanolic
solutions (067)and applied the ac admittance technique to
double-layer studies on polycrystalline gold electrodes (068).
Wandlowski and DeLevie (069-071) studied the double-
layer dynamics in the adsorption of tetrabutylammonium ions
at the mercury/water interface. Swietlow et al. (072)carried
out double-layer capacitance measurements of self-assembled
layers on gold electrodes. Studies on the structure of the
Analytical Chemistry, Vol. 66,No. 12, June 15, 1994 373R
interphases of low melting point salts and protonic hydrates
with mercury and gold ( 0 7 3 )and solvent effects in the double-
layer structure for gallium and gallium-like metals ( 0 7 4 )were
examined. Perez et al. ( 0 7 5 ) studied the Hg/aqueous KCl
interface from ambient temperature to 300 OC. Bai et al.
( 0 7 6 ) investigated the problem of real-area determinations
of rough or porous, gas-evolving electrodes and the distinction
between capacitance of the double layer and the pseudo-
capacitance due to adsorbed hydrogen. Jaworski and Mc-
Creery studied double-layer and ion adsorption effects in laser-
induced transient currents on glassy carbon electrodes ( 0 7 7 ) .
Leibig and Halsey ( 0 7 8 , 0 7 9 ) used double-layer impedance
as a probe of surface roughness.
Adsorption Studies. Because adsorption processes have a
great impact on electron-transfer kinetics, double-layer
structure, and electroanalytical techniques, efficient and
reliable methods for studying adsorption have been pursued.
Unwin and Bard ( 0 8 0 )used ultramicroelectrode voltammetry
to measure adsorption isotherms in a drop of solution. These
authors also used scanning electrochemical microscope-
induced desorption to measure adsorption/desorption kinetics
and surface diffusion rates ( 0 8 1 ) . Three-dimensional phase-
sensitive ac voltammetry was used to study the adsorption of
sodium dodecyl sulfate at the mercury/electrolytic solution
interface ( 0 8 2 ) . Gu et al. ( 0 8 3 )used fast potential relaxation
transients to distinguish between double-layer and adsorption
capacitance.
Blankenborg et al. ( 0 8 4 ) examined the reduction of Tl(1)
at a mercury surfaceand found that, for weak linear adsorption
processes, it was impossible to distinguish between the direct
reduction of TI(]) and the formation of an adsorbed Tl(1)
intermediate. Avaca et al. ( 0 8 5 )described the theory of cyclic
voltammetry for quasi-reversible electrodeposition reactions
with insoluble products. Tilak and Conway ( 0 8 6 )determined
the analytical relationships between reaction order and Tafel
slope derivatives for electrocatalytic reactions involving
chemisorbed intermediates. Song et al. ( 0 8 7 ) developed the
theory for quasi-reversible electron-transfer reactions with
adsorption of the redox species using integer and half-integer
integrals. Jin et al. ( 0 8 8 , 0 8 9 ) examined the theory for an
irreversible interfacial reaction in linear potential sweep
adsorption voltammetry. The characterization of a totally
irreversible reduction of an adsorbate ( 0 9 0 ) and quasi-
reversible surface processes ( 0 9 1 ) by square-wave voltam-
metry was reported. Rouquette Sanchez and Picard ( 0 9 2 )
developed the theoretical expressions for the steady-state
current/potential curves for the electrochemical oxidation of
a metal involving two successive charge-transfer steps with
adsorbed intermediate species. The role of surface defects in
the adsorption and electron-transfer kinetics of anthraquino-
nedisulfonate on ordered graphite electrodes was reported by
McDermott et al. ( 0 9 3 ) .
Engelman and Evans ( 0 9 4 ) used explicit finite-difference
digital simulation of the effects of rate-controlled product
adsorption or deposition in cyclic chronocoulometry. The
simulation of Frumkin-type adsorption processes by orthogonal
collocation using cyclic voltammetry was reported by Schulz
and Speiser ( 0 9 5 ) . The experimental verification of theoreti-
cally predicted effects of reactant adsorption in normal pulse
polarography was reported by Lukaszewski et al. ( 0 9 6 ) .The
374R Analytical Chemistry, Vol. 66,No. 12, June 15, 1994
semiintegral method was used to measure surface excess and
weak adsorption ( 0 9 7 , 0 9 8 ) .
E. SURFACE ELECTROCHEMISTRY
This section is organized by the nature of the working
electrode. The major theme of the articles selected for mention
here is characterization of the electrode surfaces and the
reactions of adsorbed species.
Theoretical Aspects. The articles cited in this section have
a decidedly fundamental bent; it is noted, however, that
important theory is often published in conjunction with
experimental results, so this is not an exhaustive compilation.
Leiva carried out a self-consistent calculation of the electron
density that included pseudopotentials to estimate the con-
tribution of the metal to the double-layer capacity at thin
metal films of Pb and Ag ( E l ) . Trasatti has analyzed the
variation of the work function for single crystal Au and Ag
electrodes as a function of the Epzc( E 2 ) .
Wandlowski and de Levie ( E 3 ) invoked a two-dimensional
surface cluster model to explain the admittance of "needle
peaks" that are seen in Cdl-E curves for the Hg/H20 interface
in solutions of tetrabutylammonium salts. Their theory took
into account growth and dissolution of the surface clusters
both at the perimeter edge and at the cluster/electrolyte
interface. A similar model was used by Schrettenbrunner et
al. in their analysis of film formation at the Hg/CH$N
interface ( E 4 ) . Nikitas also treated micelle formation on
electrode surfaces ( E 5 ) . H e predicted a close correlation
between aggregate formation from a dilute solution of
monomers and surface phase transformations that would result
in abrupt steps in the charge density and cdl vs E curves. In
previous papers, de Levie and co-workers considered the effect
of the time-dependent relaxation of the diffusion layer on the
value of Cdl when speciesaredesorbed from an electrode surface
( E 6 ) . Using digital simulation and assuming a Frumkin
isotherm, they explained the transients quantitatively. In the
case of a linear isotherm, they derived an explicit relation for
the time dependence of the interfacial excess for various
adsorption/desorption rate constants ( E 7 ) .
In several papers Nikitas has described surface phase
transitions and adsorbate reorientations in statistical me-
chanical and thermodynamic rigor (E8-EI0). Among the
conclusions of this work are that only irreversible phase
transitionscan take place at constant chargedensity ( E 8 ) and
that the diffuse layer capacity, and the capacity of the entire
interface, cannot be negative if the electrical double layer is
under potential control ( E l l ) . The use of the electrode
potential as the independent variable is promoted and negative
capacities are concluded to be a result of an incorrect choice
of the independent variable. Increase in surface heterogeneity
is predicted to disfavor surface phase transitions, an effect
predicted on solid electrodes but not on mercury (E12).
Nikitas has also presented a thermodynamic treatment of the
monolayer formation of a salt film on an electrode surface
(E13).
Monte Carlo statistical mechanical simulations of the free-
energy profiles of sodium ions at a metal electrode have been
made for water and T H F solutions ( E l 4 ) . In both solvents,
a single, fairly deep minimum is found corresponding to the
sodium ion with its first shell of solvent molecules in contact
with the electrode. Thus the O H P is predicted to reside about
one solvent diameter closer to the electrode than in classical
models, in which an adsorbed noncomplexed solvent layer is
assumed to exist in the inner layer.
A theoretical analysis of molecular polarization and
interactions in adsorbed monolayers permited calculation of
isotherms for adatoms and for competitive adsorption of ions
and dipoles ( E I 5 ) .
Several papers have concerned the ac impedance of surface
reactions (El6-E18). These include an analysis of the
impedance of an (Ox/R),ds couple for both planar and porous
surfaces ( E l 6 ) and for the situation where two different
adsorbed intermediates are involved in the electrode reaction
(El7).
Scott has presented electrochemical rate equations for
several reaction mechanisms involvingadsorbed intermediates
(E19). Rather than power law expressions, the rate is
expressed in a “Langmuir” isotherm model in which the
influence of electrode potential and concentration can be
assessed separately. On a similar theme, Tilak and Conway
derived relationships between reaction orders and Tafel slopes
for electrocatalytic reactions involvingadsorbed intermediates
(E20). Various adsorption isotherms were factored into their
theory, which was applied to several experimental situations
including the anodic Cl2 evolution process. Following up on
previous work, Mishra et al. predicted maxima in i-E curves
for chemisorbed states (E2I). Also expressions for i-E curves
have been derived for a two-electron reaction mechanism with
an adsorbed intermediate (E22).
Several worthwhile papers have appeared on the square-
wave voltammetry of surface reactions. SWV was used to
characterize quasi-reversible surface waves using the COOL
nonlinear least-squares algorithm for data analysis. Various
SWV peak shapes were observed, theoretically and experi-
mentally for the azobenzene system, that were dependent on
the rate constant, the S W amplitude, and the pulse width
(E23). O D e a et al. have also given SWV theory for a totally
irreversible electrolysis of an adsorbed species. Experimental
voltammograms were compared directly in real time with a
numerical solution of the boundary value problem using the
COOL algorithm to yield estimates of the transfer coefficient
and the rate constant (E24). An easily implemented theory
for quasi-reversible cyclic SWV for a surface-confined redox
couple was given by Reeves et al. (E25). Their model assumed
that lateral interactions among adsorbed species were neg-
ligible, that all surface sites were equivalent, and that there
was no diffusional component of the current from solution
species. Rate constants were extracted from the peak
separations in the classical manner of cyclic voltammetry.
Stripping SWV theory was developed for monomolecular
layers of reversible, quasi-reversible, and irreversible M/Mn+
couples in a quite general fashion (E26). In other articles,
stripping voltammograms of simple ionic salts were analyzed
in terms of theory that embraced two activity models for the
interfacial species (E27); reversible and quasi-reversible
stripping of insoluble Hg salts accumulated at Hg drop
electrodes was treated (E28);semiintegral voltammetry was
applied to situations where weak adsorption exists and both
surface and diffusional waves are observed (E29);and surface
coverages were measured using a combination of chrono-
coulometry and semiintegral voltammetry for situations where
both surface and diffusion components contributed to the
current (E30).
In a paper that illustrates well the difficulty of data
interpretation, Kano and Uno have analyzed the quasi-
reversible surface wave of several quinone couples in terms of
two mechanisms: (i) a one-step, two-electron process; (b) a
two-step E E process. In both cases Frumkin-type interactions
between adsorbed molecules were taken into account and a
Laviron approach was followed. They found somewhat better
agreement with theory for the two-step EE mechanism (E31).
Simulation of reversible CVs where both Ox and R obey
Frumkin-type adsorption isotherms using an orthogonal
collocation method demonstrated the effects of interaction
parameters (E32). The general CV behavior was that of the
classical Wopschall and Shain article. An earlier paper from
the same group concerned the effect of coadsorption of an
electroinactive product of a follow-up reaction (E33). Jin
and co-workers have also presented theory for quasi-reversible
surface waves in a manner similar to that of Laviron with
slight modifications (E34-E36). Their treatments apply to
various transformation voltammetries. Engelman and Evans
simulated the chronocoulometric response for the situation of
simultaneous adsorption and desorption of the product of an
electrode reaction (E37). Input parameters for their program
included rate constants for both the deposition/dissolution
and the adsorption/desorption processes.
Chronopotentiometric theory was presented for the process,
+
aA n e- = bBads,assuming various electrode geometries and
current/time excitation functions (E38).
Recent treatments of the metal dissolution problem include
an analysis of the steady-state i-E curves for an EEmechanism,
assuming Butler-Volmer kinetics and potential independent
constants for irreversible desorption steps (E39), and a
calculation of the current distribution in a corroding pit using
conformal mapping techniques (E40).
Several papers havedealt with the effects of rough or fractal
surfaces on double-layer impedance, mass transport, current
density, etc. ( E 4 1 4 4 4 ) .
Mercury Electrodes. A study of the adsorption of iodide
at the H g / l M NaClO interface between 30 and 453 K is
notable for the wide temperature range studied (E45). Partial
charge transfer was invoked to explain the data. Isotherm
parameters for the adsorption of iodide on H g from ethanol
were compared to values in eight other solvents (E46). Specific
adsorption of halide ions at the Hg/CH&N interface was
studied using classical techniques (E47), and differential
capacity measurements on the electrosorption of benzoic acid
at the Hg/H20 interface indicated a “gas-to-solid” phase
transformation that was driven by attractive dispersion forces
(E48).
Volume 349 of the Journal of Electroanalytical Chemistry,
which consists of papers dedicated to Professor Lucien Gierst,
contains several accounts of the formation of condensed films
at mercury electrodes (E49-E53). Capacitive pits and
condensed layer formation was described for thiouracil from
CH3CN ( E M ) ,methylisoquinoline (E55),and N B q + on Hg
( E M ) . The adsorption of 28 heterocycles and naphthalenes
on H g was analyzed in terms of an “intrinsic” Gibbs adsorption
energy and a partial charge-transfer coefficient (E57).
Analytical Chemistry, Vol. 66,No. 12, June 15, 1994 375R
 Several research groups have focused their attention on
reorientation phenomena. Adsorbates studied include
methylpyridines (E58),4-phenylpyridine (E59),uracil (E60),
and nicotinic acid ( E 6 I ) . The article of Werner et al. on the
adsorption of aniline is noteworthy due to the simultaneous
differential capacity and spectroelectrochemical measurements
of the Hg interface using second harmonic generation
techniques ( E 6 2 ) . At negative potentials, where the aniline
molecules are oriented perpendicular to the electrode surface,
the SHG signal was only dependent on the metal electrode.
Other studies include the report that the self-assembled
monolayer of a C16 alkanethiol insulated Hg by a 1-V range
( E 6 3 ) and accounts of the adsorption of the zwitterion
methionine (E64)and the highly symmetrical pentaerythritol
molecule at the Hg/NaF(,,, interface (E65). The adsorption
of a 1,4-benzodiazepine on Hg was measured in a chrono-
coulometric study (E66) and CVs of benzo[c]cinnoline were
interpreted by assuming Langmuir isotherms and diffusional
mass transport of one of the redox partners from the bulk of
the solution (E67).
Capacitance/time transients at the Hg/H20 interface have
been analyzed in detail for the adsorption of Bu4N+ ions (E68),
5-methyluracil (E69),and 2-thiouracil ( E 7 0 ) . In the Bu4N+
system, the pit nucleation and growth was independent of the
nature of the anion at low concentrations, but became anion
dependent at higher concentrations. Papadopoulos et al. used
phase-sensitive ac voltammetry to construct c d l vs E curves
for different times during the adsorption of sodium dodecyl
sulfate at Hg (E71),and Tomaic et al. obtained the volume
of surface-active condensates such as methyl oleate and
squalene from analysis of current/time transients at the DME
in seawater solution ( E 7 2 ) .
CVs of the Hg(cyclam)2+/Hg couple at Hg were com-
plicated by base hydrolysis of the free ligand and the
appearance of the Hg(OH)z/Hg wave ( E 7 3 ) . In a similar
study, adsorption of Ni(cyclam)2+l+was found at Hg where
the Ni(I)ads complex was involved in the electrocatalysis of
C02 reduction ( E 7 4 ) . Solvent effects on the kinetics of a
(NH3)&o(III/II) coupleadsorbed on Hg via a bridging ligand
were correlated with longitudinal relaxation times for Debye
solvents ( E 7 5 ) .
A Fourier transform method was used to aid in the
resolution of the diffusion peak and the postpeak that were
seen in the differential pulse polarograms of the Pb2+/Pb-
(Hg) system in chloride media where there is weak adsorption
of reactant (E76). Markedly different inhibitory behaviors
were observed in the polarography of Cd2+ and Cr042- at
n-hexyldecyltributylphosphonium-coatedelectrodes ( E 7 7 ) .
The anodic formation of HgS films was reported to proceed
via successive deposition of 2-D monolayers and 3-D islands
(E78). Mattsson et al. studied the electrocrystallization and
stripping of HgSe films which had been formed by the
reduction of Se(1V) or by the oxidation of H2Se (E79). In
the presence of selenate, the anodic polarographic current
was reported to be controlled by the precipitation of Hg2SeO4
(E80).
In the miscellaneous class, Kruijt et al. used a light
scattering method to study the diffusion-controlled growth of
an assembly of Hg spheres on a Pt surface held at constant
potential ( E 8 I ) .
316U Analytical Chemistry, Vol. 66,No. 12, June 15, 1994
Carbon Electrodes. Considerable progress has made in
the last two years in understanding the fundamental surface
electrochemistry of carbon electrodes. Notable among the
contributions are those of McCreery and his students, who
have continued their penetrating research using surface Raman
spectroscopy, a variety of nonfaradaic electrochemical mea-
surements, electron-transfer rates of the Fe(CN),j3-I4- and
related couples, surface imaging methods, and other methods
to characterize HOPG and glassy carbon (GC) electrodes. In
addition, the advent of surface microscopies into various
electrochemistry laboratories has provided remarkable atomic
level insight into what is going on at the carbon/solution
interface during electrolysis.
Kneten and McCreery reported that the electron-transfer
(ET) rates of 13 redox couples were 1-5 orders of magnitude
slower on basal plane HOPG than on laser-activated GC.
Possible reasons advanced for the low rates on HOPG were
the low density of electronic states in this material, the
hydrophobicity of the surface, and the role of the GC surface
in promoting H + transfer-coupled multistep processes (E82).
The role of defect density on the basal plane of HOPG has
been highlighted in several publications from McCreery's
laboratory. For the anthraquinonedisulfonate system the
values of ko,Cdl, and the surface coverage (I'T) were dependent
on the defect density for HOPG (E83). Highly irreversible
CVs were seen for the Fe(CN)63-/4- couple on defect-free
surfaces. Intercalation of HOPG in aqueous acid solutions
was studied by in situ Raman spectroscopy (E84). In 1 M
H3P04, neither intercalation or lattice damage was observed
at potentials up to 2.0 V vs SSCE, while in 1 M H2S04,
HNO3, or HC104, intercalation always preceded or ac-
companied lattice damage.
Slow ET was seen at fractured GC or HOPG electrodes
for the aqueous Fe3+I2+, Eu3+I2+, and V3+12+ couples,
consistent with their low homogeneous self-exchange rates
( E 8 5 ) . However, even slight oxidation of the carbon surface
gave large increases in the observed rates, suggesting oxide
mediated inner-sphere catalysis via intermediate surface
complexes.
SERS of GC and HOPG electrodes after deposition of 0.2
pmol/cm2 metallic silver permitted the formation of graphitic
oxide to be distinguished (E86). For unadorned surfaces, the
electrochemically formed graphite oxide layers were indis-
tinguishable in the SERS spectra. Electroreflectance spectra
of methylene blue on HOPG gave evidence of three different
adsorption states, two of which on the basal plane were
separated by ca. 0.1 V (E87).
Goss et al. reported the first in situ imaging of blister
formation and collapse at HOPG electrodes under oxidative
cycling in HNO3(,,, (E88). They proposed a detailed
mechanism for the submonolayer oxidation that involved
electrolyticgas evolution at subsurface active sites. The blisters
were 20-1000 nm in height and 0.5-50 pm at the base. Other
in situ STM and AFM imaging of carbon electrodes included
the study of Hendricks et al. on lead deposition on HOPG
that was previously decorated with monolayer deep pits. Lead
deposition and stripping at the rims of the pits can be seen in
the published images (E89). Bard's group also achieved
monolayer etching of the basal plane of HOPG using a STM
tip under positive bias (E90). Lines and widths as small as
 10 nm and squares 25 X 25 nm were formed. Others have
used STM to follow the nucleation and 3-D growth of Pt
deposition at HOPG surface defects (E91),the formation of
condensed layers of adenine (E92), and the deposition of
oxometalates (E93).
Glassy carbon surfaces have been most intensely studied,
no doubt due to their favorable characteristics as working
electrodes. An important account of the modification of glassy
carbon electrodes (E94) also gives a very thorough review of
GC as a solid electrode material.
The McCreery in situ laser activation technique for G C
surfaces at power densities below 30 mW/cmz produced only
slight changes in the SERS spectra, the l?T value for
phenanthrenequinone, Cdl, and the SEM appearance of the
polished surfaces (E95). However at fractured GC, or at
fractured G C activated with three 70 mW/cmz laser pulses,
a ko of 0.4 cm/s was measured for the Fe(CN)63-/k couple
in 1 M KC1. STM images of G C surfaces that had been
subjected to several pretreatment procedures showed varying
degrees of roughness (E96). However, ET rates as measured
by the ko for Fe(CN)63-Ik did not correlate with the surface
roughness. This observation was said to be consistent with
the previously widely held view that electrode activity is
determined, to a large extent, as a result of active site exposure
by means of whatever activation method is employed.
Transient currents, which had components on the mil-
lisecond time scale, were produced at GC electrodes by intense
laser pulses (9 ns at 1064 nm). They were attributed to
perturbation and restoration of the diffuse double layer and
adsorbed ions (E97).
Zhang and Coury have made the useful observation that
sonication of GC electrodes in dioxane leads to increased ET
rates for aqueous redox couples (E98). Electrodes treated in
this manner are more prone to adsorb redox-active compounds
than more conventionally treated electrodes and remain active
in aqueous solutions for days. Firouzi et al. imaged G C
surfaces using phase detection interferometric microscopy.
In NaOH(,,), application of 1.5-2.0 V vs SCE for several
seconds generated mesas with heights up to 250 nm and
diameters on the order of 30-70 pm (E99). An in situ
ellipsometric study of the electrochemical activation of G C
indicated formation of a highly porous, hydrated surface layer,
which increased monotonically with activation time (E100).
G C electrodes activated in air at 400-800 OC or in steam at
790-980 OC gave CVs that exhibited a quinone/hydroquinone-
like couple (EJOI).
An extensive account has appeared concerning the modi-
fication of GC, both surface and homogeneous modification,
by low-temperature thermolysis of poly(pheny1enediacetylene)
precursors (E94). Homogeneous incorporation of Pt, for
example, into GC produced solid electrodes with electrocata-
lytic response for the reduction of 0 2 and H+.These novel
materials were prepared by thermolysis of either mixtures of
platinum oxide microcrystallites in a carrier polymeric
precursor to GC or an organometallic polymer containing
covalent Pt(0). TEM of the electrodes indicated a narrow
size distribution of Pt clusters in the doped GC, with an average
diameter of ca. 1.6 nm (E102). Chlorine- and fluorine-doped
GC was synthesized by this method using perhalogenated
oligomeric materials ( E l 0 3 ) . Electrodes of these materials
exhibited reasonably fast kinetics for the Fe(CN)&" couple,
and interestingly, the fluoro-GC had very low double-layer
capacities, on the order of 8 pF/cmZ.
Several more conventional modifications of GC surfaces
have been pursued in the past two years. Tateishi et al. found
that ultrafine gold particles, 1-12 nm in diameter deposited
on GC, produced an active surface for the oxidation of ethanol
and acetaldehyde in alkaline solution ( ~ 0 4 )Similarly,
. silver-
modified GC was an efficient substrate for the oxidation of
small organics (E105), and G C electrodes modified with the
NiO/NiOOH couple worked well for the amperometric
detection of aliphatic alcohols (E106). Kulesza et al. reported
that the use of a Pt counter electrode in acidic media can lead
to electrodeposition of Pt particles with diameters of 20-40
nm on graphite cathodes (E107). The electrocatalytic
oxidation of As(II1) was used as a sensitive indicator for the
presence of the Pt particles. Several Russian groups have
reported the modification of G C with fluorosulfonic groups
(E108,E109) or with CF, groups (E110).Prewaves in the
CVs of aromatic carbonyl compounds at GC electrodes were
attributed to acidic surface functionalities interacting with
the C=O group of the carbonyl compound (E111,E112).
GC electrode surfaces have been modified with covalently
attached groups by the reduction of aromatic diazonium salts
(E113, E l 14). For example, attachment of phenyl groups at
coverages corresponding to a close-packed monolayer was
demonstrated. The surfaces, which could be modified further
by chemical reactions, were stable to ultrasonic cleaning and
persistent over months.
Several interesting surface electrochemical investigations
have been carried out on carbon fiber electrodes in conjunction
with their use as UMEs. Pantano and Kuhr performed
sophisticated imaging of 10-pm fiber UMEs by two methods:
(i) fluorescence from fluorophores attached to surfacecarboxyl
groups via a linker arm containing a biotin-avidin complex
and (ii) luminol ECL generated at ET sites on the surface.
Surface heterogeneity was evident at the submicrometer level
in the polished and electrochemically treated surfaces (E1 15).
Kawagoe et al., who analyzed the pH dependence of both
quinone reduction and dopamine oxidation at carbon fiber
electrodes, concluded that there were mechanistic differences
between the reactions on carbon fiber and on conventional
electrodes (E116).
Several papers have described the effects of electrochemical
pretreatments of carbon fiber electrodes (E1 17, E l 18). Swain
and Kuwana found that Dupont pitch-based carbon fibers,
which had been subjected to a sequence of high-current
anodizations, underwent a surface-reforming process when
followed by a vacuum heat treatment (E119). The ion-
exchange properties of oxidized carbon fiber bundles have
been exploited in two studies of Jannakondakis and co-workers
(E120,E121). Theionexchangecapacityofthefiberbundles
was estimated at ca. 1 mequiv/g. Carbon fiber UMEs with
cation selectivity were prepared by electropolymerization of
phenolic compounds bearing ion-exchanging carboxylic or
sulfonic groups (E122). Anodic oxidation of pyrolytic graphite
in alkaline solution did not destroy the surface structure while
introducing hydroxyl groups (E123). In acid, oxidation
occurred to depths as great as 40 nm from the edge surface.
Analflical Chemistry, Vol. 66, No. 12, June 15, 1994 377R
 Several articles with innovative aspects have appeared
describing carbon-based working electrodes. DNA-modified
glassy carbon, immobilized via covalent bonds between
deoxyguanosine residues and surface carboxylate groups,
functioned as an electrochemical probe for the complementary
oligonucleotide strand (E124). The electrochemical signal
was that of C0(phen)3~+/~+ preconcentrated by the double-
strand hybrid structure. McFadden et al. prepared carbon
electrodes by pyrolysis of natural gas onto Macor, a machinable
ceramic substrate (E125). ET rates on these surfaces for the
Fe(CN)63-/4- couple were comparable to those obtained on
conventionally polished GC. A highly active electrocatalytic
porous carbon surface for 0 2 reduction was prepared by
adsorbing anionic Co complexes into oxidized poly(pyrro1e)
followed by heat treatment at 820 "C under nitrogen (E126).
A TEMPO-modified graphite felt electrode was used for the
efficient electrocatalytic coupling of methylquinolines ( E l 27).
Wang et al. (E128) evaluated epoxy-composite pellets as
voltammetric working electrodes that were fabricated from
carbon aerogel foams with high surface area and ultrafine
pore sizes (C50 nm). Two groups have used boron-doped
diamond films as working electrodes (E129, E130). The
reduction of nitrate to ammonia in alkaline solution proceeded
withgood Coulombicefficiencyat oneofthesesurfaces (E130).
Screen-printed carbon electrodes have been promoted as
amperometric sensor electrodes (E131, E132). Conducting
salt/silicone oil paste electrodes (E133) and metal-dispersed
carbon paste electrodes (E134) were found to be electro-
catalytically active.
Studies on adsorbed molecules on graphite electrodes are
cited here and in the vast section F below on modified
electrodes. The properties of ruthenium(II1) oxide and cyanide
films on carbon substrates for electrocatalytic oxygen atom
transfer reactions has been examined. Mixed-valent
Ru( II1,IV)-oxo centers were found to show specific reactivity
toward As(II1) and CH30H oxidation (E135). Pyrolyzed Fe
and Co tetraphenylporphyrins and Fe- and Co-crowned
phthalocyanines were evaluated with respect to electrocatalysis
of the 0 2 reduction (E136, E137); covalently attached
Co'Itetraphenylporphyrin on glassy carbon effectively elec-
trocatalyzed the reduction of C02 to C O (E138);an adsorbed
Cu-phenanthroline complex on graphite electrocatalyzed the
reduction of 0 2 and H202 via an EE mechanism (E139-
E1 41); an adsorbed electroactive alizarin quinone, with the
ability to complex Fe(III/II) couples, mediated the reduction
of 0 2 and H202 at graphite electrodes (E142);and chloro-
(phtha1ocyanine)rhodium complexes on HOPG underwent a
slow solid-state electrodimerization that was coupled to the
surface redox chemistry ( E 1 4 3 ) . Finally, in several studies
Bond and co-workers have obtained meaningful voltammetry
of water-insoluble compounds by mechanically transferring
them to solid graphite electrode surfaces where surface redox
reactions could be carried out in aqueous electrolyte solutions
( E 1 4 4 , E145).
Single Crystal Surfaces. On the basis of the number of
papers and their volume, surface electrochemists have been
busy researching a variety of well-defined single crystal
electrodes in the last two years. Interlaced with diligent effort
at characterization of the interfacial structures and mechanistic
phenomena are two major themes: documentation of the role
378R AnalyticalChemistry, Vol. 66,No. 12, June 15, 1994
of surface crystal structure on interfacial phenomena and the
study of surface reconstruction reactions. It is now clear from
numerous examples that surface structure can have remarkable
effects on the mechanisms of a wide variety of electrode
reactions. In many cases this has provided great detail on the
nature of intermediates and key steps in these processes. In
addition, in the past year or so there have appeared several
really elegant applications of the new surface microscopies,
e.g., STM and AFM, to the study of phenomena at single
crystal interfaces.
