Journal

J. Am. Ceram. Soc., 93 [4] 11561163 (2010) DOI: 10.1111/j.1551-2916.2009.03525.x r 2010 The American Ceramic Society

Synthesis and Characterization of Silica/Carbon Composite Aerogels

Li Ye,z,y Zhi-Hong Ji,z Wei-Jian Han,z Ji-Dong Hu,z and Tong Zhaow,z
Laboratory of Advanced Polymer Materials, Center for Molecular Science, Institute of Chemistry, Chinese Academy of Science, Beijing 100190, China
y

Graduate University of Chinese Academy of Sciences, Beijing 100190, China

A series of monolithic silica/resorcinolformaldehyde (silica/ RF) aerogels have been prepared by a simple one-step solgel process of 3-aminopropyltriethoxysilane (APTES), resorcinol (R), and formaldehyde (F) in ethanol, followed by drying with supercritical CO2. The silica/carbon composite aerogels were obtained by pyrolysis of the silica/RF aerogels under N2 atmosphere. The silica/carbon composite aerogels exhibit low densities (0.12410.2751 g/cm3) and high porosities ( 484%). The pore morphologies of the composite aerogels have been investigated in detail by nitrogen sorption measurements, scanning electron microscopy, and transmission electron microscopy. The surface areas of these composite aerogels result from the contribution of macropores, mesopores, and micropores. Combustion in air or etching in HF solution can remove carbon or silica from the silica/carbon composite aerogels and yields monolithic or cracked unitary silica or carbon aerogels. The study indicates that when the starting APTES/R molar ratio is high (sample 3SiOCC and 2SiOCC), the silica framework is the supporting framework; and for low starting APTES/R ratio samples (sample SiOC3C, SiOC2C, and SiOCC), the carbon framework is the supporting framework. Remarkably, carbon aerogels with high surface areas of 2000 m2/g can be obtained after removing silica frameworks of composite aerogels of 3SiOCC and 2SiOCC. I. Introduction
EROGELS have attracted signicant attention due to their extraordinary properties, such as large specic surface area, low apparent density, low thermal conductivity, and high porosity, which originate from their mesoporous nanostructure.14 Because of their unique chemical and textural characteristics, aerogels could be ideal materials for commercial thermal and acoustic insulators, adsorbents, chromatographic packing, or as hosts for a variety of functional guests for optical, electrical, and chemical applications.510 The most extensively studied of these materials are silica and carbon aerogels. Conventionally, silica wet gels are often synthesized by hydrolysis and condensation of alkoxysilanes (typically tetramethoxysilane or tetraethoxysilane, TMOS and TEOS, respectively), in the presence of cosolvents.11,12 Then, the gelled silica network must be dried supercritically to remove excess water, the cosolvent(s), and the liberated alcohol (typically ethanol or methanol). Carbon aerogels are typically prepared in an aqueous solution through the solgel polymerization of resorcinol (R) and formaldehyde (F) using Na2CO3 as a catalyst, followed by supercritical drying with CO2 and carbonization

G. Sorarucontributing editor

Manuscript No. 26630. Received 31 July 2009; approved 5 November 2009. w Author to whom correspondence should be addressed. e-mail: tzhao@iccas.ac.cn

