674 Langmuir 1999, 15, 674-681

Colloidal Gold Aerogels: Preparation, Properties, and

Characterization
Michele L. Anderson,† Catherine A. Morris,† Rhonda M. Stroud,‡
Celia I. Merzbacher,§ and Debra R. Rolison*,†
Surface Chemistry Branch (Code 6170), Surface Modification Branch (Code 6670), and Optical
Physics Branch (Code 5610), Naval Research Laboratory, Washington, D.C. 20375

Received June 30, 1998. In Final Form: November 24, 1998

Colloidal metal aerogels are composite nanoscale materials that combine the high surface area and
porosity of aerogels with the unique optical and physical properties of metal colloids. As such, they are
being developed as advanced sensor, catalytic, and electrocatalytic materials. We have prepared colloidal
gold-silica aerogels containing gold colloids ranging in size from 5 to 100 nm. The results presented herein
focus on 5- and 28-nm Au-containing silica aerogels for the initial characterization of the interaction
between the metal colloid and the silica matrix. A blue-shift of the Au plasmon resonance for silica-
immobilized Au colloids (relative to the same colloids in a native Au sol) indicates an interaction between
the Au colloid and the nanoscale silica network. Transmission electron microscopy measurements have
been used to determine the average size and distribution of the colloidal Au particles, as well as to image
the nanoscale silica environment supporting an immobilized Au colloid. Small-angle neutron scattering
measurements show no significant changes in the three-dimensional structures of either the base- or
acid-catalyzed silica aerogels upon incorporation of small amounts (<0.1 vol %) of colloidal Au. However,
for base-catalyzed aerogels, nitrogen physisorption measurements reveal that the average pore size (relative
to the pure silica aerogel) decreases as the size of the Au colloid is increased above the ca. 10-nm domain
size of the silica (which implies that the Au colloid occludes pore space) while it increases for 5-nm colloidal
Au-silica aerogel. The accessibility of the Au surface in colloidal Au-silica aerogels to species introduced
from solution is demonstrated by direct adsorption of the dye methyl orange to the Au surface.

Introduction pore-filling liquid is taken above its supercritical tem-

Metal oxide gels derived from the condensation and
hydrolysis of metal alkoxide precursors (M(OR)n) have
been studied for a variety of applications, including optical,
thermal, and electronic materials,1,2 in part due to the
versatility of the physical forms achievable via this soft
chemistry (i.e., thin film, monolith, powder). Composite
structures which utilize the sol-gel as a host matrix for
molecular guests (e.g., dyes and biomolecules) have been
pursued for catalysis and sensor applications in xerogel
hosts.3-8 In xerogels, the sol (for films) or the gel (for
monoliths) is dried under ambient conditions, leading to
collapse of the pores, densification of the oxide structure,
considerable shrinkage, and (when present) physical
entrapment of the guest. Most of the physical collapse can
be eliminated by supercritically drying the gel to form a
high surface area, high-porosity, ultra-low-density mate-
rial known as an aerogel.9-13 In supercritical drying, the
* To whom correspondence may be addressed: rolison@
nrl.navy.mil.
† Surface Chemistry Branch.
‡ Surface Modification Branch.
§ Optical Physics Branch.
(1) Hrubesh, L. W. Chem. Ind. 1990, 824.
(2) Hrubesh, L. W.; Poco, J. F. J. Non-Cryst. Solids 1995, 188, 46.
(3) Braun, S.; Rappoport, S.; Zusmen, R.; Avnir, D.; Ottolenghi, M.
Mater. Lett. 1990, 10, 1.
(4) Dave, B. C.; Dunn, B.; Valentine, J. S.; Zink, J. I. Anal. Chem.
1994, 66, 1120A.
(5) Badini, G. E.; Grattan, K. T. V.; Tseung, A. C. C. Rev. Sci. Instrum.
1995, 66, 4034.
(6) Kuleshov, A. P.; Dmitrieva, G. A. J. Opt. Technol. 1996, 63, 252.
(7) Narang, U.; Dunbar, R. A.; Bright, F. V.; Prasad, P. N. Appl.
Spectrosc. 1993, 47, 1700.
(8) Ingersoll, C. M.; Bright, F. V. CHEMTECH 1997, 27, 26.
(9) Kistler, S. S. Nature 1931, 127, 741.
(10) Nicolaon, G. A.; Teichner, S. J. Bull. Soc. Chim. Fr. 1968, 1900.
(11) Gessler, H. D.; Goswami, P. C. Chem. Rev. 1989, 89, 765.
perature and pressure before extraction, which prevents
capillary forces from developing and then collapsing the
pores of the gel.
Silica aerogels (prepared from Si(OR)x) are nanoscale
materials composed of a three-dimensional network of ca.
10-nm SiO2 particles. The type (acid or base) and amount
of catalyst determine the network structure on the
nanometer scale. Silica aerogels exhibit very high porosi-
ties (75-99%), characterized by both mesoporosity (2-50
nm pore sizes) and microporosity (pores <2 nm in size),
with surface areas up to 1000 m2/g, and ultralow densities
(as low as ca. 0.003 g/cm3).1,12
Colloidal metal aerogels represent a new class of
materials which combine the low density and high surface
area of aerogels with the unique optical and physical
properties of metal colloids. Previous work on metal
particles immobilized in sol-gel matrixes has focused on
xerogel systems,14-20 with only a few reports, focused on
catalysis, describing the use of Pt- or Pd-impregnated
aerogels.21,22 Aerogels offer a critical advantage over
(12) Fricke, J. Sci. Am. 1988, 258, 92.