Platinum(n,n,n). Examples of surface structure-sensitive
reactions are the oxidation of small organic molecules such
as glucose (E146), squaric acid (E147), and ethylene glycol
(E148)at Pt single crystal electrodes in aqueous acid solution.
In the work of Llorca et al. (E146), voltammetric currents
were correlated with edge site processes. Different crystal
faces of a working electrode will display widely different
activities under identical conditions. For example, Pt( 1 10)
was found to be most active for the oxidation of squaric acid
(E147) and ethylene glycol (E148), while P t ( l l 1 ) was the
most active for the electrooxidation of glycerol in alkaline
solution (E149). For the oxidation of glucose, Tafel slopes
of 120 and 60 mV were obtained on Pt( 11 1) and Pt(100),
respectively, along with different adsorbed intermediates,
gluconolactone on Pt( 11 1) and CO on Pt( 100) (E150). On
the other hand, the oxidation of glyoxylic acid in H2S04(aq)
was reported to be mostly insensitive to the structure of Pt
single crystal electrodes (E151).
On the cathodic side, in situ electrochemical mass spec-
troscopy (EC-MS) clearly showed that only the Pt(100) face
was active for the complete hydrogenation of benzene to C6H12
(E152). Benzene was desorbed from the (111) face and
partially desorbed from the (100) face. Another EC-MS study
also revealed significant differences in the operative mecha-
nisms for the oxidation of ethylene on Pt( 11 1 ) and P t ( l l 0 )
surfaces (E153).
Interestingly, oscillatory phenomena have been reported
to be structure sensitive. Potential oscillations were seen during
the oxidation of formic acid on Pt(100), but not on P t ( l l 1 )
(E15 4 , and during the electrocatalytic oxidation of H2 in the
presence of Cu(I1) and C1- at Pt( 11 1) and Pt( loo), but not
at Pt( 110) (E155).
For inorganic systems, well-defined voltammograms for
H N 0 2 / N O were obtained at Pt( 11 l ) , but not at Pt( 100) or
P t ( l l 0 ) surfaces (E156). Rodes et al. (E157), however,
reported irreversible oxidative adsorption of N O in a CV study
of the reduction of nitrite at Pt( loo), and reduction of N02-
and NO to NH3 proceeded with an efficiency of >80% at
Pt( 100) surfaces (E158). For hydrazine oxidation in acid,
stable irreversibly adsorbed species were found at Pt( 1 lo),
while reversible adsorption, without charge transfer, occurred
on Pt(100) and P t ( l l 1 ) (E159). Nishihara et al. found
competitive adsorption with H+ on both terrace and step sites
for the oxidation of hydrazine at Pt(332) and P t ( l l 1 ) in H2-
SO4,aq) ( E I 6 0 ) .
The adsorption of HS04- (E161, ,5162) and phosphate
ions (E163)on Pt was sensitive to the surface geometries. The
hydrogen region electrode process in NaOH(,,) was found to
be strongly dependent on the exposed crystal planes at Pt
low-index and stepped surfaces ( E l 6 4 ) . Adsorbed Pd atoms
on Pt( loo), -( 11l), and -( 110) exhibited different hydrogen
adsorption behavior (EZ65), and the growth of Pt oxide films
wasfasteronPt(ll0) thanon-(loo),-(11 1)orpolycrystalline
surfaces (EZ66).
Even the electropolymerization of 3-methylthiophene was
dependent on the crystal structure of the Pt anode (EZ67).
Likewise, the optical properties of Prussian-blue films,
electrochemically grown on Pt( 11 1) and Au( 11 1) substrates,
were similar to those on glassy carbon, while on Pt( 110) little
film formation was seen (E168).
Surface reconstruction phenomena have been found to be
structure sensitive as well. Rodes and Clavilier, for example,
found that, for stepped-terracePt surfaces, the reconstruction
phenomena, which could be rationalized in part by a hard-
sphere model of the surface, were distinctly dependent on the
width of the terraces (EZ69). Restructuring was indicated
for Pt( 110) undergoing the hydrogen adsorption process in
carbonate and bicarbonate solutions (E170) and for
Pt( loo), -( 1 lo), and -( 11 1) surfaces in neutral phosphate
buffers (E17Z). However, specific adsorption of anions on
Pt( 100) in acid did not induce irreversible surface reconstruc-
tion (E172).
Sumino and Shibata have reported the surface transfor-
mations of electrodeposited films of Pt on polycrystalline
substrates, which can have (100) or (110) orientation,
depending on the experimental conditions (EZ73, E174).
Clavilier and Rodes investigated the effect of the quenching
temperature on the CV response of Pt (33 1) ,- (553), and - (443)
surfaces (EZ75).
Two major groups have addressed difficulties in the
evaluation of absolute surface coverage of adsorbed CO on
single crystal electrodes (E176, E177). Related to this is the
difficulty of determining the Epzcfor single crystal electrodes
when reconstruction occurs (EZ78). Orts et al. reported that
higher C O coverages were reached in solution than in the gas
phase for Pt( 1 1 1) in H2S04(aq)(El77). Oxidation of CO and
CO adlayer formation continue to be popular subjects for
study at single crystal electrodes (El79-EZ81). Minimal
toad, poisoning was reported for the oxidative dissociation of
methanol at Pt(100) in Na2C03(,,) (E182) and for the
oxidation of glycolic acid at Pt( 11 1) and Pt( 110) surfaces
(E183).
Detailed mechanistic studies on the important methanol
oxidation process included a study in CD30H and CH3OH
at Pt single crystal surfaces which reached the conclusion
that a C-H bond was broken in the initial step (EZ84). This
is in contrast to the UHV decomposition where 0-H undergoes
initial scission at Pt.
The orientations of nitrogen heterocycles such as substituted
pyridines at P t ( l l 1 ) surfaces have been deduced by a
combination of surface spectroscopies and electrochemistry
(EZ85,EZ86). In several instances, surface layers, which
were stable under vacuum, displayed the same electrochemical
behavior before and after evacuation.
Gomez and Clavilier studied Pt(l10) with a view to the
role of surface domains and their size on the hydrogen
desorption process (E187).Mixed adlatticesofC0 and iodine
produced immiscible domains on Pt( 111) surfaces (E188).
Optical second harmonic generation methods applied to the
Pt( 111)-iodine surface revealed symmetry changes of the
monolayer structure (EZ89).
The electrocatalytic role of bismuth adatoms has been
addressed by several authors. Chang et al. attributed the
30-40-fold enhancement of formic acid oxidation rates at
Pt(100) in HC104totheattenuationofCOad,coverage(EZ90).
Formic acid oxidation was also catalyzed on Pt( 11l), although
the major poison was not toads. In contrast, in the presence
of predosed Bi, methanol oxidation was diminished on both
Pt( 111) and -( 100). Campbell and Parsons also found that
the oxidation of methanol was inhibited by submonolayer and
monolayer coverages of both Sn and Bi on single crystal,
polycrystalline, and dispersed Pt electrodes and that Bi
submonolayers on Pt( 11 1) enhanced the oxidation of formic
acid (E191). Weaver’s group has also studied the influence
of Bi adatoms on the oxidation of ethylene glycol at Pt( 111)
(EZ92). The redox behavior of Bi on Pt( 111) indicated that
the adatom sites were dependent on the extent of surface
coverage (E193).
Copper deposition onto Pt single crystal electrodes has been
the topic of several detailed studies. Reports have noted the
dramatic effect of adsorbates on the UPD of Cu on Pt(n,n,n)
electrodes. Adsorbates studied include anions such as C1-
and H S 0 4 - (EZ94, EZ95) and organic molecules such as
hydroquinone (EZ96, E197). Cu, Pb and C O adsorbates on
Pt( 11 1) in acid inhibited hydrogen adsorption and decreased
the voltammetric peak presumably due to HSO4- adsorption
(EZ98). Cadmium submonolayers also effect the adsorption
of HSO4- on Pt( 111) (E199). Along this line, Varga et al.
reported that Cu deposition on Pt( 111) produced active and
inactive adlayers toward bisulfate adsorption (E200). In one
of the more detailed studies, Michaelis and Kolb correlated
the voltammetric waves in HzS04(aq) with copper deposition
initially into every other trough in the Pt( 1 lo)-( 1 X 1) surface,
followed by complete monolayer coverage in every trough in
the second process (E201). In situ STM of Cu UPD on
Pt(ll1) had previously indicated a two-step process (E202).
Leung et al. explained apparent discrepancies between
stripping coulometric charge and theory for complete mono-
layer coverage of Cu on Pt( 1 11) surfaces by partial charge
transfer to the substrate (E203, E204).
In the UPD of silver on iodine-covered Pt( 11 l), the Ag
deposited underneath the iodine layer to form a Pt( 11 1)AgI
surface (E205). At a thickness of two monolayers, the
adsorption behavior of bisulfate on Ag deposited on Pt( 111)
was similar to that on bulk silver (E206). Other studies include
the concentration dependence of the UPD of Ag on Pt( 11 1)
(E207), the epitaxial growth of Pd and Rh monolayers on
Pt(l1 l)andPt(100) (E208),andtheadsorptionofGeadatoms
on Pt single crystal electrodes (E209).
Gold(n,n,n). Reconstruction phenomena have been promi-
nent in studies using gold single crystal electrodes. Several
groups have investigated the anion-induced transformations
of (5 X 20) to (1 X 1) structures for Au( 100) electrodes ( E 2 1 4
E21Z). In a STM study, Gao and Weaver found that, in the
presence of iodide, the conversion of the square planar (1 X
1) surface to a hexagonal reconstructed phase was remarkably
rapid (<0.2 s) for Au(100) in aqueous solution (E2Z2). In
situ STM of Au( 111) revealed potential-dependent formation
of a ( d 3 X d 3 ) R 3 O o adlattice structure in NaI and NaBr
Analytical Chemistty, Vol. 66,No. 12, June 15, 1994 379R
solutions (E213,E214)and in HC104 (E215). STM images
of flame-annealed Au( 100) surfaces clearly showed that
cooling the surfaces in water prevented reconstruction of the
surface (E216). However, E cycling to E C Epzcgave rise to
( 5 x 27) domains in the STM images; see also ref E217.
Changes were also seen in the differential capacity consistent
with these results.
The effect of organic adsorbates (usually stabilization) on
the surface structure of gold single crystal electrodes has been
reported (E218-E221). The adsorption of pyridine on
Au(100) was shown to be complicated by the surface
reconstruction into a hexagonal( 1 11)-like surface at negative
potential (E222). On the unreconstructed surface there was
no phase transformation from flat to vertical orientation of
the adsorbate.
STM images of Au( 11 1) in dilute CN- solution revealed
the presence of monolayer pits on terrace locations that
collapsed in minutes presumably via a mobile step edge/
adatom diffusion mechanism (E223, E224). Nichols et al.
also obtained STM images of Cu deposition on Au( 11 1) and
-(100) surfaces which showed crystallites at the step edges
(E225). For Au( loo), initial Cu deposition was at the rims
of gold mesas that were one atomic layer high and 5-30 nm
in diameter (E226). In the presence of crystal violet, the
crystallites were flatter and spread more uniformly over the
surface as the deposition proceeded. Gao and Weaver reported
potential-dependent adlayer transformations for STM images
of Au( 11 1) in the presence of the I-/I3- couple (E227). At
the onset of iodide oxidation, linear polyiodide strands were
evident in the images.
Pettinger et al. have followed the surface reconstruction of
Au( 1 1 1) using SHG spectroeIectrochemical techniques (E228,
E229). The SHG response from Au( 11 1) also gave details
on the adsorbate/surface interactions during the UPD of Cu,
Ag, Pb, and T1 (E230).
Metal deposition on gold single crystals continued to be a
popular topic. Ullmann et al. achieved the deposition of very
small Cu(0) clusters, typically three to five atoms, on
Au( 1 11) by potential control of the STM tip in a CuSO4/
HzS04 solution (E231). Pb clusters were observed to grow
along a reconstruction edge on A u ( l l 1 ) (E232), and Hg
overlayers on Au( 11 1) have been imaged by AFM (E233).
Interesting papers on Ag UPD include an in situ surface
EXAFS study at Au( 11 1) that found the Ag-0 internuclear
distance to be invariant over a 0.8-V potential range (E234).
STM and AFM have also been performed on the A u ( l l 1 )
Ag/UPD interface (E235,E236). In the latter study, different
images were seen in different aqueous electrolytes, indicating
that the anion played an important role in determining the
structure of the first monolayer. Lead UPD (E237) and Bi
UPD (E238, ,5239) images were also obtained with AFM
and STM techniques. In the former, lead island formation
was seen and correlated with voltammetric peaks and elec-
trocatalytic activity.
An “electrochemical atomic layer epitaxy” protocol was
devised based on the successive UPD of atomic layers of As,
by oxidative UPD of AsH3 solution, and of Ga by reductive
UPD from Ga(II1) solutions. LEED was used to characterize
the ordered stoichiometric coverages of Ga and As on
Au( loo), -( 1 IO), and -( 11 1 ) surfaces (E240, E241). Golan
300R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
et al. electrodeposited CdSe nanocrystals, “quantum dots”, in
epitaxy with Au( 11 1) (E242). The spatial distribution of the
crystals could be controlled by variation of the temperature
and the ratio of the deposition time to the current density.
Adsorption of organic molecules at gold single crystal
electrodes has been reported for p-toluenesulfonate on
Au(3 11) (E243),benzonitrile on A u ( l l 1 ) (E244), pyridine
on Au(311) (E245), and pyridine on Au(210), where
comparison was made to pyridine adsorption at the (31 l ) ,
(1 lo), (loo), and (1 11) planes (E246). STM, AFM, and CV
were used to study the DNA bases adenine, thymine, guanine,
and cytosine adsorbed onto Au( 11 1) (E247). The Langmuir-
Blodgett transfer procedure, i.e., the film pressure, was found
to be sensitive to the surface structure for Au(l1 l ) , -(loo),
and -(110) surfaces (E248).
LEED spectra, STM images, and differential capacity vs
E curves have been acquired for the three vicinal orientations
of Au( 111) singlecrystal surfaces (E249). Xing et al. observed
that the two-electron oxidation of ascorbic acid was mostly
insensitive to the surface structure for Au(l1 l ) , -(1 lo), and
-( 100) electrodes (E250).
Other Metals. Data obtained at a Ag( 11 1) electrode were
used to test the validity of the Gouy-Chapman theory (E251).
In a separate study, the effect of crystalline heterogeneity on
the double-layer capacity was documented (E252). Anion
adsorption on Ag( 11 1) was studied by impedance techniques
(E253),and the double-layer capacity of Ag( 100) in KPFqaq)
was measured between 1.5 and 47 “ C (E254). In a compara-
tive study of SCN- adsorption on Ag( 11 1) and Pt( 11 1) from
Hubbard’s laboratory, protonation effects were detected in
the high-resolution energy loss spectra of the interfaces (E255).
Nucleation rates of Pb on Ag(l11) were explained by a
model that took into account substrate-induced strain in the
UPD monolayer (E256). The ease of formation of T1-iodide
layers was found to be the order Ag(l11) > Ag( 100) >
Ag( 1 10) > chemically polished Ag > mechanically polished
polycrystalline Ag in KI solution (E257). STM of Pb UPD
on Ag( 100) and Ag( 1 1 1) electrodes revealed formation of
well-ordered monolayers (E258).
Electrochemical reordering of a disordered palladium oxide
surface was demonstrated by McBride et al. (E259). They
found that treatment of a disordered oxidized surface with
dilute NaI solution at a potential where oxide was reduced
resulted in the appearance of the LEED pattern of a Pd( 100)
surface. The same laboratory reported reorganization of
surface bonding structures upon oxidation of CO adsorbed on
Pd( 1 11) (E260) and the dissolution of Pd in a layer-by-layer
process without loss of an iodine monolayer on a Pd(ll1)-
iodine surface (E261). Two-stage adlattice formation was
suggested for the UPD deposition of Cu on Pd( 100) (E262),
and thin Pd overlayers electrodeposited on Au( 11 1) and
Au( 100) electrodes were shown to behave in a manner similar
to Pd( 11 1 ) and Pd( loo), respectively (E263).
Differences were found in the measurement of C O surface
coverage values on Rh( 100) electrodes by coulometric and
FT-IR spectroscopic techniques (E264). Adsorption of
bisulfate on Rh( 11 1) featured adsorption plateaus over a wide
potential range, in contrast to the behavior at polycrystalline
Rh electrodes (E265). Perchlorate anions were reported to
decompose on polycrystalline Rh and Ir( 1 1 1) electrodes to
produce a surface species, probably adsorbed chloride, that
inhibited hydrogen adsorption (E266).
Only negligible electrocatalysis was seen for the oxidation
of methane when surface oxides and/or silver were deposited
on Ru(001) electrodes (E267). Wang et al. have described
a neat procedure for the preparation of Ni( 11 1) surfaces for
electrochemical study. The surfaces, which were formed under
UHV conditions, were protected with a layer of adsorbed CO
prior to transfer to solution and electrochemical stripping of
the C O (E268). The UPD of T1 and Pb on Cu( 111) films
evaporated on mica surfaces was reported (E269), and an
AFM study of potential-controlled oxygen adsorption on
Cu(100) has appeared (E270). STM images were obtained
of the silicon( 11 1) hydride phase that was revealed when an
oxide layer was removed under potential control in HFg,)
solution (E271).
Surface Imaging Techniques. As is evident in the previous
section, surface electrochemists have been applying the various
surface microscopies to the study of electrode interfaces since
the initial introduction of these techniques. The student
wishing a more complete compilation of references on this
topic should scan citations from the above sections on UMEs
and single crystal electrodes. The articles mentioned here are
perhaps more technique oriented, although the distinctions
are often arbitrary.
Vogel et al. published beautiful S T M images of Pt single
crystal electrodes subjected to the “iodine procedure” both in
air and in electrolyte solutions (E272). The images, which
were in accord with previous LEED ex situ results, were
obtained using a noncommercial STM apparatus, details of
which were given. A prospectus for STM/electrochemistry
has been published that contains many examples and impres-
sive STM images (E273). Schmickler and Widrig presented
some theoretical considerations of the STM/Echem experi-
ment (E274). The Poisson-Boltzmann equation was solved
for a sphere-plane configuration as a model for the tip-
substrate geometry (E275).
Techniques for STM tip sharpening and related applications
were extensively reviewed (E276). A combination of normal
sharpening procedure under ac voltage with the tip oriented
downward, followed by further sharpening with the tip oriented
upward, was found to be effective for tungsten tips. Oxide
layers on tungsten tips are easily removed in concentrated H F
(E277). Details were given for the preparation of STM tips
with reduced capacitive currents for use in a differential
conductance mode of operation (E278)and for electrocoating
STM tips with polyacrylic carboxylic acid (E279).
Surface microscopes have been used in novel ways to
characterize and/or to spatially modify film electrode inter-
faces. For example, Murray’s group has reported a procedure
to produce spatially patterned, laterally heterogeneous polymer-
modified electrodes using in situ AFM (E280). They used
an AFM tip to “nanodose” a defect in a thin film of insulating
poly(pheny1ene oxide) (PEO). The defects were then filled
by electropolymerized conducting polymers. Yang et al.
proposed a STM technique to measure the thickness of polymer
films on conducting substrates. The plot of tip current vs tip
displacement exhibited linear regions due to (i) approach to
the surface, (ii) penetration through the film, and (iii) contact
with the substrate (E281). In situ AFM was successfully
used to follow the electrochemical formation of PEO (E282),
while S T M images of poly(N-methylpyrrole) were noisy,
probably because the STM tip typically was buried in the
poorly conducting polymer film (E283).
Sugimoto et al. used the Bard SECM technique in a direct-
scanning mode to obtain images of a Prussian blue film
electrode that showed cracks and grain boundaries at the
submicrometer level (E284). Engstrom et al. employed SECM
to map the local electron-transfer kinetics of reactions
occurring at kinetically heterogeneous Pt disks or epoxy
impregnated RVC electrodes (E285). Several other applica-
tions of the SECM technique have been cited above in the
sectionon UMEs. The improvement in the technique involving
small-amplitude modulation of the tip position seems especially
important (B75,E286). This permits automaticdetermination
of whether a surface is insulating or conducting.
Among the many applications of STM to electrochemistry
are several reports of STM images of dissolving electrodes
(E287, E288), of metal particles deposited in the pores of
anodic aluminum oxide films (E289),and of electrochemically
grown organic semiconductors (E290). In situ STM/Echem
of silver electrodes revealed time-dependent smoothing of the
surface during redox cycles (E291), and the fractal dimen-
sionality of Au and Pt electrodeposits was determined (E292).
STM images of DNA molecules have been obtained on
Au(ll1) surfaces under potential control (E293). This
particular application, and related methodology (E294),
promises to become popular in molecular biology fields.
Fluorescence imaging of electrode surfaces was achieved
by generation of OH- in weakly buffered solutions of
fluorescein. Thus, reduction of H2O or 02, the latter at
cathodic corrosion sites, converted the dye into a strong
fluorescing species and produced images of the electrode
surface (E295). Miller et al. imaged L-B monolayer films
of a Ru-bpy surfactant by observing ECL with a sensitive
CCD camera (E296). Finally, local ac impedances were
obtained by measuring the potential difference between two
microelectrodes in a probe assembly (E297).
PolycrystallineElectrodes. An interesting comparison of
chronocoulometry, radiochemistry, and Raman spectroscopy
applied to the measurement of pyridine adsorption on gold
electrodes has appeared (E298). Agreement was found
between surface concentrations determined by the first two
techniques, but chronocoulometry, where double-layer, not
faradaic, charge densities were measured, gave the better
precision. Adsorption of HS04-, C1-, and I- on Pt was
measured by three in situ methods: radiotracers, FT-IR, and
ellipsometry (E299). Bell-shaped adsorption isotherms were
reported for 20 organic compounds on Pt (E300),and the Epzc
values and capacitance minima for Au were measured in
NaF(,,) using a piezoelectric technique (E301). An extensive
set of double-layer data at various metal electrodes in DMSO,
DMF, PC, AN, MeOH, and H 2 0 was collected and used to
analyze metal/solvent interactions and the interfacial solvent
structure (E302).
Among the papers on the oxidation of methanol at solid
electrodes are a study at mixed oxides of Pt and Sn (E303),
a study of the effect of Ru deposition where RuOHad,
intermediates were proposed (E304),a study of the effect of
adsorbed Sn atoms (E305), a detailed examination of the
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 381R
process at Pt-Ru alloys (E306), and a report of the use of
hydrophobic nickel electrodes coated with fine particles of
tetrafluoroethylene (E307). In situ FT-IR spectra revealed
several intermediates in the process at Pt, including three
forms of adsorbed CO, a COH species, and a CH-containing
species (E308). Surface-enhanced Raman spectra also have
been obtained for this system (E309).
The surface electrochemical behavior of three isomeric
pyridyl hydroquinones at polycrystalline Pt (and at P t ( l l 1 ) )
was dependent on the orientation of the adsorbed monolayers
(E310). Oxidation of ethylene glycol gave different product
distributions on Au, Pt, and Ni electrodes (E311). FT-IR
spectra indicate C2 solution intermediates in route to oxalate
and carbonate ions on gold electrodes, while formate was
formed to the greatest extent on Ni. The electrocatalytic
oxidation of toluene was seen at coatings of deposited hydrated
platinum oxides on Pt, Ni, Ti, Fe, and glassy carbon supports
(E312). Two pathways were described for the oxidation of
phenol at Pt: one occurring at the inner Helmholtz plane,
where ring cleavage took place, and one occurring at the outer
layer, where a mixture of products was formed (E313).
Squaric acid oxidation on Pt gave extensive formation of toads
and COz products over a wide potential range (E314).
Oxidation of surface mercaptoethanol films at Au proceeded
by multiple pathways (E315).
Evidence was presented to indicate that the first monolayer
of adsorbed thionine is electroinactive at Pt. On sulfur-
modified Pt, however, the first layer of adsorbed material is
electroactive (E316). In similar fashion, sulfur adlayers on
Pt changed the irreversible phenothiazine oxidation into
reversible CV behavior (E317 ) .
RDE and QCM measurement gave new insights on the
well-studied iodine/iodide system at Pt in H2S0qaq)(E318).
Michelhaugh et al. found that even submonolayer coverages
of adsorbed iodine gave fast kinetics for the quinone/
hydroquinone couple, which they took to indicated selective
ET at iodine surface sites (E319). Anodic 0-atom transfer
electrode reactions were proposed for the oxidation of I- to
IO3- at Pt, Au, Pd, Ir, and glassy carbon (B117),for anodic
reactions at PbOz electrode doped with acetate (E320), for
the oxidation of oxysulfur anions at PbO2 (E321),and for the
determination of As(II1) at Pt where a key role was assigned
to PtOH (E322). Anodic Cl2 evolution at Pt was reported to
take place on an oxide-freesurface in anhydrous trifluoroacetic
acid (E323).
Oscillating phenomena continue to stimulate electrochem-
ists, who have usually fingered CO,d, as a key intermediate
in their mechanistic speculations (E3244E327). Wolf et ai.
modeled the oscillating electrochemical reduction of peroxo-
disulfate by a system of nonlinear differential equations based
on a Nernst diffusion layer treatment for a diffusion current
term and a Butler-Volmer expression with a Frumkin
correction for the charge-transfer term (E328). Good agree-
ment between theory and experiment was obtained. The
potential oscillations seen in the galvanostatic oxidation of
formic acid on Pt were directly coupled to frequency oscillations
in the EQCM experiment (E329). Finally, a true ac battery
was based on an ingenious concentration cell that consisted
of two mass-coupled oscillating half-cells. Typical specifica-
382R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
tions were period, 58 s; current, f 2 . 5 PA; and emf, f 5 0 mV
(E330).
The formation and growth of metal oxide films have been
studied by a variety of methods including voltammetry, ac
impedance, and EQCM. These include investigations of Pt
electrodes (E331-E336), gold electrodes (E337-E340), and
Pd electrodes (E341, E336). EQCM data indicated that the
gold dissolution rate upon E cycling in H2S04(aq)was 550
ng/h (E337).
In the miscellaneous category, the relationship of area to
volume of dendritic Ag deposits on polycrystalline Pt was
found to exhibit fractal behavior with area = k ( ~ o l ) ~where
/~,
D = 2.50 f 0.03 (E342). This value is consistent with a
self-similar fractal surface. Finally, a description of a guillotine
electrode, which was tested on A1 electrodes in aqueous
solution, was noted (E343).
Miscellaneous Electrodes. Several reports have appeared
that featured superconducting working electrodes. Plots of
cdl vs T for two T1-based high-T, superconductors immersed
in fluid electrolyte solutions displayed abrupt changes in the
region of Tc ( E 3 4 4 ) . An increase in faradaic current was
observed for high- Tc superconducting electrodes in contact
with Ag+ ion conductors at low temperatures ( E 3 4 5 ) . A role
was suggested for Cooper pairs crossing the double layer and
participating in the electrode reaction. A quasi-reversible,
almost irreversible, CV for the ferrocene+/O couple was
obtained at a Bi-Pb-2223 superconducting UME at 102 K
(E346). Kuznetsov developed theory explaining the increase
in current in the Tc region for superconducting electrodes
(E347).
Conditions were given for the anodic electrosynthesis of
millimeter-sized crystals of Bao.sKo.4BiO3with Tc values of
30.5 K (E348). Superconducting thin films of Y-Ba-Cu-0
and T1-Ba-Ca-Cu-0 were electrodeposited at negative
potentials in DMSO solution (E349). Electrochemical Li-
doping of high- Tcsuperconducting films resulted in an increase
in a lattice constant and/or the T, value (E350). Electro-
polymerization of aniline on the surface of YBa2Cu3O,-a
produced a film with protective properties (E351). More
interestingly, redox cycling of poly(pyrro1e) coated on thin
superconducting films reversibly changed the Tc value by
almost 15 K (E352). The Cu(III/II/I) system was examined
at the latter surface (E353), and Ma et al. successfully
electrodeposited Cu contacts onto a superconducting substrate
(E354).
Several interesting working electrode materials containing
titanium have been studied in the last two years. Titanium
diboride, an electroconductive ceramic, exhibited a wide
potential window and was used for the reduction of C02
(E355). Ebonex, a conducting ceramic mainly composed of
the Magneli phase of titanium oxides Ti407and TiS09,coated
with PbO2, was found to be a suitable anode for ozone
generation (E356). A previous report from Pletcher’s group
had described conducting titanium oxide ceramic electrodes
(E357). Polycrystalline thin films of cubic BaTi03 were
prepared on Ti metal substrates by several methods, including
an electrochemical anodization in Ba(OH)2 solution (E358).
F. MODIFIED ELECTRODES
Charge Transport in Polymer Films. Several important
papers on this topic have appeared in the last two years.
Attention is also called to the review of Inzelt, who has surveyed
theory and experiment up to ca. 1992 (A40). Fritsch-Faules
and Faulkner simulated lateral charge transport in a thin film
of redox centers electrostatically held in a polymer matrix
( F I ) . Their model allowed for partitioning between the film
and solution, which opened two diffusional paths for the ions
in the charge transport process. In a nice experimental study,
they determined the concentration profiles in methyl-
quaternized poly(viny1pyridine) (PVP) films containing the
Fe(CN)&/”couple by means of potentiometric measurement
at arrays of 4-pm-wide Au electrodes in contact with the film
(F2). The concentration profiles under steady-state current
flow between flanking electrodes were linear. The calibration
curve relating potential to concentration was established by
chronocoulometry in a companion paper (F3). The behavior
was found to be Nernstian in spite of (i) different extent of
partitioning of ferri- and ferrocyanide, (ii) oxidation-state-
dependent mass transport, and (iii) nonideal CV behavior.