under N2 atmosphere.13,14 However, the process is very time consuming because a solvent exchange process is usually needed before the supercritical step. Because of miscibility problems, the liquid in the pores of the gels has to be exchanged with an organic solvent, such as ethanol, acetone, or pentane, which is miscible with liquid CO2. In recent years, the studies on composite materials are one of the most important research elds in material science.15 The advantage of composite materials is that, they usually exhibit the best qualities of their components and some qualities that neither constituent possess. Silica/carbon composite materials are used in different elds, such as electrode, dual-phase ller, catalyst support, and adsorbent.1618 One of the major interests is the focus on the development of electrodes or catalyst-support materials. Several methods have been applied to the preparation of silica/carbon composite materials including the pyrolysis of two-phase copolymers composed of an aromatic imide domain and a siloxane domain,19 incorporation of resole polymer or carbon black into the silica network matrix by the solgel process,18,2022 and impregnation.17 However, to our knowledge, there are few reports on the preparation of silica/carbon composite materials by the direct solgel process of the precursors of the two components, which normally yields a homogeneous distribution of all the components at a molecular level and high surface areas. Although Chen et al.23 synthesized RF/SiO2 hybrid aerogel by a direct solgel process of R, F, and TMOS in EtOH, but the gelation process of the system is very slow (more than 4 days), and a further carbonization process has not been studied. AguadoSerrano et al.24 synthesized silica/carbon composites by copolymerization of R, F, and TEOS in water, and then pyrolyzed in N2. Inuence of the synthesis parameters on pore structures was studied carefully; however, the framework structures were not referred. In the work presented here, our goal was to develop composite aerogels by a method that was more efcient and easier than traditional techniques. To this end, we have successfully synthesized silica/RF composite alcogels from 3-aminopropyltriethoxysilane (APTES), R, and F, which were then directly dried using supercritical CO2 (SCCO2). The silica/RF composite aerogels were then carbonized under N2 atmosphere to produce silica/carbon composite aerogels. This approach presents several advantages compared with traditional techniques. First, EtOH was used as a solvent, and hence the time-consuming solvent exchange step before the supercritical drying process was bypassed. In addition, direct solgel process of the precursors of the two composites was used, thus the silica/carbon composites obtained were expected to have a more homogeneous distribution of the two components at a molecular level and high surface area. In this report, we present the details of this process as well as the pore structures of the silica/RF and silica/carbon composite aerogels. The framework structures of silica/carbon composite aerogels were also studied.

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Silica/Carbon Composite Aerogels

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(1) Preparation of Silica/RF and Silica/Carbon Composite Aerogels Silica/RF composite aerogels were synthesized by a one-step sol gel process. Briey, R (99.51% purity, Xilong Chemical Co., Shantou, Guangdong Province, China), F (37 wt% in water, Xilong Chemical Co., Beijing, China), EtOH, and APTES ((EtO)3Si(CH2)3NH2, 98% purity, Chuangqi Co.) were mixed in a ask, and then water was added to start the solgel reactions. The sol was stirred for 5 min and then transferred into a glass vial. The vials were sealed and placed in an oven at 501C for 7 days. For all samples, the molar ratios of F/R and H2O/APTES were kept constant at 2. An amount of EtOH was added corresponding to a theoretical density of the nal aerogel of 0.08 g/cm3 dtheor mR0 SiO3=2 mR mF =VAPTES VH2 O VF VEtOH ; R0 CH2 3 NH2 . Structural changes were investigated by varying the APTES/R (x/y) molar ratios from 3:1 to 1:3, and the corresponding silica/RF composite aerogels were identied as xSiOCyRF. Supercritical uid extraction was performed with CO2 in a 1-L chamber (Hangzhou Huali, Hangzhou Province, China). The solvent was rst replaced by liquid CO2, then the temperature and pressure were raised above the critical point of CO2 (Tc 5 311C, pc 5 7.29 MPa). The resulting aerogels were reddishbrown lightweight monoliths and had typical aerogel properties with low densities and high porosities. Carbonization of the dried aerogels was performed in N2 ow, with heating to 8001C at a heating rate of 11C/min and a soaking time of 2 h. According to Zhang and Pantano,25 the SiC is very stable and the aminopropyl group should undergo a carbonization process; hence, silicon oxycarbide silica (CSiO3/2) was actually obtained from the silicon precursor. The silica/carbon composite aerogels obtained were identied as xSiOCyC. To remove the carbon framework, the silica/carbon composite aerogels were placed into a mufe furnace and calcined at 8001C for 2 h, and the resulting aerogels were named as xSiOCyCair. To remove the silica framework, the silica/carbon composite aerogels were placed in a plastic container and etched with HF solutions (40 wt%) for 24 h, and further washed with water and then with EtOH. Finally, the products were dried at 1001C for 12 h. The aerogels obtained were denoted as xSiOCyCHF. (2) Characterization The pore structure of the aerogels was analyzed by nitrogen sorption isotherms at 77 K (ASAP 2020, Micromeritics Instrument Corp., Atlanta, GA). The samples were degassed previously at 801C for 10 h under vacuum before each measurement. The specic surface area (SBET) was determined by the BrunauerEmmettTeller (BET) method. Total pore volume (Vp) was estimated from adsorption branches at a relative pressure (P/P0) of 0.995. The average pore diameter for cylindrical pores (D) was calculated from these values of Vp (D 5 4Vp/SBET). Micropore volume (Vmic) and micropore surface area (Smic) were calculated by the t-plot method. Pore size distributions were calculated by the BarrettJoynerHalenda (BJH) method from the desorption branch. The skeletal densities (rs) of the gels, degassed at 801C before weighting, were measured using helium pycnometry (Accupyc 1330, Micromeritics Instrument Corp.). The diameter shrinkage during aging (ta) was determined by measuring the diameter of the mould and the gel before drying. The diameter shrinkage during drying (td) was determined by measuring the diameter of the gel before and after drying. The bulk densities (rb) were obtained from the weight and physical dimensions of the monolithic samples. The porosity (Pr) of the aerogels was calculated from the bulk and skeletal densities, using the relation: Pr (%) 5 100 (1rb/rs). Fourier Transform Infrared spectroscopy (FTIR, Bruker TENSOR27, Karlsruhe, Germany) were recorded between 4000 and 400 cm1 using the KBr disk method. The microstructure of the aerogels was studied by scanning electron microscopy

