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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-


perature and pressure before extraction, which prevents
Metal oxide gels derived from the condensation and capillary forces from developing and then collapsing the
hydrolysis of metal alkoxide precursors (M(OR)n) have pores of the gel.
been studied for a variety of applications, including optical,
thermal, and electronic materials,1,2 in part due to the Silica aerogels (prepared from Si(OR)x) are nanoscale
versatility of the physical forms achievable via this soft materials composed of a three-dimensional network of ca.
chemistry (i.e., thin film, monolith, powder). Composite 10-nm SiO2 particles. The type (acid or base) and amount
structures which utilize the sol-gel as a host matrix for of catalyst determine the network structure on the
molecular guests (e.g., dyes and biomolecules) have been nanometer scale. Silica aerogels exhibit very high porosi-
pursued for catalysis and sensor applications in xerogel ties (75-99%), characterized by both mesoporosity (2-50
hosts.3-8 In xerogels, the sol (for films) or the gel (for nm pore sizes) and microporosity (pores <2 nm in size),
monoliths) is dried under ambient conditions, leading to with surface areas up to 1000 m2/g, and ultralow densities
collapse of the pores, densification of the oxide structure, (as low as ca. 0.003 g/cm3).1,12
considerable shrinkage, and (when present) physical Colloidal metal aerogels represent a new class of
entrapment of the guest. Most of the physical collapse can materials which combine the low density and high surface
be eliminated by supercritically drying the gel to form a area of aerogels with the unique optical and physical
high surface area, high-porosity, ultra-low-density mate- properties of metal colloids. Previous work on metal
rial known as an aerogel.9-13 In supercritical drying, the particles immobilized in sol-gel matrixes has focused on
xerogel systems,14-20 with only a few reports, focused on
* To whom correspondence may be addressed: rolison@
catalysis, describing the use of Pt- or Pd-impregnated
nrl.navy.mil. aerogels.21,22 Aerogels offer a critical advantage over
† Surface Chemistry Branch.
‡ Surface Modification Branch.
(12) Fricke, J. Sci. Am. 1988, 258, 92.
§ Optical Physics Branch.
(13) Hüsing, N.; Schubert, U. Angew. Chem., Int. Ed. Engl. 1998, 37,
(1) Hrubesh, L. W. Chem. Ind. 1990, 824. 22.
(2) Hrubesh, L. W.; Poco, J. F. J. Non-Cryst. Solids 1995, 188, 46. (14) Gacoin, T.; Chaput, F.; Boilot, J.-P. Chem. Mater. 1993, 5, 363.
(3) Braun, S.; Rappoport, S.; Zusmen, R.; Avnir, D.; Ottolenghi, M. (15) Akbarian, F.; Dunn, B. S.; Zink, J. I. J. Raman Spectrosc. 1996,
Mater. Lett. 1990, 10, 1. 27, 775.
(4) Dave, B. C.; Dunn, B.; Valentine, J. S.; Zink, J. I. Anal. Chem. (16) Kutsch, B.; Lyon, O.; Schmitt, M.; Mennig, M.; Schmidt, H. J.
1994, 66, 1120A. Non-Cryst. Solids 1997, 217, 143.
(5) Badini, G. E.; Grattan, K. T. V.; Tseung, A. C. C. Rev. Sci. Instrum. (17) Yazawa, T.; Kadono, K.; Tanaka, H.; Sakaguchi, T.; Tsubota, S.;
1995, 66, 4034. Kuraoka, K.; Miya, M.; De-Xian, W. J. Non-Cryst. Solids 1994, 170,
(6) Kuleshov, A. P.; Dmitrieva, G. A. J. Opt. Technol. 1996, 63, 252. 105.
(7) Narang, U.; Dunbar, R. A.; Bright, F. V.; Prasad, P. N. Appl. (18) Gacoin, T.; Chaput, F.; Boilot, J.-P.; Jaskierowicz, G. Chem.
Spectrosc. 1993, 47, 1700. Mater. 1993, 5, 1150.
(8) Ingersoll, C. M.; Bright, F. V. CHEMTECH 1997, 27, 26. (19) Mennig, M.; Schmitt, M.; Becker, U.; Jung, G.; Schmidt, H. SPIE
(9) Kistler, S. S. Nature 1931, 127, 741. Sol-Gel Optics III 1994, 2288, 130.