The charge transport was dominated by diffusion of the redox
species through solution since the diffusion coefficients were
2-3 orders of magnitude greater in solution than in the film.
The experiments of Larsson et al. (F4) on PVP films containing
Fe(III/II) redox sites either directly bound to pyridine groups
on the polymer or electrostatically bound to quaternary
pyridinium sites relate to this model. In the former situation,
the apparent charge-transfer diffusion constants (DcT)were
almost 100times smaller than in the more typical ion-exchange
polymer.
The dynamics of electron hopping in assemblies of redox
centers has been treated in a major contribution that is
pertinent to charge transport in fixed-site redox polymers (F5).
The authors found that when physical motion of the redox
centers was either nonexistent or much slower than electron
hopping, charge propagation was fundamentally a percolation
process, in which electron hops occur between a random
distribution of redox center clusters. In another paper, Blauch
and Saveant modeled the charge transport by random walk
of electrons through redox molecules in square and cubic
lattices (F6). Below a critical concentration, finite cluster
size makes charge transport impossible. Further, in their
treatment, the mean-field physical diffusion model of Dahms
and Ruff was shown to be inapplicable to systems in which
the contribution of physical diffusion to charge transport is
small compared to that of electron hopping. Rapid bounded
diffusion in systems where the redox centers are irreversibly
attached to the supramolecular structure, on the other hand,
gives rise to mean-field behavior when it exceeds the rate of
electron hopping.
In another approach, Mohan and Sangaranarayanan
incorporated an exponential dependence of electron hopping
rates on distance into a generalized diffusion/migration
equation for redox film charge transport (F7). Also Deiss et
al. published a quitegeneral digital simulation of redox polymer
CVs (F8). Their calculation accounted for mass transport by
diffusion and migration, electron hopping by a Saveant
mechanism, homogeneous reactions in the film, heterogeneous
reactions and C,-Jat the membrane/electrode interface, and
Donnan partitioning at the membrane/diffusion layer inter-
face.
Impedance techniques have been refined for the analysis
of charge transport in polymer film electrodes and successfully
applied, notably by Pickup and Albery and their respective
co-workers. Ren and Pickup have published several studies
where they used a transmission line equivalent circuit to
analyze charge transport in ion exchange polymers based on
poly(pyrro1e) (PPy) (F9-FI 1). They employed a porous
electrode model and generally found that ion mobility limited
the charge transport. A good example is their study of polymer
films of 3-methylpyrrole-4-carboxylicacid, where ion mobility
was lo3faster than electronic conductivity (F9). The results
were interpreted using a two-phase model in which ion
transport was due to counterions in the polymer phase and
excess electrolyte in the pores. Fletcher also used a porous
electrode model to interpret impedance data for conducting
polymer electrodes (F12, F13). In a similar fashion the
transmission line model of Albery and Mount was based on
a porous electrode with organic polymer and aqueous pore
phases (F14). Resistances were obtained due to bimolecular
electron exchange and anion buildup in the film. In another
treatment of polymer film ac impedance, they proposed a
transmission line model in which there were separate resistive
rails for the cation and for the anion (F15).This would apply
to the common situation when electron motion along the
polymer backbone is faster than ion conduction in the pores.
Mathias and Haas have developed theory for ac impedance
of redox polymer films under conditions where either electron
hopping or ion migration is slow relative to the other (F16).
They assumed Donnan exclusion permitting only one mobile
ion in the film. These authors have studied PVP films
containing Os(bpy)z centers under conditions of four bathing
electrolytes where the charge transport was via electron and
anion motion only (F17). (This paper gives a nice summary
of the procedures for extracting parameters from raw
impedance data.) In contrast to the above situations, ion
transport in these films was found to be much faster than
electron hopping, even for large anions such as toluene-
sulfonate.
The impedance response of poly(pyrro1e) bilayers, with
perchlorate and poly(styrenesu1fonate) counterions, indicated
that the redox reaction was outside-inside, i.e., began at the
polymer/solution interface (F18). This was consistent with
a porous electrode model and with the redox polymer model
of Albery et al. (F19). On the other hand, a chronopoten-
tiometric study concluded that an inside+mtside mechanism
was operative for lightly doped PPy (F20).
Sharp et al. gave a clear account of the interpretation of
impedance data for Nafion film electrodes containing
O~(bpy)3~+/*+ and substituted ferrocene couples (F21). The
dependence of the redox conductivity on the overall oxidation
state of the film, in their view, was in agreement with an
ion-pairing model in which electron hopping took place
between, for example, a neutral Os(I1) site and a positive
Os(III)+ site. Forster and Vos have reported correlations
between DCT and the heterogeneous electron-exchange rate-
( k o )for two redox polymers containing Os(III/II)-bpy sites
(F22, F23). The effect of the extent of loading of
O~(bpy)3~+/*+ in Nafion was significant when the amount of
Analytical Chemistry, Vol, 66, No. 12, June 15, 1994 383R
Os was greater than one-third of the available anionic groups
necessary for charge neutrality in the oxidized state. In this
case, the CVs exhibited two waves: a reversible surface wave
for the Os(III/II) couple and an irreversible wave at greater
potentials that involved ejection of the complex from the film
(F24). The ejection was elegantly verified by SECM using
a UME probe positioned above the film.
Mao and Pickup used RDE voltammetry of ferrocene to
measure the potential profile across a substituted poly(pyrro1e)
film. The gradient was nonlinear, which they took to indicate
nonmetallic conductivity where the charge transport process
is driven by a concentration gradient of oxidized sites in the
polymer matrix ( F 2 5 ) .
Aoki and Heller measured apparent electron diffusion
coefficients in a cross-linked redox polymer that contained
Os(bpy)2 redox sites. In their interpretation of the data, they
invoked hydration effects that were induced by counterions,
ionic strength changes, or protonation of basic groups on the
polymer backbone (F26). Water transport was noted in
EQCM studiesof PVPfilms containing Os(III/II)-bpy centers
(F27) and poly(viny1ferrocene) films (F28, F29). Slow
structural changes for related polymer films were seen when
the electrodes were transferred between perchloric and
toluenesulfonic acid solutions (F30). For poly( l-hydroxy-
phenazine) films, the typical featureless CV was shown to
involve two ion-exchange coupled steps: one with proton
transport and the other with anion uptake and solvent loss
(F31). Hydration effects were also noted for the solid-state
charge transport in hexacyanoferrate films with fixed
Fe(III/II) sites ( F 3 2 ) .
An equivalent circuit proposed for the interpretation of
impedance data at redox polymer electrodes contained two
capacity terms: one for the substrate/polymer interface and
one for the polymer/solution interface (F33). Also the effect
of surface roughness of the substrate on the impedance of
polymer films has been considered ( F 3 4 ) . The combination
of ac impedance spectroscopy and "electromodulated optical
transmittance spectroscopic impedance" was used by Amemiya
et al. to study charge transport in polymer film electrodes
(F35, F36).
Hillman and Bruckenstein have pointed out the important
role of slow solvent transport in several studies of the redox
kinetics of permselective polymer films. Electron transfer,
solvent uptake, and polymer reconfiguration in a cube scheme
were incorporated into a general model (F37). Often observed
phenomena such as "break-in" processes, charge and mass
trapping, structural changes with redox cycling, and variation
of charge transport rate and Eo' values with time were
encompassed by their theory. For a polythionine redox film,
the kinetics were described in terms of a scheme of squares
involving electron, proton, and solvent transfer (F38). The
EQCM data showed that the coupled motion of electrons and
protons preceded the rate-limiting solvent transfer in both
anodic and cathodic steps. One of the later papers in the
general Bruckenstein and Hillman treatment of the EQCM
experiment has appeared in the last two years (F39). Proton
transfer was also shown to be involved in the charge transport
process operative in thin ubiquinone-Qlo films ( F 4 0 ) .
A two-phase model was employed to explain the surprisingly
large electrochemical diffusion coefficients in polyacrylate
304R Analytical Chemistty, Vol. 66, No. 12,June 15, 1994
gels ( F 4 1 ) . In spite of high gel viscosities, high diffusivity in
thecontinuous aqueous phase was invoked to explain the data.
Electrocatalysis at Modified Electrodes. This subject, a
raison d'stre of modified electrode research, has seen relatively
little theoretical activity in the last two years. The general
treatment of electrocatalysis at polymer-modified electrodes
containing microparticles stands out however ( F 4 2 ) . Equa-
tions were derived for the flux as a function of the number
of particles per unit volume, the film thickness, the substrate
and mediator concentrations, and the particle radii. Eight
cases were described, along with the respective flux equations,
that differed in the reaction orders with respect to the above
experimental variables. In a second paper on metal oxide/
Nafion composite amperometric sensors, the kinetics were
cast in the context of the Michaelis-Menten formalism (F43).
Anson and Xie have addressed several important aspects
of data analysis for the estimation of rates of cross-reactions
that occur during electrochemical catalysis at polymer-
modified electrodes using the Koutecky-Levich equation (F44,
F45). In a later paper, a modified kinetic model, which
assumed an array of film mediator couples with a Gaussian
distribution of Eo' values, was developed (F46). When the
parameters of the distribution were selected to fit the i-E
curve for the non-Nernstian surface wave of the mediator
couple, significant improvement in the agreement between
experimental and calculated currents was obtained for several
cases involving redox couples in Nafion coatings.
Numerous articles continue to be published on various
polymer-modified electrodes designed to be catalytic for
specific processes. The ones cited here will be organized in
terms of the electrode reaction catalyzed and not by the nature
of the polymer matrix. Electrocatalysis of 0 2 reduction was
achieved at a porphyrin ligand coordinated by four Ru(NH3)5
groups in Nafion (F47), and by metal phthalocyanines in
various matrices (F48-F50). Cobalt(I1) complexes in Nafion
( F 5 1 ) and Prussian Blue/poly(aniline) (F52) films catalyzed
the reduction of C02. Electrocatalytic reduction of nitrite
took place at quite positive potentials at PVP films containing
Os-bpy complexes (F53, F54);a mixture of N20, N2, NH2-
OH, and NH3 was obtained at thin polymeric films of an
iron(II1) protoporphyrin (F55).Oxyanions such as chlorate
and bromate were reduced at conducting polymer electrodes
doped with molybdate species (F56,F57). Poly(pyrro1e) films
were robust enough to mediate the reduction of dichromate
in acid (F58).Electrocatalytic films for the reduction of the
disulfide bond in cystine (F59)and for the Cu(II/I)-mediated
reduction of cytochrome c and tyrosinase (F60) have been
described. Substituted poly(pyrro1e) films with Pd(I1) and
Rh(II1)-bpy centers were used, respectively, for the hydro-
genation of organic compounds (F61) and the catalysis of
hydrogen evolution (F62). Catalytic activity was imparted
to insoluble liquid crystal films of a cationic surfactant on
graphite electrodes by vitamin B I Zhexacarboxylate (F63).
On the oxidation side, several different polymer film
electrodes have been used for the electrocatalytic oxidation
of NADH (F64-F66). Pyrrole-substituted Mn tetraphen-
ylporphryrins were precursors to catalytic polymer films for
the epoxidation of alkenes and the oxidation of thioacetamide
(F67). Ru(V/IV)-oxygen complexes in Nafion and poly-
(pyrrole) films mediated the oxidation of alcohols (F68,F69).
Electropolymerization of several free-base and metalated
porphyrins produced conductive redox polymers with elec-
trocatalytic activity for a variety of reactions (F70,F71),and
a porous Ti02 ceramic coated with Nafion containing RuOz/
IrOz catalyst was an efficient electrode for oxygen evolution
(F72).
Polymer film matrices have been employed in enzyme
electrodes since the initial work on things such as the urease
electrode of Updike and Hicks. The use of redox polymers
and conducting polymers in conjunction with mediating species
continues to be an active research area. Many different
variations, and some not so different, have been published in
the last two years on this topic, especially with glucose oxidase
as the enzyme system. Only a few of these will be mentioned
here. Ye et al. described a glucose electrode, which was made
with Heller’s epoxy redox polymer and a quinoprotein glucose
dehydrogenase, that exhibited exceptionally high current
densities, 1.8 mA/cm2 (F73). An improved glucose sensor
was fabricated via the substituted pyrrole route using glucose
oxidase that had been covalently modified with pyrrole (F74).
Your reviewer also liked the description of a glucose sensor
“switch” that was based on a poly( 1,2-diaminobenzene) film
containing the enzyme, which was polymerized on top of a
poly(ani1ine) electrode (F75). Another crafty approach was
that of Anzai et al. who electrodeposited avidin on Pt and then
complexed the surface with biotinylated glucose oxidase (F76).
The mediated redox enzyme concept has been applied to
enzyme systems other than glucose oxidase to develop sensors
for other species including amino acids (F77),fructose (F78),
lactate (F79),NADH (F80), and others (F81).
Papers also continue to appear on electrocatalytic ap-
plications of surface-modified electrodes without a (often
resistive) polymer film component. Some of these have been
cited under Carbon Electrodes. Shi and Anson have studied
their cobalt porphyrin substituted with Ru(NH& groups via
pyridyl ligands when it is adsorbed on graphite (F82). The
currents for oxygen reduction were greater at these surfaces
than at Nafion film surfaces containing the same complexes,
but the stability was not as good. In another study it was
found that the number of Ru(NH& groups on the complex
determined whether a two-electron or a four-electron pathway
was followed (F83), with the trisubstituted pomplex giving
the latter behavior. For protoporphyrin IX-modified glassy
carbon electrodes a two-step reduction of 0 2 was observed for
pH >12, and a four-electron reduction for pH <11 (F84).
Electrocatalytic reduction of 0 2 and H202 was also observed
at pyrolytic graphite coated with Fe and Co phthalocyanines
possessing fused crown ether substituents (F85). The iron
system gave a four-electron reduction wave for oxygen. Ni-
tetraazamacrocycle surfaces were found to be electrocata-
lytically active for the reduction of C 0 2 (F86)and for the
oxidation of alcohols (F87).
Indium tin oxide (ITO) electrodes treated with Cl$3Co-
(CO)4produced SiCo sites that were reactive toward alcohol,
amine, thiol, amide, and carboxylate functionalities (F88).
This was the basis of a general method for modifying I T 0
electrodes.
Ion-Exchange Polymer Film Electrodes. Several thorough
studies of Nafion membranes have appeared. Verbrugge et
al. measured the porosity, proton diffusion coefficient, and
electrokinetic permeability ofNafion-1 17 over the temperature
range 20-90 OC (F89), and Zawodzinski et al. determined
the water uptake and transport properties of the same form
of Nafion under polymer electrolyte fuel cell conditions (F90).
The effects of water on the diffusional or photoluminescence
properties of Nafion films have been reported by others (F91,
F92). Cha et al. found that the adhesion of Nafion films to
Pt substrates could be improved by an underlayer of an
alkanethiol (F93).
Parthasarathy et al. have measured electrode kinetics for
02 reduction at Nafion/Pt interfaces under a wide range of
experimental conditions (F94496).Their article describing
the results at Nafion-impregnated porous gas-diffusion
electrodes gives a brief review of the present status of fuel cell
research (F96). Uribe et al. have also measured oxygen
reduction kinetics at a Nafion/Pt electrode under fuel cell
conditions (3’97).Tafel slopes obtained at gold-coated Nafion
membranes indicated that initial 0 2 - formation was the slow
step (F98).
The incorporation of small particles into Nafion membranes
will often lead to enhanced electrochemical properties relative
to the bare metal or an unmodified polymer film. Liu et al.,
who examined ways to platinize Nafion surfaces, reported
that the best method was to impregnate the film with Pt(I1)
followed by a borohydride reduction (F99).The oxidation of
methanol at metalized Nafion membranes has been further
studied (F100,FlOl).
The reduction of aromatic nitro compounds was performed
at Pt/Nafion membranes that also served to separate the
aqueous counter electrode compartment of the cell from the
nonaqueous cathodic compartment containing the substrate
(F102).
The partitioning of redox couples between Nafion films
and aqueous solutions has been a popular study. Recent
examples include a report of supporting electrolyte effects on
the partitioning of couples such as O~(bpy)2Clz+/~ (F103)
and the effect of oxidation state on the partitioning of U0z2+
(F104).Audebert et al. found that Nafion gels prepared with
alkyl phosphates exhibitedselectivity with respect to absorption
of organic compounds (F105).The problem of exchange of
ions out of ion-exchange polymer-modified electrodes during
analysis was alleviated by the expedient of transferring the
modified electrode, after preconcentration of ions such as T1+
and Pb2+,from dilute solution into a cell with a solid electrolyte
that minimized release of the ions (FlO6,F107).
Electrochemical control of a variety of ion-exchange
interfaces other than Nafion films is readily achieved. Zeolite
composite electrodes have been used for the oxidation of small
molecules (F108)and modified with electroactivecouples such
as Ti4+/3+(F109),Co(II1)-salen complexes (FlIO), and
Ag(I/O) (FI 11). Voltammetry of electroactive species
absorbed into clay-modified electrodes has yielded information
on the nature of the various clays employed in the studies
(FI12-Fl15). Proton “gating” of the electrochemical response
of bilayer clay-modified electrodes containing ion-exchanged
sulfonated phenylporphyrin anions was reported (FI16).The
overall process mimicked rectifier behavior. An a-cyclodextrin
polymer film electrode containing the 4-nitrophenol/4-
nitrophenolate guest system had cation-exchange membrane
properties (FI17). Kutner and Doblhofer found that the
Analytical Chemistty, Vol. 66, No. 12, June 75, 1994 38SR
release of ferroceniumcations from cyclodextrin film electrodes
was dependent on the degree of ionization of fixed carboxylic
sites on the polymer ( F 1 1 8 ) and a poly(pyrrole)/cyclodextrin-
modified electrode exhibited some size exclusion selectivity
(F119).
Several novel analytical applications of ion-exchange
polymer electrodes have appeared in the last two years. A
Nafion film electrode was used to preconcentrate a cobal-
tocenium-labeled amphetamine, acting as a hapten, prior to
SWV analysis in a homogeneous electrochemical immunoassay
procedure (F120, F121). A dual-electrode FIA/LCEC
detector was based on in situ formation of metal complexes
formed by the electrochemically controlled release of a
pyrrolidine dithiocarbamate ligand from a poly(pyrro1e) film
(F122). Nitrosoamine, in the protonated form, was precon-
centrated into Nafion-modified electrodes and analyzed by
voltammetry (F123). Electrodes modified with quaternized
PVP films plus ion-exchanged Fe(CN)64-, Mo(CN)g4-, or
IrC163- species were used to preconcentrate and determine
Ag(1) (F124), and a hydrophobic poly(dimethyldially1-
ammonium chloride) film was used in a three-electrode
amperometric oxygen sensor (F125). Electrochemical “tran-
sistors” featured gates consisting of protonated PVP, which
concentrated electroactive anionic complexes from solution.
Drain currents for these species were turned on when the gate
was polarized in the Eo’ region for each complex (F126).
It is common for polymer films synthesized from conducting
polymer-type precursors or for redox polymers to have ion-
exchange properties that dominate their response. Several
studies of systems of this nature will be cited, although their
classification as ion-exchange, redox, or conducting polymer-
modified electrodes is arbitrary in several instances.
Anion-exchange polymer films were prepared by the
oxidation of pyrrole monomers substituted in the 3-position
with cationic groups (F127) and the oxidation of a pyrrole-
substituted pyridinium salt in the presence of 3-methyl-
thiophene (3-MeTP) (F128). A poly(pyrro1e) copolymer with
a propanesulfonate arm was permselective to K+ a t low
coverage ( F 129),and a poly(o-phenylenediamine) redox film
was permselective to I- and Br- (F130). However, PPy films
in aqueous acid solution were not permselective to CI- with
both K+and H + contributing to the charge transport process
(F131). FT-IR was used to follow ion incorporation into PPy
films containing entrapped dodecyl sulfate anions (F132).
Perchlorate ions were excluded, while carbonate ions were
slowly incorporated from aqueous solution. For poly(pyrrole)/
poly(styrenesu1fonate) (PPy/PSS) bilayers, EQCM data
indicated that oxidation involved cation transport a t low
potentials, and anion transport a t high potentials ( F 1 3 3 ) .
Redox cycling of a sulfonated PPy film effected modulation
of the surface pH of the film/KCI(,,, interface between pH
5.6 and 8.2 (F134). Anomalous CV reduction peaks in the
initial negative-going potential sweep for PPy films in water
and CH3CN were shown to be due to cation uptake by the
film ( F 1 3 5 ) .
Ion motion and release by polymer films has been monitored
by several different methods including observation of the
deflection of a HeNe laser beam a t PPy/solution interfaces
(F136, F137). Interestingly, ion transport across the PPy/
solution interface took place both in the faradaic and in the
386R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
capacitive potential regions. One group has coined the term
“cyclic deflectogram” for these experiments (F138). Chen et
al. used a flow cell with downstream electrochemical detection
to verify release of Fe(CN)& from oxidized PPy (F139) and
controlled release of ATP from PPy was monitored by UV
absorption spectrophotometry (F140).
Nonuniform CdS particles were electrochemically gener-
ated and incorporated into PPy/PSS membranes (F141).PPy
films containing a tetraaza [ 14lannulene-Cu pendant group
were demetalized to produce a film that efficiently extracted
metal ions from solution (F142).
Ionophore Films. UME studies of charge transport in
poly(ethy1ene oxide) films have continued to appear (B103,
F143-FI46). Other examples can be found in a collection of
short papers presented a t a symposium on polymer electrolytes
(F147).
For the TCNQ0I-I2- redox couples in PEO, the apparent
diffusion coefficients were enhanced by electron transfer
between redox partners (F143). Long-range electron transfer
a t distances up to 1.6 nm was invoked to explain the data. For
the case of a bis(fulva1ene)diironsalt in a low molecular weight
poly(ethy1ene glycol)/LiC104 medium, however, physical
diffusion dominated electron hopping in the charge transport
process (F148). U M E steady-state currents of ferrocene in
PEO matrices were found to vary with the chain length of the
polymer molecules (F149).
Intriguing electroactive ionophores were synthesized by
attaching oligo(ethy1ene glycol) chains to tetrathiafulvalene
and Co-bpy complexes (F150). Voltammetry a t very slow
sweep rates of the neat room-temperature liquids, which was
well-behaved due to the lack of natural convection in the high-
viscosity media, was used to determine apparent self-diffusion
coefficients.
Voltammetry in COz supercritical fluids was performed
using a U M E coated with PEO/LiCF3S03 to impart con-
ductivity to the film (F151). Glassy carbon electrodes coated
with Kryptofix-222 gavevery sensitive ( 10-l2 M level) square-
wave peaks for the selective determination of H g in natural
waters (F152). Other applications include the direct electron
transfer to a ferredoxin a t a phosphatidylcholine-modified
Au electrode (F153),the irreversible reduction of retinal at
phospholipid-coated Hg electrodes (F154),and the diffusion-
controlled CV of amphophilic viologen cations a t lipid
electrodes (F155).
In a more theoretical vein, the galvanostatic charging and
discharging of a (-)Li/solid polymer electrolyte/porous
electrode cell was modeled with a high degree of sophistication
(F156). Input parameters for thesimulation included (among
others) the diffusion coefficient of Li in the solid matrix, the
total concentration in the solid, the conductivity of the solid.
the electrode porosity, the exchange current density, and the
thicknesses of the separator and the porous composite electrode.
Nahir and Buck analyzed the current/time transients, which
exhibited potential-dependent, limiting values a t short times,
obtained in a chronoamperometric study on PVC membranes
containing valinomycin (F157). Their model was based on
a fixed-site membrane with a permeable charged species.
Redox Polymer Films. Several quite interesting studies
with ferrocene polymers have been described. Albagli et al.
reported the electrochemical behavior of ferrocene-containing
homopolymers and block copolymers that had polydispersities
as low as 1.05 (FI58). The oxidative deposition of these
polymers from solution depended on the molecular weight
and also could be controlled by the size of a nonelectroactive
block in the polymer chain. A polymer with a ferrocene-
silane backbone displayed surface electrochemistry consistent
with two successive oxidation steps, at different potentials,
involving fractions of the ferrocene repeat units (FI59). An
EQCM study of ferrocene-derivatized siloxane polymer film
revealed significant dependence on the anion of the supporting
electrolyte (FI60).Electrochemicalcontrolof a polymer phase
transition was reported for a novel acrylamide-vinylferrocene
copolymer film (FI61).Above and below the phase change
transition temperature, the film was either shrunken or swollen,
respectively, in aqueous solutions.
Intriguing porphyrin polymers with an alternating one-
dimensional structure of oligothiophene electron donor units
spaced apart by phosphorus porphyrin electron acceptor units
were electrosynthesized (FI62). Photoirradiation markedly
increased the conductivity of the materials. Deronzier et al.
have reported further on their procedure for electropolymer-
ization of substituted pyrroles possessing electroactive groups
such as metallotetraphenylporphyrins(FI63).PPy films were
prepared cross-linked by entwined 1,lO-phenanthroline com-
plexesofCu(I), Co(II), Zn(II), and Ag(I), which weretethered
to the PPy backbone by alkyl spacer arms of variable lengths
(FI64). In another intricate variation on this theme, redox-
active Fe&d2+ centers were immobilized on L-cystine-deriva-
tized PPy (FI65). The electropolymerized films were reduced
chemically to give ionic pendant cysteinyl(su1fide) groups that
ion-exchanged the Fe-S boxes.
Bommarito et al. established that the ratio of Os to Ru in
copolymers of poly(viny1bpy) was markedly dependent on the
method of polymerization (FI66). In a companion paper,
molecular weight and size effects on the transport properties
of the metal polymers were investigated (FI67).A photoredox
procedure has been devised for the synthesis of poly(viny1bpy)-
Ru(I1) films on transparent surfaces (FI68).
Several papers describing the electrochemistry of viologen
polymers have appeared (F169-FI72). One of the more
interesting concerned the trapping of electronic charge at
negative potentials by sulfonated anthraquinone anions that
were electrostatically bound to a polymer containing viologen
cation units (FI69). The trapped charge could be released
by pH change to alkaline conditions, which lowered the quinone
Eo’ value, or by the use of redox mediators in solution. The
E l p value of the pendant viologen polymer of Katz et al. was
dependent on the ionization state of the poly(acry1ic acid)
backbone (FI72).
Other polymer redox films of interest were a poly-
(aminonaphthalene) used as a pH sensor for pH of greater
than ca. 4 (FI 73),poly(pheny1)s with pendant ethers or poly-
(ether)s (FI74),and a quinone polymer film prepared by the
electrooxidation of 5,6-dihydroxyindole at glassy carbon
(FI75). Films of electrooxidized 5-carboxyindole were
insulating in either the fully oxidized or fully reduced states,
but conducting when partially oxidized (FI 76). Redox
polymers with a tetrathiafulvalene functionality were based
ona poly(thiophene) backboneor a 1,3,5-benzenecore (FI77,
F178). In the former case thevoltammetry was a superposition
of that of the TTF and PT units. Thio-substituted quinones
adsorbed on Au and Pt(Hg) provided a simple means of
modifying electrode surfaces (FI79).
Redox polymers with molecular weights up to 20K were
covalently attached to Pt, ITO, and n-Si electrodesvia siloxane
bonds at one end of the polymer chain. The interface structure
was disordered, as indicated by the surface coverages which
were only 2% of that of a close-packed monolayer of
alkanethiols (FI 80).
Prussian Blue and films continue to attract attention as
exemplified by the long-term stability study of Stilwell et al.
(F181).The pH of the electrolyte solution was the critical
factor, with redox cycle lifetimes greater than los easily
achieved for pH 2-3. The voltammetry and chrono-
amperometry of thin films of silver ferricyanide featured
asymmetric CVs and exponential current decay (FI82).
Kulesza et al. carried out Prussian Blue voltammetry in the
absence of liquid electrolyte using a simple two-electrode,
large glassy carbon/UME configuration (FI83). Other
studies of similar systems have been published in the last two
years (FI84-FI89).
Electrochromism and Pattern Formation in Polymer
Electrodes. There have been several advances in the related
areas of electrochromics and pattern formation at modified
electrodes. Since these applications tend to cut across the
ordinary lines of classification for modified electrodes, they
will arbitrarily be collected into a separate section.
Yoneyama and co-workers have produced impressivelyhigh
quality light image formation in a poly(ani1ine) (PAn)/TiO2,
PAn/TiOz, film (FI90,F191). A poly(ani1ine) image of a
human subject is shown in the publications from Yoneyama’s
laboratory. Illumination of the film was performed in pH 7
phosphate buffer containing methanol as a hole scavenger
under conditions of low PAn conductivity to prevent image
spreading. The yellow images of reduced PAn were easily
erased by polarizing the films at 0.5 V vs SCE. Images in
metal-bpy polymer films were also produced by a combination
of photochemistry and electrochemistry (FI92). In this case,
a spatially controlled image of the original mask was produced.
Poly(ani1ine)-methylene blue-Nafion composite film elec-
trodes, which had been further modified with Ru(bpy)32+,
developed images upon illumination (FI93).
In another approach, procedures were given for the
photoproduction of very small, patterned tungsten nuclei in
a microlithographic resist consisting of phosphotungstic acid
and poly(viny1 alcohol). The nuclei served as nucleation sites
for the subsequent electroless deposition of Ni. Features with
dimensions on the order of 0.3 pm were formed (FI94).
Another method for creating microstructure and patterned
images in polymer films involved photochemical ligand loss
from metal redox polymer films containing tetramethyl-bpy
complexes of ruthenium. The photochemical reaction created
“voids” that could be filledvia reaction with osmium phosphine
complexes (FI95).Brumfield et al. also created patterns in
polymer films by deposition of conducting polymers into defects
that had been formed in insulating films with an AFM tip
(E280).