(SEM, Hitachi S-4800, Tokyo, Japan) and transmission electron microscopy (TEM, JEOL JEM-1011, Tokyo, Japan).

III. Results and Discussion (1) Synthesis (A) Silica/RF Aerogels: When gels were prepared using TEOS as a silica precursor and ammonia as a catalyst, gelation occurred very slowly. As shown in Table I, when TEOS/R 5 1 and R/cat. 5 10 (alcogel 2#), it took 2 days for the system to gel; however, when APTES was used as a silica precursor and no catalyst was used (alcogel SiOCRF), it took only 128 min for the system to gel. And the gelation is strongly accelerated when increasing the amount of either APTES or resorcinolformaldehyde (RF). A solution of pure APTES in EtOH does not gel for days. It is known from the literature26 that 3-aminopropyltrimethoxysilane [APTMS, (MeO)3Si(CH2)3NH2] quickly reacts with water, but no gel is formed. The hydrolysis behavior of APTMS solutions was explained by the formation of intramolecular hydrogen bonds in the hydrolyzed species (between NH2 and OH groups), which inhibit the formation of the gel network. The solution of APTES undoubtedly would experience the same process, and hence no gel was formed either. On the other hand, a solution of pure R and F in EtOH is also stable in the absence of a catalyst, while adding ammonia as a catalyst (R/cat. 5 20) resulted in the formation of precipitates after a period of time. When the mixtures of APTES/R/F are reacting, gels were formed in 1 or 2 h. One of the reasons for the gelation may be the mild catalysis of RF polymerization by the amino groups of APTES. Furthermore, the intermolecular formation of hydrogen bridges between the amino groups of APTES and phenolic hydroxy groups could promote the hydrolyzed species of APTES to gel. Although intramolecular hydrogen bonds are entropically favorable, the hydroxy groups attached to C atoms (phenolic hydroxy groups) are more acidic than those attached to silicon atoms, and therefore should preferentially act as hydrogen donors in hydrogen bonds. As mentioned previously, the gelation is strongly accelerated when increasing the amount of either APTES or RF. Therefore, we conclude that the gelation process of the two systems (APTES and RF) is catalyzed by each other, and the system with the higher concentration gels rst, then the other system gels, and an interpenetrating framework is formed. After supercritical drying, all aerogels were obtained as reddish-brown cylindrical monoliths (Fig. 1). Table II shows the characteristic data of composite aerogels silica/RF. Although the theoretical density was adjusted to 0.08 g/cm3, the experimentally determined bulk densities of the nal materials were between 0.082 and 0.129 g/cm3 due to the shrinkages during aging and drying. The values of ta and td appeared to relate to the starting APTES/R ratios but were not showing an obvious law. The porosity of the silica/RF aerogels is in the 90%94% range. FTIR spectra of the silica/RF composite aerogels are shown in Fig. 2. KBr was used as the background for the FTIR measurements. It is evident from Fig. 2 that OSiO bonds are present in all the ve silica/RF samples as indicated by the peaks