(13) Hüsing, N.; Schubert, U. Angew. Chem., Int. Ed. Engl. 1998, 37,
22.
(14) Gacoin, T.; Chaput, F.; Boilot, J.-P. Chem. Mater. 1993, 5, 363.
(15) Akbarian, F.; Dunn, B. S.; Zink, J. I. J. Raman Spectrosc. 1996,
27, 775.
(16) Kutsch, B.; Lyon, O.; Schmitt, M.; Mennig, M.; Schmidt, H. J.
Non-Cryst. Solids 1997, 217, 143.
(17) Yazawa, T.; Kadono, K.; Tanaka, H.; Sakaguchi, T.; Tsubota, S.;
Kuraoka, K.; Miya, M.; De-Xian, W. J. Non-Cryst. Solids 1994, 170,
105.
(18) Gacoin, T.; Chaput, F.; Boilot, J.-P.; Jaskierowicz, G. Chem.
Mater. 1993, 5, 1150.
(19) Mennig, M.; Schmitt, M.; Becker, U.; Jung, G.; Schmidt, H. SPIE
Sol-Gel Optics III 1994, 2288, 130.
(20) Wang, J.; Pamidi, P. V. A. Anal. Chem. 1997, 69, 4490.
(21) Mizushima, Y.; Hori, M. Appl. Catal. A 1992, 88, 137.

10.1021/la980784i CCC: $18.00 © 1999 American Chemical Society

Published on Web 01/07/1999
Colloidal Gold Aerogels
xerogels for optimizing the colloidal metal for catalytic
and chemical sensing applications in that the high porosity
of an aerogel permits rapid analyte flux to and from the
metal particles in a manner difficult to achieve with a
guest-host structured xerogel.
The nanoscale functionality of colloidal metal aerogels
must be understood in order to optimize their properties
as catalysts, sensors, and advanced materials. Specifically,
changes in the gel structure as a function of the size and
presence of the metal colloid must be determined, as must
the effect of the surrounding gel-derived network on the
physical and chemical properties of the immobilized metal
colloid. Of particular importance for colloidal Au-silica
aerogels is the accessible surface area of the Au colloids
once they are immobilized in the aerogel, in terms of
catalytic activity and the area available for functional
derivatization (e.g., modification by direct adsorption of
dyes to the surface or by self-assembly of reagent-tagged
thiols).
This paper addresses the effect of immobilizing colloidal
Au (sized at either 5 or 28 nm) in a silica aerogel structure
on the network and properties of each component of this
composite nanoscale material. The optical properties of
these materials have been characterized by UV-visible
absorption spectroscopy, while structural characterization
has been achieved using a combination of contrast-
matching small-angle neutron scattering (SANS), trans-
mission electron microscopy (TEM), and physisorption
measurements. The appropriateness of each of these
techniques for describing colloidal metal aerogels is also
discussed.
Experimental Procedures
Colloid Preparation. A range of Au colloidal sols was
purchased (BBInternational), and nominally 10-nm Au colloidal
sols were prepared by citrate (Na3C6H5O‚2H2O, Alfa AESAR,
99%) reduction of tetrachloroauric acid (HAuCl4, 99%, Alfa
AESAR, 49% Au).23 All glassware was cleaned in a base bath
and rinsed copiously with 18 MΩ cm water (Barnstead NAN-
Opure) prior to preparation of or use with the Au sols. A 1%
citrate solution (2.5 mL) was added (under flowing argon purified
by passing through a Drierite/4-Å molecular sieve tower) to 200
mL of deaerated boiling water, immediately followed by addition
of 2.0 mL of a 0.79% solution of HAuCl4 (transparent yellow in
color). This solution was refluxed for 35 min under flowing Ar
during which it developed a purple-black color, followed by the
deep cranberry color characteristic of a 10-nm Au sol.24 This
colloidal sol was cooled to ambient under flowing Ar and then
transferred to an amber reagent bottle for storage. High-
resolution transmission electron microscopy (described below)
of the purchased 5-nm colloidal Au sol and the colloidal Au sol
prepared in-house has shown that these sols have mean particle
diameters of 5.6 ( 0.3 and 28 ( 5 nm, respectively.
Aerogel Preparation. Acid- and base-catalyzed silica aero-
gels were prepared by procedures similar to those previously
published.25-27 For base-catalyzed gels, two beakers were pre-
pared: one with 3.939 mL of tetramethoxysilane (TMOS, Alfa
AESAR, 98%) and 4.519 mL of methanol (MeOH), the other with
4.514 mL of MeOH, 1.524 mL of H2O, and 5.2 µL of NH4OH (30%
in H2O, Aldrich). The two solutions were combined and stirred
for 1 min, and the mixture was poured into cylindrical molds (13
× 57 mm, filled with ca. 3 mL of clear, transparent sol) and
(22) Ye, S.; Vijh, A. K.; Wang, Z.-Y.; Dao, L. H. Can. J. Chem. 1997,
75, 1666.
