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electrochemical PCET processes are crucial for advancing HER reaction for a CPET process (Figure 1A). Although the
and other catalytic processes. Studies of PCET reaction formation of high-energy, charged intermediates are circum-
mechanisms to date have primarily involved organic substrates vented, this termolecular reaction can give rise to a high kinetic
relevant to biological charge transport pathways, with only a few barrier. As such, stepwise ET-PT or PT-ET mechanisms are
examples of transition metal-based systems.8−11 Further, while a often favored kinetically.37,38 Conversely, for electrochemical
rich literature exists for the study of homogeneous-based PCET, PCET, the reaction between the PCET substrate and the proton
where electron and proton transfers occur between discrete donor/acceptor occurs at an essentially infinite electrode surface
molecules (Figure 1A),9,12−16 there are fewer reports which (Figure 1B). As such, the kinetic barriers for an electrochemical
CPET process will be different than the termolecular
homogeneous example.
Second, the electron transfer driving force changes during a
potential-sweep electrochemical experiment. It has been
demonstrated that via careful selection of chemical oxidants,
the PCET oxidation of a tungsten-hydride bond can be induced
to undergo a CPET mechanism.10 In an electrochemical
experiment such as cyclic voltammetry, the driving force for
electron transfer changes as a function of time. This suggests that
the PCET mechanism may change during a single experiment as
the potential is swept (Figure 2). It has already been
spectroscopy. Both techniques take advantage of changes in the py, which has a time resolution of microseconds due to the
absorption profiles during a reaction to gain mechanistic and necessary mixing time, transient absorption spectroscopy allows
kinetic information; specific details are discussed below. investigation of kinetics in the pico- to nanosecond regime.
2.1.1. Stopped-Flow Spectroscopy. Stopped-flow spectros- 2.2. Electrochemistry. Electrochemical methods have vast
copy is a powerful tool for extracting kinetic information and has precedent in the study of reaction mechanisms,25,26 and
been used to examine PCET in various systems.10,40−43 Stopped- consequently, electrochemistry has been increasingly utilized in
flow has been applied to the study of both catalytic cycles and the study of PCET reactions. One key benefit of electrochemistry
elementary reaction steps where the reaction is accompanied by is the dynamic control over the energy of electrons. Of the
clear spectral changes. In a typical stopped-flow experiment, the multitude of electrochemical techniques, cyclic voltammetry has
contents of two syringes are rapidly mixed and the absorbance of emerged as the favorite tool for uncovering reaction mechanisms
the system recorded over time, either as full spectra at designated and determining rate constants due to the rich information
time delays or as single-wavelength kinetics traces (absorbance vs available from current−potential responses and the extensive
time). A general-purpose UV−vis absorption spectrometer may analytical methods established for interpreting resulting data.
be used in cases where reaction kinetics are slow.44 Additionally, cyclic voltammetry is a nondestructive technique;
Stopped-flow methods are amendable to monitoring the only the minute volume of reactants immediately next to the
reaction between many reagent types or even combinations of working electrode (the reaction layer) is involved in a
reagents. For PCET studies, these may be chemical reductants, measurement. Finally, over the last 5 years, great strides have
oxidants, hydride donors, acid, or base, for example. Once the been made in the development of mathematical models to extract
two solutions have been rapidly mixed, the absorbance is quantitative kinetic information from cyclic voltammograms of
recorded as a function of time. When monitoring a single multielectron, multisubstrate reactions. Presented here is a brief
elementary step, pseudo-first-order conditions are often summary of the electrochemical tools most commonly used in
employed, enabling the reaction kinetics to be fit to a single our laboratory; more extensive discussions are available.26,32
exponential to extract an observed rate constant kobs. For 2.2.1. Kinetic Analysis Using Catalytic Plateau Current and
complex reactions, the kinetics traces can be fit using a kinetics Half-Wave Potential. In the case of electrochemical catalysis
model based on a series of differential equations describing the under ideal conditions with no limiting side phenomena or
concentrations of each reactant, intermediate, and product as a substrate depletion, an S-shaped response with superimposable
function of time. Obtaining rate constants through stopped-flow forward and reverse traces is obtained by cyclic voltammetry.32
measurements has been shown to corroborate electrochemically An observed rate constant kobs can be extracted using the
derived rate constants.24,40,41 experimental catalytic plateau current (ipl, which is independent
2.1.2. Transient Absorption Spectroscopy. Time-resolved of scan rate) and the potential at which half the catalytic current is
optical monitoring techniques can also be coupled to photo- reached (Ecat/2). For a two-electron catalytic process and
triggering methods to initiate PCET reactions. In traditional laser assuming that both electron transfers occur at the electrode
flash-photolysis methods, excited-state reductants (including with the second reduction being easier than the first, the catalytic
ruthenium, rhenium, iridium, and copper polypyridyl com- plateau current is given by eq 1 where [Cat]0 is the bulk solution
plexes) are employed to initiate the one-electron reduction of a catalyst concentration, D is the catalyst diffusion coefficient, F the
redox-active molecule upon excitation by a pulsed laser.8,45−53 In Faraday constant, and A is the electrochemically accessible
the presence of a proton source, reduction will often be electrode surface area.