Table I. SolGel Parameters in Preparing the Alcogels

Alcogel Silica precursor Silica precursor/R Catalyst (R/cat.) Gel time

1# 2# SiOC3RF SiOC2RF SiOCRF 2SiOCRF 3SiOCRF

TEOS TEOS APTES APTES APTES APTES APTES

1 1 1/3 1/2 1 2 3

Ammonia (100) 7 days Ammonia (10) 2 days 75 min 85 min 128 min 75 min 70 min

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Fig. 1. Photographs of selected composite aerogels and the resulting unitary aerogels, as labeled.

located at 460 cm1. The characteristic absorption band due to SiOSi at 1050 cm1 is rst covered by the absorption band of CO at 1100 cm1 and then appeared as a shoulder band as the APTES/R ratio increased. The peak that arose from SiOH bonds on the silica surface was observed around 920 cm1, and the band centered at 3430 cm1 was attributed to the OH

stretch of the SiOH and the COH groups of silica and RF moiety. (B) Silica/Carbon Aerogels: After carbonization at 8001C for 2 h, all samples turned to black monoliths (Fig. 1). The line shrinkage upon carbonization is in the range of 27.8% 36.9%, and the mass loss is between 49.8% and 56.7%

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Aerogel

ta (%)

td (%)

rb (g/cm3)

rs (g/cm3)

Pr (%)

wt%

tp (%)

SiOC3RF SiOC2RF SiOCRF 2SiOCRF 3SiOCRF

3.7 5.6 5.6 2.6 2.7

9.6 13.5 6.7 2.9 1.1

0.120 0.129 0.109 0.084 0.082

1.323970.0205 1.326170.0119 1.350070.0122 1.334070.0130 1.341870.0057

91.0 90.3 91.9 93.7 93.9

56.3 56.7 55.1 49.9 49.9

31.7 36.9 34.2 30.0 27.8

wt%, mass loss during carbonization; tp, shrinkage in diameter during carbonization; RF, resorcinolformaldehyde.

(Table II). The mass loss is due to two main reasons: one is the pyrolysis of the RF framework; another is the pyrolysis of the organic groups (either aminopropyl group or the nonhydrolyzed ethoxy group) on the silica framework. The silica/carbon composite aerogels obtained also showed low densities and high porosities. The results are listed in Table III. A comparative FTIR spectra of composite aerogel SiOCC and pure silica and pure carbon aerogels are shown in Fig. 3. Obviously, the spectroscopy of aerogel SiOCC is a superposition of the spectra of silica and carbon aerogels, except that the spectrum of pure silica shows absorption bands around 2950 and 1400 cm1, which are due to the organic groups on the silica framework. (Note: the pure silica aerogel has not been pyrolyzed, thus the organic groups are reserved.)