(10) Nicolaon, G. A.; Teichner, S. J. Bull. Soc. Chim. Fr. 1968, 1900. (20) Wang, J.; Pamidi, P. V. A. Anal. Chem. 1997, 69, 4490.
(11) Gessler, H. D.; Goswami, P. C. Chem. Rev. 1989, 89, 765. (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 Langmuir, Vol. 15, No. 3, 1999 675

xerogels for optimizing the colloidal metal for catalytic covered with Parafilm. Acid-catalyzed gels were prepared by
and chemical sensing applications in that the high porosity adding 4.5 mL of a pH 4.6 potassium hydrogen phthalate/NaOH
of an aerogel permits rapid analyte flux to and from the buffer to a beaker containing 2.621 mL of TMOS, 0.545 mL of
metal particles in a manner difficult to achieve with a 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,
guest-host structured xerogel. and covered with Parafilm.
The nanoscale functionality of colloidal metal aerogels Both acid- and base-catalyzed gels were aged in their molds
must be understood in order to optimize their properties for 1 day, then transferred to ca. 20-mL glass vials and rinsed
as catalysts, sensors, and advanced materials. Specifically, 8-12 times with acetone over 3-4 days. The base-catalyzed gels
changes in the gel structure as a function of the size and were rinsed with ethanol at least 3 times before washing with
presence of the metal colloid must be determined, as must acetone, which reacts with the base catalyst to form a yellow-
the effect of the surrounding gel-derived network on the orange product (possibly due to base-catalyzed formation of the
physical and chemical properties of the immobilized metal enol tautomer of acetone). The gels were then introduced into a
colloid. Of particular importance for colloidal Au-silica supercritical dryer (Fisons Bio-Rad E3000), and the acetone was
aerogels is the accessible surface area of the Au colloids replaced with liquid CO2, which was brought above its critical
temperature and pressure (Tc ) 31 °C; Pc ) 7.4 MPa) and then
once they are immobilized in the aerogel, in terms of released to dry the gels. Gel shrinkage during the supercritical
catalytic activity and the area available for functional drying step was minimal. The dried gels were sintered at 500 °C
derivatization (e.g., modification by direct adsorption of for 2 h, also with minimal shrinkage. The base-catalyzed gels
dyes to the surface or by self-assembly of reagent-tagged and aerogels were almost transparent, while the acid-catalyzed
thiols). aerogels were a translucent white.
This paper addresses the effect of immobilizing colloidal Colloidal gold aerogels were made by preparing an acid- or
Au (sized at either 5 or 28 nm) in a silica aerogel structure base-catalyzed silica sol, as described above, and adding a volume
on the network and properties of each component of this of Au sol equivalent to the volume of silica sol to produce a 50:50
composite nanoscale material. The optical properties of vol % sol of Au:SiO2. This colloidal mixture was stirred for ca.
1 min and then poured into molds and treated as described above.
these materials have been characterized by UV-visible
The finished aerogel monoliths were identical in appearance to
absorption spectroscopy, while structural characterization the pure silica gels (i.e., nearly transparent or translucent for
has been achieved using a combination of contrast- base- and acid-catalyzed silica sols, respectively), but with a pink
matching small-angle neutron scattering (SANS), trans- coloration due to the immobilized colloidal Au. To ensure that
mission electron microscopy (TEM), and physisorption any observed changes to the silica structure and properties were
measurements. The appropriateness of each of these attributable to the presence of the colloidal Au and not due to
techniques for describing colloidal metal aerogels is also volume dilution of the standard silica sol, diluted silica blanks
discussed. 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
Experimental Procedures equivalent volume of H2O to produce a 50:50 vol % SiO2:H2O sol
(designated as diluted SiO2), which was then treated in the same
Colloid Preparation. A range of Au colloidal sols was manner as the other samples.