(23) Horisberger, M.; Rosset, J. J. Histochem. Cytochem. 1977, 25,
296.
(24) Turkevich, J.; Garton, G.; Stevenson, P. C. J. Colloid Sci. Suppl.
1954, 1, 26.
(25) Russo, R. E.; Hunt, A. J. J. Non-Cryst. Solids 1986, 86, 219.
(26) Merzbacher, C. I.; Barker, J. G.; Swider, K. E.; Rolison, D. R.
J. Non-Cryst. Solids 1998, 224, 92.
(27) Ellerby, L. M.; Nishida, C. R.; Nishida, F.; Yamanaka, S. A.;
Dunn, B.; Valentine, J. I.; Zink, J. I. Science 1992, 225, 1113.
Langmuir, Vol. 15, No. 3, 1999 675
covered with Parafilm. Acid-catalyzed gels were prepared by
adding 4.5 mL of a pH 4.6 potassium hydrogen phthalate/NaOH
buffer to a beaker containing 2.621 mL of TMOS, 0.545 mL of
H2O, and 0.035 g of 0.04 N HCl, which had been sonicated for
10 min; the mixture was stirred for 1 min, poured into molds,
and covered with Parafilm.
Both acid- and base-catalyzed gels were aged in their molds
for 1 day, then transferred to ca. 20-mL glass vials and rinsed
8-12 times with acetone over 3-4 days. The base-catalyzed gels
were rinsed with ethanol at least 3 times before washing with
acetone, which reacts with the base catalyst to form a yellow-
orange product (possibly due to base-catalyzed formation of the
enol tautomer of acetone). The gels were then introduced into a
supercritical dryer (Fisons Bio-Rad E3000), and the acetone was
replaced with liquid CO2, which was brought above its critical
temperature and pressure (Tc ) 31 °C; Pc ) 7.4 MPa) and then
released to dry the gels. Gel shrinkage during the supercritical
drying step was minimal. The dried gels were sintered at 500 °C
for 2 h, also with minimal shrinkage. The base-catalyzed gels
and aerogels were almost transparent, while the acid-catalyzed
aerogels were a translucent white.
Colloidal gold aerogels were made by preparing an acid- or
base-catalyzed silica sol, as described above, and adding a volume
of Au sol equivalent to the volume of silica sol to produce a 50:50
vol % sol of Au:SiO2. This colloidal mixture was stirred for ca.
1 min and then poured into molds and treated as described above.
The finished aerogel monoliths were identical in appearance to
the pure silica gels (i.e., nearly transparent or translucent for
base- and acid-catalyzed silica sols, respectively), but with a pink
coloration due to the immobilized colloidal Au. To ensure that
any observed changes to the silica structure and properties were
attributable to the presence of the colloidal Au and not due to
volume dilution of the standard silica sol, diluted silica blanks
were prepared by removing a small aliquot of the about-to-gel
silica sol (prior to addition of the Au sol) and diluting with an
equivalent volume of H2O to produce a 50:50 vol % SiO2:H2O sol
(designated as diluted SiO2), which was then treated in the same
manner as the other samples.
Physical Characterization. UV-visible absorption spectra
for the colloidal gold sols and aerogel monoliths were obtained
using an HP 8452 diode array single-beam spectrophotometer
in the spectrum/peaks mode. Powdered aerogels brushed or Au
sols evaporated onto holey-Al grids were analyzed using a Hitachi
H-9000 high-resolution transmission electron microscope. Ni-
trogen physisorption measurements (at 77 K) of the various
aerogel monoliths were obtained using a Micromeritics ASAP
2010 accelerated surface area and porosimetry system. Reported
surface areas are based on a multipoint BET analysis, and
average pore sizes and distributions were determined using data
reduction programs provided by Micromeritics, including their
DFTplus program. The data were best fit using the BJH equation
with a cylindrical pore geometry.
SANS data were collected on a 30-m SANS spectrometer at
the National Institute of Standards and Technology (NIST,
Gaithersburg, MD) using configurations and data analysis
procedures detailed elsewhere.26,28 Samples for the SANS studies
were aerogel disks ca. 1-2 mm thick dry cut (with a diamond
saw) from cylindrical monoliths. In contrast-matching SANS,
the aerogel pores were filled with a H2O/D2O mixture that
matched the neutron scattering properties of either SiO2 (42:58
vol % H2O:D2O) or Au (26:74 vol % H2O:D2O). The sintered
aerogels were rewetted by placing them in a saturated environ-
ment of the appropriate contrast-matching fluid at 85 °C for at
least 9 h prior to immersing the sample in H2O/D2O.
Results and Discussion
Preparation of a Colloidal Gold Aerogel. As detailed
in Experimental Procedures, colloidal gold-silica com-
posite aerogels are made by adding an aqueous sol of
colloidal Au to an about-to-gel silica sol. As hydrolysis
and condensation reactions continue in the silica sol to
form a three-dimensional network of silica particles (or
(28) Merzbacher, C. I.; Barker, J. G.; Swider, K. E.; Ryan, J. V.;
Bernstein, R. A.; Rolison, D. R. J. Non-Cryst. Solids 1998, 225, 234.
676 Langmuir, Vol. 15, No. 3, 1999
Figure 1. UV-vis spectra for 5- and 28-nm Au sols and colloidal
Au-silica aerogels (in which the silica sol is derived from base-
catalyzed (bc) sol-gel chemistry).
gel), the metal colloids become incorporated into the gel.