(2) Pore Morphology The pore structures of the composite aerogels before and after carbonization were characterized by nitrogen adsorption desorption isotherms. As shown in Fig. 4, all nitrogen sorption isotherms do not reach saturation at a relative pressure close to unity, but they do show hysteresis, which is usually associated with capillary condensation in mesopores. From the lower pressure part of the curves, we conclude that they should correspond to type IV isotherms for mesoporous materials and type II for macroporous materials.27 The pore size distributions of the composite aerogels also show the existence of a pore system extending into the macropore region. The BET surface area, pore volume, average pore diameter, micropore volume, and micropore surface area of the samples according to the isotherms of the samples were calculated and the results are summarized in Table IV. The total pore volume can also be calculated via the bulk and skeletal densities using the relation: V0 p 5 1/rb1/rs, and the corresponding average pore sizes (D0 ) can be calculated by the 4V0 p/SBET method. The results are also listed in Table IV. The nitrogen adsorption method tends to underestimate Vp, particularly when isotherms do not reach saturation,28 but the values calculated by this method are still included here for comparison with data reported previously for other kinds of aero-

gels. By comparing the micropore surface areas of silica/RF aerogels with that of silica/carbon aerogels, it is found that micropores in silica/carbon aerogels are far more abundant than those in silica/RF aerogels. What is more, the micropore surface area of silica/carbon aerogel increases with decreasing initial APTES/R ratio, indicating that micropores are mainly developed in the pyrolysis process of the RF component and might be a path for evolving volatile components. The average pore size decreased after carbonization due to the shrinkage. Additional information regarding the porous structure can be revealed by SEM and TEM. Figure 5 shows the SEM microphotographs of composite aerogel SiOCRF (with APTES/R ratio equals 1) and its carbonized sample SiOCC. Microscopically, they are pretty similar to both acid-catalyzed RF aerogels29 and typical base-catalyzed silica aerogels.30 The spherical secondary nanoparticles (4060 nm in diameter) stack into grape-like aggregates and interconnect in different directions into a network. There are many mesoand macropores among the interconnected nanoparticles. A comparison of Figs. 5(a) and (b) shows that the pore width of SiOCC composite aerogel is smaller than that of SiOCRF composite aerogel, which is in conformity with nitrogen sorption results and reects the shrinkage during carbonization. The TEM images of samples SiOCRF and SiOCC are shown in Fig. 6. The frameworks of composite aerogels are composed of interconnected three-dimensional networks of sphere-like particles that typically 1020 nm in size. There is no apparent difference in the particle size for the composite aerogels before and after carbonization. From TEM micrographs, there are many meso- and micropores among in the nanoparticles of SiOCC aerogel.

(3) Framework Structures of Silica/Carbon Composite Aerogels To understand the structures of silica and carbon in the composite aerogels, the silica/carbon composite aerogels were placed in a mufe furnace and calcined at 8001C for 2 h to completely burn off the carbon framework or etched with HF to remove the silica framework. As shown in Table III, the weight retentions of the composite aerogels after removing one of the frameworks are proportional to their specic precursor ratios. The unitary aerogels obtained are either monolithic or cracked depending on the starting APTES/R ratio (as shown in Fig. 1). When the starting APTES/R ratio is high (sample 3SiOCC and

Table III. Characteristics of Silica/Carbon Composite Aerogels

Aerogel rb (g/cm3) rs (g/cm3) Pr (%) Air (wt%) HF (wt%)

SiOC3C SiOC2C SiOCC 2SiOCC 3SiOCC

Fig. 2. Fourier Transform Infrared spectroscopy spectra of silica/ resorcinolformaldehyde (RF) composite aerogels.

0.198 0.275 0.220 0.126 0.096

1.776270.0184 1.789270.0142 1.818370.0316 1.865770.0290 1.785070.0327

88.9 84.6 87.9 93.2 93.1

18.0 23.7 37.7 61.4 70.0

78.4 73.6 60.7 40.9 31.7

Air (wt%), weight retention of the composite aerogels after burning off carbon framework; HF (wt%), weight retention of the composite aerogels after etching silica framework.