A novel display device was based on the pH change, induced
by the oxidation of a PPy film in NaCl(,,), that caused a
reversible flocculation of a poly(L-lysine) microgel (Fl96).
Analytical Chemistty, Vol. 66,No. 12, June 15, 1994 387R
 Instantaneous detection of light intensity changes and image
production were achieved with a 64-element array contacting
a bacteriorhodopsin film on a Sn02-transparent electrode
(F197). SEM was used to detect images formed in irradiated
self-assembled monolayers containing photoactive aryl azide
groups (F198). Micropatterning of PPy on insulating surfaces
was performed by growing the conducting polymer film across
surfaces that were hydrophobic (F199-F201). A maskless
local deposition procedure was based on the electrodeposition
of poly(ani1ine) a t laser-irradiated sites (F202).
Papers describing modified electrodes with good electro-
chromic properties continue to appear. Recent examples
include L-B films of several rare earth bis(phtha1ocyanine)s
(F203), Cu and Ni phthalocyanine films (F204), poly-
(viologen) films (F205), poly(vinylo1igothiophene) (F206),
poly(quino1inium) salts (F207), and poly(aniline)/W03
composite films (F208,F209). Related to this application is
the report of a procedure for growing a poly(thiophene) film
that was transparent in the visible region for both the oxidized
and reduced states ( F 2 I 0 ) . Siekierski et al. also described a
poly(thiophene) that was highly transparent in the conductive
state (F211). The electrochromic specifications of a PPy/
Prussian Blue/KzS04(aq),poly(benzylvio1ogen) system were
especially impressive (F212).
Light emission from conjugated polymers of the poly@-
phenylenevinylene) type, which has been reported by several
laboratories (F213-F215), represents an intriguing approach
to large area displays. The flexible LEDs of Gustafsson et
al. were fabricated from free-standing films of poly(ethy1ene
terephthalate) as a substrate, PAn as the hole injecting contact,
an electroluminescent layer, and a calcium metal negative
electrode (F215). Greenham et al. achieved quite high
efficiencies with poly(cyanoterephtha1ylidiene) LEDs-up to
4% photon out per electron injected (F216). For the sandwich
cell, Al/poly(thiophene)/ITO, light emission was seen at
applied voltages of 10 V (F217). Photoluminescence intensity
and wavelength from poly(3-hexylthiophene) was dependent
on the regioregularity of the polymer chain (F218).
Conducting Polymer Electrodes. Recent work on elec-
trochemical aspects of electronically conducting polymers,
e.g., poly(pyrrole), poly(aniline), poly(thiophene) (PT), etc.,
will be reviewed here. The equally vast literature on the solid-
state physics of these and related systems will not be covered.
Synthetic Aspects. Radical cation coupling reactions have
been suggested as the carbon-carbon bond formation steps
for several pyrroles (F219) and for 3-MePT (F220) based on
double-potential step chronoamperometric and spectroelec-
trochemical data, respectively. RRDE and EQCM techniques
have also been employed to good effect to distinguish between
coupling mechanisms and to identify intermediates in the
electrosynthesis of conducting polymers (F221, F222). Elec-
tropolymerization of pyrrole in the presence of a N-meth-
ylphenothiazine mediator proceeded via a catalytic scheme
(F223).
STM images and in situ video recording of the nucleation
and growth of 3-MePT were reported (F224, F225). The
electropolymerization and deposition process of PT-3-acetic
acid was concluded to proceed via a two-dimensional layer-
by-layer nucleation mechanism (F226, F227). The fast CV
study of Vuki et al. (B63)indicated that, a t room temperature,
388R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
the growth of PAn nucleation centers, and not slow electron
or counterion motion, limited the current. At low temperature,
ion transport controlled the current a t long times. Perhaps
related to this is the observation of spatial variation of the
PAn conductivity, on the order of 20-30 nm, corresponding
to granular metallic regions (F228).
Several papers have addressed the question of the molecular
weights of electrosynthesized polymers. Wei and Tian found
that the applied potential influenced the molecular weight of
electrosynthesized 3-alkyl-PT (F229). The molecular weight
exhibited a maximum of greater than 50K at an intermediate
potential (1.6 V vs SCE) and was lower in the presence of
additives such as 2,2'-bithiophene. The molecular weight of
electrosynthesized PAn, which was less cross-linked than the
chemically synthesized material, was estimated to be greater
than 50K (F230). Also low-temperature ( 0 "C) was found
to give increased doping levels and conjugation lengths for
PPy electrosynthesis (F231). Photocurrent spectroscopy a t
I T 0 electrodes provided evidence that the first traces of
electrosynthesized 3-MePT had long conjugation lengths
(F232).
Two reports have described the effect of sweep rate on the
morphology of PAn films: fast sweep rates (20 V/s) gave the
more uniform dense films (F233, F234). Ellipsometry and
EQCM data indicated that a periodic cathodic bias during
anodic growth of PAn resulted in morphological changes
characteristic of increased long-range order (F235). p -
Phenylenediamine increased the rate of PAn electropolymer-
ization and altered the morphology of the resulting film (F236).
Improved yields were obtained for the electropolymerization
of thiophene in the presence of ultrasonic waves (F237).
Electropolymerization of pyrrole from aqueous carbonate
solutions produced pinhole-free insulating films, ca. 100-300
nm thick (F238). Two groups have studied theoveroxidation
and degradation of PPy (F239, F240), and the deactivation
of 3-MePT in the presence of C1- was partially restored by
oxidationinCH3CN (F241). In thelattercase, thereactivated
film was chlorinated. Conditions were given for the elec-
trosynthesis of brominated PPy (F242),and PPy films have
been grown in the presence of zwitterionic buffers (F243).
3-MePT conducting fibers as long as 10 cm were grown
in a capillary flow cell where the fluid flow pattern, in part,
governed the shape and diameter of the fiber (F244).
Especially interesting was the fabrication of flexible, conductive
composite fibers by electrolysis along the surface of polyester
and Kelvar strings attached to the electrodes (F245). PAn
has been grown on nylon and glass cloth via chemical oxidation
of aniline-permeated substrates (F246),and PPy electrosyn-
thesized in a nematic liquid crystal medium exhibited only
slightly anisotropic conductivity and no evidence of crystallinity
( F 2 4 7 ) . Several papers have described the synthesis of PPy
either on Ta or within the pores of sintered Ta electrodes
(F248-F250).
A wide variety of different conducting polymer films have
been electrosynthesized. Recent interesting examples include
highly anisotropically conducting films produced by the
electroreduction of a soluble naphthalenedicarboximidein the
presence of a polycation (F251),films of electropolymerized
thiophene, bithiophene, and terthiophene in the presence of
Keggin heteropolyanions (F252), poly(o-anisidine) (F253),
and poly(o-toluidine) (F254). Let it be noted that 1992 was
a good year for the electrosynthesis of poly(parapheny1ene)
(F255-F262).
Several studies have appeared on the electrosynthesis of
bickey ball films (8'2634265). Jehoulet et al. found that
films fully reduced to a (260- state were poor electronic
conductors, while partially reduced films displayed enhanced
electronic conductivity (F263). Reduction took place with a
large structural reorganization and intercalation of the
supporting electrolyte cation.
Electrochemical Characterization. There have been sev-
eral spectroelectrochemical studies ofoligothiophene molecules
with four to eight thiophene units linked at a-position. These
molecules exhibited EE behavior coupled to a-dimer formation
of the radical cation to form a diamagnetic species (F266-
F270). A significant aspect of this observation is that the
a-dimer dication, and the corresponding a-dimer radical
cation, are possible alternative structures for the bipolarons
and polarons, respectively, in "doped" organic metals of the
PT type. The sexithiophene CVs obtained by Bauerle et al.
(F270) revealed a 2+/+/0/-/2-/EEEE system with a 2-V
separation between the anion and cation formation waves. Xu
and Horowitz boldly predicted the chain length of PT by
comparison of its oxidation potential to an extrapolated value
obtained for oligomers with four to six thiophene units (F271).
Guay et al. have also looked at thiophene oligomers with up
to seven thiophene rings (F272-F274). For molecules with
orthogonally fused thiophene oligomers, there was no indica-
tion of a-dimer formation in the oxidized forms.
A very nice comparison of the electrochemistry of a
conducting polymer as a thin film and in solution was made
by Jozefiak et al. on high molecular weight-substituted
polyacetylenes (F275). The thin-film voltammetry of these
molecules was well-behaved, showing oxidative and reductive
doping steps separated by ca. 2 V. The cis-polyacetylene film
voltammetry was irreversible indicating rapid cis to trans
isomerization following electron transfer. In contrast, the
solution CVs did not exhibit well-defined peaks, which the
authors attributed to multiple, highly coupled redox states
having a greater degree of conformational and rotational
freedom than in the solid state.
Only a few of the many studies on the electrochemical
redox switching of conducting polymer films will be mentioned
here. The CV and ac impedance study of Duffitt and Pickup
on PPy indicated that a nonequilibrium state of PPy containing
excess electrolyte and solvent was formed upon reduction and
reoxidation of PPy in CH3CN (F276). Changes in the ionic
resistance of the films were explained by slow transport of salt
and/or solvent out of the films. Son and Rajeshwar reported
a significant role for 0 2 in the redox switching of PPy. In the
presence of oxygen there was a direct transition to a bipolaron
state, while in a nitrogen atmosphere a neutral to polaron to
bipolaron transition was observed (F277). Van Dyke et al.
showed that the insulator to conductor transition for PPy could
be extended by ca. 0.7 V in the negative direction by treatment
of the PPy films with degassed NaOH solution (F278). The
effect was rationalized by the relative affinities of the PPy
cationic sites for OH-and BF4- ions. Spectroelectrochemistry
of 3-MePT indicated that two redox processes were operative
for the formation of radical cation(po1aron) and dication-
(bipolaron) states, both of which were shown to be charge
carriers (F279). (See the Accounts of Chemical Research
article by Tolbert for a good molecular-based view of the
chemical basis for conductivity in organic metals (F280),)
Differential pulse voltammetry of a novel electrically
conductive butylphthalocyaninato silicon polymer was inter-
preted in terms of the bandwidth and structure of the solid-
state molecular orbital (F281). The two DPV peaks were
correlated with maxima in the'density of states of the valence
band.
Theory for conducting polymer voltammetry incorporated
the Butler-Volmer equation in order to take into account slow
electron transfer at the polymer/metal interface (F282).
Doblhofer argued that, since the potential of solvated
conducting polymer systems such as PT remains relatively
constant as they are oxidized, they are best described as redox
polymers (F283).
Several interesting experimental and theoretical treatments
of the pH-driven conductor to insulator transition for PAn
films have appeared. Donnan potential expressions and
electroneutrality were employed to explain the pH dependence
of the transition for PAn and PAn/poly(vinylsulfonate)
mixtures and the effect of NaCl concentration on the
conductivity of emeraldine films (F284, F285). Another
treatment of the PAn protonation equilibria required only
one apparent pK, value (ca. 5 ) to account for the experimental
conductivity/pH curve (F286). Theory for order-disorder
transitions in binary alloys was applied to benzenoidquinonoid
and quinonoidquinonoid segments in PAn (F287), and a
model for PAn oxidation and protonation was presented that
accounted for the interactions between the positively charged
protons and polarons in a one-dimensional chain (F288). On
the experimental side, EQCM of PAn revealed significant
mass changes only in the pH interval between 1 and 3 where
the reduced form is practically unprotonated and the half-
oxidized form is protonated (F289).
Applications. An informative review of the use of
conducting polymer electrodes in batteries has appeared in
which fundamental problem areas with regard to com-
mercialization were identified (F290). PPy and poly(N-
methylpyrrole) have been compared with an eye to use as a
positive electrode. The latter material cycles 0.6 V more
positive than PPy, but loses Coulombic capacity upon cycling
(F291). Gravimetric charge densities up to 270 A h kg-l
were determined for PAn in propylene carbonate/LiClOp
solution (F292).
The incorporation of metal particles into conducting
polymer films has been a strategy explored for a variety of
electrocatalytic applications. Recent examples include Pb02/
PPy (F293),Pt/PAn (F294),Pd/(PAn or PPy) (F295),and
Pt/PPy (F296, F297) composite film electrodes. A good
exampleis thearticleof Chen et al., whostudied the permeation
of H2 and 0 2 into composite films of PPy containing
nanometer-sized Pt particles (F297). Conditions for the
preparation of PPy films containing homogeneous distributions
of W 0 3 and 0.4-pm Ti02 particles have been given (F298,
F299).
Two interesting applications of conducting polymers as
membranes stand out. Martin and co-workers reported that
oxidized PPy membranes, supported in the pores of a
Analytical Chemistry, Vol. 66, No. 12, June 15, 1994 389R
polycarbonate membrane, could transport electrons across
the membrane between a donor/acceptor pair, while simul-
taneously transporting ions to maintain charge neutrality
(F300). More interestingly, they also demonstrated that
glucose oxidase could exchange electrons with the membrane
and drive the oxidation of glucose in a transmembrane manner.
Nafion/PAn and free-standing PAn membranes have been
used as porous gas diffusion membrane electrodes for the
oxidation of SO2 and N2H4, and for the reduction of NO2 and
0 2 (F301).
The volume change that takes place when polymer films
are redox cycled is the basis for possible servomechanical
devices, in which a conducting polymer film is firmly attached
to an electroinactive substrate, e.g., commercial adhesive tape
in one example (F302). The curvature or bending of such
strips has been studied by several groups (F303-F305). The
dimensional changes, driven by proton or redox doping, were
largely reversible for PAn films; values of percent elongation
up to ca. 10% were reported for oriented films in the
perpendicular direction to the draw axis (F305). A velocity
of 5 X m/s was reported for the propagation of the oxidized
zone on a PAn strip (F306).
Conducting polymer diodes and transistors are other
curiosities that continue to attract attention. McCoy and
Wrighton configured two conducting polymer “gates” as a
push-pull amplifier such that there was no crossover distortion
when the output current went through zero (F307). Fox
discussed ways to control directional charge transport in
electroactive polymer arrays, including some voltammetry on
PT/PPy and PPy/PT bilayers (F308). Buck et al. have
discussed the analogies and differences between liquid/solid
polyelectrolyte diodes and conventional solid-state semicon-
ductor diodes (F309). They gave conditions for the chemical
mimicking of p-n junctions involving ion-exchange and redox
polymers. The experimental study of Han et al. on Nafion
bilayers supported their ideas (F310). These workers reported
diode behavior for a Nafion bilayer prepared by sandwiching
two films together at 150 OC in a mechanical press-one film
was loaded with F e ( ~ h e n ) 3 ~ +and
, the other with Fe-
hen)^^+/^+. Others have reported diode-like behavior for
junctions such as poly(bithiophene)/Si and PPy/poly-
(p-phenylenevinylene) (F31I ) .
Chemically deposited PPy has been used as a precoat for
the metalization of printed circuit boards ( F 3 1 2 ) . Electro-
deposited PPy on carbon fibers improved the bonding between
the fibers and an epoxy resin matrix (F323).
Self-Assembled Monolayers. The surface chemistry of
self-assembled monolayers, especially of alkanethiols bonded
to well-defined gold surfaces, is a field to itself which has
blossomed in the last decade. The ability to manipulate inter-
facial structure via the chemistry of SAMs is unprecedented.
There are now a significant number of modified electrode
studies in which the interface exhibits novel phenomena due
to its microstructure in either the lateral or perpendicular
direction.
Several research groups have addressed the question of
how the potential gradient across a SAM affects charge
transport and the voltammetric response at a SAM-modified
electrode. Smith and White showed that non-Nernstian wave
shapes were a function of the thickness and dielectric constant
390R Analytical Chemistry, Vol. 66,No. 12,June 15, 1994
of the film, the surface concentration of the adsorbate, the
supporting electrolyte, the solvent dielectric constant, and the
Epzc( F 3 1 4 ) . Correction procedures that take into account
the potential a t the “plane of electron transfer” were described
that are similar to Frumkin $2 corrections for irreversible
electron-transfer reactions. The electric field strength in a
SAM a t a roughened Ag electrode was measured by observa-
tion of the Stark effect on the fluorescence spectra of a dye
molecule in the film (F315). A value of ca. 4 X lo4 V/cm
was found at a point in the diffuse region of the double layer.
The nature of a S A M interface was also probed by measure-
ment of redox potentials of viologen groups positioned a t
different locations with respect to the interface. One conclu-
sion of this study was that hydration of the viologen dication
was the principal factor in determining the Eli2values (F316).
Kitamura reported spike-like voltammetric peaks, indicative
of attractive interactions in the adsorbed state, were dependent
on the alkyl chain length for N,N’-dialkylviologen cations a t
H g electrodes (F317). Creager and Weber calculated the
effect of ions on the potential distribution, and the resulting
effect on electron-transfer rates, across a monolayer (F318).
Electron tunneling through thiol SAMs a t gold electrodes
has been a popular topic. Becka and Miller reported that the
tunneling coefficient, 1.08 f 0.20 per CH2 group, was almost
independent of the potential and the redox couple in solution
(F319). On the other hand, for redox molecules as different
as ubiquinone and Fe(CN)63-, Takehara et al. found a marked
difference in the effect of n-alkanethiol SAMs on the electron-
transfer kinetics (F320). A careful and detailed study of
electron-transfer kinetics of pentaammine(pyridine)Ru com-
plexes tethered to gold via an alkanethiol linkage provided
evidence for the existence of a small fraction of fast electron-
exchange centers that dominated the currents a t low over-
potential (F321). Analysis of the data for molecules with
(CH?)lo-l* tethers suggested that through-bond tunneling, as
opposed to through-space tunneling, was the mechanism of
electron transfer. Curtin et al. also investigated the effect of
the length of the tethering arm on the low-temperature CVs
obtained on ferrocene thiol SAMs (F322). The influence of
film thickness on electron-transfer rates was very clear for an
electrode covered with multilayer films of a metal phosphonate
structure (F323). Obeng et al. reported “b1ocking”properties
of rigid rod thiols on Au (F324). In other studies Finklea and
co-workers obtained nearly ideal CV surface waves for
electroactive thiols containing pendant p y R ~ ( N H 3 ) 5 ~ + / ~ +
redox centers on gold electrodes (F325, F326).
Electrodes modified with self-assembling molecules with
terminal acid/base or ionic groups can enhance or suppress
selected electrode reactions, depending on the state of the end
group. For example, rates of cationic couples such as
R u ( N H ~ ) ~ ~and + / anionic
~+ couples such as Fe(CN)63-/4- a t
SAMs with terminal ionic groups were affected in markedly
different ways by solvent effects (F327). The effect of pH
on the response of SAMs has been reported for the latter
couples a t thioctic acid-coated electrodes (F328), for
Fe(CN)63-/4- at 4-pyridyl sulfide electrodes (F329),and for
carboxylic thiol SAMs on a Q C M surface (F330). SAMs of
HS(CH2),C02H on Au discriminated against ascorbate anions
in the voltammetric analysis of dopamine, with n = 5 giving
the optimum differentiation (F331). Related to these studies
is the prediction that maxima and minima will appear in i-E
curves of molecular films containing acid/base groups that
are due to variations of the differential capacity (F332).
Activity and ion-pairing effects have been noted at SAM
modified electrodes. For the ( N H ~ ) ~ R u ~couple
+ / ~ +attached
to Au in an organized monolayer, activity coefficient effects
were consistentwith a model in which one anion was transferred
between solution and the metal center in the monolayer for
each electron transferred (F333). (This paper also contains
a good example of the influence of liquid junction potentials
on measured electrode potentials.) Ion-pairing effects were
invoked to explain the very rapid electron-transfer kinetics of
a SAM of a redox-active Os(III/II)-bpy complex (F334) and
for the (ferrocene)+/Ocouplein an n-alkanethiol SAM (F335).
The lateral diffusion of octadecylferrocene in a L-B bilayer
assembly was found to be dependent on the fluidity of the
monolayer film (F336). In a previous paper Majda and co-
workers documented the transition between two-dimensional
diffusion and steady-state mass transport for the microband
voltammetry of CIS-ferrocene surfactant films (F337). Katz
et al. reported that treatment of disordered viologen films, in
which ester links were in the tethering arms, with Cl&H
produced distinctly ordered behavior (F338). Mixed mono-
layers of Cl&H and ClsOH have also been characterized
electrochemically using ubiquinone probe molecules (F339),
Reductive desorption of alkanethiols on evaporated Au
surfaces was the basis of a method reported for the measure-
ment of thiol surface coverage (F340). Porter and co-workers
have also observed the potential controlled electrodeposition
and stripping of alkanethiols in ethanolic KOH (F341).
Nanoporous SAMs on Au were prepared by spontaneous
adsorption of two thiols from solution. The structure and
electrochemical responseof the interface could be manipulated
by variation of the ratio of the thiols and their nature (F342).
Cyclic voltammograms were obtained at a L-B interface
containing 8-cyclodextrinchannels using the “horizontal touch
method” (F343). Inhibition of the electron-transfer process
for permeable species was seen when uncharged electroinactive
guest molecules such as cyclohexanol were present in solution.
A laser desorption procedure was described for the preparation
of mixed thiol monolayers that functioned as “ion-gate”
interfaces (F344). Kim and Bard were able to form pits and
aggregates in alkanethiol SAMs by control of the bias voltage,
the tunneling current and the position of a STM tip (F345).
Gold electrodes treated with cystamine were further
functionalized by treatment with trans-stilbene diisocyanate.
This produced a reactive surface for attachment of redox
proteins and other electroactive groups (F346). Lu et al.
published CV evidence for one of the more intricate of modified
electrodes with a covalentlyattached donor/acceptor catenane
complex (F347). The procedure involved attachment of both
terminal thiols of substituted aromatic donor “needle”
molecules to the electrode surface. Other interesting modified
electrodes include the L-B films of rigid rod oligoimides and
thiol-terminated SAMs of oligoimidesof Miller and colleagues
(F348, F349).
The &/trans isomerization of a single L-B monolayer of
a polymeric azobenzene was followed after irradiation using
a “displacement current” technique (F350). (In this method,
the cell consists of two parallel electrodes where one is in air
ca. 1 mm above the surface of the L-B film.) A CV study
of this isomerization over the temperature range 3-41 “ C has
also appeared (F351).This system is the basis of coulometric
actinometer since the more easily reduced cis form of the
azobenzene can be quantified using Faraday’s law (F352-
F354).
Several groups have studied electron transfer to biologically
important molecules such as cytochrome c at SAM-modified
electrodes (F3554358). These and related interfaces have
been touted as ideal physiologicalmembrane-mimetic systems
for the study of redox proteins (F355,F359).
A hydrophobic hydrogenase enzyme was immobilized in
a bilayer assembly containing CIS-viologen as an electron
mediator (F360). Efficient coupling of the enzymatic activity
to the electrodesurface was realized using both potentiometric
and steady-state voltammetry. Mediated electron transfer to
the redox enzyme glutathione reductase covalently attached
to a cysteic acid ester monolayer was achieved by reaction of
the SAM/enzyme surface with a viologen mediator (F361).
Reports of molecular diode-like behavior have appeared.
SAMs of a u-substituted ferrocenyl alkanethiol on gold were
shown to exhibit unidirectional electron transfer in the presence
of the Fe3+/2+coupleinwater (F362). The monolayer surface
mediated reduction of Fe3+, but inhibited the oxidation of
Fe2+. Asymmetric i-E curves indicative of “molecular
rectification” were also obtained for L-B sandwich cells
containing a donor/acceptor surfactant molecule (F363)and
for a flavolipid/cytochrome c heterolayer prepared by L-B
techniques (F364).
Several miscellaneous studies were noted. Thevoltammetry
of L-B films of phospholipids functionalized with an-
thraquinone groups revealed anion effects related to the
supramolecular structure of the monolayers (F365). Reduc-
tive dechlorination of an aryl chloride was carried out in a
cationic surfactant film (F366).The CV behavior of simple
cations at phosphatidylserine-coated Hg electrodes was mark-
edly pH dependent. These films were relatively impermeable
to cations (e.g., T1+ or Pb2+) at low pH or in the presence of
strongly bound ions such as La3+ (F367). Electron-transfer
rates of amphiphilic ferrocene-substituted surfactants in
cationic micellar media indicated that the molecules were
oriented with cationic headgroups toward the electrode surface
(F368). Disordering effects were deduced from a CV study
on SAMs of a cholesteryl viologen (F369). Salt formation
was indicated for redox cycling of bis(phtha1ocyaninato)-
Yb(II1)-stericacid L-B films (F370). Formation of a porous
deposit was indicated when methylviologen was reduced on
glassy carbon electrodes in the presence of sodium alkyl sulfate
surfactants (F371). A two-capacitor model was advanced to
explain double-layer capacity data obtained at thiol-coated
Au electrodes (F372).
Other Modified Electrodes. Electrochemistry in gel
matrices has been the subject of several interesting studies.
Rillema et al. performed photochemistry on the R ~ ( b p y ) 3 ~ + /
viologen system in a hydrogel matrix where the diffusion
coefficients were only 1 order of magnitude smaller than in
aqueous environments (F373). A sol/gel Si02 film doped
with R ~ ( b p y ) 3 ~was
+ ceramic in nature and porous enough
to allow electron transfer to the electrode substrate (F374).
Electropolymerization of aqueous solutionsof acrylamide gave
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 301R
thin poly(acry1amide) films on carbon fiber electrodes with
number-average molecular weights up to 430 000 (F375).The
reversible, cooperative complexation of surfactants in a
polymer gel was the basis of a device that converted
electrochemical energy into mechanical energy (F376).
Modified electrodes with permselective and electrocatalytic
properties were prepared by casting cellulose acetate films,
which had been hyrolyzed in base to provide porosity, over
electrodeposited Pt and Pd surfaces (F377). Christie et al.
found that poly(viny1 chloride) gave better selectivity than
cellulose acetate as a barrier membrane in amperometric
sensors for H202 and phenolics (F379).
G. B I OELECTROCHEM I STRY
Books and Reviews. Smyth wrote a new book that surveys
the voltammetric analysis of a large number of small organic
and inorganic molecules of biological importance (GI).
Schultz and Taniguchi edited the proceedings volume for the
Fifth International Symposium on Redox Mechanisms and
Interfacial Properties of Molecules of Biological Importance,
held in May 1993 (GZ). This is an excellent collection of
richly diverse, high-quality papers that give a clear sense of
the state of bioelectrochemistry as of 1993. The electro-
chemistry and spectroelectrochemistry of proteins, enzymes,
small molecules, membranes, and cells, as well as new concepts
and techniques, are covered. Volume 221 of the Methods in
Enzymology series will be of great interest to metalloprotein
chemists as it covers physical and spectroscopic methods for
probing metal ion bioenvironments. Of special interest to
electrochemists are the three chapters by Stankovich and co-
workers on EPR spectroelectrochemical titrations of redox
enzymes (G3),Armstrong and co-workers on the voltammetry
ofadsorbed metalloproteins ( G 4 ) ,and Hill and Hunt on direct
and indirect enzyme electrochemistry (G5).
A brief yet succinct overview of the electrochemistry of
biopolymers (proteins, polynucleotides) was provided by Cox
and Przyjazny (G6). Ewing et al. discussed aspects of
performing analytical chemistry (electrochemistry, separa-
tions, identification) in microenvironments, specifically single
nerve cells (G7). The roleof voltammetric methods in research
and development of pharmaceuticals was reviewed by Kauff-
mann and Vir6 (G8). Volk et al. discussed the application of
electrochemistry/mass spectrometry for the elucidation of
biological redox mechanisms (G9).
Many reviews and some books relating to amperometric
biosensors were published over the past two years. In several
excellent reviews, the crucial issue of coupling enzymatic
reactions to current-carrying electrodes was addressed
authoritatively. Encompassing reviews regarding enzyme/
electrode coupling were provided by Ikeda (GIO) and Bour-
dillon (GI!).Gorton et al. reviewed the topic of biosensors
based on apparent direct electron-transfer reactions of per-
oxidases (GI2). In another very informative review, Heller
reviewed his and others’ work on redox “wiring” of enzymes
to electrodes (G13).Redox “wiring” was also covered by
Boguslavsky et al. in their article, which was more narrowly
focused on ferrocene-derivatized siloxane and ethylene oxide
polymers (G14).
A very timely review article on glucose oxidase, with an
emphasis on properties important to biosensor development,
392R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
was published by Wilson and Turner ( G I 5 ) . A general
biosensor review was given by Ivnitskii et al. (G16), which
included reference to numerous Russian language papers.
Hilditch and Green reviewed the topic of disposable elec-
trochemical biosensors and discussed requirements that are
needed for commercial viability (GI7).
Several books on biosensors that include chapters on
amperometric sensors were recently published, but your
reviewer has, regrettably, yet to examine them except for Table
of Contents listings. Among these is the second volume in the
Adcances in Biosensors series edited by Turner ( G I 8 ) . This
volume appears to contain a number of chapters of interest
to amperometric biosensor scientists. Another book, edited
by Nakamura et al., is concerned with immunochemical assays
and biosensors (GI 9) and includes two chapters on ampero-
metric biosensors and electrochemical immunoassay.
The use of chemically modified carbon-type electrodes was
reviewed by Wring and Hart (G20) with an emphasis on
mediation reactions in biosensors.
Bilayer lipid membranes were reviewed for electrochemical
sensing applications by Nikolelis and Krull ( G Z I ) and for
bioelectronic devices in a comprehensive review of BLMs by
Ottova-Leitmannova and Tien (C22).