accompanied by a protonation reaction.12,54,55 As in stopped-
flow spectroscopy, the distinct optical signatures of the different i pl = 2FA[Cat]0 D kobs (1)
redox forms of the catalysts, as well as the protonated species,
allow the reaction intermediates and products to be spectroscopi- eq 1 is often divided by the one-electron peak current in the
cally detected and monitored. However, in these phototriggered absence of substrate, i0p, given by the Randles−Sevcik equation
transient absorption experiments, it is the change in the sample (eq 2, where F is the Faraday constant, T is temperature, and υ is
absorbance (as opposed to the absolute absorbance) that is scan rate) to yield eq 3, which eliminates the need for the
monitored as a function of time. Data can be recorded as diffusion coefficient and electrode surface area to be
difference spectra at designated time delays or as single- independently determined:
wavelength kinetics traces, depending upon experimental setup. DυF
While phototriggered reactions typically involve the initiation i p0 = 0.446FA[Cat]0
of electron transfer, proton transfer reactions may be photo- RT (2)
initiated as well using photoacids.12 Photoacids are species that
become powerful proton donors in their electronic excited states, i pl kobsRT
allowing in situ generation of a proton donor upon pulsed laser = 0.448
i p0 υF (3)
excitation.56,57 Beginning with the reduced metal species,
photoexcitation of the photoacid will promote proton transfer
Expressions for kobs as a function of the rate constants for the
to yield a PCET reaction intermediate. Like photoinduced
electron transfer reactions, proton transfer reactions can also be first and second chemical steps, k1 and k2 respectively, can be
monitored optically if protonation is accompanied by a distinct derived for specific mechanisms.28 For the mechanisms ECEC
change in absorption. While identifying the conditions to and EECC, assuming S-shaped catalytic responses, expressions
phototrigger an electron transfer or proton transfer reaction for kobs as well as Ecat/2, the potential at which half of the plateau
for a laser flash-photolysis experiment may be challenging, current is reached, are given in Table 1 as a function of k1, k2, and
especially when other reactive substrates are present in solution, E1/2, the potential of the electrochemical event triggering
this time-resolved spectroscopy allows much faster reactions to catalysis. In many cases, either k1 or k2 is rate limiting, resulting
be optically monitored. Compared to stopped-flow spectrosco- in a collapse of the equations in Table 1 simpler expressions.
3646 DOI: 10.1021/acscatal.6b00778
ACS Catal. 2016, 6, 3644−3659
ACS Catalysis Perspective
Table 1. Values of kobs and Ecat/2 as a Function of the Rate figures of merits of different homogeneous catalysts by
Constants of the Two Chemical Steps Considered28,39 illustrating the trade-off between activity and overpotential.
The turnover frequency is defined as the moles of product
ECEC EECC generated per unit of time divided by the moles of the active form
k1 of the catalyst present in the reaction-diffusion layer, and the
k1
kobs k1 1+
k1 expression of the maximal turnover frequency TOFmax is
⎛ k2 ⎞
1+
k2 k2 ⎜⎜1 +
⎝
⎟⎟
k1 ⎠
dependent upon the mechanism considered.28,32
⎛ ⎞ TOFmax
RT ⎛ k1⎞ RT ⎜ k1 ⎟ TOF =
ln⎜1 ⎟ ⎡ − η − Ecat/2)⎤⎦
Ecat/2 E1/2 + ln⎜1 + ⎟ E1/2 + +
F ⎝ k2 ⎠ F
⎜
⎛
k 2 ⎜1 +
k2 ⎞
⎟⎟
F Solv
1 + exp⎣ RT (E HA/H
⎝ ⎝ k1 ⎠ ⎠ 2 (5)
Recently, a methodology was outlined for the direct depending on the acid structure, concentration, and the nature of
electrochemical determination of ESolv HA/H2 via measurement of the solvent.
the open circuit potential of an electrochemical cell containing homoconjugation: BH+ + B → BHB+ (7)
the respective acid and 1 atm of H2 gas at equilibrium in the
solvent studied.69 To date, the experimental complexity of the dimerization: 2BH → (BH)2 (8)
measurement has limited its use.