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Table IV. Pore Structure Data for Composite Aerogels Silica/RF and Silica/Carbon
Sample SBET Smic Vp (m2/g) (m2/g) (cm3/g) Vmic (cm3/g) D (nm) V 0p (cm3/g) D0 (nm)

SiOC3RF SiOC3C SiOC2RF SiOC2C SiOCRF SiOCC 2SiOCRF 2SiOCC 3SiOCRF 3SiOCC

437 573 555 563 745 489 215 369 87 166

24 305 38 288 41 206 7 163 13 63

1.08 0.98 1.60 1.19 1.81 1.05 0.73 0.66 0.35 0.39

0.003 9.88 7.58 69.38 0.141 6.84 4.49 31.33 0.009 11.56 7.00 50.43 0.133 8.43 3.08 21.86 0.006 9.73 8.43 45.28 0.094 8.56 4.00 32.68 0.0001 13.61 11.16 207.54 0.074 7.20 7.40 73.82 0.003 16.14 11.45 526.50 0.028 9.27 9.86 237.50

V0 p, calculated from the bulk and skeletal densities via V0 p 5 1/rb1/rs; D0 , calculated by the 4V0 p/SBET method.

Fig. 3. Fourier Transform Infrared spectroscopy spectra of (a) silica aerogel, (b) C aerogel, (c) SiOCC composite aerogel, (d) aerogel SiOC CHF, and (e) aerogel SiOCCHFair.

2SiOCC), the monolithic shape was reserved after burning off the carbon framework, but cracked after removing the silica framework in HF, which means the silica framework is the supporting framework. However, low APTES/R ratio samples (sample SiOC3C, SiOC2C, and SiOC3C) behaved reversely, that is, the monolithic shape was reserved after etching in HF but cracked after burning off the carbon framework, which means the C framework is the supporting framework.

Fig. 4. Nitrogen adsorptiondesorption isotherms of composite aerogels (a) before and (b) after carbonization. Inset is the corresponding pore size distribution.

FTIR spectra in Fig. 3 show that the sample calcined in the mufe furnace (SiOCCair) showing a spectrum of pure silica aerogel, except for the absence of some organic groups absorptions, and the spectrum of sample SiOCCHF (etched in HF) is indistinguishable from that of pure carbon aerogel. The textural properties of these unitary aerogels were studied using nitrogen sorption techniques, as shown in Fig. 7 and Table V. The nitrogen sorption isotherms of unitary aerogels xSiOC yCair or xSiOCyCHF are quite similar to that of their mother composite aerogels, which do not reach an adsorption plateau up to the maximum pressure but show hysteresis, meaning a coexistence of mesopores and macropores. However, comparing with that of composite aerogels, the isotherm curves of the unitary aerogels rose sharply at low relative pressure and reached a higher adsorption volume, suggesting more micropores and larger total pore volume caused by removing one of the frameworks. What is more, for aerogels with a high initial APTES/R ratio, removing the silica framework caused maximal adsorbed quantity increase more remarkably than burning off the carbon framework, and vice versa. Materials properties of all the unitary aerogels are summarized in Table V. The SBET values of unitary aerogels are far higher than their mother composite aerogels (shown in Table IV) and the increase corresponds to the relative amount of the framework removed. In addition, the pore volumes of the unitary aerogels are higher than their mother composite aerogels. These results can be explained by the new pores caused by the removal of carbon or silica frameworks. Comparing with the composite aerogels, the unitary aerogels have a lower density and a higher porosity, but the dispersion is not so distinct. Remarkably, samples 2SiOCCHF and 3SiOCCHF have extremely high BET surface areas of about 2000 m2/g, almost 57 times higher than their parent silica/carbon composite aerogels. The large surface areas are mainly contributed by the micropores, which were caused by the removal of silica frameworks from the composite aerogels. Aerogels SiOC3C HF, SiOC2CHF, and SiOCCHF whose mother composites have a lower content of silica show a lower BET surface area of 9971438 m2/g, possibly due to fewer micropores. A closer inspection of samples SiOCCair and SiOCCHF by SEM is shown in Fig. 5. The microstructures of samples SiOC Cair and SiOCCHF are indistinguishable from their parent aerogel SiOCC (compare Figs. 5(c) and (d) with (b)). The mesoand macropores are also dened by the bead-like colloidal particles that are linked together to form the aerogel framework. TEM images (Figs. 6(c) and (d)) showed that when one of the frameworks of the composite aerogel SiOCC was removed, the stacking structure was looser, but the particle size did not show an apparent difference. It is notable that plenty of micropores existed in the secondary nanoparticles of the aerogel SiOCC HF, which were caused by the removal of silica frameworks