purchased (BBInternational), and nominally 10-nm Au colloidal Physical Characterization. UV-visible absorption spectra
sols were prepared by citrate (Na3C6H5O‚2H2O, Alfa AESAR, for the colloidal gold sols and aerogel monoliths were obtained
99%) reduction of tetrachloroauric acid (HAuCl4, 99%, Alfa using an HP 8452 diode array single-beam spectrophotometer
AESAR, 49% Au).23 All glassware was cleaned in a base bath in the spectrum/peaks mode. Powdered aerogels brushed or Au
and rinsed copiously with 18 MΩ cm water (Barnstead NAN- sols evaporated onto holey-Al grids were analyzed using a Hitachi
Opure) prior to preparation of or use with the Au sols. A 1% H-9000 high-resolution transmission electron microscope. Ni-
citrate solution (2.5 mL) was added (under flowing argon purified trogen physisorption measurements (at 77 K) of the various
by passing through a Drierite/4-Å molecular sieve tower) to 200 aerogel monoliths were obtained using a Micromeritics ASAP
mL of deaerated boiling water, immediately followed by addition 2010 accelerated surface area and porosimetry system. Reported
of 2.0 mL of a 0.79% solution of HAuCl4 (transparent yellow in surface areas are based on a multipoint BET analysis, and
color). This solution was refluxed for 35 min under flowing Ar average pore sizes and distributions were determined using data
during which it developed a purple-black color, followed by the reduction programs provided by Micromeritics, including their
deep cranberry color characteristic of a 10-nm Au sol.24 This DFTplus program. The data were best fit using the BJH equation
colloidal sol was cooled to ambient under flowing Ar and then with a cylindrical pore geometry.
transferred to an amber reagent bottle for storage. High- SANS data were collected on a 30-m SANS spectrometer at
resolution transmission electron microscopy (described below) the National Institute of Standards and Technology (NIST,
of the purchased 5-nm colloidal Au sol and the colloidal Au sol Gaithersburg, MD) using configurations and data analysis
prepared in-house has shown that these sols have mean particle procedures detailed elsewhere.26,28 Samples for the SANS studies
diameters of 5.6 ( 0.3 and 28 ( 5 nm, respectively. were aerogel disks ca. 1-2 mm thick dry cut (with a diamond
Aerogel Preparation. Acid- and base-catalyzed silica aero- saw) from cylindrical monoliths. In contrast-matching SANS,
gels were prepared by procedures similar to those previously the aerogel pores were filled with a H2O/D2O mixture that
published.25-27 For base-catalyzed gels, two beakers were pre- matched the neutron scattering properties of either SiO2 (42:58
pared: one with 3.939 mL of tetramethoxysilane (TMOS, Alfa vol % H2O:D2O) or Au (26:74 vol % H2O:D2O). The sintered
AESAR, 98%) and 4.519 mL of methanol (MeOH), the other with aerogels were rewetted by placing them in a saturated environ-
4.514 mL of MeOH, 1.524 mL of H2O, and 5.2 µL of NH4OH (30% ment of the appropriate contrast-matching fluid at 85 °C for at
in H2O, Aldrich). The two solutions were combined and stirred least 9 h prior to immersing the sample in H2O/D2O.
for 1 min, and the mixture was poured into cylindrical molds (13
× 57 mm, filled with ca. 3 mL of clear, transparent sol) and
Results and Discussion
(22) Ye, S.; Vijh, A. K.; Wang, Z.-Y.; Dao, L. H. Can. J. Chem. 1997, Preparation of a Colloidal Gold Aerogel. As detailed
75, 1666. in Experimental Procedures, colloidal gold-silica com-
(23) Horisberger, M.; Rosset, J. J. Histochem. Cytochem. 1977, 25,
296. posite aerogels are made by adding an aqueous sol of
(24) Turkevich, J.; Garton, G.; Stevenson, P. C. J. Colloid Sci. Suppl. colloidal Au to an about-to-gel silica sol. As hydrolysis
1954, 1, 26. and condensation reactions continue in the silica sol to
(25) Russo, R. E.; Hunt, A. J. J. Non-Cryst. Solids 1986, 86, 219. form a three-dimensional network of silica particles (or
(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.; (28) Merzbacher, C. I.; Barker, J. G.; Swider, K. E.; Ryan, J. V.;
Dunn, B.; Valentine, J. I.; Zink, J. I. Science 1992, 225, 1113. Bernstein, R. A.; Rolison, D. R. J. Non-Cryst. Solids 1998, 225, 234.