Even under repeated washings or during the supercritical
drying procedure, the metal colloids remain immobilized
in the gel structure and do not wash out. In a guest-host
xerogel structure, the collapse of the network around a
guest provides a physical entrapment;3-8,14-20 however,
this mechanism is less obviously applied to a guest-host
aerogel structure.
We have successfully formed composite aerogels with
a diverse chemical and size range of suspended particu-
lates including: colloidal Au sized at 5, 10, 20, 30, 50, and
100 nm; colloidal Pt sized at 2-3 nm; zeolite powders
(sized at 0.1-1 µm), colloidal TiO2 (Degussa P25); pow-
dered TiO2 aerogel; powdered poly(methyl methacrylate)
(sieved to <44 µm); and carbon black (Vulcan XC-72).29
Using about-to-gel silica sol as a “nanoglue” to incorporate
suspended particles into an aerogel network affords
enormous design flexibility in creating new mesoporous
materials.
The exact nature of the interaction between colloidal
silica (or networked colloidal silica) and the colloidal guest,
in this instance Au, is an issue we are seeking to
understand. The nanoscale dimensions of the guest and
host make it difficult to directly measure the structural
relationship of the Au colloid and its effect on the aerogel;
therefore, a combination of analytical techniques has been
used to characterize the composite aerogels. The physical
and chemical data we describe below with 5-nm and 28-
nm colloidal Au aerogels initiates such studies.
Optical Characterization. One method for probing
the properties of these new colloidal Au-SiO2 aerogels is
through changes in the surface plasmon resonance of the
immobilized Au particles as compared to that in the sol.
Normalized UV-vis absorption spectra for 5-nm and 28-
nm colloidal gold suspensions and for base-catalyzed
colloidal Au:SiO2 aerogel monoliths are shown in Figure
1. Pure base-catalyzed SiO2 is optically transparent
throughout this region. The spectral peak at ca. 500-550
nm is attributed to the Au surface plasmon resonance.30,31
As the diameter of the Au colloid increases, the absorption
peak shifts to longer wavelengths, consistent with reported
experimental results and theoretical calculations based
on Mie’s theory.32-34 Such a red-shift, accompanied by peak
(29) Morris, C. A.; Anderson, M. L.; Merzbacher, C. I.; Stroud, R. M.;
Rolison, D. R. Manuscript in preparation.
(30) Mie, G. Ann. Phys. (Leipzig) 1908, 25, 377.
(31) Heilweil, E. J.; Hochstrasser, R. M. J. Chem. Phys. 1985, 82,
4762.
Anderson et al.
broadening, is also observed when aggregation of the
particles is induced upon H2O evaporation from the as-
prepared sol.33
Absorbance maxima of 506 nm (66-nm fwhm) and 512
nm (59-nm fwhm) were obtained for the 5-nm and 28-nm
sols, respectively. This absorbance maximum is blue-
shifted by ca. 10 nm after immobilizing either 5-nm or
28-nm Au in the silica aerogel. On the basis of the optical
trends observed for the Au sols as well as the TEM studies
of the composite aerogels (see below), the colloids are not
agglomerated in the aerogel. We attribute the observed
blue shift to a SiO2-Au interaction, although Au surfaces
are known to be vitreophobic.35 Mulvaney et al. have
synthesized colloidal Au particles encased in dense silica
shells (after first priming the gold surface with a silane
modifier) and observe a red-shift for the Au plasmon
resonance.35,36 Our colloidal Au-SiO2 composite aerogels
are chemically and physically distinct from the Au core-
SiO2 shell particles in that the aerogel-immobilized Au is
not presilanized and it sees a low-density silica (which
has a refractive index more representative of air). Due to
scattering from the acid-catalyzed silica network, no UV-
vis spectra could be obtained for the acid-catalyzed
colloidal Au-silica aerogels.
High-Resolution TEM. Despite the insulating nature
of silica and the low Au colloid concentration (ca. 1012
particles/mL) in the composite aerogels, high-resolution
TEM micrographs of single colloidal Au-silica particles
were obtained and are shown in Figure 2. The top image
shows a single 22-nm Au colloid (the dark spheroid) nestled
in nanoscale silica. The slightly elliptical appearance of
the Au colloid is typical for particles in metal sols, which
generally exhibit some polydispersity in both metal colloid
size and shape.33,34 Measurements on several Au particles
in this aerogel indicate an average particle size of 21.7 (
0.8 nm. Higher magnification of the Au colloid (the lower
image in Figure 2) reveals a polycrystalline surface
surrounded by amorphous silica (as indicated by the
uniform gray mottled regions around and slightly edging
over the gold particle). Several domains of lattice fringes
are apparent which have a spacing of 0.288 nm, corre-
sponding to the 〈110〉 planes of the Au face-centered cubic
(fcc) lattice.37
The size of the aerogel-incorporated Au colloids as
derived from the TEM measurements is twice that
expected based on the UV-vis results. A related discrep-
ancy was reported by Yazawa et al.,17 who observed a
10-fold larger Au particle size by TEM than that deter-
mined by spectroscopy. Despite a correlation between the
absorption maximum, fwhm, and the Au particle size,
changes in the linear absorption spectrum are often
masked by distributions of particle sizes and shapes and
by the large bulk value of the imaginary part of the complex
dielectric response,34 particularly for particles larger than
ca. 5 nm. Bloemer et al.34 have reported a slight red-shift
in the absorbance maximum with increasing particle size
for 5-30 nm Au sols but obtained the same fwhm of ca.