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Fig. 5. Scanning electron microphotographs of: (a) composite aerogel SiOCresorcinolformaldehyde (RF), (b) composite aerogel SiOCC, (c) aerogel SiOCCair, and (d) aerogel SiOCCHF.

Fig. 6. Transmission electron microscopic images of: (a) composite aerogel SiOCRF, (b) composite aerogel SiOCC, (c) aerogel SiOCCair, and (d) aerogel SiOCCHF.

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different directions into a network. The surface areas of these materials, which are a sum of macropores, mesopores, and micropores, are in the range of 87744 and 166573 m2/g before and after carbonization, depending on the initial APTES/R ratio. Combustion at 8001C in air or dissolution in HF solution can remove carbon or silica from the silica/carbon composite aerogels and yield monolithic or cracked pure silica or carbon aerogels. The results show that, when the starting APTES/R ratio is high (sample 3SiOCC and 2SiOCC), the silica framework is the supporting framework. However, for low starting APTES/R ratio samples (sample SiOC3C, SiOC2C, and SiOCC), the carbon framework is the supporting framework. Especially, samples 3SiOCCHF and 2SiOCCHF have high surface areas of 2000 cm2/g, which are mainly contributed by the micropores inside the secondary carbon nanoparticles caused by the removal of silica frameworks from the composite aerogels. The ultra-high surface areas and interconnected pore structures of carbon aerogels would benet their peculiar applications, such as electrodes, adsorbents catalyst supports, and so on.