676 Langmuir, Vol. 15, No. 3, 1999 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
Figure 1. UV-vis spectra for 5- and 28-nm Au sols and colloidal are chemically and physically distinct from the Au core-
Au-silica aerogels (in which the silica sol is derived from base- SiO2 shell particles in that the aerogel-immobilized Au is
catalyzed (bc) sol-gel chemistry). not presilanized and it sees a low-density silica (which
has a refractive index more representative of air). Due to
gel), the metal colloids become incorporated into the gel. scattering from the acid-catalyzed silica network, no UV-
Even under repeated washings or during the supercritical vis spectra could be obtained for the acid-catalyzed
drying procedure, the metal colloids remain immobilized colloidal Au-silica aerogels.
in the gel structure and do not wash out. In a guest-host High-Resolution TEM. Despite the insulating nature
xerogel structure, the collapse of the network around a of silica and the low Au colloid concentration (ca. 1012
guest provides a physical entrapment;3-8,14-20 however, particles/mL) in the composite aerogels, high-resolution
this mechanism is less obviously applied to a guest-host TEM micrographs of single colloidal Au-silica particles
aerogel structure. were obtained and are shown in Figure 2. The top image
We have successfully formed composite aerogels with shows a single 22-nm Au colloid (the dark spheroid) nestled
a diverse chemical and size range of suspended particu- in nanoscale silica. The slightly elliptical appearance of
lates including: colloidal Au sized at 5, 10, 20, 30, 50, and the Au colloid is typical for particles in metal sols, which
100 nm; colloidal Pt sized at 2-3 nm; zeolite powders generally exhibit some polydispersity in both metal colloid
(sized at 0.1-1 µm), colloidal TiO2 (Degussa P25); pow- size and shape.33,34 Measurements on several Au particles
dered TiO2 aerogel; powdered poly(methyl methacrylate) in this aerogel indicate an average particle size of 21.7 (
(sieved to <44 µm); and carbon black (Vulcan XC-72).29 0.8 nm. Higher magnification of the Au colloid (the lower
Using about-to-gel silica sol as a “nanoglue” to incorporate image in Figure 2) reveals a polycrystalline surface
suspended particles into an aerogel network affords surrounded by amorphous silica (as indicated by the
enormous design flexibility in creating new mesoporous uniform gray mottled regions around and slightly edging
materials. over the gold particle). Several domains of lattice fringes
The exact nature of the interaction between colloidal are apparent which have a spacing of 0.288 nm, corre-
silica (or networked colloidal silica) and the colloidal guest, sponding to the 〈110〉 planes of the Au face-centered cubic
in this instance Au, is an issue we are seeking to (fcc) lattice.37
understand. The nanoscale dimensions of the guest and The size of the aerogel-incorporated Au colloids as
host make it difficult to directly measure the structural derived from the TEM measurements is twice that
relationship of the Au colloid and its effect on the aerogel; expected based on the UV-vis results. A related discrep-
therefore, a combination of analytical techniques has been ancy was reported by Yazawa et al.,17 who observed a
used to characterize the composite aerogels. The physical 10-fold larger Au particle size by TEM than that deter-
and chemical data we describe below with 5-nm and 28- mined by spectroscopy. Despite a correlation between the
nm colloidal Au aerogels initiates such studies. absorption maximum, fwhm, and the Au particle size,
Optical Characterization. One method for probing changes in the linear absorption spectrum are often
the properties of these new colloidal Au-SiO2 aerogels is masked by distributions of particle sizes and shapes and
through changes in the surface plasmon resonance of the by the large bulk value of the imaginary part of the complex
immobilized Au particles as compared to that in the sol. dielectric response,34 particularly for particles larger than
Normalized UV-vis absorption spectra for 5-nm and 28- ca. 5 nm. Bloemer et al.34 have reported a slight red-shift
nm colloidal gold suspensions and for base-catalyzed in the absorbance maximum with increasing particle size
colloidal Au:SiO2 aerogel monoliths are shown in Figure for 5-30 nm Au sols but obtained the same fwhm of ca.
1. Pure base-catalyzed SiO2 is optically transparent 50 nm for 5-, 10-, 15-, and 30-nm Au sols. We have found
throughout this region. The spectral peak at ca. 500-550
nm is attributed to the Au surface plasmon resonance.30,31
(32) Wilcoxon, J. P.; Martin, J. E.; Schaefer, D. W. Phys. Rev. A 1989,
As the diameter of the Au colloid increases, the absorption 39, 2675.
peak shifts to longer wavelengths, consistent with reported (33) Khlebtsov, N. G.; Bogatyrev, V. A.; Dykman, L. A.; Mel’nikov,
experimental results and theoretical calculations based A. G. Opt. Spectrosc. 1996, 80, 128.
on Mie’s theory.32-34 Such a red-shift, accompanied by peak (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.