50 nm for 5-, 10-, 15-, and 30-nm Au sols. We have found
(32) Wilcoxon, J. P.; Martin, J. E.; Schaefer, D. W. Phys. Rev. A 1989,
39, 2675.
(33) Khlebtsov, N. G.; Bogatyrev, V. A.; Dykman, L. A.; Mel’nikov,
A. G. Opt. Spectrosc. 1996, 80, 128.
(34) Bloemer, M. J.; Haus, J. W.; Ashley, P. R. J. Opt. Soc. Am. B
1990, 7, 790.
(35) Liz-Marzán, L. M.; Giersig, M.; Mulvaney, P. Chem. Commun.
1996, 731.
(36) Liz-Marzán, L. M.; Giersig, M.; Mulvaney, P. Langmuir 1996,
12, 4329.
(37) CRC Handbook of Chemistry and Physics, 77th ed.; Lide, D. R.,
Ed.; CRC Press: New York, 1996.
Colloidal Gold Aerogels
Figure 2. Transmission electron micrographs of a 28-nm Au:
SiO2(bc) aerogel showing a Au particle (dark spot) and its SiO2
environment (top image), and a close-up of the multiple
crystalline domains of the Au colloid amidst amorphous silica
(surrounding gray mottled areas).
similar results for the same range of colloid sizes, with a
red-shift of ca. 6 nm in absorbance peak position between
5- and 30-nm Au sols, and a range of fwhm values of 49-
66 nm (increasing as particle size decreases). Also, TEM
measurements on the Au sol used to prepare the composite
aerogel in Figure 2 indicate a range of Au particle sizes
from nearly spheroidal (20 × 21 nm ( 1 nm) to elliptical
(26 × 40 nm ( 1 nm). On the basis of these results, the
TEM measurements provide a more accurate indication
of the colloidal Au particle size, shape, and size distribu-
tion.
Small-Angle Neutron Scattering (SANS). Small-
angle scattering has been used to characterize aerogels
due to its sensitivity to structural features over a length
scale of 1-200 nm.38,39 In the case of our colloidal Au-
silica aerogels, this length scale covers not only a critical
(38) Schaefer, D. W.; Keefer, K. D. Phys. Rev. Lett. 1986, 56, 2199.
(39) Craievich, A.; Aegerter, M. A.; dos Santos, D. I.; Woignier, T.;
Zarzycki, J. J. Non-Cryst. Solids 1986, 86, 394.
Langmuir, Vol. 15, No. 3, 1999 677
Figure 3. SANS of acid-catalyzed SiO2 and colloidal Au:SiO2
composite aerogels.
range for the SiO2 structure but also the size of the Au
particles incorporated into the SiO2 structure.
The small-angle neutron scattering results for acid-
catalyzed silica aerogels with and without colloidal Au
are shown in Figure 3. The scattering curve for the
standard (undiluted) silica aerogel is similar to those
published previously.38,40 The curve for the diluted silica
aerogel is largely similar to that of the undiluted sample,
except at low scattering vectors, q, indicating that the
structures of the two materials are also similar. The
transition to a slope of nearly zero at low q occurs at length
scales that correlate with the size of the largest scatterers
(q ) 2π/length). The shift in this transition to lower values
of q for the diluted aerogel indicates that the fractal
network structure extends to longer lengths.
To probe the influence of the colloidal Au guest on the
structure of the silica network, the pores were filled with
a Au contrast-matching fluid. We have previously shown
that the pores of silica aerogel (e88% porosity) can be
refilled with water without affecting the network struc-
ture.26 The slope of the curve for the Au-matched acid-
catalyzed composite aerogel is essentially identical to the
curve for the dry silica (see Figure 3).41 The high-q cutoff
occurs at slightly lower values of q because of incoherent
background scattering from the hydrogen in the pore-
filling liquid. Rather than a near-zero slope at low q, the
slope becomes steeper, which is a feature observed for all
rewetted aerogels and is attributed to the presence of a
few large (micrometer size) bubbles.26,28,42
On the basis of the similarity of the scattering curves
of the pure SiO2(ac), dry Au:SiO2(ac) (not shown), and the
Au-matched Au:SiO2(ac) aerogels, the acid-catalyzed silica
structure is unaffected by incorporation of small amounts
of either 5-nm or 28-nm colloidal Au. However, we cannot
(40) Emmerling, A.; Gross, J.; Gerlach, R.; Goswin, R.; Reichenauer,
G.; Fricke, J.; Haubold, H.-G. J. Non-Cryst. Solids 1990, 125, 230.
(41) The scattered intensity from the Au-matched Au:SiO2 samples
is less than that from the pure SiO2 samples, due to the smaller contrast
between silica and gold vs silica and air.
(42) Merzbacher, C. I.; Barker, J. G.; Swider, K. E.; Rolison, D. R.
Adv. Colloid Interface Sci. 1998, 76-77, 57.