Small Molecules of Biological Importance. Our ability to
efficiently oxidize and reduce small biological molecules a t
electrode surfaces carries important ramifications. From a
biochemical perspective, this ability opens the way for powerful
investigations of the redox energetics and dynamics of these
molecules in the context of biological function. From an
analytical perspective, efficient redox conversion obviously
provides a basis for sensitive voltammetric or amperometric
detection of the molecules per se. Furthermore, for those
particular molecules serving as enzyme cofactors, their
electrodic behavior can assume paramount importance with
regard to designing amperometric biosensors. Because many
small molecules of biological importance are organic species,
they typically do not undergo clean facile electron-transfer
reactions a t metal electrodes. Large redox overpotentials and
electrode fouling tend to be standard fare, and thus, numerous
investigations over the years have sought to minimize these
factors through mediation and electrocatalytic strategies. This
trend continued during the past two years. In the coverage
that follows, we have not included studies of pharmaceuticals
or investigations of complex chemical reactions coupled to
electrolysis. Our emphasis is decidedly interfacial. Porphyrin-
modified electrode studies directed toward catalysis of 0 2 are
also not included.
Substantial interest continued with regard to the electro-
chemistry of nicotinamide adenine dinucleotide (NAD/
NADH). The oxidation of N A D H is a pivotal component in
the design of dehydrogenase-based enzyme electrodes. Typi-
cally, however, unmediated NADH oxidation proceeds a t large
overpotentials with comcomitant electrode fouling. Kuhr et
al. described a most interesting and potentially useful CV
study of NADH oxidation at carbon fiber microelectrodes
(G23). By using judicious electrochemical pretreatment (to
minimize N A D H adsorption) in combination with fast 100
V/s scan rates (to minimize electrode fouling), reproducible
electrooxidation of N A D H was achieved at bare carbon fiber
surfaces. The application of this approach to the development
of hydrogenase-based microelectrodes was also considered.
In past years, some very successful mediators have been
developed by Gorton and others specifically for NADH
oxidation. Perhaps the best one, Meldola blue, was incor-
porated successfully by Hale et al. into a siloxane polymer
structure that is easily deposited on electrodes by evaporation
(G24). A more complicated approach to the mediated
oxidation of NADH involves the incorporation of a second
enzyme, e.g., diaphorase, specifically to oxidize NADH, with
the mediator then oxidizing thediaphorase (G25). Yet another
potential solution to the problem at hand is direct electro-
catalytic oxidation of NADH on electrochemically grown
conducting polymers, although few have been found to date
that function in this capacity. Two promising candidates were
reported on, namely, poly(indo1e-5-carboxylic acid) (G26)
and poly(thionine) (G27).
Reduction of NAD+ to NADH, also a difficult reaction,
is important synthetically in bioreactors but less so from an
analytical standpoint. The incorporation of rhodium com-
plexes in polymer film electrodes resulted in the catalysis of
this reaction with good selectivity for 1,4-NADH and without
the formation of NAD dimers (G28,G29). Catalyticreduction
of NAD+ by hydrogenase at platinum electrodes was also
described (G30).
Basic electrochemical investigations of catechols and
catecholamines on carbon-type electrodes emphasized vol-
tammetric discrimination capabilities. Such studies are of
direct relevance to in vivo neurochemical studies, which are
reviewed under In Vivo and Cellular Electrochemistry.
Tokuda and co-workers investigated the effects of electro-
chemical pretreatment on the oxidation of dopamine (DA)
(G31). Discrimination against DOPA and DOPAC, but not
ascorbic acid, can be achieved by employing a "mild"
pretreatment. Caution against the indiscriminate use of
"strong" pretreatments for DA detection was given. Over the
last few years, McCreery's group has provided much valuable
insight into carbon electrode voltammetry. Of relevance to
this section is a detailed investigation of theirs concerned with
the adsorption of catechols on glassy carbon surfaces (G32).
Whereas DA, 4-methylcatechol, and DOPAC all adsorb
strongly on fresh-fractured GC, the interaction is weak on
polished surfaces apparently due to impurity adsorption.
Electrochemical pretreatment leads to adsorptive preference
for DA, a cation, due to oxidation of the GC surface. Reverse
differential-pulse voltammetry was used by Matysik et al. in
a study aimed at discriminating among a serious of catechols
(G33). Nafion coatings are frequently used with carbon
electrode studies of neurotransmitters to electrostatically
discriminate against ascorbate and other anions. A new
electrostatic approach was described by Malem and Mandler
in which COOH-terminated alkanethiolate self-assembled
monolayers on gold were effective in discriminating against
ascorbate during the detection of DA (G34).
The direct oxidation of carbohydrates, alcohols, and amino
acids is now performed routinely at noble metal electrodes
due to the efforts of Dennis Johnson and co-workers. In the
latest chapter, Vandeberg and Johnson report on the pulsed
electrochemical detection of the sulfurous compounds cysteine,
cystine, methionine, and glutathione, at picomolar detection
limits (G35). Lacourse and Johnson have described an
automated optimization of all waveform parameters for the
pulsed amperometric detection of several representative
carbohydrates (G36). Wang's group has been developing
chemically modified electrodes for HPLC and FIA deter-
mination of various biological compounds. Accounts were
given of the design and characterization of a Prussian Blue
electrode for glucose detection (G37) and a polymer film
electrode containing nickel (0xy)hydroxide catalyst for car-
bohydrate and amino acid oxidations (G38). The oxidation
of glucose can also occur readily at organic conducting salt
electrodes as shown by Zhao and Lennox for TTF/TCNQ
(G39). Electrodes based on HMTTeF-TCNQ (where HMT-
TeF represents hexamethylenetetratellurafulvalene)(G40)
exhibited especially good versatility for a number of other
important oxidations including glutathione, cysteine, dopa-
mine, and ascorbate. This latter electrode is considerably
more resistant to dissolution than TTF/TCNQ. These and
other papers from this group shed considerable light on the
biological oxidations that occur at organic conducting salt
electrodes.
The interaction of amino acids with copper has also been
examined electrochemically. Weber's group, in efforts to
develop detection schemes for nonelectroactive peptides, have
exploited the biuret reaction, which produces electroactive
Cu(I1)-peptide complexes. The influence of tyrosine, an
electroactive amino acid, on the electrochemical response was
addressed in a recent report (G41).
An amperometric sensor was described by Malinski and
Taha for the detection of nitric oxide (G42),a molecule whose
biological importance has only begun to be appreciated in the
past few years. This sensor, which is constructed by elec-
tropolymerization of a Ni-porphyrincatalytic filmon a carbon
fiber electrode, had a detection limit of 10 nM. Furthermore,
it was sufficiently miniaturized, 0.5-m fiber diameter, to
monitor N O release from a single cell.
Several other important molecules were the subject of
significant investigations. The electrochemistry of the co-
enzyme pyrroloquinolinequinone (PQQ) was found to be
reversible under acidic conditions at bis(4-pyridy1)disulfide-
modified gold electrodes (G43). The oxidation of biliverdin,
a key intermediate derived from bile metabolism, was examined
by thin-layer spectroelectrochemistry and its formal potential
was reported (G44). Hemin adsorbed on pyrolytic graphite
electrodes was examined in-depth by UV/visible electro-
reflectance (G45). The adsorption and voltammetry of
ubiquinones was examined at the mercury electrode (G46).
Flavins and related compounds were explored electro-
chemically in both solution and monolayer formats. Verhagen
and Hagen described somevery nice electrochemistry of flavin
adenine dinucleotide (FAD) at glassy carbon electrodes (G47).
High electron-transfer rates were measured for adsorbed FAD,
which appeared to act as a surface mediator for the subsequent
reaction of diffusing FAD. The electrochemical behavior of
solution FAD (and also a ubiquinone) was examined by
Takehara et ai. at gold electrodes covered by n-alkanethiolate
self-assembled monolayers (G48). FAD was able to partition
into the monolayer, but its electron-transfer rate decreased as
film thickness increased, apparently due to increased ET
distance. Nakashima et al. incorporated flavin molecules into
synthetic lipid bilayers on gold electrodes (G49). In this study,
Analytical Chemistry, Vol. 66,No. 12, June 15, 1994 3B3R
they demonstrated the regulation of flavin E T through control
of the thermal phase transition of the bilayer. Mallik and
Gani immobilized an isoalloxazine species on a gold electrode
and conducted a detailed study of the effect of pH on its
surface redox potential and electron-transfer rate constant
(G50). pH-dependent conformational changes play a key role
in the observed electrochemical properties.
Protein Electrochemistry (emphasizing interfacial electron
transfer and biochemical studies). Exciting advances continue
to emerge from the protein electrochemistry field, which has
experienced a very active two-year period. Whereas simply
obtaining a reproducible voltammetric response for small redox
proteins remained a challenge some ten to fifteen years ago,
that situation has since changed quite decisively. Obtaining
voltammograms for cytochromes, ferredoxins, and small blue
copper proteins is now a commonplace endeavor. Developing
a clear, molecular-level understanding of such “simple”
protein/electrode reactions, however, remains a challenge,
and indeed, many publications and much controversy have
ensued. Other major trends during this time period include
the following: direct electronic communication between
electrodes and larger enzymes; voltammetry of protein and
enzyme monolayers; and the increasing success of protein
voltammetry in solving significant biological problems.
“Simple” Electron- Transfer Proteins (Cytochromes,Ferre-
doxins, Blue Copper Proteins). Gold electrodes modified with
adsorbed “promoters” are widely used in electrochemical
investigations of small E T proteins. Several recent papers
addressed the mechanism by which such promoters work.
Niki’s group described a spectroelectrochemical study of the
cytochrome c reaction a t a gold electrode in the presence of
the original Eddowes/Hill promoter 4,4’-bipyridyl (G51).They
concluded that the interaction of this promoter with cyto-
chrome c is relatively weak and that it acts in the adsorbed
state to inhibit the unfolding of coadsorbed cytochrome c as
well as to provide a suitable interface. An electrochemical
QCM study was reported that provided evidence for weak
adsorption of 4,4’-bipyridine on gold electrodes (G52). Cotton
and co-workers reported the interesting result that even more
weakly adsorbed molecules, namely, 2,2’-bipyridine and
pyrazine, could exhibit promoter activity for cytochrome c
electrochemistry when appropriate adsorption protocols are
followed (G53). These molecules had previously been viewed
as nonpromoters.
The most successful gold electrode promoter for cytochrome
c electrochemistry is the strongly adsorbing bis(4-pyridyl)
disulfide, which was first described by Taniguchi. Ellipso-
metric evidence was described supporting the idea that bis-
(4-pyridyl) disulfide prevents unfolding of irreversibly ad-
sorbed cytochrome c at the gold surface (G54), and it was
furthermore suggested that electron transfer occurs in some
manner through an adsorbed monolayer of cytochrome c. In
situ STM images of the bis(4-pyridyl) disulfide/gold interface
in water suggested ordering of the organic monolayer (G55).
In an interesting study from Taniguchi’s group, the effect of
chemical modification of surface lysines, Le., conversion to
negative charge, was examined (G56). Promoter-modified
electrodes turned out to be significantly less adept a t
recognizing modified cytochrome c molecules than cytochrome
oxidase. Haladjian et al. used modified gold electrodes in the
394R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
first reported electrochemical investigation of rusticyanin
(Thiobacillus ferrooxidans), a blue copper protein with a
molecular weight of ca. 16.5 kDa (G57). An especially
intriguing observation was that the direct electrochemistry of
this basic protein (IEP = 9.1) was promoted well by bis(4-
pyridyl) disulfide but not by several other known promoters
of cytochrome c (IEP = 10) electrochemistry. Finally, an
examination of the influence of promoter surface coverage on
cytochrome c electrochemistry was described by Bond et al.
(G58). At submonolayer coverage of bis(4-pyridyl) disulfide,
a sigmoidal voltammetric wave shape resulted, which was
attributed to radial diffusion a t microscopic reactive sites.
A different approach for promoting the electrochemistry
of small proteins involves the use of lipid-modified electrodes.
Nakashima et al. reported that cytochrome c undergoes direct
electron-transfer reactions a t gold electrodes modified by a
Langmuir-Blodgett mercaptophosphatidylcholine monolayer
(G59). Tollin and co-workers described a self-assembled
lecithin bilayer-modified gold electrode that successfully
promoted the direct electrochemistry of thioredoxins (ca. 12
kDa molecular mass) via their disulfide/dithiol redox activity
(G60). In previous studies, this particular modified electrode
had shown electroactivity for metalloproteins.
Conductive metal oxide electrodes, particularly indium
oxide, also continue to be useful for studies with small E T
proteins. It was shown definitively that the presence of
deamidated or oligomeric forms of cytochrome c interfere
with the reaction of this protein a t indium oxide, but much
less so a t promoter-modified gold (G61). Daido and Akaike
reported a detailed ionic strength and pH study of the reaction
of cytochrome c a t indium oxide (G62);their results supported
Coulombic interfacial attraction as the dominating factor.
Indium oxide electrodes also were shown to give good responses
for negatively charged ferredoxins in the presenceof polylysine
(G63). Coulombic attraction is also known to be the
dominating force in the interaction of cytochrome c with tin
oxide electrodes. Using chronoabsorptometry, Collinson and
Bowden determined adsorption isotherms for this system as
a function of ionic strength, solution composition, and oxidation
state (G64). A report of a “solid-state” promoter of cyto-
chrome c, namely, a porous layer of y-alumina on glassy
carbon, was presented (G65). These results may have
ramifications for those who use alumina polishing media.
Edge-plane pyrolytic graphite (EPG) has been widely used
in studies of small negatively charged proteins, typically in
the presence of inorganic cationic promoters. Datta et al.
proposed that, for ferredoxin reactions at EPG, the promoter
induces a weak adsorption of the protein with Frumkin
isotherm behavior subsequently resulting from lateral repulsive
interactions (G66). EPG direct electrochemistry was used to
characterize the thermodynamic and E T kinetic behavior of
four plastocyanins (G67), with the finding that the parsley
species behaved significantly different from poplar, spinach,
and cucumber. Analysis of CV results using a microelectrode,
radial mass transfer, model provided support for the view that
the EPG surface is electroactively nonuniform toward protein
electron transfer.
There were a growing number of significant studies that
emphasized the direct electrochemistry of protein solutions
as a means to address questions of biochemical importance.
 Clearly there is a growing recognition of the potential of this
approach for investigating protein energetics and dynamics,
duein part to thecontinued maturing of the technique. Indium
oxide electrodes were used in a combined electrochemical/
spectroscopic (CD)/calorimetric (DSC) study of cytochromes
c from a variety of vertebrate species, as described by
Hawkridge and co-workers (G68). Conformational stability
of the cytochromes was linked to differences in amino acid
sequences and the physiological temperature of the source
organism. Barker and Mauk utilized CV in conjunction with
edge-plane pyrolytic graphite electrodes to examine the
alkaline form of cytochrome c and some variants (G69). They
reported the first measurement of the formal potential of the
alkaline form of cytochrome c and gave a complete thermo-
dynamic description of the pH-dependent redox cycle involving
the native and alkaline forms. McLendon and co-workers
measured the formal potential of guanidine hydrochloride-
unfolded cytochrome c and determined a 10 kcal/mol
difference in stabilization energy between the reduced and
oxidized forms of the protein (G70). Independent confirmation
of this result was given by Pielak and co-workers (G71) and
extended to urea denaturation conditions. Both of these studies
made use of the bis(4-pyridyl) disulfide-modified gold
electrode. Cysteine-modified gold electrodes were used in
the first example of a high-pressure protein electrochemical
experiment (G72). A determination of the difference in molar
volume between ferri- and ferrocytochrome c confirmed that
ferrocytochrome c has a more compact structure. Initial
electrochemical reports appeared for the following small
electron-transfer proteins: Achromobacter cycloclastes
pseudoazurin (G73),a blue copper protein from Alcaligenes
faecalis (G74), and cytochrome c‘ from Rhodospirillum
rubrum (G75). This latter paper also presented some
interesting results bearing on the role of promoters for
cytochrome electrode reactions. Reports also continued to
appear in which electron-transfer proteins serve the role of
mediators for complex enzyme systems, thus allowing bi-
molecular interactions and catalytic reactions to be investi-
gated in a physiologically relevant manner. Electrochemical
studies of this type were conducted on the 66-kDa hexaheme
enzyme nitrite reductase from Desulfouibrio desulfuricans
(G76), another nitrite reductase from Alcaligenes faecalis
(G77), and Desulfouibrio gigas hydrogenase (G78), an 89-
kDa molecule containing one nickel and three F e S centers.
Electrochemistry of protein monolayers is a subject that
is continuing to generate increasing interest. Although
scattered reports can be found in the literature from a decade
or more ago, it is only within the last several years that the
potential of this approach has become more evident. During
the last two-year period, Armstrong’s group continued their
work with ferredoxins adsorbed on aminocyclitol-modified
pyrolytic graphite electrodes. Their CV study of the kinetics
of thiolate ligand binding to the (3Fe-4S) cluster of the protein
ferredoxin I11 from Desulfouibrio africanus (G79) is an
excellent example of the capability of monolayer electro-
chemistry for probing the coupling of ligand exchange and
electron transfer. Bowden’s group continued their studies of
cytochrome monolayers emphasizing elucidation of electron-
transfer kinetics and mechanisms. The use of COOH-
alkanethiolate self-assembled monolayers (SAMs) as plat-
forms for docking basic cytochromes appears promising. In
a CV and impedance study of horse cytochrome c adsorbed
on Au/S(CHz)l&OOH, the electron-transfer rate was found
to be consistent with predictions from nonadiabatic Marcus
theory (G80). Collinson et al. demonstrated the covalent
attachment of electroactive cytochrome c to SAM/Au
electrodes using carbodiimide coupling in conjunction with
electrostatic orientation (G81). In a related study, Cooper et
al. described the quasi-reversible voltammetry of cytochrome
c covalently attached to the N-acetyl cysteine-modified gold
electrode via carbodiimide chemistry (G82). Cytochrome
CISAM electrodes were used by Reeves et al. to demonstrate
the application of square-wave voltammetry to quasi-reversible
surface species (G83). There were a number of other quite
interesting cytochrome monolayer studies. Ueyama et al.
demonstrated vectorial electron transfer across a flavolipid
L-B monolayer-modified electrode to an adsorbed layer of
cytochrome c (G84). Cytochrome c was also found to be
electroactive when adsorbed to electrodes modified by a
composite layer consisting of a triblock polyanion and a cationic
lipid (G85).These layers showed a marked pH dependence
of the cytochrome response.
Prior spectroscopic and spectroelectrochemical studies have
contributed importantly to our understanding of electroactive
protein monolayers and it seems a sure bet that this area will
continue to intensify. Using SERS, Hobara et al. showed
that cytochrome c immobilized by adsorption on the bis(4-
pyridyl) disulfide/silver electrode exhibited a native 6cLS
configuration and formal potential, in contrast to its behavior
at bare silver or bis(Cpyridy1) disulfidelgoldelectrodes (G86).
Visible absorption spectra of ferri- and ferrocytochrome c
monolayers on tin oxide electrodes, reported by Collinson and
Bowden (G87),also supported a native conformational state
for the protein on this electrode material. Mantele and co-
workers described FT-IR thin-layer spectroelectrochemical
characterizations of cytochromes utilizing unmediated elec-
trochemistry at modified gold minigrid electrodes. This
technique, which provides reduced minus oxidized difference
spectra, should complement Raman techniques nicely in
providing detailed structural information associated with redox
changes in metalloproteins in solution. In one of their papers,
a detailed characterization of horse cytochrome c redox
chemistry in terms of secondary structure as a function of pH,
temperature, and electrode promoter was provided (G88). In
another paper, detailed structural changes associated with
the redox chemistry of tetrahemic cytochromes c3 were
described (G89). This technique is well-suited to proteins
which can be prepared at reasonably high concentrations,
typically millimolar or greater.
Myoglobin and Hemoglobin. The prospects for the direct
electrochemistry of these oxygen carriers improved signifi-
cantly during this time period. Sample purity was previously
established as an important element in achieving myoglobin
voltammetry at indium oxide electrodes. Tominaga et al.
demonstrated quantitatively that surface hydrophilicity of the
indium oxide electrode is also a crucial factor in this reaction
(G90). They achieved quasi-reversible cyclic voltammetric
responses for both sperm whale and horse myoglobin at highly
hydrophilic In203 surfaces prepared by extensive detergent
sonication. An earlier paper from the same group had
Analytical Chemistty, Vol. 66, No. 12, June 15, 1994 0 395R
described their initial voltammetric results for the horse
myoglobin species (G91). The redox energetics, electron-
transfer kinetics, and ligand dissociation kinetics of
horse metmyoglobin and cyanomyoglobin were explored by
Hawkridge and co-workers a t the indium oxide electrode
surface (G92). Only the six-coordinate species Mb(II1)L (L
= CN-, HzO) were found to undergo facile electron transfer,
with the cyano form exhibiting a considerably enhanced E T
rate. Rickard and co-workers described thin-layer spectro-
electrochemical measurements of redox potential as function
of pH and heterogeneous E T rates for hemoglobinon an indium
oxide electrode (G93). Finally, polyethylene oxide-modified
myoglobin was found to be stableand electroactive (irreversible
ET a t indium oxide) in a PEO oligomer medium (‘394).
Other electrodes besides indium oxide have been developed
in past years for use with the globins. Hemoglobin was found
to be electroactive at polymerized Azure A film electrodes
(G95) and at thionine-modified electrodes (G96). These two
electrodes were each capable of driving both the reduction
and oxidation directions of the Fe(III)/Fe(II) hemoglobin
conversion.
Enzymes: Unmediated Electrochemistry. Achieving elec-
trical communication between redox enzymes and electrodes
continues to be one of the most interesting and promising
areas of protein electrochemistry. Articles concerned with
establishing enzyme/electrode interfacial communication have
been selected for this subsection. Those articles focusing more
on electrocatalytic aspects can be found under Enzyme
Electrodes.
An important activity that continues to flourish is the
unmediated electrochemistry of native unmodified redox
enzymes, including integral membrane proteins. Complexes
originating from the mitochondria of various species were the
topic of several accounts. The terminal complex, cytochrome
oxidase, was immobilized electroactively into a membrane
environment on n-octadecanethiol-modified gold electrodes
using a cholate dialysis procedure (G97). Voltammetry
consistent with direct electron transfer between the electrode
and oxidase was observed, as was the catalytic turnover of
solution cytochrome c. Salamon et al. reported that bovine
cytochrome oxidase directly transfers electrons when incor-
porated into lecithin bilayer-modified indium oxide electrodes,
the two observed voltammetric processes being assigned to
the heme a and CUAcenters (G98). Spinach cytochromef.
another integral protein, was also found to be electroactive at
the same type of electrode. Armstrong and co-workers
described the direct electrochemistry of Escherichia coli
succinate dehydrogenase (hydrophilic portion of complex 11)
immobilized by adsorption on edge-oriented pyrolytic graphite
electrodes (G99). Unusual “diode-like’’ behavior was observed
under conditions of linear potential scan, as evidenced by the
severe retardation of the reverse reaction, fumarate reduction,
as the driving force was increased. Using the same monolayer
approach, a detailed description of the chemically reversible
electrochemistry of E . coli fumarate reductase was also given
( G I 0 0 ) . Redox potentials for the FAD and (4Fe-4s) centers
were obtained, and a turnover number of 840 s-l for
electrocatalytic fumarate reduction reported from RDE
measurements. Other electrochemical experiments with
mitochondrial enzymes were published by Monbouquette and
396R Analytical Chemistry, Vol. 66, No. 12, June 15, 1994
Kinnear. In one study they successfully immobilized elec-
trocatalytically active fumarate reductase in self-assembled
monolayers on gold electrodes using a dialysis procedure
(GIOI). Electrochemistry and electrocatalytic functioning
of E. coli fumarate reductase in micellar media was also
described although the electrode coupling in this case was
mediated by decylubiquinone ( G I 0 2 ) .
Additional evidence supporting the existence of direct
interfacial electron transfer was provided for a number of
other redox enzymes, including the following two reports on
hydrogenase. Bianco and Haladjian reported that hydrogenase
from Desulfovibrio vulgaris (Hildenborough) transfers elec-
trons directly a t pyrolytic graphite electrodes in the presence
of polylysine (G103). At small overpotentials, reversible
hydrogen electrode behavior could be observed. Direct electron
transfer of hydrogenase (Thiocapsa roseopersicina) was also
reported to occur a t cadmium sulfide particles under
illumination (G104). The redox properties of human and
bovine copper-zinc superoxide dismutase (SOD) species as a
function of pH, single site mutations, and inhibitors were
characterized by direct electrochemistry a t gold electrodes
using 1,2-bis(4-pyridyl)ethene as a promoter (GI05, G106).
Shinohara reported the direct electrochemistry of the 40-
kDA flavoenzyme sarcosine oxidase a t textured titanium
dioxide semiconductor electrodes (GI07).
Efficient enzyme/electrode electron transfer is critically
important for the functioning of amperometric biosensors. A
survey of publications on “wired”enzymes, enzymes entrapped
in electronically conductive materials, and mediated coupling
of enzymes for sensors, can be found in the section on Enzyme
Electrodes. To conclude the present section, we highlight
three reports of unmediated electrochemistry of unmodified
enzymes of particular importance to bioanalysis. Zhao et al.
reported that when horseradish peroxidase is irreversibly
adsorbed on colloidal gold particles, direct electron transfer
between the heme and the gold takes place ( G I 0 8 ) . The
electronic coupling may be related in some manner to the
curvature of the gold substrate; the same behavior was absent
for planar electrodes. lkeda et al. described some interesting
observations regarding direct electron transfer between de-
hydrogenases and various electrodes (G109). Alcohol dehy-
drogenase and D-glUCOnate dehydrogenase from bacterial
membranes, upon being irreversibly adsorbed on bare metal
or carbon electrodes, showed significant electrocatalytic
activity in the absence of mediators. Finally, a promising
example that highlights the possibilities for trace voltammetric
detection of sulfur-containing proteins was presented.
Adenosine deaminase was detected at a reported limit of 2
ppb using adsorptive stripping square-wave voltammetry at
mercury electrodes (GI I O ) .
Other Studies ofproteins and Enzymes. A powerful FT-
I R thin-layer spectroelectrochemical technique was utilized
to provide the first vibrational IR spectra for the primary
electron donor of photosynthetic reaction centers from
Rhodobacter sphaeroides and Rhodopseudomonas viridis
(GI I I ) . Redox-driven difference spectra were generated using
direct electrochemistry a t a gold minigrid electrode. In a
second study, FT-IR spectroelectrochemistry and photo-
chemistry were employed to provide unprecedented insight
into the interactions of the quinone electron acceptors in the
R. sphaeroides reaction center (GI 12). Both mediated and
direct electrochemistry were exploited in this study. Stank-
ovich and co-workers described a very nice application of
mediated EPR spectroelectrochemistry to the redox thermo-
dynamics of electron-transfer flavoprotein-ubiquinone oxi-
doreductase (ETF-QO), an iron-sulfur flavoprotein from the
inner mitochondrial membrane (GI 13). Three overlapping
redox potentials associated with the two redox centers were
resolved, making possible the first complete thermodynamic
description of electron transport from fatty acid oxidation
substrates to the mitochondrial respiratory chain. Mediation
was also used in an investigation of Fe(II1) reduction in ferritin
performed using thin-layer spectroelectrochemistry (GI 14).
An in-depth investigation of mediator/enzyme kinetics was
reported by Coury et al. for sulfite oxidase, a molybdoheme,
in reactions with several organic mediators (GII5).
Sagara et al. described an interesting method for the
determination of molar absorptivities of electron-transfer
proteins using optically transparent thin-layer spectroelec-
trochemistry (GI 16). This method, which conveniently does
not require accurate knowledge of protein concentration, was
applied to C-type cytochromes.
A few papers of note also dealt with the interfacial behavior
and electrochemistry of proteins not normally the subject of
redox electrochemical studies. Randriamahazaka and
Nigretto carefully examined the adsorption behavior of
thrombin, a protease from the blood-clotting cascade, on
carbon paste electrodes for a wide range of experimental
conditions (GI 17). Subsequently, a voltammetric assay for
thrombin was developed based on the ability of irreversibly
adsorbed thrombin to cleave an electroactive label from its
substrate (GI 18). Roscoe et al. investigated the irreversible
adsorption behavior of a whey protein, @-lactoglobulin, on
platinum electrodes as a function of temperature and pH
(G119). A SERS examination by Reipa et al. of insulin
adsorbed on silver electrodes indicated that binding to the
electrode occurred primarily via ionized tyrosine and carboxy
terminal ends at potentials positive of the pzc (G120). The
adsorption of human serum albumin on tin oxide electrodes
was characterized in a careful experiment by Asanov and
Larina utilizing total internal reflection fluorescence spec-
troelectrochemistry (GI 21).
Photobioelectrochemistry. In addition to some funda-
mental studies on reaction centers cited in the preceding
section, there were some other projects of interest. Katz
and co-workers examined chemical aspects of Pt and Pt-
amalgamated electrodes in relation to quinone mediation of
adsorbed photosynthetic reaction centers (G122, GI23).
Photoexcitation of Ti02 particles was used to drive the
superoxide dismutase catalytic cycle via photogenerated
superoxide (GI24). Finally, soluble mediators were used as
electron donors in photoelectrochemical characterization of
pigments in thylakoid membrane fractions (GI25).