A recent report investigating the kinetics of the CPET reaction heteroconjugation: BH+ + H 2O → BH3O+ (9)
between acids and gold electrodes in acetonitrile shed light on
the influence of acid structure in terms of steric hindrance.70 Homoconjugation is particularly strong for phenols and
Faster kinetics of the CPET process to the electrode were carboxylic acids. For example, phenolate is reported to have a
measured for triethylammonium compared to diisopropylethy- homoconjugation constant close to 16 000 M−1, while benzoate
lammonium. This effect was attributed to the increased Tolman has a constant of almost 4000 M−1.64 By contrast, aniline has a
cone angle of 200° for the diisopropylethylammonium cation much lower homoconjugation constants of 4 M−1;64 it is often
compared to 150° for triethylammonium. assumed that most aniline derivatives have low homoconjugation
The possibility of interactions between catalysts and conjugate constants.72 As was recently demonstrated in the study of
bases is another parameter to be considered in the choice of acid/ [Ni(PR2 NR2 ′)2]2+ hydrogen evolution catalysts, failure to account
base pairs for mechanistic studies. The influence of base structure for homoconjugation when determining rate constants from
has recently been highlighted in our study of catalytic proton cyclic voltammetry data can lead to misinterpretations of the
reduction by cobaloxime complexes with substituted aniliniums influence of added base as well as errors in the determination of
as an acid source (see below). It has been shown that during the rate constants. However, careful consideration of homoconjuga-
course of catalysis, as conjugate base aniline is generated, the tion can permit accurate determination of kobs and mechanistic
aniline molecules can bind to the cobalt center, influencing what assignment.39
the active catalyst is and so altering the cyclic voltammetry Acid dimerization is another process to consider, especially
responses.71 This effect is readily apparent in the cyclic when the acid dimer has a lower pKa than the parent acid. The
voltammetry of Co(dmgBF2)2(CH3CN)2 (dmgBF2 = difluor- presence of an acidic species with a different pKa than the parent
oboryldimethylglyoxime) with and without added 4-MeO- acid may result in multiple PCET mechanisms, complicating
aniline (Figure 3). Upon base addition, the CoIII/II wave kinetic and mechanistic analysis. Dimerization can occur in
aprotic organic solvents when interaction between two acid
molecules yields a stabilization greater than solvation by the
aprotic organic solvent. Dimerization has been found to
influence the reactivity of carboxylic acids in acetonitrile.73
Heteroconjugation arises between acids and bases of a
different species; for example, the interaction of a carboxylic
acid with water. In the context of electrochemical studies in
acetonitrile, the effect of heteroconjugation has only been
considered when water is added to the organic solvent.73
2.3.3. Reduction of Acids at Electrode Surfaces. For
solutions containing protic species, an important control
experiment to keep in mind is at what potential these protic
species are directly reduced at the electrode. In other words,
control experiments for each individual component of an
electrochemical system are crucial. Glassy carbon electrodes
have long been used in the study of fuel-forming catalysts,
especially hydrogen evolution, due to their low background
activity for direct, heterogeneous acid reduction. While the
background activity is less significant than on other electrode
materials such as platinum, direct acid reduction at glassy carbon
electrodes still occurs. Our group recently published a systematic
Figure 3. Cyclic voltammograms recorded at 100 mV/s in 0.25 M study of the direct reduction of 20 acids in acetonitrile on glassy
[Bu4N][PF6] of 0.38 mM of Co(dmgBF2)2(CH3CN)2 in the absence carbon electrodes.74 These acids spanned over 35 pKa units in
(a) and presence (b) of 2 mM 4-methoxyaniline. Reprinted with acetonitrile, with the experimental direct acid reduction
permission from reference 71. Copyright 2016 American Chemical potential, reported as the current inflection potential (Einf),
Society. covering a range of over 2 V.