678 Langmuir, Vol. 15, No. 3, 1999
Table 1. BET Surface Areas and Average Pore Diameters for Silica and Colloidal Gold-Silica Aerogels
surface area ((100 m2/g)
acid-catalyzed base-catalyzed
SiO2 752 992
SiO2:H2O (50:50 vol.%) 811 1063
5-nm Au:SiO2 (50:50 vol.%) 767 937
28-nm Au:SiO2 (50:50 vol.%) 781 979
30-nm Au:SiO2 (50:50 vol.%) 856
a Taken as the average of calculations based on the adsorption and desorption isotherms.
Figure 4. SANS of base-catalyzed SiO2 and colloidal Au:SiO2
composite aerogels.
use SANS to address the average structure of the colloidal
Au in these composite aerogels. The scattered intensity
from the Au component, expressed in the SiO2-matched
sample for both acid-catalyzed (Figure 3) and base-
catalyzed (Figure 4) 28-nm Au:SiO2 aerogels, is essentially
at background levels (thus the noise at high q seen in
Figures 3 and 4), which is reasonable due to the low Au
concentration in these samples.
SANS spectra for the analogous base-catalyzed silica
(SiO2(bc)) and colloidal Au-SiO2(bc) series are shown in
Figure 4. Unlike the acid-catalyzed samples, scattering
from the standard and diluted SiO2 samples does differ,
both in the shape of the roll-off to near-zero slope and in
the slope of the near-linear region (-0.5 < q < 0.5 nm-1).
These differences indicate that structural changes are
induced by diluting the base-catalyzed SiO2 sol with pure
water prior to gelation. A pure water dilution of the
standard base-catalyzed silica sol does not appear to be
a good control for these gels, most likely because the base-
catalyzed sol is unbuffered (whereas the acid-catalyzed
sol was prepared in a pH 4.6 buffer). We confirmed that
a shift to lower pH does occur when base-catalyzed silica
sol is diluted (50:50 vol %) with pure water.
The shape of the spectra for both the dry and the Au-
matched 28-nm Au:SiO2(bc) does, however, mimic that of
the undiluted SiO2(bc) aerogel (except at the extremes of
q, for the reasons stated above). Diluting the base-
catalyzed silica sol with Au sol does not lower the pH of
the unbuffered silica sol to the extent that pure water
Anderson et al.
average pore diametera ((0.9 nm) total pore volumea ((0.04 cm3/g)
acid-catalyzed base-catalyzed acid-catalyzed base-catalyzed
8.8 13.4 1.53 2.73
8.4 9.1 1.47 1.72
8.3 14.8 1.41 3.04
8.3 12.7 1.39 2.81
12.4 2.30
does, so the kinetics of gelation are more comparable to
the undiluted silica sol.
Physisorption Characterization. Adsorption and
desorption isotherms determined from N2 physisorption
measurements on acid- and base-catalyzed SiO2 and
colloidal Au:SiO2 aerogels are shown in Figure 5. All of
the isotherms exhibit essentially the same shape, including
a small amount of hysteresis between the adsorption and
desorption isotherms. This behavior is characteristic of
materials with both micro- and mesoporosity (pores <2
and 2 nm to 50 nm in size, respectively).43 The relatively
small degree of hysteresis indicates that the energetics of
the pore-filling and -emptying processes are similar in
nature. Isotherms for acid- and base-catalyzed SiO2
aerogels in their standard (undiluted) form are identical
in appearance to those shown and are similar to published
results.44-46
As seen in Figure 5, the volume of adsorbed gas per
gram of sample is considerably greater for the base-
catalyzed gels than for their acid-catalyzed counterparts.
Consequently, the BET surface areas for the base-
catalyzed gels, as derived from their isotherms, are >900
m2/g, compared with ca. 750-820 m2/g for the acid-
catalyzed gels. Surface areas for each of the aerogels
investigated are listed in Table 1. These results are
consistent with the current understanding that acid-
catalyzed silica gels have a ramified, branched structure,
while base-catalyzed SiO2 consists of a three-dimensional
network of condensed particles with roughened surfaces,47
and they are in agreement with reports in the literature
of higher surface areas for base-catalyzed than for acid-
catalyzed silica aerogels.39
The average pore diameter and total pore volume of the
aerogels can also be extracted from the isotherms and are
reported in Table 1. The average pore diameter is ca. 4-5
nm larger in the base-catalyzed gels than in the acid-
catalyzed ones, and the pore size upper limit (after which
there is no significant pore density) is ∼46 nm for all of
the acid-catalyzed gels and ∼162 nm for all of the base-
catalyzed gels. The average pore size of 8.8 ( 0.9 nm in
the standard acid-catalyzed SiO2 is identical to that of the
diluted sample within measurement error and decreases
by <0.5 nm for the Au-containing gels, regardless of the
size of the Au colloid. Similarly, the total pore volumes for
all of the acid-catalyzed samples are essentially the same.
Unlike the acid-catalyzed aerogels, the size of the
incorporated colloidal Au does influence the average pore
size and total pore volume in base-catalyzed gels. Incor-
(43) Webb, P. A.; Orr, C. Analytical Methods in Fine Particle
Technology; Micromeritics Instrument Corp.: Norcross, GA, 1997.
(44) Schuck, G.; Dietrich, W.; Fricke, J. In Aerogels; Fricke, J., Ed.;
Springer-Verlag: Berlin, 1986.