Enzyme Electrodes. The design and development of
amperometric biosensors in which enzyme reactions are
coupled to amperometric or voltammetric electrodes was the
single largest subject area reviewed in terms of number of
papers considered. Papers selected for citation in the present
document generally displayed either an emphasis on funda-
mental scientific advancement or an emphasis on the dem-
onstration and characterization of new materials, concepts,
or strategies. The reader should note that Janata’s chapter
on sensors in this same issue (GI26) includes comprehensive
coverage of amperometric biosensors. Furthermore, in odd
years, amperometric biosensors are included in the Application
Reviews issue, most recently by Wang in the Clinical
Chemistry chapter (GI27).
Glucose sensors based on the glucose oxidase catalytic cycle
continued to dominate the amperometric biosensor field over
the last two years. The availability and stability of this enzyme,
as well as its obvious application in the monitoring of diabetes,
have been key factors in its popularity. An informative review
article on glucose oxidase was cited earlier (G15). A new
development that is sure to have major impact on the glucose
sensor field is the recently reported crystal structure of partially
deglycosylated glucose oxidase from Aspergillus niger at 2.3-A
resolution (GI28). One other comment of general interest is
the oft-discussed application of glucose sensors for in vivo
monitoring. Although impressive advances have been made
in the development of glucose sensing devices, a number of
imposing problems stand in the way of their implementation
as long-term implantable devices, as succinctdy reviewed by
Reach and Wilson (GI 29).
Theory. Albery and co-workers continued their analysis
of steady-state amperometric biosensor behavior with con-
tributions concerning enzyme/electrode coupling via homo-
geneous solution mediators (GI30), which is of relevance to
the mechanism of conducting organic salt electrodes, and also
multienzyme sensors (G131). The mechanisms attendant to
the functioning of organic salt enzyme electrodes were also
addressed from a different viewpoint (GI32).
Two theoretical sensor studies in which the enzyme catalysts
are incorporated into polymer films were given. In one, the
steady-state response of glucose oxidase/poly(pyrrole)- (PPy-)
based sensors was extended to include the case where a PPy-
oxidizable mediator (benzoquinone) was present in the film
(GI33). In the other, steady-state and transient responses
were provided for mediated enzyme electrocatalysis within
both electronically conductive and insulating polymer films
(GI 34).
Finite-volume modeling was applied to evaluate the
transient response behavior of various electrode configurations,
including the case of a free enzyme layer confined by a
semipermeable membrane and for enzyme immobilized on
either size of a polymer membrane adjacent to the electrode
(GI35). Explicit-point modeling of transient and steady-state
responses was performed for the case of fully soluble enzyme
(glucose oxidase), substrate (glucose), and mediator (GI36).
Digital simulation was also used to model the case of
submonolayer coverage of an enzyme whose interaction with
its substrate releases a redox label that can be detected
electrochemically (GI 37). The intended applications are in
assaying proteases in turbid samples and for characterizing
certain components from the blood coagulation system.
Pardue and co-workers presented two alternative measure-
ment schemes to the usual nonequilibrium steady-state current
measurements. Utilizing a thin-layer cell configuration,
complete reaction of substrate in a small fixed volume gives
rise to equilibrium-based measurements of concentration
(GI 38),which can extend the linear dynamic range and reduce
Analytical Chemistry, Vol. 66, No. 12, June 15, 1994 397R
 dependence on certain experimental variables. In another
study, transient currents measured a t short times were used
with appropriate theoretical models that predict the steady-
state currents that would result at longer times (G139).
Glucose oxidase entrapped within an osmium-based redox
polymer film on a glassy carbon electrode was employed as
the experimental system in these two studies.
Lyons et al. described a theoretical model for a hetero-
geneous thin-film sensor in which Michaelis-Menten kinetics
apply to substrate/product conversion a t dispersed catalytic
particles within a Nafion film (C140). Although the system
examined was dopamine oxidation, the theory also has
relevance to enzyme electrodes.
Tatsuma and Watanabe reported theoretical descriptions
for the case of monolayer and bilayer enzyme electrodes in
which a soluble mediator is responsible for enzyme/electrode
communication. Both transient (G141) and steady-state
(G142) responses were described and compared with results
using glucose oxidase sensors.
Redox “Wired” Enzymes. Some important developments
were reported that bear upon the mechanism of electron
transfer to the FAD sites in glucose oxidase. Mikkelsen,
English, and co-workers provided an insightful characterization
of ferrocene-modified glucose oxidase molecules (GI 4 3 ) .They
concluded that the location of lysine modification sites results
in long-range ferrocene-to-flavin intramolecular electron
transfer as the rate-limiting factor in electrochemical conver-
sion. This view is supported by the available crystal structure
for the enzyme (G128). Another pertinent paper of funda-
mental interest, although not dealing specifically with “wiring”,
is the detailed voltammetric study reported for the glucose/
glucose oxidase reaction mediated by one-electron reagents
(G144). Apparently the mediator forms a precursor complex
with glucose oxidase in a site near the flavin. Interesting
experimental measurements of mediator complexation with
glucose oxidase were reported for hydroquinonesulfonate
(G14.5, G146).
Polymer Film Electrodes. Since Degani and Heller’s
seminal papers on ferrocene-modified glucose oxidase in the
1980s, the redox “wiring” approach to coupling enzymes and
electrodes has flourished, especially as regards entrapment of
the enzyme within redox polymer films. Heller’s review is a
good introduction to this area (G13). It is now possible to
prepare three-dimensionally stable polymer films that provide
a friendly hydrogel microenvironment for enzymes as well as
good electrical communication with the substrate electrode.
Aoki and Heller reported fundamental measurements of
electron-transfer diffusion coefficients for osmium( II/III)/
poly(viny1pyridine) (Os-PVP) hydrogel films as a function of
thedegree of diepoxide cross-linking (G147). “Redoxepoxies”
of the Os-PVP type have been quite successful for entrapping
redox enzymes in the construction of reagentless biosensors.
Heller’s group reported several examples including horseradish
peroxidase sensors for hydrogen peroxide and NAD(P)H
detection (G148), oxidase sensors for detection of L-cu-
glycerophosphate and L-lactate (G149), and a glucose de-
hydrogenase sensor for glucose detection (GI 50). Bienzyme
sensors based on Os-PVP polymers were also described by the
same group (G151) as well as by Michael and co-workers
( G 1 5 2 ) . In these devices, Os-PVP-wired horseradish per-
398R Analytical Chemistry, Vol. 66, No. 12,June 15, 1994
oxidase is oxidized by the hydrogen peroxide generated by the
reaction of a second enzyme with the substrate. This strategy
can be used with difficult-to-“wire” enzymes such as choline
oxidase for detection of choline. Evidence supporting the
feasibility of a trienzyme sensor incorporating acetyl-
cholinesterase was also reported (G152). Michael’s group
also demonstrated that Os-PVP/peroxidase sensors could be
used to detect H202 in CO2-based fluid near its critical point,
the first example of its type (G153).
Glucose oxidase sensors based on entrapment within other
redox polymers was also reported. Ferrocene-based polymers
for this purpose were described by several groups. These
included ferrocene-substituted polylysines (GI 5 4 , polymers
based on ferrocenylenemethylene structure (GI 5 3 , ferro-
cenylsiloxane-ethylene oxide copolymers (GI 56),ferrocenyl-
acrylamide-acrylic acid copolymers (G157),and commercially
availablepoly(viny1ferrocene)(G158). The latter two papers
also discussed theoretical considerations regarding steady-
state sensor response. Other reported redox polymers that
were successfully used to wire glucose oxidase included a
tetrathiafulvalene-substitutedsiloxane polymer (G159) and
polymercapto-p-benzoquinone (GI 60).
The second major focus in developing polymeric enzyme
sensors has been the entrapment of enzymes within polypyrrole
and other conducting polymers, which was first described by
Foulds and Lowe in the 1980s. An advantage of this approach
is the ability to prepare the polymer/enzyme film by a one-
step electropolymerization, which is attractive from a com-
mercialization perspective. The functioning of conventional
polypyrrole-type enzyme electrodes is not as straightforward
as for the redox polymer film electrodes. Typically, the PPy
matrix appears to function primarily as a three-dimensional
support for the enzyme with electrochemical communication
occuring via internal redox of a mediator (e.g., oxidation of
H102) or cosubstrate species. During this two-year time
period, polypyrrole was clearly the material of choice for most
researchers, usually in combination with glucose oxidase, which
generates H202 that is oxidized at the substrate electrode.
Rotating ring disk studies by BClanger et al. examined, among
other factors, the effect of PPy film thickness and glucose
concentration (G161). The catalytic reaction was found to
mainly occur a t the PPy/solution interface except a t high
glucose concentration. In an interesting study, Cooper and
Bloor coimmobilized catalase with both glucose oxidase and
glucose apooxidase to investigate the mechanism of the PPy
biosensor (GI 62). They concluded that electron transfer
between PPy and entrapped enzyme is very inefficient.
Significant rates of electron transfer were noted, however,
when a small electron-transfer protein, cytochrome c, was
entrapped within PPy (G163), In other studies, Tatsuma et
al. prepared horseradish peroxidase/PPy electrodes (G164)
and bienzyme PPy electrodes that contained both peroxidase
and glucose oxidase (G165). A role for the PPy in enhancing
electrochemical communication between the electrode and
enzymes was proposed.
Coentrapment of electron-transfer mediators along with
enzymes in conducting polymers was described by several
groups. In the case of glucose oxidase amperometric sensors,
the rationale for using a mediator is avoidance of the HzOz
product. The high potentials needed to oxidize H201 are
sufficient also tooxidize key interferents, e.g., ascorbate, urate,
glutathione, etc. Operation at lower potentials is clearly
desirable. Some concern has also been raised that H202 can
irreversibly oxidize PPy in an uncontrolled fashion, which
may be a further unwanted side effect. When mediators are
employed, however, their downside is leachability, which must
be controlled adequately in order to fabricate practical devices.
Bartlett et al. demonstrated that coimmobilized ferricyanide
can mediate the glucose oxidase reaction while entrapped
within the PPy film (GI66). Yoneyama and co-workers
coimmobilized 8-naphthoquinonesulfonate,NAD, and glucose
dehydrogenase into PPy using a single-step process to produce
a mediated PPy sensor for glucose (GI67). Also using a one-
step deposition process, Aizawa and co-workers prepared a
PPy/fructose dehydrogenase sensor for detecting fructose that
incorporated either ferricyanide or a ferrocene derivative as
mediator (GI68). Thesamegroup also described a composite
film sensor for fructose detection that was comprised of PPy,
TTF/TCNQ, and fructose dehydrogenase (GI69). The
stability of this sensor was found to be superior to a TTF/
TCNQ/fructose dehydrogenase sensor. Using another strat-
egy, Sun and Tachikawa created a glucose sensor in which a
PPy/glucose oxidase film was deposited over polymetallo-
phthalocyanine (PMePc) films (GI 70). Oxidation of H202
occurred at a 0.7-V lower potential, apparently due to catalysis
at the PMePc/PPy interface.
The reaction mechanisms for polypyrrole amperometric
sensors, including solution mediator reactions, were examined
using cyclic voltammetry, impedance spectroscopy, and
rotating disk voltammetry by Lyons et al. (GI71). Cases
were considered for mediator reaction only at the PPy surface
as well as partitioning into the film. This particular study did
not address enzyme issues in particular. One other related
report examined the reaction of the benzoquinone mediator
at polyaniline films used in biosensor applications (GI 72).
In other applications involving enzymes entrapped within
PPy, the possibility of controlling the activity of the entrapped
enzyme via anion doping/undoping was demonstrated using
phosphate and pyruvate oxidase (GI73). Sadik and Wallace
reported that the utility of PPy/antibody sensors for human
serum albumin was significantly improved using pulsed
amperometric detection (GI 7 4 ) . The mechanism for signal
generation is not, however, clear.
Several papers addressed the issue of electropolymerization
procedure with the objective of improving enzyme activity
and stability. Lowe and co-workers obtained significant
improvement on both counts by covalently copolymerizing
glucose oxidase into a PPy film via pyrrole-derivatized surface
residues (GI 75). In a following study, the method of pyrrole
attachment to glucose oxidase was evaluated, and the kinetic
properties of the modified enzyme were measured (GI76).
Cosnier and Innocent described the clever use of a pyrrole-
substituted cationic surfactant as the monomer for forming
a PPy/tyrosinase electrode for detection of phenols (GI77).
A film of the cationic monomer and the anionic enzyme (IEP
= 4.7) was first deposited on a glassy carbon electrode after
which electropolymerization was conducted in LiC104 elec-
trolyte. The generality of this particular approach was
addressed in additional studies with glucose oxidase and choline
oxidase (GI 7 8 ) . One other nonconventional approach to
forming bioconductive polymers is to use the enzyme as the
polymerization initiator. Under mild conditions, it has been
shown that bilirubin oxidase initiates polymerization and
retains activity in the resultant film of poly( 1,5-dihydroxy-
naphthalene) (GI 79).
The possibility of establishing direct electronic com-
munication between PPy and enzyme monolayers was ad-
dressed in the following two papers. An amperometric
response for glucose was obtained with glucose oxidase
adsorbed on the surface of PPy, which partially filled the
pores of an electrode-supported filtration membrane (GI80).
Identical responses were obtained under 0 2 or argon with no
mediators present. A different approach was taken in the
development of a fructose sensor, where a monolayer of fructose
dehydrogenase was first adsorbed on Pt, followed by encase-
ment in electropolymerized PPy to a thickness of roughly
50-80 A (GI8I). Evidently the PPy was able to convey
electrons between the electrode and the prosthetic group of
the enzyme, pyrroloquinoline quinone (PQQ).
There are promising new examples of enzyme “switches”
based upon the conductivity properties of conductive polymer
films. In these devices, the redox and chemical state of the
polymer thin film, and hence its conductivity, are controlled
by the reaction products of enzymes, typically immobilized
in an adjacent overlayer. Acidification increases the con-
ductivity of polypyrrole. A sensor,for penicillin was described
in which the conductivity of a PPy film responded reversibly
to pH changes produced by the action of a penicillinase
overlayer (GI82). Conductivity control by pH was also the
basis for a glucose sensor based on polyaniline (GI83). In
this paper, the conductivity of a polyaniline film appears to
be controlled by pH changes produced by the production of
gluconic acid in a glucose oxidase/polyaniline overlayer. A
new redox-dependent polyaniline film switch for glucose was
developed (GI84),which appears to have faster response time
than the original PPy switch. Here, the generation of reduced
mediator (TTF) by the action of glucose oxidase results in
reduction of the polyaniline film to its insulating state.
The issue of selectivity is of course critically important for
developing sensors well-suited for measurements on physi-
ological samples. As mentioned earlier in the discussion on
mediated PPy amperometric glucose sensors, the electrooxi-
dation of interferents such as ascorbate, urate, acetaminophen,
glutathione, and other species must be adequately minimized.
Several interesting approaches based on electrically insulating
polymer films have been reported. Maidan and Heller crafted
a multilayer electrode consisting of an Os-PVP “wired” glucose
oxidase layer on glassy carbon, with an overlayer of horseradish
peroxidase for catalytic preoxidation of interferents by H202
(GI 85). This approach provides impressive performance but
does require a constant source of H202, which can be added
externally or generated internally via an additional enzyme
system. Christie et al. examined plasticized poly(viny1
chloride) as conventional permselective membranes for use
with various amperometric biosensors and found this material
to be markedly superior to cellulosic membranes for exclusion
ofionicinterferentssuchas ascorbateandurate (Gl86).Some
progress in reducing the ascorbate interference for H202-
detecting glucose electrodes was described by Lowry and
ONeill in work on Nafion-covered TTF/TCNQ-based sensors
Analytical Chemistty, Vol. 66,No. 12, June 15, 1994 399R
(G187). One simple yet effective approach involved the
addition of stearic acid, which is known to increase the
overpotential for oxidations of anions.
A different but more difficult solution to the interference
problem is to build permselectivity directly into the enzyme-
containing polymer film. In this regard, Centonze et al.
obtained good results with a strategy based on conventional
electrooxidation of H202 but with a nonconducting over-
oxidized PPy/glucose oxidase electrode (GZ88). The one-
step procedure resulted in a permselective film that worked
well in rejecting some common interferents. Disagreement
arose over the mechanism of ascorbate interference in H202-
detecting glucose sensors with glucose oxidase entrapped within
permselective poly(o-phenylenediamine) films. Lowry and
O’Neill contend that, in addition to primary interference due
to ascorbate electrooxidation a t the substrate electrode,
oxidation of ascorbate can also occur in a homogeneous
reaction with H202 generated in the sensor (G189). On the
other hand, Palmisano and Zambonin ascribe “nonprimary”
interference to structural changes in the sensor arising directly
from ascorbate electrooxidation, Le., electrode fouling (GI 90).
Electrochemically deposited poly(pheny1ene oxide) film elec-
trodes may also prove to be useful as enzyme-entrapping
permselective layers (G191). An initial study of this type of
material with entrapped glucose oxidase examined the influ-
ence of the phenol monomer on the resulting sensor perfor-
mance but did not report on interferences (G192). Initial
evaluations of the permselective capability of Nafion when
glucose oxidase was directly incorporated were not very
promising (G193, G194).
The discovery during the mid- 1980s that many enzymes
can function catalytically in organic media had led to the
development of organic-phase amperometric biosensors.
Adsorption has been a favored mode of immobilization due
to insolubility of the enzymes. Wang and co-workers have
demonstrated the advantages of enzyme entrapment within
an Eastman AQ poly(ester-sulfonic acid) polymer phase for
horseradish peroxidase and tyrosinase (G195) and for laccase
(GI 96).
Monolayer- Type Electrodes. Included in this subsection
are studies on enzyme electrocatalysis and amperometric
biosensors in which enzymes are immobilized in monolayer
or submonolayer configurations. Related monolayer enzyme
electrochemistry citations can be found under Enzymes:
Unmediated Electrochemistry. Sensor configurations of the
enzyme monolayer type have potential advantages, e.g., rapid
response times, as well as drawbacks, e.g., restricted dynamic
range.
Direct electron transfer between enzymes and conductive
substrates, if efficient, would of course be a highly desirable
basis for fabricating monolayer biosensors because exogenous
mediators would not be required. The peroxidases have been
the most highly studied enzymes in this regard, and interest
continued unabated during this two-year period. Using
rotating disk voltammetry, Scott et al. characterized the
electrocatalytic functioning of baker’s yeast cytochrome c
peroxidase (CCP) that had been irreversibly adsorbed on edge-
oriented pyrolyticgraphite electrodes (G197). Adsorbed CCP
appears to function similarly to solution CCP with regard to
its reactions with H202 and known inhibitors. Using
400R Analytical Chemistry, Vol. 66,No. 12, June 15, 1994
voltammetry and ellipsometry, Armstrong et al. investigated
the mechanism for CCP adsorption onto edge-oriented
pyrolytic graphite electrodes in the presence of neomycin
(G198). Evidence supported a heterogeneous adsorption
model a t submonolayer enzyme coverage involving localized
electrocatalytic sites that behaved voltammetrically as
microelectrodes. Gorton’s group has played a very active role
in the area of mediatorless peroxidase biosensor development,
and some of their prior and recent results along with a historical
summary can be found in ref G12. This is an excellent article
for researchers who wish to get up to speed in this particular
area (as of 1992). With an eye toward immunoassay
applications, H o et al. fabricated mediatorless peroxide sensors
based on direct electron transfer between adsorbed horseradish
peroxidase (HRP) and activated carbon or platinized activated
carbon electrodes (G199). Kulys et al. reported that the
electroenzymatic reduction of H202 at mediatorless carbo-
diimide-immobilized H R P graphitic electrodes was activated
by various organic hydride donors (G200), which might
indicate that not all adsorbed peroxidase molecules were
electroactive.
Having previously shown that electrocatalytically active
heme nonapeptide could be covalently attached to tin oxide
electrodes, Tatsuma and Watanabe characterized its ability
to function as an interference-typesensor for various imidazoles
(G201). Coordination of imidazole ligands to the ferric iron
blocks the catalytic current associated with H202 reduction.
Evidence for direct electrical communication was provided
by Ikeda and co-workers for two enzymes of analytical
importance, diaphorase (Bacillus stearothermophilus) and
ferredoxin-NADP+ reductase (G202). On carbonaceous
electrodes, unmediated catalytic currents were detected in
the presence of substrate.
A number of papers dealt with the issue of covalent
immobilization strategy. Carbodiimide coupling has proven
its worth in many applications, both bioelectrochemical and
otherwise. To this end, a useful and general modification of
carbon surfaces by electroreduction of substituted aromatic
diazonium salts has been applied to the immobilization of
glucose oxidase on glassy carbon (G203). 4-Phenylacetic acid
groups attached to the GC surface can serve as sites for
subsequent carbodiimide coupling of enzymes. Willner et al.
covalently attached glutathione reductase to gold electrodes
via a chemisorbed cysteic acid active ester reagent (G204).
In situ redox “wiring” of the enzyme with bipyridinium relays
was subsequently achieved using carbodiimide coupling
chemistry. The same group described an alternative means
for achieving covalent attachment to gold via an isothiocyanate
reagent, trans-stilbene-( 4,4’-diisothiocyanate)-2,2’-disulfonic
acid, bonded to chemisorbed cystamine (G20.5). Streptavidin-
biotin coupling is another very useful bonding technology.
Quite reasonable selectivity was achieved in a glucose sensor
in which streptavidin-glucose oxidase was attached to a
biotinylated self-assembled phospholipid bilayer (G206).
Several other covalent enzyme immobilization schemes that
might prove useful were noted by your reviewer (G207-GZ09)
although the studies cited were nonelectrochemical in nature.
The work being carried out by Whitesides’ group regarding
protein adsorption on self-assembled monolayers (G210)may
also be of relevance to monolayer enzyme electrode designers.
 The immobilization and electrocatalytic behavior of
Desulfovibria gigas hydrogenase on amphiphilic bilayers was
described by Parapleix et al. (G211). Immobilization was
largely driven by hydrophobic interactions, and the mediated
electrocatalysis involved two-dimensional diffusion of octa-
decylviologen species in the pores of aluminum oxide films on
gold.
Finally, the fabrication and performance of light-activated
glucose sensors based on n-type silicon substrates were
described by Dicks et al. (G212). An enzymelmediator
monolayer configuration was achieved by adsorbing glucose
oxidase onto a ferrocene-derivatized polypyrrole layer that
had been electropolymerized on n-Si.
Carbon Paste and Other Bulk Composite Electrodes. A
new trend in biosensors that has emerged in recent years is
the incorporation of enzyme (and mediator, if required)
directly into carbon paste and other bulk carbon composite
materials. Among the potential advantages of these reagent-
less bioelectrodes are ease of fabrication, electrode stability,
and surface renewal by simple abrasion or other mechanical
means. Wang’s group described a number of developments
in this area including the incorporation of horseradish
peroxidase into carbon paste and graphite/epoxy for the
detection of organic peroxides (G213). No mediators were
required as the H R P was able to communicate directly with
the carbon particles. The graphite/epoxy vehicle was also
successfully used with dehydrogenase enzymes, in particular
alcohol dehydrogenase, by incorporating NAD+ in addition
to the enzyme (G214). A reagentless carbon paste alcohol
sensor was designed along these same lines but with the
additional inclusion of ruthenium catalyst for lowering the
overpotential for N A D H oxidation (G215). Enzyme-
incorporated graphite/Teflon bulk composite sensors were
also described (G216).
Incorporation of additional catalysts in enzymatic carbon
paste electrodes was also accomplished by Mizutani et al.
(G217). They observed significantly lowered overpotentials
for H202 oxidation in glucose sensors when either platinum
black or cobalt phthalocyanine was dispersed in the matrix.
Kulys and co-workers described their results with several
enzymatic carbon paste amperometric sensors that utilized
incorporated mediators. Methylene green was used as the
mediator in a pyruvate sensor based on entrapped pyruvate
oxidase (G218) and an L-lactate sensor based on entrapped
L-lactate oxidase (G219). A carbon paste/diaphorase/
mediator composite was investigated for the electrocatalytic
oxidation of NADH; Meldola blue proved to be a superior
mediator to methylene green in this system (G220). A whole-
cell carbon paste electrode for L-lactate was fabricated by
incorporation of the yeast Hansenula anomala along with
mediators (G221). Cytochrome b~ was suggested as the
biocatalytically involved site in the yeast.
Smit and Rechnitz described an interesting Mn2+ sensor
in which horseradish peroxidase and a mediator, 1,2-naptho-
quinone, were directly incorporated into a carbon paste medium
(G222). The presence of manganese ion stimulates the
mediated enzymatic reduction of 0 2 , resulting in a current
increase. A detailed voltammetric investigation was reported
for a carbon paste glucose sensor utilizing glucose oxidase
and dimethylferrocene as mediator (G223). Control of the
catalytic rate was shown to be highly dependent on the amount
of incorporated mediator. A novel composite glucose sensor
was designed by incorporating glucose oxidase along with a
mediator, cobalt phthalocyanine, into a colloidal emulsion of
graphitic particles (G224). Formation of the biocatalytic layer
is accomplished by simple evaporative deposition of the
emulsion on a glassy carbon substrate.
Microenzyme Electrodes. Tissue and other in vivo ap-
plications along with detection in microenvironments constitute
two of the main goals that are driving efforts to miniaturize
enzyme electrodes. In addition, miniaturization also holds
open the potential for faster responding sensors as well as
their eventual incorporation into integrated microelectronic
devices. Papers selected for this section displayed an obvious
“micro” theme, although in most case! the reader will note
that there is considerable topical overlap with one or more
other sections. Pantano and Kuhr described the construction
and performance of monolayer dehydrogenase sensors based
on 10-pm carbon fibers (G225). Enzymes were covalently
attached to the carbon surface via avidin-biotin chemistry,
and the amperometric signals arose from electrooxidation of
enzyme-generated NADH. An extremely fast glutamate
sensor based on this strategy exhibited a response time of 300
ms, one of the fastest known. Carbon fibers were also evaluated
by Csoregi et al. for constructing mediatorless peroxide sensors
based on apparent direct electron transfer with immobilized
horseradish peroxidase (G226). Carbodiimide attachment
of H R P to heat-treated graphite fibers resulted in the best
performance. Carbon fiber disk electrodes, 7 pm, coated with
a cross-linked layer of alkaline phosphatase displayed very
good performance in thedetection of 4-aminophenyl phosphate
(G227). One other carbon fiber-based device, although
technically not a microsensor, is the redox-“wired” lactate
probe described by Wang and Heller (G228). The unique
design feature of this miniprobe is its mechanical flexibility,
conferred by bundling together several hundred 7-pm carbon
fibers. Microenzymatic sensors were also reported in which
carbon fibers were used primarily as conductive supports.
Wightman and co-workers described TTF/TCNQ-type en-
zyme biosensors for glucose and acetylcholine based on
capillary-encased recessed-tip 7-pm carbon fibers (G229).
With outside diameters on the order of 20 pm, these electrodes
are well-suited for in vivo tissue applications. Wang and
Angnes reported that a one-step electrostatic codeposition of
rhodium and glucose oxidase on carbon fibers results in glucose
microelectrodes that exhibit a significantly lessened over-
potential for HzOz electrooxidation (G230). Finally, carbon
films were employed to make nanoband enzyme electrodes of
35-50 nm thickness by enzyme entrapment within a poly-
(0-phenylenediamine) overlayer (G231).
Another popular electrode material for microenzymatic
sensors is platinum. Karube and co-workers fabricated
cylindrical-geometry glucose sensors from 2-hm Pt fibers by
entrapping enzymes in photo-cross-linkable polymer layers
(G232). The responses were of the mediated-type, and various
experimental parameters were evaluated. Abe et al. con-
structed implantable glucose sensors from platinized-carbon
ring electrodes with a cross-linked glucose oxidase catalytic
overlayer (G233). Response times as low as 270 ms were
reported, and interference by oxygen was investigated.
Analytical Chemlstry, Vol. 66, No. 12, June 15, 1994 401R
 Other platinum-based microelectrodes included those for
cholesterol and cholesterol ester, in which enzymes were
adsorbed on a porous carbon composite supported on a
recessed-tip 50-km Pt wire (G234), and a glucose sensor
utilizing monolayer glucose oxidase immobilized in a poly-
(phenol) film on 25-pm Pt wires disk electrodes (G235).
Other Enzyme Electrode Studies. For convenience, a
number of other significant reports concerning various aspects
of amperometric biosensors are collected together here. For
the many workers developing biosensors based on the elec-
trooxidative detection of HzOz, the paper by Zhang and Wilson
describing detailed studies of this reaction a t Pt and Pt/Ir
electrodes should be important (G236). The reaction at neutral
pH is not fully understood; the studies reported here
concentrate on physiological buffer conditions pertinent to
biosensor operation. Experimental variables (pH, tempera-
ture, electrode conditioning) were found to exert a strong
effect on the reaction, and the use of a protective cellulose
acetate membrane was found to be advantageous.
A significant contribution to the understanding of organic
conducting salt electrodes was due to Lennox and co-workers
(G237) in a detailed electrochemical study of TTF/TCNQ
and hexamethylenetetratellurofulvalene(HMTTeF)/TCNQ.
Both silicone oil and polystyrene binders were used. Their
results support the homogeneous mediation mechanism for
the electrooxidation of ascorbate, NADH, and reduced glucose
oxidase. An evaluation of background currents gave evidence
for the view that these salts undergo dissolution even at
potentials at which they are normally considered to be stable.