These results are visually summarized in Figure 4, where the
reversibility and potential is modified, without apparent changes color intensity reflects the current intensity observed as a
to the CoII/I wave. Separate UV−vis titration experiments percentage of the current observed at Einf. This study
demonstrated that one and two aniline molecules can reversibly underscored four factors influencing the observed voltammo-
coordinate to the catalyst.71 grams: electrode fouling, irreproducibility from scan to scan,
2.3.2. Acid Homoconjugation, Heteroconjugation, and curve crossing, and acids with erratic backgrounds. The influence
Dimerization. Acid and base molecules are well-known to of adding water to each acid was also studied. While no significant
interact in solution via the processes of homoconjugation, peak shifts were observed with water addition, the current
heteroconjugation, and dimerization. These three processes, increased for a number of acids known to have a high
depicted in eqs 7 to 9, have a varying degree of importance homoconjugation constants. The current increase was proposed
3648 DOI: 10.1021/acscatal.6b00778
ACS Catal. 2016, 6, 3644−3659
ACS Catalysis Perspective
Table 2. Metal Complexes Known to Electrochemically Degrade in Organic Solventsa under Catalytic Conditions To Form
Electrode-Adsorbed Heterogeneous Materialsb
a
All examples were in either acetonitrile or dimethylformamide. bThis table does not include examples where the homogeneous catalyst only
degrades after harsh prolonged catalysis; e.g., ref 90.
Until recently, it was not clear if the EC′ Zone Diagram could Diagram could be qualitatively extended to multielectron,
be directly extended to the more complex multielectron, multisubstrate reactions.92 In addition to υ, [CA]0, and [Cat]0,
multisubstrate reactions associated with fuel production.92 the pKa of added acids could also be used to traverse the zone
However, voltammograms have now been reported for the diagram as it was found that the observed rate constant is linearly
catalytic reduction of protons from a series of eight para- dependent on acid strength.71,92
substituted aniliniums to hydrogen by the catalyst Co- Using the methods detailed above in section 2.2.1, global rate
(dmgBF2)2(CH3CN)2. Notably, the voltammetric responses constants can be extracted from the plateau region of S-shaped
recorded for varying kinetic and excess factors apparently voltammograms of Zone KS (and the related Zone KD) for both
spanned all of the waveform shapes associated with the EC′ Zone EC′ and various multielectron, multisubstrate reactions, such as
Diagram. Detailed analysis confirmed that the EC′ Zone the ECEC pathway.26,28 Further, it has long been known that
3650 DOI: 10.1021/acscatal.6b00778
ACS Catal. 2016, 6, 3644−3659
ACS Catalysis Perspective
kinetic information can also be extracted from waveforms in the the [Co(dmgBF2)2(CH3CN)2]0/− couple. Notably, the Ecat/2
“total catalysis” region (Zone KT2) for a simple EC′ (the half-wave potential of the sigmoidal response) shifts to
reaction.32,91 The catalytic peak potential of a total catalysis values positive of E°′([Co(dmgBF2)2(CH3CN)2]0/−). For acids
voltammogram varies as a function of ke, υ, [CA]0, and [Cat]0 (see of pKa > ca. 9.5, the catalytic response currents approach a
section 4.1).32 More recently, peak shift analysis has been plateau shape as the acid concentration is increased; these
extended to the ECEC mechanism and demonstrated, under catalytic plateau currents (ipl) were found to be first-order in both
limiting conditions, to provide information about the rate acid concentration and catalyst concentration, consistent with
constant k1.71 Ultimately, the primary utility of a multielectron, prior results.97
multisubstrate zone diagram is its use as a navigational tool to These three observations provide evidence to support
modify experimental conditions in order to enter either the zones assignment of the reaction mechanism (Figure 6A). Specifically,
in which kinetic information can be extracted. the shifting Ecat/2 indicates that the first chemical step (C1,
protonation of [Co(dmgBF2)2(CH3CN)2]− to form a putative
3. CASE STUDIES: REACTION MECHANISMS AND CoIII-hydride intermediate) is rapid, and the subsequent
KINETICS OF H2-EVOLVING CATALYSTS chemical step(s) is(are) rate-limiting. Previously, two independ-
The electrochemical and spectroscopic methods discussed in ent theoretical124,126 and one experimental125 study have shown
section 2 have been applied in concert to elucidate the reaction that the CoIII-hydride intermediate is more readily reduced than
pathways of catalysts for hydrogen evolution. Recent work has the parent CoII species, indicating that this intermediate will be
focused on two highly active catalysts, Co(dmgBF2)2(CH3CN)2 spontaneously reduced. Further, based on the influence of acid
(dmgBF 2 = difluoroboryldimethylglyoxime) and [Ni- and catalyst concentration on the catalytic plateau current, the
(P2PhN2Ph)2]2+ (P2PhN2Ph = 1,3,5,7-tetraphenyl-1,5-diaza-3,7-di- rate-limiting step for catalysis is also first-order in both acid and
phosphacyclooctane) (Scheme 2). In addition to identifying catalyst, indicating a second (rate-limiting) protonation step
(C2) and an overall heterolytic route for hydrogen production.