(29) Morris, C. A.; Anderson, M. L.; Merzbacher, C. I.; Stroud, R. M.; 1996, 731.
Rolison, D. R. Manuscript in preparation. (36) Liz-Marzán, L. M.; Giersig, M.; Mulvaney, P. Langmuir 1996,
(30) Mie, G. Ann. Phys. (Leipzig) 1908, 25, 377. 12, 4329.
(31) Heilweil, E. J.; Hochstrasser, R. M. J. Chem. Phys. 1985, 82, (37) CRC Handbook of Chemistry and Physics, 77th ed.; Lide, D. R.,
4762. Ed.; CRC Press: New York, 1996.
Colloidal Gold Aerogels 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.
Figure 2. Transmission electron micrographs of a 28-nm Au: To probe the influence of the colloidal Au guest on the
SiO2(bc) aerogel showing a Au particle (dark spot) and its SiO2 structure of the silica network, the pores were filled with
environment (top image), and a close-up of the multiple a Au contrast-matching fluid. We have previously shown
crystalline domains of the Au colloid amidst amorphous silica that the pores of silica aerogel (e88% porosity) can be
(surrounding gray mottled areas). refilled with water without affecting the network struc-
ture.26 The slope of the curve for the Au-matched acid-
similar results for the same range of colloid sizes, with a catalyzed composite aerogel is essentially identical to the
red-shift of ca. 6 nm in absorbance peak position between curve for the dry silica (see Figure 3).41 The high-q cutoff
5- and 30-nm Au sols, and a range of fwhm values of 49- occurs at slightly lower values of q because of incoherent
66 nm (increasing as particle size decreases). Also, TEM background scattering from the hydrogen in the pore-
measurements on the Au sol used to prepare the composite filling liquid. Rather than a near-zero slope at low q, the
aerogel in Figure 2 indicate a range of Au particle sizes slope becomes steeper, which is a feature observed for all
from nearly spheroidal (20 × 21 nm ( 1 nm) to elliptical rewetted aerogels and is attributed to the presence of a
(26 × 40 nm ( 1 nm). On the basis of these results, the few large (micrometer size) bubbles.26,28,42
TEM measurements provide a more accurate indication On the basis of the similarity of the scattering curves
of the colloidal Au particle size, shape, and size distribu- of the pure SiO2(ac), dry Au:SiO2(ac) (not shown), and the
tion. Au-matched Au:SiO2(ac) aerogels, the acid-catalyzed silica
Small-Angle Neutron Scattering (SANS). Small- structure is unaffected by incorporation of small amounts
angle scattering has been used to characterize aerogels of either 5-nm or 28-nm colloidal Au. However, we cannot
due to its sensitivity to structural features over a length
scale of 1-200 nm.38,39 In the case of our colloidal Au- (40) Emmerling, A.; Gross, J.; Gerlach, R.; Goswin, R.; Reichenauer,
G.; Fricke, J.; Haubold, H.-G. J. Non-Cryst. Solids 1990, 125, 230.
silica aerogels, this length scale covers not only a critical (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
(38) Schaefer, D. W.; Keefer, K. D. Phys. Rev. Lett. 1986, 56, 2199. between silica and gold vs silica and air.
(39) Craievich, A.; Aegerter, M. A.; dos Santos, D. I.; Woignier, T.; (42) Merzbacher, C. I.; Barker, J. G.; Swider, K. E.; Rolison, D. R.
Zarzycki, J. J. Non-Cryst. Solids 1986, 86, 394. Adv. Colloid Interface Sci. 1998, 76-77, 57.
678 Langmuir, Vol. 15, No. 3, 1999 Anderson et al.

Table 1. BET Surface Areas and Average Pore Diameters for Silica and Colloidal Gold-Silica Aerogels
surface area ((100 m2/g) average pore diametera ((0.9 nm) total pore volumea ((0.04 cm3/g)
acid-catalyzed base-catalyzed acid-catalyzed base-catalyzed acid-catalyzed base-catalyzed
SiO2 752 992 8.8 13.4 1.53 2.73
SiO2:H2O (50:50 vol.%) 811 1063 8.4 9.1 1.47 1.72
5-nm Au:SiO2 (50:50 vol.%) 767 937 8.3 14.8 1.41 3.04
28-nm Au:SiO2 (50:50 vol.%) 781 979 8.3 12.7 1.39 2.81
30-nm Au:SiO2 (50:50 vol.%) 856 12.4 2.30
a Taken as the average of calculations based on the adsorption and desorption isotherms.