Wilde et al. described results of a CV investigation of charge
accumulation a t TTF/TCNQ electrodes operating in glucose
oxidase biosensors (G238),a phenomenon apparently due to
the surface accumulation of a reduced species as a result of
glucose oxidation. Xanthine sensors based on the im-
mobilization of xanthine oxidase on TTF/TCNQ/silicone oil
substrates were reported by Korell and Spichiger (G239).
Exploiting hydrophobic interactions during immobilization
resulted in the best performance. Sim analyzed the steady-
state kinetic behavior of an ethanol sensor based on the
confinement of alcohol dehydrogenase between a membrane
and an N-methylphenazinium (NMP)/TCNQ electrode
(G240).
Several additional studies were reported that focused on
mediator development. In a detailed study, Fraser et al.
examined a series of mediators comprised of tris(4,4’-
substituted-2,2’-bipyridine) complexes of Fe(II), Ru(II), and
Os(II), as electron acceptors for glucose oxidase (G241). It
was concluded that the overall charge on the mediator was
critical, with + 5 providing optimum electron-transfer kinetics,
apparently due to interaction with the anionic active site of
the enzyme. Effective heterogeneous mediation of tyrosinase
and cytochrome c was achieved through the incorporation of
a tetradentate Cu(II)/Cu(I) complex in a Nafion overlayer
on glassy carbon (G242). Other mediators reported during
this time period included nickelocene, which operates at a
lower potential than ferrocene for glucose sensors (G243),the
water solubilization of T T F by complexation with 2-
hydroxypropyl-0-cyclodextrin(G244),and a dimethyl(meth-
y1thio)-substituted tetrathiafulvalene (MTTTF) for use in
glucose sensors (G245).
402R Analytical Chemistry, Vol. 66,No. 12,June 15, 1994
Can electrodes communicate with intact livingcells? Using
mediators, the answer is “yes”, as has been demonstrated
periodically in the past. The ability to establish lines of
electroenzymatic communication between electrodes and
whole cells suggests new approaches for enzyme biosensors as
well as for microbiological research. Along these lines, Ikeda
et al. have reported mediated bioelectrocatalytic reactions of
Gluconobacter industrious immobilized on carbon paste
electrodes (G246, (3247). In the presence of ferricyanide as
mediator, both glycerol and fructose were oxidized at high
rates, apparently by dehydrogenases in the cell membranes
(G246),and in the presence of p-benzoquinone as mediator,
the oxidation of glucose proceeded (G247). Earlier, an
example of a bulk yeast carbon paste electrode due to Kulys
was cited (G221).
A novel photoelectrochemical device was developed and
characterized by Cohen and Weber for potential applications
in automated immunoassay and biosensors (G248). Using
an optical fiber, the device is able, via an O z / R ~ ( b p y ) 3 ~ + /
light reaction, to generate H202, which can then be detected
amperometrically a t a gold ring electrode. In their paper, the
device was used as a sensor to detect catalase a t subnanomolar
concent ration.
Martin and co-workers reported a self-contained sensor
concept in which the internal solution components and
electrodes are confined to one side of an ultrathin film
composite membrane (G249). The glucose/glucose oxidase
system was used as a test system.
The concept of using bilayer lipid membrane properties in
combination with enzymatic reactions as a basis for chemical
sensing was described by Nikolelis et al. (G250). The presence
of acetylcholine resulted in small transient currents across
BLMs incorporating acetylcholinesterase. The signal arises
from a change in double-layer properties attributed to
generation of hydrogen ion by the enzymatic reaction.
The entrapment of active glucose oxidase in sol/gel matrices
was reported by Audebert et al. (G251). Voltammetric
monitoring in the presence of ferrocene mediator and glucose
was used to evaluate the activity of enzyme. Ellerby et al.
described the entrapment of functional proteins (cytochrome
c, superoxide dismutase, myoglobin) in porous, optically
transparent, sol/gel matrices (G252). Although not an
electrochemical study, this study could suggest possibilities
for the design of electroenzymatic experiments and sensors.
Polynucleotides and Nucleic Acids. Palecek and col-
leagues, to whom we owe much of our knowledge of
polynucleotide interactions at electrode surfaces, discussed
the voltammetry of various types of DNA a t H M D E and
carbon electrodes (G253, G254). By exploiting the strong
affinity of DNA for these surfaces, the analysis of nanogram
or lower quantities in sample sizes of 5 L becomes possible
using adsorptive transfer stripping voltammetry methods.
Characterization by this method of various forms of DNA,
i.e., calf thymus, plasmid, single-strand vs double-strand,
denatured, and supercoiled, is described in these two papers.
Supercoiled DNA was found to resist denaturation on the
mercury surface in the potential range of -0.1 to -1.5 V vs
SCE (G254).
Covalent immobilization of polynucleotides on electrodes
was also reported. Maeda et al. affixed disulfide-modified
calf thymus DNA to gold electrodes by chemisorption (G255),
which inhibited the CV response for a ferri-/ferrocyanide
solution. The inhibition, however, was found to be reversibly
modulated in a concentration-dependent manner by the
addition of quinacrine, a cationic drug that binds to DNA,
thereby reducing its negative charge. Carbodiimide coupling
was employed by Millan et al. to covalently attached a synthetic
double strand of DNA, poly(dG)poly(dC), and also denatured
calf thymus DNA, to glassy carbon electrodes (G256). The
presence of surface DNA was subsequently detected by
voltammetry of preconcentrated Co(bpy)j3+, a redox probe
that binds strongly to the surface-bound DNA.
The investigation of DNA and its binding with small
molecules is another profitable area in bioelectrochemistry.
Rodriguez and Bard continued their work with a study of the
binding of calf thymus DNA by a complex formed from
Mn(II1) porphyrin (MnP) and distamycin A (Dis), an
oligopeptide antibiotic and biological inhibitor (G257). Both
compounds are known individually as binders of DNA, but
only the Mn(II1) species is electroactive. A stoichiometry of
MnP(Dis)z was found for the complex.
Thorp’s group continued their efforts on electrocatalytic
cleavage of DNA by transition metal complexes. A detailed
study of the binding and catalytic behavior of Ru1I(tpy)(bpy)Z-
toward calf thymus DNA was reported (G258). The
active cleavage form of this compound is the two-electron
RutVelectrooxidation product. A similarly functioning species
but with increased binding affinity for DNA was obtained by
replacing the two bipyridine ligands with a single planar
dipyridophenazine ligand (G259). Crystallography of this
compound indicated the presence of significant *-stacking
interactions that help to explain its higher affinity for DNA.
In Vivo and Cellular Electrochemistry. Central to progress
in these areas is, of course, the ability to fabricate ultra-
miniaturized electrodes with adequate performance charac-
teristics. The interested reader should also consult the section
on Microenzyme Electrodes, which spedfically addresses
ultramicroenzyme electrodes. In vivo electrochemistry,
especially in the area of neurochemistry, has continued to
grow in popularity, and the literature has become quite
extensive. Here we note only a limited number of papers of
analytical or general interest. Adams’ group described real-
time monitoring of electrically stimulated norepinephrine
(NA) release in the rat thalamus in the presence of 3,4-
dihydroxyphenylacetic acid (DOPAC) (G260, G261). The
electrooxidation of these neurotransmitters was followed by
fast chronoamperometry at Nafion-coated carbon fibers.
Separation of the N A faradaic signal from that due to DOPAC
was achieved by differentially controlling the electrode kinetics
of the two species by electrochemical pretreatment procedures.
Young and Michael reported that electrochemically stimulated
dopamine release in the rat striatum could be followed in
real-time by fast-scan CV with 500-ms resolution with respect
to individual stimulation trains (G262). A critical review and
discussion of sensor/tissue interactions associated with in vivo
use of carbon paste electrodes in the brain was provided by
O’Neill (G263). A careful analysis of signal-to-noise issues
attendant to trace analysis of dopamine in the rat brain by
fast-scan CV was presented by Wightman and co-workers
(G264). In vivo detection of 100 nM dopamine a t S / N of 25
was achieved. A new method for in vivo voltammetric
monitoring in the rat brain using a “dialysis electrode” was
described by Albery et al. (G265). This device, which utilizes
an internal electrode to monitor substances crossing the dialysis
membrane, was able to detect glutamate in real time. For in
vivo monitoring in subcutaneous tissue, needle-type enzyme
sensors for lactate (G266) and glucose (G267) were designed
by Wilson’sgroup with careful attention to oxygen interference
effects.
Cellular electrochemistry includes voltammetric measure-
ments made either inside (intracellular) or outside (extra-
cellular) single living cells. These types of measurements
became feasible during the mid-1980s. Ewing’s group was
very active in the area of intracellular electrochemistry,
reporting voltammetric measurements made in the giant
dopamine neuron of the pond snail Planorbis corneus (G268,
G269). In one study, platinized carbon ring electrodes of
2-10-pm diameter were used to monitor intracellular oxygen
levels, which were shown to vary with oxygen levels in the
bathing solution (G268). The same type of electrode was also
used to monitor internal dopamine levels while varying the
dopamine concentration in the bathing medium (G269).Active
membrane transport of dopamine was suggested as a mecha-
nism. Multiple pulse voltammetry was also shown to be an
effective means for minimizing electrode fouling for the
intracellular measurement of dopamine (G270). Ewing et al.
also wrote a general review on the topic of analytical chemistry
in single nerve cells, which addresses the role of ultramicro-
electrode voltammetry (G7).
In the area of extracellular voltammetry, Wightman and
co-workers continued their fascinating investigations of
exocytotic events at single bovine adrenal medullary cells in
culture (G271). The shape of amperometric current spikes,
monitored by carbon fiber disk electrodes positioned 5 pm
from individual cells and analyzed using diffusional theory,
was assigned to catecholamine release associated with single
exocytotic events. Estimates of intravesicular catecholamine
concentrations were made. Another impressive extracellular
investigation was described in a paper by Kennedy et al.
(G272). Chemically stimulated secretions (believed to be
insulin) from individual pancreatic 0-cells were monitored
amperometrically using ruthenium oxide/cyanoruthenate-
modified carbon fiber electrodes. Current spikes were at-
tributed to individual exocytotic events.
Immunological and Recognition-Based Electrochemistry.
A clever new strategy for homogeneous electrochemical
immunoassay was detailed by Degrand and co-workers (G273,
G274) in which a cationic redox-labeled hapten partitions
into a Nafion film where it can be detected voltammetrically.
The antibody-hapten-label complex is unable to enter the
film from the assay solution. This strategy was demonstrated
in assays for amphetamine (G273) and phenytoin (G274) by
attaching the redox label cobaltacenium. Detection limits in
the nanomolar range were reported.
Two groups reported new results on the alkaline phos-
phatase/4-aminophenyl phosphate, an important system for
electrochemical immunoassay. Yamaguchi et al. pushed the
detection limits for 4-aminophenol, the enzymatic product of
the reaction, to 500 pM by exploiting enzymatic recycling
with diaphorase (G275). Subattomole detection of alkaline
Analytical Chemistry, Vol. 66,No. 12, June 15, 1994 403R
phosphatase was reported. Thompson et al. examined buffer
composition to optimize the same system and also reported
subattomole detection, in this case for IgG-alkaline phos-
phatase (G276).
Huet and Bourdillon described a method aimed at
electrochemical regeneration of the solid phase for automation
of heterogeneous electrochemical immunoassays (G277).The
key step, surface cleaning of glassy carbon via an oxidative
potential step, could be applied for 150 cycles before
mechanical resurfacing was required.
A more esoteric approach a t present, but one which holds
promise for future development, is the use of mono-, bi-, and
multibilayer membranes for sensing recognition events.
Umezawa and co-workers reported further studies of coulo-
metric ion channel sensors in which L-glutamic acid interaction
with bilayer-incorporated glutamate receptor (GluR) ion
channel proteins trigger an ioncurrent (G278). Amplification
factors of IO5, detection limits of 30nM, and a high selectivity
for L-glutamate over D-glutamate, were reported. In another
approach, alkyl-derivatized cyclodextrin (the “host”) was
incorporated into a monolayer (G279). By subsequently
monitoring the electrochemistry of channel-permeable p -
quinone, detection of channel blocking molecules (the “guest”)
was observed. A different approach to sensing is being explored
by Nikolelis and Krull, who monitor transient changes in the
electrochemical properties of bilayer membranes as a result
of biological interactions. Small transient ion currents were
detected when thyroxin interacted with BLM that contained
the antibody protein, due to alterations in the double-layer
structure (G280).
Another novel example to sensor design based on receptor
binding was provided by Wang et al. (G281). In this approach,
multilayers of tyrosine hydroxylase deposited on a gold
electrode by L-B technology were used to preconcentrate
phenothiazine drugs before detection by stripping voltam-
metry.
Miscellaneous Bioelectrochemical Studies. Bard and co-
workers described the application of scanning electrochemical
microscopy to thecharacterization of surface enzyme reactions
(G282). By using a microelectrode to monitor redox feedback
of a soluble mediator, the catalytic oxidation of glucose by
immobilized glucose oxidase could be detected.
In the complex area of microbial biofilms, which was not
covered in this review, one particular article that may be of
interest to bioelectrochemists concerned the monitoring of
biofilm formation using a quartz crystal microbalance (G283).
Although a separate section on membranes was not created
for this review, there are a number of relevant papers scattered
throughout it. One more is the paper by Plant in which
biomimetic membranes were created by self-assembly of a
phospholipid/alkanethiolate bilayer on gold electrodes (G284).
H. CHARACTERIZATION OF REDOX REACTIONS
Electron-TransferMechanisms. The algorithms that have
been developed over the years have become powerful techniques
for the elucidation of electron-transfer mechanisms. The
application of these techniques to actual mechanistic studies
has grown as instrumentation has become more sophisticated
and computers have become more powerful. In particular,
the fast scan rates that are accessible by ultramicroelectrodes
404R Analytical Chemistry, Vol. 66,No. 12,June 15, 1994
have enabled the electrochemist to utilize a wide time scale
for the study of electrochemical reactions. For example, Bond
et al. ( H Z )examined theoxidation of mer-W(CO)3(pI-dpm)-
(112-dpm) to mer-W(CO)2(p2-dpm)12+ over a wide range of
scan rates and electrode surfaces. Under most conditions, a
single two-electron wave was observed. But, with the scan
rates accessible by a 3-pm microelectrode, two one-electron
waves were observed, due to the presence of an unstable
intermediate. A two-electron wave was also examined by
Pierce and Gieger ( H 2 ) . The electrochemical reduction of
bis(hexamethylbenzene)ruthenium(II) occurred in either a
single two-electron wave or two one-electron waves, depending
upon experimental conditions. Digital simulation was used
to determine the E O , k,, and a values for each step using scan
rates between 0.4 and 100 V/s. Huang and Gosser used cyclic
chronoamperometry and cyclic voltammetry to determine the
kinetic parameters in the E& reduction of methylcobalamin
in D M F ( H 3 ) . Andrieuxet al. ( H 4 )reportedon improvements
and estimation of precision in the cyclic voltammetry
determination of rate constants and activation parameters of
coupled first-order reactions. This work was then applied to
halide cleavage of chloroanthracene radical anions. The
reductive cleavage of the nitrogen halide bond in aromatic
N-halosultams was studied to determine controlling factors
of stepwise vs concerted reductive cleavages ( H 5 ) .
Fast-scan cyclic voltammetry was used by Yang and Bard
to study the initial stage in the electropolymerization of aniline
in aqueous solutions ( H 6 ) and the dimerization of N,N-
dimethylaniline in acetonitrile ( H 7 ) . Andrieux et al. ( H 8 )
used fast-scan cyclic voltammetry to measure the redox
potentials of unstable couples such as thiophenoxide ions. The
redox potentials were measurable at ultramicroelectrodes even
though the dimerization reaction rates varied from 2 X lo8
to 2 X 1O l 0 M-I s-l. The square reaction scheme was observed
by Bond et al. ( H 9 ) in the fac/mer isomerization a t electron
transfer of a Cr(CO)3(q3-L) complex. Digital simulation of
the steady-state and non-steady-state cyclic voltammograms
allowed the elucidation of the mechanism. Digital simulation
was also used to elucidate the kinetic parameters in the metal-
hydride cleavage of trans-[FeH(CNR)(dppe)2]+(HIO),which
involved an ECECE mechanism.
Accurate measurements of heterogeneous rate constants
can provide important information about the electron-transfer
events. Anxolabehere et al. ( H I I ) examined the standard
rate constants for the iron(I)/iron(“O”) wave for a series of
iron porphyrins. By using the Marcus-Hush model, they found
that the rate-controlling factor in these fast reactions was
solvent reorganization. Brielbeck et al. ( H I 2 ) studied the
heterogeneous and self-exchange rate constants for a series
of fully a-methylated cycloalkane- 1,2-diones. They explained
the significant changes in heterogeneous rate constants by the
significant reorganization energy required by the cyclic 1,2-
diones. Even greater changes were observed by Nelsen et al.
( H I 3 ) for conformationally protected hydrazines, which
yielded electrochemically irreversible electron-transfer pro-
cesses.
Organic Electrochemistry. The electrochemistry of or-
ganic compounds continues to be a fruitful area of research,
driven by their importance in electroanalytical methods and
by a need to understand the structure and reactivity of unstable
organic intermediates. A significant number of articles
appeared over the past two years on the oxidation of
carbohydrates. Marioli and Kuwana ( H I 4 studied the
electrochemical oxidation of carbohydrates at copper elec-
trodes in alkaline solutions using cyclic voltammetry and
rotating ring disk electrode experiments. It was demonstrated
that the important step in the oxidation was the interaction
of the carbohydrate with the oxide/hydroxide layer covering
the electrode. Oxidation beyond gluconic acid was observed
and involved C-C bond cleavage. Burke and Ryan also showed
that the hydrous oxide layer was important in the oxidation
of glucose at a gold electrode (HI5). Electrochemical and
polarimetric techniques were used in the oxidation of D-glucose
on palladium (HI6). Saccharose oxidation was examined for
its potentiality as a raw material for electrosynthesis (HI7).
Chromatographic analysis of the electrolyzed solutions led to
the identification of numerous monocarboxylic acids, some of
them resulting from the breaking of the C-0-C bond.
Surfaces modified with adatoms such as lead, thallium, or
bismuth were active in the oxidation of glucose. The
electrocatalytic properties depended upon the adatoms, with
bismuth leading to significant amounts of glucuronic acid
(H18).Lead adatoms on platinum also led to the selective
oxidation of D-gluconic acid to oxalic, tartaric, and 5-keto-
D-gluconic and D-glucuronic acids (HI9).
Another class of compound reactions for which there was
significant mechanistic activity was the reduction of nitro
compounds. Ruhl et al. (H20) studied the reduction of some
a-substituted nitroalkanes. The reduction of 2,2-dinitropro-
pane led to a nitronate and nitrite by an ECE/DISPl
mechanism. The nitronate that was formed reacted with
starting material to form nitrite and a uic-dinitro dimer. By
contrast, 1-nitro-cyclohexyl-p-tolylsulfone reduced by cleav-
age of the C-S bond to eject p-toluenesulfinate. Laviron et
al. (H21) studied the reduction of 4-nitropyridine in solutions
with acidities that varied from strongly acidic to pH 9.6. Three
main reduction steps occurred: the nitro compound was
reduced (2e-) to the dihydroxylamine, the dihydroxylamine
dehydrated to give the nitroso compounds, and then the nitroso
compound was reduced (2e-) to the hydroxylamine. The global
reaction was of the ECE type and was analyzed using the
theory of Nadjo and Saveant. Danciu et al. (H22, H23)
examined the electroreduction of 4,4f-dinitrodibenzylin water/
alcohol solutions. On mercury, the reduction occurred in two
steps consisting of one- and three-electron transfers for each
nitro group. Baumane et al. (H24) studied the mechanism
and products of the electrochemical reduction of 4-(nitro-
phenyl)-substituted 1,Cdihydropyridines. The reduction on
mercury led to free radicals of nitro- and nitrosobenzene, and
the dihydropyridine itself was only reduced if the compound
was N-substituted. Dumanovic et al. (H25)examined
1-nitropyrazole and found that the reduction in acidic media
led to cleavage of the N-N bond and the formation of nitrous
acid. At pH >4, the nitro group was reduced to form a
nitrosamine. Mirallesroch et al. (H26)examined the elec-
trochemical conversion of a-nitrobenzylic compounds into the
corresponding oximes.
Anne et al. (H27, H28)examined the electrochemistry of
synthetic analogues of NADH and NAD dimer analogues.
Medebielle et al. (H29) investigated the perfluoroalkylation
of pyrine and pyrimidine bases by electrochemically induced
SRNI substitution. Combellas et al. (H30) carried out selective
substitutions of 1,4-dichlorobenzene with 2,6-di-tert-but-
ylphenoxide using the electrochemically induced S R Nmecha-
~
nism. Mortensen et al. ( H 3 I ) studied the voltammetry of
highly reduced oligoanthrylene systems and were able to
generate the tetraanion of all the species studied. Cleghorn
and Pletcher reported on the mechanism of the electrocatalytic
hydrogenation of organic molecules at palladium black (H32)
and palladium on nickel cathodes (H33). Mahdavi et al. (H34)
examined the electrocatalytic hydrogenation of phenanthrene
at Raney nickel electrodes. The electrochemical fluorination
of benzene was carried out at +2.5 V in acetonitrile using
tetraalkylammonium fluoride salts (H35).
Delgado et al. (H36) examined the electrochemistry of an
alkali metal complex of quinone crown ethers and showed
that the formation constants with the alkali metal with the
attached crown ether varied with the redox state of the quinone.
The binding of the alkali metal was qualitatively and
quantitatively different from simple ion pairing. Urove and
Peters (H37)examined the electrochemical reduction of
cyclohexanecarbonyl chloride at mercury cathodes. Pritts et
al. (H38) reported on a method to quantitatively determine
volatile products formed in the electrolysis of organic
compounds. Wandlowski et al. (H39) studied the electro-
chemical oxidation of 2,6-dichloro- 1,4-phenylenediamine.
Potential step and digital simulation of the voltammetric data
was used to determine the kinetic parameters.
OrganometallicElectrochemistry. Redox-induced changes
in the conformation, bonding, or solvation of the metal atom
of a complex can be readily probed by the use of electro-
chemical techniques. Electron-transfer-induced isomerization
of cobalt, nickel, and palladium cyclooctatetraene complexes
was examined by Geiger et al. (H40). The Ni and Pd
complexes retained their 1,5-conformation upon reduction,
while the Co complex underwent rapid isomerization to the
1,3-isomer in the 19e-species. The differences were explained
by the role played by the ligand vs metal composition of the
redox orbital. Osella et al. reinvestigated the electrochemical
behavior of the Coz(CO)b(ethynylstradiol)complex and found
evidence of efficient recombination of the electrogenerated
fragments (H41). They also found electrochemical evidence
for the reorientation of alkynes on trimetallic clusters during
a two-electron reduction (H42). Karpinski and Kochi (H43)
used electron-transfer chain (ETC) catalysis in the electro-
chemical deligation of bis(arene)iron(II) dications. Mecha-
nistic studies were carried out using normal and reverse-pulse
voltammetry. Sanaullah et al. (H44) used chemical and
electrochemical methods to examine the redox-associated
conformation changes in the bis( 1,4,7-trithiacyclononane)-
copper(II/I) system. Electrochemical studies on niobocene-
ketene complexes yielded redox-induced ketene fragmentation
reactions (H45).
Solvent effects on the redox behavior of organometallic
complexes were examined by several groups. Boudon et al.
(H46) studied the effects of axial anions and solvent on the
redox behavior of nickel complexes with C-functionalized
tetraazamacrocycles. McDevitt and Addison (H47) examined
medium effects on the redox properties of tris(2,2’-bipyridyl)-
ruthenium complexes. The medium was also found to
Analytical Chemistry, Vol. 66,No. 72, June 75, 1994 405R
modulate the two-electron activity of ferrocene metallocyclam
conjugates ( H 4 8 ) . Mu and Schultz ( H 4 9 ) studied the effect
of methanol binding on the redox potential and electron-
transfer reactivity of chloro(tetrapheny1porphinato)manganese-
(111).
The use of inert solvents such as liquid sulfur dioxide and/
or microelectrodes has enabled the voltage range to be
extended, and highly reduced or oxidized species were observed.
Liquid sulfur dioxide was used to study the oxidation of
M(b~y)3~+complexes where M = Ni, Zn, and Cd (H50,H 5 1 ) .
Very negative and very positive potentials wereused to generate
Cp2C02+,Cp2C02-, and Cp2Ni2- ( H 5 2 ) . Ruthenium com-
plexes are quite interesting in that they can undergo a large
number of redox processes. Four one-electron-transfer steps
were observed in the voltammetry of truns-[R~(tpy)(O)~-
(H20)l2+(H53). Ruthenium(I1) complexes of 2,2’-bipyridine
and 2-pyridylpyrazine were examined up to -3.1 V a t -54 OC
in D M F using cyclic voltammetry ( H 5 4 ) . By the use of
convolution techniques and digital simulation, it was possible
to determine between 8 and 12 redox steps, depending upon
ligation. Krejcik and Vlcek (H55)found that [(Ru-
(bpy)2)zbpml4+ yielded 14 one-electron waves, 2 of which
were metal based and 12 ligand based. Deblas et al. ( H 5 6 )
used pyridines with appended metallocyclam subunits as
versatile building blocks to supramolecular multielectron redox
systems. Reversible electrogenerated triply oxidized nickel
porphyrins and porphycenes were reported by Kadish et al.
( H 5 7 ) ,where they were able to generate a stable nickel(II1)
x-dication.
The oxidation state of the metal atom in the electro-
generated complex was the focus of several studies. Guldi et
al. (H58)investigated whether chromium(II1) porphyrins were
reduced to Cr(I1) porphyrins or Cr(II1) porphyrin r-cation
radicals. Kadish et al. ( H 5 9 ) examined the site of electro-
reduction of rhodium porphyrins. A very complex redox
scheme was elucidated for the reduction of a-bonded
iron(II1) porphyrins in noncoordinating solvents ( H 6 0 ) .
Strojanovic and Bond ( H 6 1 ) examined the conditions under
which the reduction of cobaltocenium cation could be used as
a standard voltammetric reference process in organic and
aqueous solvents. Kaminsky et al. ( H 6 2 ) reported on a
reference electrode for organic solvents based on modified
polyethylenimine loaded with ferrocyanide/ferricyanide.
Inorganic Electrochemistry. The electrochemistry of
buckminsterfullerene and related complexes attracted the
attention of many researchers. Xie et al. ( H 6 3 )detected the
hexaanions, c606- and C706-, using electrochemistry . The
electrochemistry of c 6 0 was also studied in liquid ammonia
( H 6 4 ) . The kinetics and thermodynamics ( H 6 5 )and the role
of solvation ( H 6 6 ) in the electroreduction of c60 in aprotic
solvents was investigated. Fast-scan cyclic voltammetry and
scanning electrochemical microscopy ( H 6 7 ) were used to
determine the kinetic parameters for the electroreduction of
c 6 0 . An electrochemically reversible oxidation of c 6 0 and
C70 was reported ( H 6 8 ) ,as was the electrochemistry of C60H2
( H 6 9 ) . Penicaud et al. ( H 7 0 ) electrocrystallized c 6 0 for the
synthesis andcharacterization of (Ph4P)2C6oIX. Li et al. ( H 7 1 )
reported on unusual electrochemical properties of the chiral
c 7 6 . Lerke et al. ( H 7 2 ) studied platinum, palladium, and
nickel derivatives of buckminsterfullerene. Three to four waves
406R Analytical Chemistry, Vol. 66, No. 12,June 15, 1994
were observed, and the initial reduction led to the loss of the
metal fragment. Koefod et al. ( H 7 3 ) studied the electro-
chemistry of an iridium buckminsterfullerene complex and
found evidence for a c60 localized reduction.
Sudha et al. ( H 7 4 ) reported on electrochemical evidence
for a two-electron-reduction process in a p-oxobis(F-acetate)-
diruthenium(II1) complex with a terminal 1 -methylimidazole
ligand. The electrochemistry of the incomplete cubane-type
clusters, M3S4 ( M = Mo, W), was examined ( H 7 5 ) ,as well
as some molybdenum mononitrosyl complexes containing
oxobiphenyl ligands ( H 7 6 ) . The influence of pyridine sub-
stituents on binuclear rhenium(V) clusters was studied as a
redox tuning procedure ( H 7 7 ) . Low-temperature voltam-
metry was used to study the reduction and oxidation of
[ Re2(NSC)g] 2- (H78). The electrochemical reduction mecha-
nism of a Ru3(C0)12 was investigated in considerable detail
by voltammetric techniques ( H 7 9 ) . Cyr et al. ( H 8 0 )studied
the electrochemistry of boron-capped 99Tc-dioximecomplexes.
Choi et al. ( H 8 1 ) studied the electrochemical reduction of
thionyl chloride by cyclic voltammetry, chronocoulometry,
and chronoamperometry. Opekar and Langmaier ( H 8 2 )
reported a procedure for electrochemically controlled genera-
tion of carbon monoxide.
Activation of Small Molecules. The direct electrolysis or
electrocatalytic activation of small molecules has been an active
area of research. The largest area is probably the activation
of carbon dioxide. These studies have involved both the direct
reduction of carbon dioxide and the coupling of C 0 2 to a
substrate. Reports on theelectrocatalyzed reduction of carbon
dioxide have included the catalysis by molybdenum-iron-
sulfur clusters ( H 8 3 ) ,nickel phosphine clusters ( H 8 4 ) ,iron,
cobalt, and nickel terdentate complexes ( H 8 5 ) , osmium
bipyridyl complexes ( H 8 6 ) ,and rhenium bipyridyl complexes
incorporated into a coated Nafion membrane ( H 8 7 ) . Elec-
trocatalytic surfaces have been reported for the direct reduction
of carbon dioxide, such as ruthenium-titanium oxide ( H 8 8 ) ,
Cu + Au electrodes ( H 8 9 ) ,Perovskite-type electrocatalysts
( H 9 0 ) ,palladium ( H 9 1 )or copper-modified palladium ( H 9 2 )
electrodes, and nickel electrodes a t high pressure ( H 9 3 ) .