Scheme 2. Co(dmgBF2)2(CH3CN)2 (left) and Together, these data support a heterolytic ECEC pathway for H2
[Ni(PPh Ph 2+
2 N2 )2] (right) evolution from anilinium acids in acetonitrile. Notably, this
assignment is consistent with that from theoretical work54,124 as
well as conclusions from photocatalysis and laser flash photolysis
experiments.112,125
Of note, a homolytic route involving the bimetallic reaction of
two CoIII-hydride species has previously been recognized as a
viable pathway for H2 production by both computational
studies124,126 and thermochemical analysis.54 While clear
evidence diagnosing a homolytic pathway for hydrogen
production has not yet been reported, 29 recent work
dominant PCET reaction pathways, these studies have yielded investigating the cleavage of H2 by Co(dmgBF2)2(CH3CN)2
new insight into the kinetics of elementary reaction steps and under high H2 pressures suggests this reaction proceeds via a
revealed linear free energy relationships between rate constants
homolytic cleavage route.127−129 As such, a homolytic reaction
for these individual steps and acid pKa. The complexities of
pathway for hydrogen production may be accessible under
proton source reactivity in acetonitrile have also been established
alternative experimental conditions, or could be occurring as a
through the investigation of reaction kinetics as a function of
minor parallel pathway.
various acid parameters.
With this mechanistic assignment, kinetic details for
3.1. Mechanistic Study of Electrocatalytic H2 Evolution
by a Cobaloxime. Cobaloximes and their derivatives have been elementary steps can be elucidated through analysis of the
incorporated as catalysts in both electrochemical and photo- voltammograms. The second-order global rate constants for
chemical H2 production cycles.93−123 While their operating catalysis were determined from the analysis of the acid
mechanisms have been explored in depth under certain concentration-dependent plateau currents for acids with pKa >
conditions using both experimental and theoretical meth- ca. 9.5 (Figure 6B). As the plateau current reflects the observed
ods,54,93,94,96−98,124−126 electroanalytical methods were recently rate constant, kinetic details of the rate-limiting step can be
applied to explore the reaction pathways and kinetics of gleaned directly. As described above, the second protonation is
Co(dmgBF2)2(CH3CN)2 (dmgBF2 = difluoroboryldimethyl- the rate-limiting step under these conditions and described by
glyoxime) as a function of acid strength.71,92 Through the use rate constant k2. Across the series of aniliniums with pKa > ca. 9.5,
of a series of analogous acids, specifically para-substituted catalysis was found to accelerate as the strength of acid increased
aniliniums, complicating factors resulting from different and a linear correlation is observed between log(k2) and acid pKa
homoconjugation constants across dissimilar acids were reduced, (slope = −0.77). For acids with pKa < ca. 9.5, catalytic
allowing studies to focus on the direct effect of acid pKa on voltammograms remained peaked and the catalytic responses
reaction kinetics and mechanism. It should be noted that were determined to be controlled by diffusion of the acid to the
Co(dmgBF2)2(CH3CN)2 decomposes in the presence of strong reaction layer. As such, second-order rate constants could not be
acids; in the extreme case of strong acid and reducing conditions determined for these acids; however, extrapolation of the linear
cobalt-containing nanoparticles form, as noted in Table 2 above. relationship determined for weaker acids allows these rate
In our studies of Co(dmgBF2)2(CH3CN)2, great care was taken constants to be estimated.
to limit the extent of decomposition.71 Rate constants for the first protonation step (k1) were
Cyclic voltammograms of Co(dmgBF2)2(CH3CN)2 recorded determined from foot-of-the-wave (FOWA) analysis. Like k2, a
in acetonitrile in the presence of para-substituted aniliniums linear correlation between log(k1) and pKa was observed (slope =
exhibit an increase in cathodic current and loss of reversibility at −0.97). Values for k1 are ca. 3 orders of magnitude greater than
3651 DOI: 10.1021/acscatal.6b00778
ACS Catal. 2016, 6, 3644−3659
ACS Catalysis Perspective
determined from this limiting current value (ca. 125 s−1) likely
reflects either an H−H bond formation step or H2 release.
Kinetic and mechanistic insight gained from comprehensive
analysis of the catalytic voltammograms contributes to a more
detailed picture of hydrogen evolution from cobaloximes.