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-
Figure 4. SANS of base-catalyzed SiO2 and colloidal Au:SiO2 catalyzed silica gels have a ramified, branched structure,
composite aerogels. while base-catalyzed SiO2 consists of a three-dimensional
network of condensed particles with roughened surfaces,47
use SANS to address the average structure of the colloidal and they are in agreement with reports in the literature
Au in these composite aerogels. The scattered intensity of higher surface areas for base-catalyzed than for acid-
from the Au component, expressed in the SiO2-matched catalyzed silica aerogels.39
sample for both acid-catalyzed (Figure 3) and base- The average pore diameter and total pore volume of the
catalyzed (Figure 4) 28-nm Au:SiO2 aerogels, is essentially aerogels can also be extracted from the isotherms and are
at background levels (thus the noise at high q seen in reported in Table 1. The average pore diameter is ca. 4-5
Figures 3 and 4), which is reasonable due to the low Au nm larger in the base-catalyzed gels than in the acid-
concentration in these samples. catalyzed ones, and the pore size upper limit (after which
SANS spectra for the analogous base-catalyzed silica there is no significant pore density) is ∼46 nm for all of
(SiO2(bc)) and colloidal Au-SiO2(bc) series are shown in the acid-catalyzed gels and ∼162 nm for all of the base-
Figure 4. Unlike the acid-catalyzed samples, scattering catalyzed gels. The average pore size of 8.8 ( 0.9 nm in
from the standard and diluted SiO2 samples does differ, the standard acid-catalyzed SiO2 is identical to that of the
both in the shape of the roll-off to near-zero slope and in diluted sample within measurement error and decreases
the slope of the near-linear region (-0.5 < q < 0.5 nm-1). by <0.5 nm for the Au-containing gels, regardless of the
These differences indicate that structural changes are size of the Au colloid. Similarly, the total pore volumes for
induced by diluting the base-catalyzed SiO2 sol with pure all of the acid-catalyzed samples are essentially the same.
water prior to gelation. A pure water dilution of the Unlike the acid-catalyzed aerogels, the size of the
standard base-catalyzed silica sol does not appear to be incorporated colloidal Au does influence the average pore
a good control for these gels, most likely because the base- size and total pore volume in base-catalyzed gels. Incor-
catalyzed sol is unbuffered (whereas the acid-catalyzed
sol was prepared in a pH 4.6 buffer). We confirmed that (43) Webb, P. A.; Orr, C. Analytical Methods in Fine Particle
Technology; Micromeritics Instrument Corp.: Norcross, GA, 1997.
a shift to lower pH does occur when base-catalyzed silica (44) Schuck, G.; Dietrich, W.; Fricke, J. In Aerogels; Fricke, J., Ed.;
sol is diluted (50:50 vol %) with pure water. Springer-Verlag: Berlin, 1986.
(45) Einarsrud, M.-A.; Farbrodt, L. E.; Haereid, S. In Chemical
The shape of the spectra for both the dry and the Au- Processing of Advanced Materials; Hench, L. I., West, J. K., Eds.; John
matched 28-nm Au:SiO2(bc) does, however, mimic that of Wiley: New York, 1992.
the undiluted SiO2(bc) aerogel (except at the extremes of (46) Brinker, C. J.; Scherer, G. W. Sol-Gel Science; Academic Press:
q, for the reasons stated above). Diluting the base- New York, 1990.
(47) Fricke, J.; Emmerling, A. In Chemical Processing of Advanced
catalyzed silica sol with Au sol does not lower the pH of Materials; Hench, L. L., West, J. K., Eds.; John Wiley: New York, 1992;
the unbuffered silica sol to the extent that pure water pp 3-17.