Carbon dioxide may also be electrochemically activated by
the reductive addition of CO2 to quinones in acetonitrile (H94).
Carbon dioxide can be coupled electrochemically by a nickel
catalyst to 1,3-enynes ( H 9 5 ) ,diynes ( H 9 6 ) ,or alkenes ( H 9 7 ) .
p-Anisic acid was formed from the reduction of p-iodoanisole
at mercury in DMF, saturated with carbon dioxide ( H 9 8 ) .
The electrocatalytic generation of C2 and C3 compounds was
reported for the reduction of C 0 2 on a cobalt complex-
immobilized dual-film electrode ( H 9 9 ) . Kyriacou et al.
(H100) examined the influence of CO? partial pressure and
the supporting electrolyte cation on the product distribution.
Naitoh et al. (H101) studied the electrochemical reduction
of carbon dioxide in methanol a t low temperature.
The electroactivation of other small molecules have also
been reported. Formaldehyde was oxidized on ultrafine gold
particles, supported on glassy carbon substrates (H102).
Methanol was electrooxidized on rhenium-tin oxide, platinum-
tin oxide, and iridium-tin oxide, and the results were compared
with the oxidation on platinum (H103). The electrocatalytic
oxidation of methanol at PTFE-bonded electrodes was studied
for a direct methanol/air fuel cell ( H 1 0 4 ) . Wong et al.
reported on the electrocatalytic oxidation of methanol (HZ05)
and benzyl alcohol (HZ06) with a monooxoruthenium(V)
complex. Cavalca et al. (HZ07) examined electrochemical
modification of methanol oxidation selectivity and activity on
a platinum single-pellet catalytic reactor. Gasteiger et al.
(HZ08)studied methanol electrooxidation on well-character-
ized Pt-RN alloys. A quadruply aza bridged closely inter-
spaced cofacial porphyrin was used to catalytically reduce
dioxygen (HZ09). A rotating disk electrode was used to study
the catalytic alkaline cyanide oxidation (HZZ0).A cobalt-
(111)-mediated electrochemical oxidation was used to destroy
chlorinated organics (HI Z I). F430-Model compounds, which
contain nickel isobacteriochlorins, will dehydrohalogenate
alkyl halides (H1Z2). Lojou et al. (HZZ3)examined the
electroreduction of aryl halides in D M F on a cadmium-
modified gold electrode. Che and Dong (HZZ4)applied
ultramicroelectrodes to the electrocatalytic reduction of
organohalides by metalloporphyrins. The electrocatalytic
reduction of nitrate was studied with foreign lead adatoms
(H115).Gur and Huggins (HZZ6)studied the direct
electrochemical conversion of carbon to electrical energy in
a high-temperature fuel cell.
Electrosynthesis. Electrosynthetic procedures have often
been the impetus for detailed mechanistic studies by elec-
trochemical techniques. The interplay between electrosyn-
thesis and electroanalytical studies has been quite synergistic
over the years. One area of active research is the direct
electrosynthesis of solid material. Matsumoto et al. (HZZ7)
reported a new preparation method of Lac003 Perovskite
using electrochemical oxidation. Wade et al. (HI 18) elec-
trosynthesized ceramic materials and precursors, while Singh
and Tanveer electrosynthesized (CdHg)Se (HZ19, HZ 20) and
(ZnCd)Se (HZ2Z). Dennison (HZ22) studied the cathodic
deposition of CdS from aqueous solution. Roberts et al.
(HI 23) investigated the mechanism and electrosynthesis of
the superconductor Bal,K,Bi03. The direct dissolution of
solid electrodes has also been used electrosynthetically. Halo
and mixed-halo complexes of palladium(I1 and IV) were
synthesized by the dissolution of a sacrificial palladium anode
(HZ24). Cathodic dissolution of an AuTe2 electrode led to
the formation of A ~ 3 T e 4 ~(HZ25).
- lished, the cited articles either feature some experimental
Niyazymbetov and Evans (HZ26, HZ27) reported on the
utility of carbanions and heteroatom anions in electroorganic
synthesis. Biaryls and aromatic carboxylic acids were
synthesized by palladium-catalyzed electrosynthesis using
triflates (HZ28). Freshly metal coated electrodes were used
to electrosynthesize 1,2-diketones by reduction of aromatic
esters (HZ29). Gard et al. (H130) reported an efficient
electrochemical method for the synthesis of nitrosobenzene
from nitrobenzene. Momota et al. (HZ3Z)reported the
electrochemical fluoridation of aromatic compounds in liquid
R4NF.mHF. Wendt et al. (HZ32, HZ33) studied the anodic
synthesis of benzaldehydes from the anodic oxidation of
toluene. Amino acids were synthesized from a molybdenum
nitride via nitrogen-carbon and carbon-carbon bond formation
reactions involving imides and nitrogen ylides (H134). a-
Nitrobenzylic acids were converted into oximes using mac-
roscale electrolysis (HI 35). .The hydrodimerization of di-
methyl maleate in methanol using an undivided cell was
reported by Casanova et al. (HZ36). Franklin et al. (HZ37)
reported a method for the destruction of halogenated hydro-
carbons accompanied by the generation of electricity.
Kunai et al. (HI 38) synthesized poly(disilany1ene)ethylenes
by the electrolysis of bis(chlorosily1)ethanes. Chakravorti et
al. (HZ39)reported the first electrosynthesis of transition metal
peroxofluorocomplexes (HZ39). The selectiveelectrosynthesis
of (CH&C60 provided a novel method for the controlled
functionalization of fullerenes (HZ40).Ferrate(V1) was
prepared using an alternating current superimposed on the
direct current (HZ4Z).
Micelles and Surfactants. Micellar media can provide
for some very interesting electrochemistry because of their
ability to solubilize material in aqueous solutions. Nikitas
(H142)reported a simple model for micellization and micelle
transformations on electrode surfaces. Myers et al. (HZ43)
studied solution microstructure and electrochemical reactivity.
They examined the effect of probe partitioning on electro-
chemical formal potentials in microheterogeneous solutions.
Abbott et al. (HZ44)studied electron transfer between
amphiphilic ferrocenes and electrodes in cationic micellar
solution, and the correlations between solvent polarity scales
and electron-transfer kinetics, as applied to micellar media
(HZ45). Gouniliet al. (HZ46) studied theinfluenceofmicelles
and microemulsions on the one-electron reduction of 1-alkyl-
4-carbomethoxypyridinium ions. The rate enhancement and
control in electrochemical catalysis using a bicontinuous
microemulsion was examined (HZ47), and this method was
used to debrominate alkyl vicinal dibromides with neutral
metal phthalocyanines (HZ48). An adsorbed film of cationic
surfactant was used to dechlorinate 9-chloroanthracene
(HZ49). Takisawa et al. (H150)reported on ultrasonic
relaxation and electrochemical studies of the micellization of
sodium decyl sulfate and decyltrimethylammonium bromide
in glycerol/water mixtures. Phani et al. (HZ51)developed
a microemulsion-based electrosynthesis of polyparaphenylene.
I. SPECTROELECTROCHEMISTRY
The following survey is organized principally by technique.
While most spectroelectrochemical methods are well estab-
aspect of general interest or illustrate particularly well the
versatility of a given technique.
On-line electrochemical mass spectroscopy, which is a
powerful technique for the study of complex electrode reactions
of small molecules, has been applied to a variety of problems.
Included among these are studies of redox reactions of alcohols
on Pt and Au (11-13) and on carbon-based electrodes (14).
The working electrode of the latter study was made from
PTFE-bonded carbon supporting Pt and Pt-Ru catalysts on
Norit BRX. The working electrode of Munk and Skou was
a microporous gold film on a commercial silicone rubber
membrane (15). E C / M S has provided detailed mechanistic
insight into the role of surface structure at single crystal
electrodes during electrode reactions of unsaturated com-
pounds (E152, E153, 16).
E C / M S studies have appeared on the oxidation of
formaldehyde (Z7-110), acetonitrile (11I), DMSO and sul-
folane (Z12),and propylene carbonate (113,114). The latter
article provides a good example of the use of isotopicallylabeled
Analytical Chemktry, Vol. 66, No. 12, June 15, 1994 407R
solvents (D2O and H2I80) to trace the origin of intermediates
and products of the electrode reactions (114).
An on-line EC/MS study of 0 2 reduction under conditions
of a methanol fuel cell allowed parallel reactions to be sorted
out (115). Information on the reductive pathways for CH3-
CC13 a t the Pt/H2S04 interface (116) and for nitrite at
graphite-supported CuO electrodes (11 7) was obtained. A
porous Ni-plated Teflon membrane allowed the electroless
Ni-P deposition to be followed by mass spectroscopy (118).
The oscillatory reaction involving bromate, malonic acid, and
the Ce4+i3+couple was followed by potentiometry and mass
spectroscopy. The production of COz(,) tracked the potential
oscillations in this system (119).
Several simplified designs of differential EC/MS interfaces
have appeared (120,121).
Articles continue to appear in which X-ray methods have
been used to probe the electrode/solution interface. These
techniques can give detailed specific information, i.e., bond
lengths, in the best of circumstances, but require access to a
synchrotron radiation source. Two new descriptions of cell
designs for in situ X-ray spectroelectrochemistry were noted
(122, 123). The latter employed transmission geometry
through a drop of solution maintained on the electrode surface
by capillary action.
Adlayer formation via UPD of metals are well-suited to
study by X-ray methods. Recent systems examined include
theUPDofPbandThonAu(l11)(124),CuUPDonPt(lIl)
(125) and Pt( 100) (126),Cu deposition on carbon-supported
Pt (127),Ag UPD on Au( 11 1) (E234),and iodine adsorption
on Pt single crystal electrodes (128). In the UPD study at
Au( 11 l ) , it was found that the Au-Pb distance was potential
dependent, while the Au-Th distance was not (124). I n the
surface EXAFS study of Cu UPD, chloride ion was shown to
play an important role in the ordering of the adlayer (125).
In situ X-ray methods have been used to follow intercalation
reactions of Moo3 (129),Li,CoOz (130), and V6OI3 (131)
electrodes. In situ X-ray spectra demonstrated the conversion
of cu-PbOz to the p-form on Pt substrates (132) and the
formation of Cu20 layers by the reduction of Cu02’- in
concentrated KOH (133). In situ XANES of Fe-26Cr
stainless revealed peaks for Cr(V1) that could be correlated
with the transpassive voltammetric wave (134).Near-edge
EXAFS spectra demonstrated that disulfide bond scission
occurred upon electroreduction of a sulfur polymer (135).
In situ X-ray methods have monitored surface roughness
ofPt(l11) andAu(IOO)electrodes(Z36.137)andtheformation
of oxides on dispersed Pt/C fuel cell electrodes (138).
Spectroelectrochemistry in the UV/visible region of the
spectrum is routinely practiced in the characterization of
inorganic, organic, and biological redox couples. On the
theoretical side, Wei et al. have published several papers on
spectroelectrochemistry under “long-path-length’’ conditions,
i.e., with the light beam parallel to the working electrode
(139-143). One of the papers contains theoretical expressions
for derivative linear sweep and derivative cyclic voltabsorp-
tometry, e.g., expressions for d(ABS)/dE],k, under thin-layer
conditions (140). The case of semiinfinite linear diffusion
was also addressed. The catalytic EC’ mechanism has also
been treated under these conditions (144,145). Zamponi et
al. have presented derivative linear sweep voltabsorptometry
400R Analytical Chemistry, Vol. 66,No. 12,June 15, 1994
theory for surface waves and OTTLE cells (146). The
relationship between the d(ABS)/dt vs E curve and the
corresponding voltammetric parameter is one of equivalence
in most situations.
A spectroelectrochemical sensor for Cl2 based on a planar
optical waveguide was described (147). This novel device
employed a thin Lu-biphthalocyanine film on IT0 that could
be electrochemically reset to the reduced state. Oxidation of
the film by dissolved chlorine, which was monitored at 950
nm, resulted in an integral signal that was linear in the 0-30
ppm range. The transmittance changes were detected using
a transverse magnetically polarized evanescent wave. Wave-
length modulation spectroscopy was used to obtain spectra of
methylene blue and Co tetrasulfonated phthalocyanine couples
on graphite electrodes (148).The instrument described had
a resolution of ca. 0.002 absorbance unit.
Several papers on experimental aspects were noted. A
simple procedure was given for the synthesis of SnO2 and the
preparation of SnO2-coated I T 0 glass electrodes (149). An
optically transparent carbon film electrode, with electro-
chemical properties similar to glassy carbon, was prepared by
the pyrolysis of an aromatic anhydride on a quartz substrate
(150). The general method of modifying I T 0 electrodes of
Chen et al. deserves mention again (F88). Salbeck has
published two standard designs for thin-layer cells, in one of
which only Teflon components contact the solution (151,152).
Shimazu et al. performed simultaneous UV/visible spectro-
electrochemistry and QCM (153). Optically transparent
contacts to the quartz crystal were used in a transmission
mode configuration.
Fluorescence spectroelectrochemistry was shown to be a
sensitive method for the detection of intermediates and
products of electrode reactions (154,155).These authors gave
details of their flow cell, which was used with a commercial
luminescence spectrometer. Littig and Nieman also obtained
excellent sensitivity with an electrochemical FIA chemi-
luminescence method (156). Electrochemical reduction of
0 2 to H202 triggered the chemiluminescence of acridinium
esters in a flow cell giving a LOD in the 10-fmol range. The
sophisticated fluorescence imaging of electrode surfaces cited
above can also be mentioned here (E115, E295).
Two simple cell designs for luminescence spectroelectro-
chemistry have appeared (157,158).
Articles on ECL that were noted included a report that
ultrasonic radiation markedly enhanced the ECL intensity in
the R~(bpy)3~+/0xalate system (159)and the observation of
the ECL of perylene in a room-temperature molten salt (160).
A weak photoemission seen during the evolution of 0 2 a t Pt
in water was assigned to the recombination of singlet oxygen
molecules (161).
FT-IR spectroelectrochemical studies on adsorbed C O
continue to give detailed information on the interfacial
structure and electrode reactions. The spectra of Roth and
Weaver indicated a terminal coordination of C O over a wide
potential range at Pt/nonaqueous interfaces (162).Bands in
the ATR-IR spectra of CO on Pt were assigned to a linearly
bonded C O and possibly a multiply bonded species (163).
FT-IR spectra of CO on Ni electrodes in KOH(,,) indicated
oxidation via bridge-bonded C O to generate carbonate ions
(164).Cation effects on the IR spectra of C O adsorbed on
Pt were interpreted in terms of an electrochemical Stark effect
in which the cation altered the position of the outer Helmholtz
plane (165). Quantum mechanical X, calculations, which
assumed a Pt4 cluster as a model for the electrode surface,
were used to calculate the potential dependence of uco at Pt
electrodes (166).
C O coverages on Pt were obtained from FT-IR absorbance
values after oxidation of C O to C02 in a thin-layer cell (E264).
Differences were noted between the in situ and the ex situ
IR reflection absorption spectra of HSO4- adsorbed on
P t ( l l 1 ) (167). The in situ spectra indicated adsorption at
positive potentials and a potential dependence of A,,.
Adsorption of CH3CN on gold was followed by subtractively
normalized FT-IR spectroscopy which gave a picture of the
double layer containing two types of CH3CN and H 2 0 in the
interfacial region (168).
In situ FT-IR spectroelectrochemistry was performed on
cobalt electrodes in NaOH(,,, (169),Si single crystal wafer
electrodes (170),and Ru electrodes in aqueous acid and alkaline
solutions (171).
In several instances, in situ infrared spectroscopy has given
information on the orientations of molecules at electrode
surfaces. For example, anthraquinonedisulfonatesadopted a
flat orientation initially and then a more perpendicular
configuration as the adsorption proceeded (172).Polarization
modulation FT-IR spectra of thick phenazine and pheno-
thiazine films indicated that most of the molecules were
oriented either perpendicular (in one case) or parallel (in two
cases) to the electrode surface (173). In situ reflectance IR
spectra indicated that the very narrow CV wave seen for
heptylviologen on Hg was due to a faradaic reaction (174).
While solution spectroelectrochemical studies have been
generally omitted from this survey, attention will be called to
the extensive set of data, including IR band assignments, for
nine p-quinone molecules in five solvents (175).
On the experimental side, a three-electrode IR optically
transparent thin-layer electrochemical cell was detailed that
allowed minimal diffusionof 0 2 into thecell (176).Electrodes
used in ATR spectroelectrochemical cells included a gold
minigrid placed on the surface of a ZnSe element (177)and
a BaF2 crystal coated with a 30-nm Au layer (178).A detailed
description of the problems that arise in the use of Ge or GaAs
crystals for ATR spectroelectrochemistry has appeared (179).
FT-IR external reflection spectroelectrochemistry has been
carried out using a step-scanning, phase-modulated spec-
trometer and controlled-potential electrochemical modulation
of the signal (180).Since Fourier frequencies due to movement
of the interferometer mirror are reduced to zero in step-
scanning spectrometers, cross-talk between the Fourier
frequencies and modulation of the electrode potential is
minimized. The feasibility of the technique was established
for the surface oxidation of C O on Pt. For spectra obtained
with more conventional instruments, simple trapezoidal
integration of the EMIRS spectra led to improved spectra
and more convincing peak assignments (181,182).
In situ spectroelectrochemistry was performed using
synchrotron radiation in the far-IR region, which is 100-
1000 times brighter than conventional black body radiation
(183,184).The decomposition of C104- in an acid electrolyte
was indicated by the appearance of bands due to adsorbed
chloride.
Real-time surface-enhanced Raman spectroscopy (SERS)
of the electrooxidation of Pt, Rh, Ru, and Au surfaces was
performed using a charge-coupled device detector. Raman
bands in the 250-850-cm-l region were assigned to metal-
oxygen vibrations; M-0 and M-OH vibrations were distin-
guished by the use of D20 solvent (185). SERS spectra
acquired during the oxidation of C O at Au, Pt, and Rh films
on gold substrates detailed the interrelations between C O and
metal surface oxidation processes (186). In situ SERS of
adsorbed oxygen on Ag was performed under a wide range
of conditions on various supports, including YzO3-stabilized
ZrO2 (187). SERS spectra were reported for oxide films at
Ti and copper electrodes (188,189).
Pemberton and co-workers have continued their studies of
the orientation of adsorbed alcohol molecules at silver and
gold electrodes (190-194). They deduced the orientations,
which were generally potential dependent, from the relative
intensities of the symmetric and the asymmetric C-H
vibrations of the methyl and methylene groups in the
adsorbates. Interestingly, their spectra indicated that the
solvent structure and orientation were maintained upon
emersion from butanol solvents (192).
SERS of adsorbed pyridine and related molecules continues
to be a popular topic. Often perpendicular, or nearly
perpendicular, orientations are reported (195-197),although
SERS spectra of indole on roughened Ag were interpreted in
terms of a parallel orientation (198). Articles appeared on
SERS of pyridine adsorption on Cu and Ag (199),the effect
of Pb UPD on pyridine adsorption on Cu electrodes (1100),
and 4-mercaptopyridine adsorption at mechanically polished
polycrystalline Pt (1101). A SERS study of coadsorbed
nicotinic acid and 3-acetylpyridine on Ag featured detailed
band assignments (1102).
The intensity of SERS spectra of pyridine on Ag, as
activated in the usual fashion by redox cycling, was found to
be related to the magnitude of the cathodic charge applied in
the activation and was roughly independent of the anion (1103).
In situ SERS has been used to good effect to identify
intermediates and products of electrode reactions. Systems
studied recently include the oxidation of diphenylamine in
CH3CN (1104,the oxidation of o-aminophenol(1105,1106),
the surface redox chemistry of p-mercaptoaniline (1107),the
oxidation of adsorbed sulfur on gold (1108),and the oxidation
of pyrite in neutral solutions (1109). SERS spectra of the
43N'+ cation radical in CH3CN were obtained in a flow cell
without interference from dimeric products (1110). SERS of
organic sulfides was carried out at a rotating silver electrode
in order to eliminate experimental artifacts due to photo-
reactions (1111). Other SERS electrochemical studies in-
cluded electrodeposition of Ag from a cyanide bath (1112),
the Cu/CuSCN electrode (1113),and Ni electrodes in the
presence of electrodeposited Ag (1114).
Time-resolved SERS was impressively performed in a pulse
mode at low power in order to detect intermediates of electrode
reactions on the nanosecond time scale (1115). Time-resolved
SERS spectra for the reduction of heptylviologen on Ag
indicated the existence of nucleation phenomena at short times
(1116).
Analytical Chemistry, Vol. 66, No. 12, June 15, 1994 409U
 In situ Raman spectra of Zn-phthalocyanine films on Au
and glassy carbon electrodes were obtained with a confocal
spectrometer. A significant aspect of this study was that the
irradiated spot on the electrode surface had a diameter of less
than 1 ym (1117).
Simonet and co-workers have used spin traps to detect
radical intermediates in the electrochemical reduction of
several species (1118,11 19). For the reduction of (C6Hs)dP+
in nonaqueous solvents, it appeared that the CsH5' radical
was not an intermediate. ESR was also used to follow the
intercalation of lithium into V2O5 cathodes (1120). The time
frame accessible in the ESR-electrochemistry experiment was
ca. 1 s in the study of Dunsch and Petr (1121).
13C N M R spectra were obtained for I3C-enriched C O on
Pt-black surfaces under potential control (1122). Line
narrowing and chemical shifts were seen associated with
changes in the CO bonding at the surface. Another original
spectroelectrochemical study was the in situ determination of
atomic magnetic susceptibility using a nonspinning cell that
operatedin the boreof a 400-MHzNMR spectrometer (1123).
The test system for this study was a 0.1 M Fe(CN)63-/4COUpk
in D20 solution.
Several applications of ellipsometry to electrochemistry
have been described by Hamnett (1124). Ellipsometric
transients were followed during adsorption of thiols on gold,
growth of metal oxide films, and growth and switching of
polymer films. The time scale was relatively slow, on the
order of seconds, but the author predicted advances in
instrumentation that would allow measurements in the
millisecond range, as well as spatial resolution of ca. 10" cm2.
Chao et al. measured effective dielectric constants for the
electrode/solution interface at single crystal electrodes using
an ellipsometry method (1125).
Electrochemical quartz microbalance methodology has
proved to be useful for the study of a variety of interfacial
processes as evidenced by the many applications to surface
electrochemistry and polymer film electrodes cited above.
Several recent papers have addressed experimental artifacts
that can arise with this technique. The problem of nonuniform
mass sensitivity across a QCM electrode surface was treated
authoritatively by Hillier and Ward (1126). Bacskai et al.
have also considered the QCM response for uneven coatings
of polymer films (1127). The effect of surface microstructure
on the QCM response was analyzed, and the analysis applied
to roughened Ag/AgCI surfaces (1128). Frequency shifts on
the order of a few hertz (e20 Hz) were seen for EQCM
experiments with nonadsorbing couples for 5-MHz AT-cut
quartz crystals (1129). These shifts were assigned to changes
in the density and viscosity of the depletion layer at the
electrode surface.
EQCM of poly(bithiophene) electrodes indicated that rigid
films were electrodeposited from CH3CN up to 50 nmol/cm2
electroactive sites and that the Sauerbrey equation was valid
(1130). For thicker films departure from rigidity was seen.
The dependence of the superficial energy of a QCM
oscillator on elastic strain and stress predicted by the Lippmann
equation was experimentally verified (1131). By use of a dual
QCM oscillator, connected to the EQCM via a pressure
chamber, the effects of mass and surface energy could be
separated.
410R Analytical Chemistty, Vol. 66, No. 12, June 15, 1994
A fast EQCM apparatus was used to study ion-exchange
reactions of poly(pyrro1e); a resolution of a few nanograms
in a measuring time of 1 ms was achieved (1132). The EQCM
experiment was performed with 30-MHz AT-cut quartz
crystals that had been chemically milled to produce a thin
disk surrounded by a thick quartz ring (1133). The resulting
high-frequency operation afforded significantly increased
sensitivity.
J. INSTRUMENTATION
Circuit diagrams have been published for an instrument
that simultaneously measured the electrode potential and the
resistance of an electrolyte solution ( J I ) and for several
potentiostats (J2-J4). The single op amp potentiostat of
Amatore and Lefrou allowed for ohmic drop compensation at
sweep rates up to 300 kV/s. An instrument for digital ac
voltammetry has also been described (J5).
A Fourier transform impedance spectrometer, which
operated in the frequency range 10-3-105 Hz, was described
in some detail (56). Schefold gave details of an instrument
for intensity-modulated photocurrent spectroscopy that em-
ployed a red LED as the light source ( J 7 ) . It was used in a
nice study of charge transfer at p-InP single crystal electrodes.
A simple impedance instrument was described for measure-
ment of double-layer capacities ( J 8 ) .
Several experimental apparatuses designed for operation
under extreme conditions were noted. These include an
automatic setup for impedance measurements on two-electrode
cells over a frequency range from to lo7 Hz and a
programmed temperature range from room temperature to
1100 K ( J 9 ) . Pressure effects on electrochemical potentials
were measured with a cell that withstood pressures up to 10
kbar (J10). The Ag/AgCl reference electrode potential was
found to be relatively pressure insensitive in this study. The
high-pressure cell of Sachinidis et al. operated at pressures up
to 1.5 kbar ( J I 1 ) . Cyclic voltammograms of several metal/
metal oxide couples were obtained at 700-900 OC in an yttria-
stabilized zirconia oxygen ion conducting electrolyte (J12).
As noted above, low-temperature electrochemistry has been
performed at superconducting UMEs; details of a cell design
were given by Green et al. (E346).
Several cleverly designed flow cells have been described
including a RVC spectroelectrochemical detector for LCEC
( J 1 3 ) ,a carbon fiber cell (514, and a flow reactor containing
mosaics of ion-exchange membranes and bipolar metal
electrodes (J15). In the latter device, electrons and ions were
transported in the same or opposite directions by the driving
forces of redox potential and concentration gradients.
A technique called "current spike polarography" was used
to study aqueous/air interfaces and thin films of solution held
in a silver ring (J16). In the latter situation, a small volume
of solution (0.01 mL) was positioned just below a DME
capillary and the i-E-t transients were measured as the Hg
drop touched and fell through the solution. Comparison of
the zero current potential with that of the bulk solution
polarogram gave an estimate of the surface potential of the
electrolyte solution.
Reference electrodes recommended for nonaqueous solvents
included the 13-/1- couple in CH3CN (J17), a cross-linked
poly(ethy1eneimine) film electrode loaded with Fe(CN)63-/4
 (JZ8), and Mg(Hg) amalgam in D M F (J19). An electrode,
consisting of 6 Ag/AgCl wire embedded in PTFE/alumina/
KCl layers pressed into pellet form, performed nicely as a
pressure-insensitivereference electrode for in situ natural water
studies (J20). The standard potentials of glass electrodes
with internal solutions of zwitterion buffers were reported to
vary linearly with temperature over the range 5-50 OC (J2Z).
Construction of a miniature, needle-type, working electrode/
reference electrode assembly, 0.5 mm in diameter, for sensing
glucose was described (522). A dual-reference electrode
consisting of a SCE and a Pt wire connected by a 0.1-pF
capacitor was recommended on the basis of its high impedance
response (523).
Tieman et al. employed a three-electrode sensor made by
screen printing Pt onto a ceramic substrate (J24),and a very
simple procedure for sealing gold into glass using glass
soldering powder was reported (J25).
Experimental details were given for fitting DMEs with
commercially available PTFE tips for use in media that attack
glass capillaries (J26). The same group reported on a simple,
automatic HDE, DME, SHDE apparatus (J27). A Hg film
electrode covered by a cellulose membrane was used to quantify
metal species directly on a TLC plate (J28).
Several interesting descriptions of porous electrodes have
appeared. The gas-sensing electrodes of Tierney and Kim
had fast response times due to the absence of a semipermeable
membrane and the fact that the gas molecules came directly
in contact with the working electrode (J29). They used two
types of porous substrates: an alumina ceramic and a
micromachined silicon wafer with an array of 10-pm holes.
Microporous gold films, which replicated the structure of an
anodic porous alumina template, had a narrow distribution
of pore diameters around a value of 100 nm (J30). Tang and
Chan constructed gas diffusion electrodes by electrodeposition
of Ag on commercially available Ni mesh ( J 3 1 ) . An open
pore network Pt electrode was stabilized by a procedure that
involved heating Pt and yttrium oxide powders at T I 1500
“ C (J32). To drive home the reoccurring observation that
little is new these days, a fascinating description of a French
patent granted to P. L. Hulin in 1893 for a “flow-through
porous electrode” is recommended reading (J33).
A technique for iR, compensation involved measurement
of the ac impedance at high frequency and adjustment of the
applied potential under computer control by thevalue of Id&
( J 3 4 ) . The measurement and correction routine was com-
pleted in ca. 2 ms using a 12-bit, 10-ps ADC and a 486 PC.
Details of software packages for interfacing PAR 273 and
174 potentiostats have been published (535,J36).
Andrieux et al. found that digital and analog filtering of
CV i-E data, while decreasing random error on peak potential
measurements, resulted in increased systematic error (J37).
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