Specifically, it was learned that upon reduction of the CoII
species, rapid protonation (k1) yields a CoIII-hydride species
(that may undergo tautomerization128−130). This intermediate is
readily reduced to form a CoII-hydride (k2). The subsequent
second protonation step is 3 orders of magnitude slower than the
first step. The resulting CoII−H2 species releases H2 to close the
catalytic cycle via an acid-independent step with a first-order rate
constant of 125 s−1.
3.2. Mechanistic Study of Electrocatalytic H2 Evolution
by [Ni(P2PhN2Ph)2]2+. [Ni(P2PhN2Ph)2]2+ (P2PhN2Ph = 1,3,5,7-
tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane) and its family
of hydrogen production/oxidation catalysts have been thor-
oughly studied over the past decade, with the notable result of
clearly demonstrating the importance of the secondary
coordination sphere in catalytic reactions.131−136 While original
reports assumed a single catalytic mechanism, the possibility of
multiple catalytic routes has been recently examined.24,39,137
Two generic pathways have been identified: an ECEC pathway,
whereby the first protonation occurs on the NiI species after a
single reduction, and an EECC pathway, where double reduction
to form a Ni0 species occurs prior to both protonations.
Two recent experimental studies probing these parallel
reaction pathways approached the problem very differently.
Wiedner and co-workers examined the reactivity of [Ni-
(PPh Ph
2 N2 )2]
2+
using dimethylformamidium (DMFH+) as the
proton source.39 DMFH+ is a relatively strong acid in acetonitrile
with a pKa of 6.1, resulting in cyclic voltammograms with both
the ECEC and EECC pathways readily apparent. Using a mixture
of electrochemical techniques, primarily based around FOWA,
the overall contributions of the two different pathways were
deconvoluted. In work in our lab, we utilized a weaker acid
(anilinium, pKa = 10.6) to isolate the EECC mechanism and then
used several of the previously discussed methods to determine
Figure 6. (A) Reaction mechanism for hydrogen evolution catalyzed by the individual rate constants of the elementary reaction steps.24
Co(dmgBF2)2(CH3CN)2 as supported by detailed analysis of catalytic 3.2.1. Electrochemical Studies To Elucidate Kinetics of Ni0
CVs. (B) Rate constants k1 and k2 determined from FOWA and plateau Protonation and Subsequent Reactivity. While analysis of
current analysis, respectively, of acid concentration-dependent catalytic
voltammograms of Co(dmgBF2)2(CH3CN)2 and a series of para-
cyclic voltammograms under pseudo-first-order conditions is
substituted aniliniums. k2 values for acids 6, 7, and 8 were extrapolated useful for extracting kinetic information, experiments carried out
from the linear relationship established at higher pKa values. kΩ under more stoichiometric catalyst:substrate conditions can
represents an acid-independent step and was determined from catalytic provide additional information on how the reaction proceeds. In
voltammograms recorded at high acid concentrations in which the the analysis of [Ni(PPh Ph 2+
2 N2 )2] , stoichiometric addition of
voltammetric responses were acid concentration and pKa-independent. anilinium confirmed rapid reactivity of acid with the Ni0 species
Acids identity: (1) 4-methoxyanilinium, (2) 4-t-butylanilinium, (3) by a signature kinetic peak shift (discussed further in section 4.2)
anilinium, (4) 4-chloroanilinium, (5) 4-trifluoromethoxyanilinium, (6) and the appearance of a new oxidation feature on the return trace.
4-(methylbenzoate)anilinium, (7) 4-trifluoromethylanilinium, and (8) Given that two electrons and a single proton had been
4-cyanoanilinium. Adapted with permission from ref 71. Copyright 2016
transferred to the catalyst, it was natural to assume hydride
American Chemical Society.
formation. Independent synthesis and cyclic voltammetric
analysis of a NiII-hydride confirmed that the new oxidation
those of k2, consistent with the interpretation of an ECEC feature observed did correspond to the hydride species (Figure
pathway with a rate-limiting second chemical step. 7).24
At high acid concentrations, the plateau currents reach a With the first chemical step established as hydride formation,
limiting value that is acid concentration and pKa-independent. we next examined the details of this elementary step under
This observation extends to both the weaker acids and the catalytic conditions. First, a rate constant was determined by
stronger acids described above which exhibit only peak-shaped analyzing the kinetic peak shift of the NiI/0 wave in the presence
voltammograms in their acid-dependent region. Across the range of acid. Conveniently, catalytic turnover could be prevented on
of acids explored, this limiting plateau current is constant, though the electrochemical time scale, even under pseudo-first-order
the concentration of the acid required to reach this limiting value conditions, by the addition of excess base. This rate constant was
increases as acid strength decreases. The first-order rate constant corroborated with FOWA. FOWA uniquely provides the rate
3652 DOI: 10.1021/acscatal.6b00778
ACS Catal. 2016, 6, 3644−3659
ACS Catalysis Perspective
Figure 8. Observed rate constants obtained from the current plateau (blue circles) for the reaction of [Ni(PPh Ph 2+
2 N2 )2] and anilinium, and from stopped-
flow kinetics traces (red circles) for the reaction of NiII-hydride and anilinium. Black circles represent the fit for the mechanism shown in the right panel,
and the appropriate kinetics models are shown for the time-resolved (red) and steady-state (blue) kinetics. Data from ref 24.