(45) Einarsrud, M.-A.; Farbrodt, L. E.; Haereid, S. In Chemical
Processing of Advanced Materials; Hench, L. I., West, J. K., Eds.; John
Wiley: New York, 1992.
(46) Brinker, C. J.; Scherer, G. W. Sol-Gel Science; Academic Press:
New York, 1990.
(47) Fricke, J.; Emmerling, A. In Chemical Processing of Advanced
Materials; Hench, L. L., West, J. K., Eds.; John Wiley: New York, 1992;
pp 3-17.
Colloidal Gold Aerogels
Figure 5. N2 adsorption (+) and desorption (O) isotherms for silica and colloidal gold-silica aerogels.
poration of 28-nm Au colloids, despite their low concen-
tration, results in a nearly 1-nm decrease in average pore
diameter for the base-catalyzed system, and a further
average pore size decrease is observed for a nominally
(manufacturer-based) 30-nm Au:SiO2(bc) sample; see
Table 1. The total pore volume in standard SiO2 and in
28-nm Au:SiO2 is nearly identical, while a decrease in
total pore volume is observed for the 30-nm Au:SiO2
sample. These results are consistent with a loss of pore
volume relative to the pure silica aerogel resulting from
occlusion of pore space by Au colloids. It is expected that
colloidal Au-SiO2 gels containing even larger diameter
Au particles would show additional loss of pore volume
and a corresponding smaller average pore diameter.
Langmuir, Vol. 15, No. 3, 1999 679
The average pore diameters and total pore volumes
reported for the base-catalyzed aerogels reflect measure-
ments on samples from two separate batches. The
significant deviation in the physisorption character of the
water-diluted silica samples as compared to the other base-
catalyzed aerogels (with and without Au) may be related
to the structural differences we observed by SANS for the
water-diluted SiO2(bc) aerogel. For unbuffered silica sols,
the water-diluted sample does not appear to reflect the
generic base-catalyzed structure either by SANS or by N2
physisorption and is therefore not a good control for
dilution effects.
Given the scale of the connected mesoporous network
in these aerogels, it is somewhat surprising that 5-nm Au
680 Langmuir, Vol. 15, No. 3, 1999
Figure 6. Schematic of the preparation of colloidal gold aerogels
showing the sol-gel processing method and the steps at which
colloidal Au and thiol modifiers may be introduced.
particles remain in the SiO2 network following gelation
and do not wash out.48,49 While some of the 5-nm Au
particles may be trapped in pores from which they cannot
escape, the fact that no apparent loss of 5-nm Au occurs
upon washing or supercritical drying indicates that a
unique structural composite has been formed. Base-
catalyzed silica aerogel is understood to consist of ∼10-
nm colloidal particles of SiO2 that are arranged in a
three-dimensional pearl necklace structure.38 Given the
similarity in size of the colloidal Au to the colloidal SiO2
the 5-nm Au particles may be incorporated into the three-
dimensional SiO2 structure. An average pore diameter of
14.8 ( 0.9 nm was determined for a 5-nm Au:SiO2(bc)
aerogel from the physisorption measurements, which is
several nanometers larger than that for standard SiO2-
(bc) gels. A corresponding increase in total pore volume
(from 2.73 cm3/g for SiO2 to 3.04 cm3/g for 5-nm Au:SiO2)
was also observed. Incorporation of the 5-nm Au colloids
into the SiO2 network is consistent with this result and
would explain why these small particles remain in the gel
after washing.
Design of Catalysts, Electrocatalysts, and Sensors.
The efficient transport of gas- and liquid-phase species
through the porous aerogel structure can be further
exploited by chemically tailoring the silica-immobilized
metal colloids for specific applications. On the basis of the
affinity of Au for thiolates,50 the formation of self-
assembled monolayers (SAMs) of thiols on the Au colloid
surface is an attractive route to functionalizing these
nanoscale composites for specific applications, particularly
in cases where direct adsorption of the sensing element
to the metal particle is not possible. Modification of the
colloidal Au-silica aerogel with thiols is facilitated by the
high porosity of the aerogel structure and by the various
opportunities to modify these composites.
As indicated in Figure 6, molecular modifiers (e.g.,
thiols) may be introduced onto the colloidal Au prior to
immobilization in the silica network. Thiols introduced
at this stage can be used either to prevent aggregation of
the colloidal Au (for preconcentration of the Au sol prior
to addition to the silica sol) or to introduce a desired sensing
element, since gel-trapped organics are known to survive
the washing and supercritical drying procedures without
degradation.51 Considerable interest in the properties of
(48) This result is distinctly different from the case in which a
preformed silica gel soaked in Au sol visibly takes up Au colloid but the
“absorbed” colloid visibly flushes out of the gel by washing.
(49) Swider, K. E.; Rolison, D. R. Unpublished results, 1996.
(50) Nuzzo, R. G.; Zegarski, B. R.; Dubois, L. H. J. Am. Chem. Soc.
1987, 109, 733.
(51) Morris, C. A.; Rolison, D. R. Unpublished results, 1997.
Anderson et al.
Figure 7. UV-vis spectra for a colloidal Au sol, a colloidal
Au:SiO2(bc) gel (pores filled with acetone), an acetone solution
of methyl orange, and the colloidal Au:SiO2(bc) gel following
exposure to methyl orange and copious rinsing with acetone.