Colloidal Gold Aerogels Langmuir, Vol. 15, No. 3, 1999 679

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- The average pore diameters and total pore volumes
tration, results in a nearly 1-nm decrease in average pore reported for the base-catalyzed aerogels reflect measure-
diameter for the base-catalyzed system, and a further ments on samples from two separate batches. The
average pore size decrease is observed for a nominally significant deviation in the physisorption character of the
(manufacturer-based) 30-nm Au:SiO2(bc) sample; see water-diluted silica samples as compared to the other base-
Table 1. The total pore volume in standard SiO2 and in catalyzed aerogels (with and without Au) may be related
28-nm Au:SiO2 is nearly identical, while a decrease in to the structural differences we observed by SANS for the
total pore volume is observed for the 30-nm Au:SiO2 water-diluted SiO2(bc) aerogel. For unbuffered silica sols,
sample. These results are consistent with a loss of pore the water-diluted sample does not appear to reflect the
volume relative to the pure silica aerogel resulting from generic base-catalyzed structure either by SANS or by N2
occlusion of pore space by Au colloids. It is expected that physisorption and is therefore not a good control for
colloidal Au-SiO2 gels containing even larger diameter dilution effects.
Au particles would show additional loss of pore volume Given the scale of the connected mesoporous network
and a corresponding smaller average pore diameter. in these aerogels, it is somewhat surprising that 5-nm Au
680 Langmuir, Vol. 15, No. 3, 1999 Anderson et al.

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.
Figure 7. UV-vis spectra for a colloidal Au sol, a colloidal
Au:SiO2(bc) gel (pores filled with acetone), an acetone solution
particles remain in the SiO2 network following gelation of methyl orange, and the colloidal Au:SiO2(bc) gel following
and do not wash out.48,49 While some of the 5-nm Au exposure to methyl orange and copious rinsing with acetone.
particles may be trapped in pores from which they cannot The UV-vis spectrum of a SiO2(bc) gel exposed to methyl orange
escape, the fact that no apparent loss of 5-nm Au occurs and rinsed thoroughly exhibited no spectral features over this
upon washing or supercritical drying indicates that a region.
unique structural composite has been formed. Base-
catalyzed silica aerogel is understood to consist of ∼10- Au colloids and of SAM-modified Au particles has led to
nm colloidal particles of SiO2 that are arranged in a a variety of preparations in the literature for thiolated
three-dimensional pearl necklace structure.38 Given the Au colloids which deter aggregation of the Au particles
similarity in size of the colloidal Au to the colloidal SiO2 and/or which contain thiols tagged with specific func-
the 5-nm Au particles may be incorporated into the three- tionalities.52-56
dimensional SiO2 structure. An average pore diameter of Alternately, molecular modifiers can be introduced to
14.8 ( 0.9 nm was determined for a 5-nm Au:SiO2(bc) a preformed colloidal Au-silica gel from solution during
aerogel from the physisorption measurements, which is washing or to a dried, sintered aerogel from the solution
several nanometers larger than that for standard SiO2- or gas phase, as shown in Figure 6. Our preliminary studies
(bc) gels. A corresponding increase in total pore volume have included the exposure of silica and colloidal Au-
(from 2.73 cm3/g for SiO2 to 3.04 cm3/g for 5-nm Au:SiO2) silica gels immersed in acetone (i.e., not yet supercritically
was also observed. Incorporation of the 5-nm Au colloids dried) to an acetone solution of methyl orange.
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 The pores in both gels visibly fill with the methyl orange
exploited by chemically tailoring the silica-immobilized solution, based on color changes of clear to yellow and
metal colloids for specific applications. On the basis of the pink to orange for silica and colloidal Au-silica, respec-
affinity of Au for thiolates,50 the formation of self- tively. Followed by extensive rinsing with acetone, the
assembled monolayers (SAMs) of thiols on the Au colloid methyl orange completely leaches out of the silica gel
surface is an attractive route to functionalizing these (which becomes clear again) but is partially retained by
nanoscale composites for specific applications, particularly the colloidal Au-silica gel (which remains orange). UV-
in cases where direct adsorption of the sensing element vis spectra of these gels in acetone (i.e., the pores are
to the metal particle is not possible. Modification of the filled with acetone) confirm these results, as shown in
colloidal Au-silica aerogel with thiols is facilitated by the Figure 7. Adsorption to the Au colloid surface results in
high porosity of the aerogel structure and by the various a broadening of the methyl orange absorption peak at 416
opportunities to modify these composites. nm and a red-shift of ∼2 nm. A similar peak shift (∼4 nm)
As indicated in Figure 6, molecular modifiers (e.g., and broadening are observed for the colloidal Au plasmon
thiols) may be introduced onto the colloidal Au prior to resonance.57 Lee et al.58 have also reported only minor
immobilization in the silica network. Thiols introduced
at this stage can be used either to prevent aggregation of (52) Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R.
the colloidal Au (for preconcentration of the Au sol prior J. Chem. Soc., Chem. Commun. 1994, 801.