However, the discrepancy was reconciled by considering the Changing the proton source structure significantly affects its
possibility of an off-cycle intermediate, which has been reactivity (as will be shown in the following sections).
extensively explored in several previous studies.39,136,138−142 The effect of added base on reaction kinetics was explored.
These works reveal that the [Ni(PR2 NR2 ′)2]2+ molecules can be When base is added to solution, the reaction kinetics were
protonated in an “exo” position on the pendant amine which observed to slow. A trend between amount of base necessary to
prohibits catalytic turnover. This effectively inactivates the slow the reaction and acid pKa was observed. The higher the pKa,
catalyst prior to catalytic turnover. The “exo” position proton the less base required to lower the observed reaction rate (when
must be removed, followed by protonation in the “endo” position pKa is greater than 8.6, reactivity of acids below a pKa of 8.6 do
for productive catalysis to occur. Under the conditions accessed not have a pKa dependence as illustrated in Figure 10).
3.3.2. Molecular Association. Two different forms of
in cyclic voltammetry, an increase in the acid concentration
molecular association were examined, homoconjugation and
results in an increase in the concentration of the inactive catalyst,
dimerization (aggregation and heteroconjugation were also
reducing the apparent rate constant and giving the appearance of
considered for studies involving water). The list of proton
acid concentration independence. The time-resolved (stopped-
sources with recorded homoconjugation constants in the
flow) kinetics do not exhibit acid independence because no
working range of [Ni(PPh Ph
2 N2 )2]
2+
(pKa < 12) is limited, but
equilibrium can be established between the inactive and active
the effect could be examined through the comparison of 4-
forms of the catalyst. However, the generation of the inactive
cyanoanilinium (pKa = 7, log(KHC) = 0.1),73 p-toluenesulfonic
catalyst affects the kinetics analysis of the fast component and the
acid (pKa = 8.6, log(KHC) = 3),74 and dimethylformamidium
slow component observed corresponds conversion of the
(pKa = 8.6, log(KHC) = 1.7).74 While this series of acids had only
inactive species to the active species followed by hydrogen
small differences in their pKa values, the reaction rate constants
release.24 were found to be highly dependent on the homoconjugation
3.3. Reactivity of NiIIH with Various Proton Sources. As constants, with fast reaction rate constants observed for the acids
the reaction of the NiII-hydride with acid was established to be with larger homoconjugation constants (p-toluenesulfonic acid
the rate-limiting step for hydrogen production, this elementary (130 000 M−1 s−1) > dimethylformamidium (12 750 M−1 s−1) >
reaction step provided a convenient platform to take a deeper p-cyanoanilinium (750 M−1 s−1 )).73 In past work, the
look at the influence of the proton source on reaction acceleration of acid−base reactivity for acids with large
mechanisms in acetonitrile. Reactivity of the NiII-hydride with homoconjugation constants has been attributed to a lowering
a series of acids were examined using the same stopped-flow of the “effective” pKa as a result of stabilization of generated
procedure described for the reaction with anilinium (section conjugate base via homoconjugation with acid.69,72,136,143−145
3.2.2). The effect of various parameters, including pKa, presence However, rate constants for this series span more than 2 orders of
of base, molecular association, and interaction with water, were magnitude, and this span is too large to be accounted for simply
explored.73 by homoconjugation. Likely, larger homoconjugation constant
3.3.1. Acid pKa. As discussed above, pKa is the most commonly correlate with increased hydrogen bonding abilities, and these
considered parameter for acids in PCET studies. In the reaction acids may better stabilize the proton transfer transition state.