The UV-vis spectrum of a SiO2(bc) gel exposed to methyl orange
and rinsed thoroughly exhibited no spectral features over this
region.
Au colloids and of SAM-modified Au particles has led to
a variety of preparations in the literature for thiolated
Au colloids which deter aggregation of the Au particles
and/or which contain thiols tagged with specific func-
tionalities.52-56
Alternately, molecular modifiers can be introduced to
a preformed colloidal Au-silica gel from solution during
washing or to a dried, sintered aerogel from the solution
or gas phase, as shown in Figure 6. Our preliminary studies
have included the exposure of silica and colloidal Au-
silica gels immersed in acetone (i.e., not yet supercritically
dried) to an acetone solution of methyl orange.
The pores in both gels visibly fill with the methyl orange
solution, based on color changes of clear to yellow and
pink to orange for silica and colloidal Au-silica, respec-
tively. Followed by extensive rinsing with acetone, the
methyl orange completely leaches out of the silica gel
(which becomes clear again) but is partially retained by
the colloidal Au-silica gel (which remains orange). UV-
vis spectra of these gels in acetone (i.e., the pores are
filled with acetone) confirm these results, as shown in
Figure 7. Adsorption to the Au colloid surface results in
a broadening of the methyl orange absorption peak at 416
nm and a red-shift of ∼2 nm. A similar peak shift (∼4 nm)
and broadening are observed for the colloidal Au plasmon
resonance.57 Lee et al.58 have also reported only minor
(52) Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R.
J. Chem. Soc., Chem. Commun. 1994, 801.
(53) Grabar, K. C.; Freeman, R. G.; Hommer, M. B.; Natan, M. J.
Anal. Chem. 1995, 67, 735.
(54) Hostetler, M. J.; Green, S. J.; Stokes, J. J.; Murray, R. W. J. Am.
Chem. Soc. 1996, 118, 4212.
(55) Nelles, G.; Schönherr, G.; Jaschke, M.; Wolf, H.; Schaub, M.;
Küther, J.; Tremel, W.; Bamberg, E.; Ringsdorf, H.; Butt, H.-J. Langmuir
1998, 14, 808.
(56) Weisbecker, C. S.; Merritt, M. V.; Whitesides, G. M. Langmuir
1996, 12, 3763.
(57) The absorbance peak for the Au sol used in the modification
study differs from those reported above (i.e., it is red-shifted compared
with the 5- and 28-nm sols) because the average colloid size for this
in-house prepared sol is larger.
(58) Lee, P. C.; Meisel, D. J. Phys. Chem. 1982, 86, 3391.
Colloidal Gold Aerogels
changes in the absorption spectra for dyes adsorbed to
metal particles in solution. On the basis of these results,
methyl orange adsorbs exclusively to the Au surface in
the colloidal Au-silica aerogel. These preliminary results
demonstrate that incorporation of colloidal Au into a silica
network does not block molecular access to the Au surface
and that the nanoscale metal and silica components of
the mesoporous material may be differentially modified.
Conclusions
Composite aerogels of colloidal Au-colloidal silica can
be produced in which nanoscale preformed Au colloids
are immobilized in both acid- and base-catalyzed silica
aerogel structures and remain trapped following washing
and supercritical drying. UV-vis measurements show a
blue-shift in the absorbance maximum of silica-im-
mobilized Au colloids, indicative of a Au-SiO2 interaction.
However, spectroscopic determination of Au particle sizes
appears to give unreliable results for the relatively large
particle sizes involved here, and a more direct method
such as TEM is required for accurate size determination.
SANS studies detect no significant structural changes
in acid- or base-catalyzed silica due to the presence of
small amounts of Au colloid. However, physisorption
measurements show a decrease in BET surface area and
average pore size for base-catalyzed gels containing large
Au colloids (i.e., Au particles J10 nm in diameter),
indicating that the Au colloids occlude pore space in the
Langmuir, Vol. 15, No. 3, 1999 681
standard silica aerogel. The increase in average pore size
for colloidal 5-nm Au:SiO2(bc) compared with that for
standard base-catalyzed silica is consistent with incor-
poration of the 5-nm Au particles into the three-
dimensional SiO2 network and explains why these Au
colloids remain trapped in the silica structure despite its
extensive mesoporosity.
The surface of the silica-immobilized Au colloid is
accessible for modification by externally introduced re-
agents, as verified for the direct adsorption of methyl
orange from a pore-filling solution. Determination of what
fraction of the total Au surface area is truly accessible is
currently underway, but these initial results demonstrate
the feasibility of tailoring colloidal metal aerogels to
produce novel sensing, catalytic, and electrode materials.
Acknowledgment. This research was supported by
the Office of Naval Research and DARPA. We thank Dr.
Karen Swider (ASEE/NRL Postdoctoral Associate, 1993-
1996) for preliminary experiments showing the incorpo-
ration of colloidal gold into acid-catalyzed silica gel, Dr.
John Barker (NIST) for assistance with the SANS
experiments (supported by the National Science Founda-
tion under agreement No. DMR-943101), and Professor
Nicholas Leventis (University of MissourisRolla) for
helpful comments. M.L.A. also thanks the American
Society for Engineering Education for postdoctoral support.
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