(53) Grabar, K. C.; Freeman, R. G.; Hommer, M. B.; Natan, M. J.
to addition to the silica sol) or to introduce a desired sensing Anal. Chem. 1995, 67, 735.
element, since gel-trapped organics are known to survive (54) Hostetler, M. J.; Green, S. J.; Stokes, J. J.; Murray, R. W. J. Am.
the washing and supercritical drying procedures without Chem. Soc. 1996, 118, 4212.
(55) Nelles, G.; Schönherr, G.; Jaschke, M.; Wolf, H.; Schaub, M.;
degradation.51 Considerable interest in the properties of Küther, J.; Tremel, W.; Bamberg, E.; Ringsdorf, H.; Butt, H.-J. Langmuir
1998, 14, 808.
(48) This result is distinctly different from the case in which a (56) Weisbecker, C. S.; Merritt, M. V.; Whitesides, G. M. Langmuir
preformed silica gel soaked in Au sol visibly takes up Au colloid but the 1996, 12, 3763.
“absorbed” colloid visibly flushes out of the gel by washing. (57) The absorbance peak for the Au sol used in the modification
(49) Swider, K. E.; Rolison, D. R. Unpublished results, 1996. study differs from those reported above (i.e., it is red-shifted compared
(50) Nuzzo, R. G.; Zegarski, B. R.; Dubois, L. H. J. Am. Chem. Soc. with the 5- and 28-nm sols) because the average colloid size for this
1987, 109, 733. in-house prepared sol is larger.
(51) Morris, C. A.; Rolison, D. R. Unpublished results, 1997. (58) Lee, P. C.; Meisel, D. J. Phys. Chem. 1982, 86, 3391.
Colloidal Gold Aerogels Langmuir, Vol. 15, No. 3, 1999 681

changes in the absorption spectra for dyes adsorbed to standard silica aerogel. The increase in average pore size
metal particles in solution. On the basis of these results, for colloidal 5-nm Au:SiO2(bc) compared with that for
methyl orange adsorbs exclusively to the Au surface in standard base-catalyzed silica is consistent with incor-
the colloidal Au-silica aerogel. These preliminary results poration of the 5-nm Au particles into the three-
demonstrate that incorporation of colloidal Au into a silica dimensional SiO2 network and explains why these Au
network does not block molecular access to the Au surface colloids remain trapped in the silica structure despite its
and that the nanoscale metal and silica components of extensive mesoporosity.
the mesoporous material may be differentially modified. The surface of the silica-immobilized Au colloid is
accessible for modification by externally introduced re-
Conclusions agents, as verified for the direct adsorption of methyl
Composite aerogels of colloidal Au-colloidal silica can orange from a pore-filling solution. Determination of what
be produced in which nanoscale preformed Au colloids fraction of the total Au surface area is truly accessible is
are immobilized in both acid- and base-catalyzed silica currently underway, but these initial results demonstrate
aerogel structures and remain trapped following washing the feasibility of tailoring colloidal metal aerogels to
and supercritical drying. UV-vis measurements show a produce novel sensing, catalytic, and electrode materials.
blue-shift in the absorbance maximum of silica-im-
Acknowledgment. This research was supported by
mobilized Au colloids, indicative of a Au-SiO2 interaction.
the Office of Naval Research and DARPA. We thank Dr.
However, spectroscopic determination of Au particle sizes
Karen Swider (ASEE/NRL Postdoctoral Associate, 1993-
appears to give unreliable results for the relatively large
1996) for preliminary experiments showing the incorpo-
particle sizes involved here, and a more direct method
ration of colloidal gold into acid-catalyzed silica gel, Dr.
such as TEM is required for accurate size determination.
John Barker (NIST) for assistance with the SANS
SANS studies detect no significant structural changes
experiments (supported by the National Science Founda-
in acid- or base-catalyzed silica due to the presence of
tion under agreement No. DMR-943101), and Professor
small amounts of Au colloid. However, physisorption
Nicholas Leventis (University of MissourisRolla) for
measurements show a decrease in BET surface area and
helpful comments. M.L.A. also thanks the American
average pore size for base-catalyzed gels containing large
Society for Engineering Education for postdoctoral support.
Au colloids (i.e., Au particles J10 nm in diameter),
indicating that the Au colloids occlude pore space in the LA980784I