of NiII−hydride with acid, the anticipated linear free energy To our knowledge, proton source dimerization has yet to be
relationship is obtained between the log of the reaction rate and considered in the PCET fuel forming literature. While there are
the acid pKa (Figure 10). With a sufficiently strong driving force no recorded dimerization constants for proton sources with a pKa
for proton transfer the reaction rate constant becomes substrate less than 12, carboxylic acids are known to dimerize in
pKa independent (pKa < 8.6). The data in Figure 10 is limited to a acetonitrile and this generally results in a pKa for the dimerized
series of structurally related para-substituted aniline derivatives. species that is ∼3.5 units lower than the monomer.64 No
dimerization constants are recorded for trifluoroacetic acid (pKa
= 12.6) and trichloroacetic acid (pKa = 10.8). However, the
reaction of trifluoroacetic and trichloroacetic acid with the NiII-
hydride is second-order in acid, as would be expected for a highly
reactive acid dimer with a very low dimerization constant. This is
an important finding as trifluoroacetic acid is often used in
electrocatalytic studies; indeed, many studies report second-
order kinetics with trifluoroacetic acid.136,146−151
3.3.3. Addition of Water to Acetonitrile Solutions. Because
the target for most H2 evolution electrocatalytic systems is to
operate in water, water is often intentionally added to acetonitrile
solutions during catalysis to probe catalyst water stability and
performance.140,152 Consequently, it is important to understand
how the addition of water affects the proton source being
employed. Two cases are considered here: (1) water becomes
protonated and thereby hydronium is available to act as a proton
source, or (2) water heteroconjugates with the proton source,
affecting its reactivity. Hydronium has a very low pKa in
acetonitrile (2.2), but the ability of water to form large aggregates
Figure 10. Second-order rate constants vs acid pKa for the reaction of with concurrent stabilization of the hydronium ion significantly
NiII-hydride with para-substituted aniliniums. The linear region between increases its effective pKa with increasing water concentration.
pKa 12 to 8.6 has a slope of −0.7. Reprinted with permission from ref 73. Figure 11 demonstrates the influence of water on the rate
Copyright 2016 American Chemical Society. constant of reaction with NiII-hydride and acid over a range of
3654 DOI: 10.1021/acscatal.6b00778
ACS Catal. 2016, 6, 3644−3659
ACS Catalysis Perspective
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intermediates, inducing CPET may result in catalysts with (23) Bediako, D. K.; Solis, B. H.; Dogutan, D. K.; Roubelakis, M. M.;
decreased required operating potentials and thus higher Maher, A. G.; Lee, C. H.; Chambers, M. B.; Hammes-Schiffer, S.;
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reaction mechanisms through experimental parameters. 15006.
■
(24) Rountree, E. S.; Dempsey, J. L. J. Am. Chem. Soc. 2015, 137 (41),
AUTHOR INFORMATION 13371−13380.
(25) Bard, A. J.; Faulkner, L. R. Electrochemical Methods: Fundamentals
Corresponding Author and Applications, 2nd ed.; John Wiley & Sons, Inc.: Hoboken, 2001.
*E-mail: dempseyj@email.unc.edu. (26) Savéant, J.-M. Elements of Molecular and Biomolecular Electro-
Author Contributions chemistry; John Wiley & Sons, Inc.: Hoboken, 2006.
‡ (27) Costentin, C.; Drouet, S.; Robert, M.; Savéant, J. M. J. Am. Chem.
These authors contributed equally (N.E. and B.D.M).
Funding Soc. 2012, 134 (27), 11235−11242.
(28) Costentin, C.; Savéant, J.-M. ChemElectroChem 2014, 1 (7),
This work was supported by the University of North Carolina at 1226−1236.
Chapel Hill and the David and Lucile Packard Foundation. (29) Costentin, C.; Dridi, H.; Savéant, J.-M. J. Am. Chem. Soc. 2014,
Notes 136 (39), 13727−13734.
The authors declare no competing financial interest. (30) Savéant, J.-M. Chem. Rev. 2008, 108 (7), 2348−2378.
■ ACKNOWLEDGMENTS
This work was supported by the University of North Carolina at
(31) Roubelakis, M. M.; Bediako, D. K.; Dogutan, D. K.; Nocera, D. G.
Energy Environ. Sci. 2012, 5 (7), 7737−7740.
(32) Rountree, E. S.; McCarthy, B. D.; Eisenhart, T. T.; Dempsey, J. L.
Inorg. Chem. 2014, 53 (19), 9983−10002.
Chapel Hill. J.L.D. acknowledges support from a Packard (33) Venkataraman, C.; Soudackov, A. V.; Hammes-Schiffer, S. J. Phys.
Fellowship for Science and Engineering.
■
Chem. C 2008, 112 (32), 12386−12397.
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