References
N. Husing and U. Schubert, Aerogels-Airy Materials: Chemistry, Structure, and Properties, Angew. Chem. Int. Ed., 37 [12] 2245 (1998). 2 H. D. Gesser and P. C. Goswami, Aerogels and Related Porous Materials, Chem. Rev., 89 [4] 76588 (1989). 3 A. C. Pierre and G. M. Pajonk, Chemistry of Aerogels and Their Applications, Chem. Rev., 102 [11] 424366 (2002). 4 J. Fricke and A. Emmerling, Aerogels, J. Am. Ceram. Soc., 75 [8] 202735 (1992). 5 H. Du, B. Li, F. Kang, R. Fu, and Y. Zeng, Carbon Aerogel Supported PtRu Catalysts for Using as the Anode of Direct Methanol Fuel Cells, Carbon, 45 [2] 42935 (2007). 6 G. M. Pajonk, Some Applications of Silica Aerogels, Colloid Polym. Sci., 281 [7] 63751 (2003). 7 L. Sorensen, G. F. Strouse, and A. E. Stiegman, Fabrication of Stable LowDensity Silica Aerogels Containing Luminescent ZnS Capped CdSe Quantum Dots, Adv. Mater., 18 [15] 19657 (2006). 8 J. Choi, C. B. Shin, and D. J. Suh, Co-Promoted Pt Catalysts Supported on Silica Aerogel for Preferential Oxidation of CO, Catal. Commun., 9 [5] 8805 (2008). 9 A. Rigacci, J. C. Marechal, M. Repoux, M. Moreno, and P. Achard, Preparation of Polyurethane-Based Aerogels and Xerogels for Thermal Superinsulation, J. Non-Cryst. Solids, 350, 3728 (2004). 10 T.-Y. Wei, T.-F. Chang, S.-Y. Lu, and Y.-C. Chang, Preparation of Monolithic Silica Aerogel of Low Thermal Conductivity by Ambient Pressure Drying, J. Am. Ceram. Soc., 90 [7] 20037 (2007). 11 A. Soleimani Dorcheh and M. H. Abbasi, Silica Aerogel; Synthesis, Properties and Characterization, J. Mater. Process. Technol., 199 [13] 1026 (2008). 12 A. V. Rao and S. D. Bhagat, Synthesis and Physical Properties of TEOSBased Silica Aerogels Prepared by Two Step (AcidBase) SolGel Process, Solid State Sci., 6 [9] 94552 (2004). 13 R. W. Pekala, Organic Aerogels from the Polycondensation of Resorcinol with Formaldehyde, J. Mater. Sci., 24 [9] 32217 (1989). 14 R. W. Pekala, C. T. Alviso, F. M. Kong, and S. S. Hulsey, Aerogels Derived from Multifunctional Organic Monomers, J. Non-Cryst. Solids, 145, 908 (1992). 15 R. M. Jones, Mechanics of Composite Materials, 2nd edition, Taylor & Francis, Philadelphia, PA, 1999. 16 M. J. Wang, K. Mahmud, L. J. Murphy, and W. J. Patterson, Carbon-Silica Dual Phase Filler, a New Generation Reinforcing Agent for Rubber. Part I. Characterization, Kautsch. Gummi Kunstst., 51 [5] 34860 (1998).
1

Fig. 7. Nitrogen adsorptiondesorption isotherms of unitary aerogels derived from silica/carbon composite aerogels after (a) burning off the carbon framework and (b) etching the silica framework.

from the composite aerogels. However, aerogel SiOCCair did not show the same phenomenon.

IV. Conclusions
Monolithic silica/RF composite aerogels with high porosity (490%) were synthesized by an easy and time-efcient method. In this process, APTES, R, and F are polymerized in EtOH with no catalyst. The resulting alcogels are dried directly using SCCO2 to afford silica/RF composite aerogels that can then be carbonized under N2 atmosphere. The framework of the composite aerogels (before and after carbonization) consists of spherical secondary nanoparticles (4060 nm in diameter), which stack into grape-like aggregates and interconnect in

Table V. Pore Structure Data for the Aerogels After Remove One of the Frameworks
Sample SBET (m2/g) Smic (m2/g) Vp (cm3/g) Vmic (cm3/g) D (nm) V0 p (cm3/g) D0 (nm) rb (g/cm3) Pr (%)

SiOC3Cair SiOC3CHF SiOC2Cair SiOC2CHF SiOCCair SiOCCHF 2SiOCCair 2SiOCCHF 3SiOCCair 3SiOCCHF

1252 997 1131 1088 1048 1438 706 2070 307 2088

245 609 343 660 326 840 523 1342 206 1340

2.79 1.55 3.23 1.85 1.98 2.21 0.69 1.97 0.45 1.84

0.010 0.282 0.146 0.305 0.140 0.389 0.243 0.620 0.095 0.615

8.90 6.22 11.37 6.79 7.57 6.15 3.89 3.80 5.86 3.53

5.17 4.20 5.73 8.75 9.87

20.74 15.46 15.94 50.37 128.62

0.175 0.209 0.158 0.107 0.090

90.4 87.8 90.3 93.8 94.6

V0 p, calculated from the bulk and skeletal densities via V0 p 5 1/rb1/rs; D0 , calculated by the 4V0 p/SBET method.

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