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Textural and mechanical characteristics of carbon aerogels synthesized by polymerization of resorcinol and formaldehyde using alkali carbonates as basication agents
Sergio Morales-Torres, Francisco Jose Maldonado-Hodar,* Agust n Francisco Perez-Cadenas and Francisco Carrasco-Mar n
Received 18th February 2010, Accepted 26th April 2010 DOI: 10.1039/c003396k Five organic aerogels were prepared simultaneously by polycondensation of resorcinol and formaldehyde using dierent alkali carbonates (M2CO3, M = Li, Na, K, Rb and Cs) as basication agents. The gelation time depended on the carbonate used, increasing from Li2CO3 to Cs2CO3. The porosity of the samples is dened during this process, when the three-dimensional packing of primary particles is formed. The slower the gelation, the greater the overlapping of primary particles and the formation of clusters, leading to a mechanical reinforcement of the samples and the progressive displacement of their pore size distribution (PSD) towards larger pores. Carbonization produces certain shrinkage of the structure and increases the microporosity and the Young modulus of the samples. Carbon aerogels change from mesoporous to macroporous materials as the counter-ion size of the carbonate increases.

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1. Introduction
Carbon aerogels are one of the most promising new carbon forms for many applications such as adsorbents, catalysts, capacitors, etc.15 These potentialities are the result of their unique properties: purity, homogeneity and above all, controllable porosity. The most commonly used of the dierent precursors and synthesis methods developed in the last few years is the solgel polymerization of resorcinol (R) and formaldehyde (F) catalyzed by Na2CO3 in aqueous (W) solutions (C), which was originally developed by Pekala.6,7 The mechanism of this reaction has already been studied and the textural characteristics of RF carbon aerogels are related to the R/F, R/W, and R/C ratios.69 The role of Na2CO3 as a catalyst is associated with the ability of CO32 species to initiate the polymerization reaction by the abstraction of protons from the R molecules. This process favours the addition reaction of F to R anions, which nally condense forming a three-dimensional polymeric network. The role of the counter-cations of the carbonate species has however been somewhat neglected in the literature. Metals are active in many catalyzed reactions. We have previously prepared transition-metal-doped carbon aerogels,1012 in order to make use of the activity of these materials in dierent reactions.1315 The presence of transition metals strongly inuences the RF polymerization, carbonization and activation processes, and consequently, the textural and chemical characteristics of organic aerogels and their corresponding carbon aerogel derivatives. Similar results were obtained by other authors.1618

Department of Inorganic Chemistry, Faculty of Sciences, University of Granada, Avda. Fuentenueva s/n, 18071, Granada, Spain. E-mail: fmaldon@ugr.es; Fax: +34 958248526; Tel: +34 958240444

With regard to the alkali cations, small changes in the nature of the carbonate precursor produce strong textural changes,19,20 as was observed in samples prepared using Na2CO3, K2CO3, NaHCO3 and KHCO3. Fairen-Jimenez et al.19 indicated that Na2CO3 leads to carbon aerogels that are denser than those prepared with K2CO3, and the mean pore width is also strongly aected. Horikawa20 however found larger mesopore volume when Na2CO3 was used, while the PSD was only slightly modied. Comparisons are however dicult because dierent experimental conditions were used in these studies. More recently, Job et al.21 described that the pore texture of carbon xerogels is independent of cation size, but depends on the charge and concentration of the counter-cation. This fact can be explained due to the screening by the ions in solution by electrostatic repulsion between the organic colloids. The screening eect of M2+ (alkaline earth) was more eective than that of M+ (alkali), in spite of the fact that the latter was twice as concentrated as the former. In the presence of M2+, the polymerization-induced phase separation occurs earlier and the pore size of M2+-doped samples is larger than that of the alkali-metal-doped xerogels. Again the comparison is dicult. These results could be inuenced by the experimental conditions used: a high polymerization rate is induced by curing directly at a high temperature (85 1C/48 h) and the drying method used to obtain the xerogels leads to a large shrinkage (and consequently mechanical reinforcement) in comparison with that obtained using supercritical drying methods. On the basis of these ndings, the present study systematically investigates the synthesis of organic aerogels from RF in the presence of M2CO3, where M is an alkali metal (Li, Na, K, Rb and Cs). Great care was taken to ensure that all the other synthesis parameters (R/F, R/C, R/W, pH, cure, drying and carbonization conditions) remained constant. The inuence of
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the dierent cations on the polymerization process can therefore be analyzed and related to the chemical, porous and mechanical properties of the synthesised organic aerogels and their carbon aerogel derivatives.

with a deformation velocity of 1 mm min1. The pellet length/ diameter ratio was 1.5. The corresponding compressive stressstrain curves were analyzed to obtain the Youngs modulus (E), the maximum strength (s) and the deformation capacity (e)

2. Experimental
2.1 Synthesis

3. Results and discussion

The eect of the dierent alkali carbonates on RF polymerization can be observed with the naked eye during the polymerization process. Gelation occurs during the rst few hours at 50 1C, and the smaller the counter-cation the faster the gelation process, in such a way that gelation times vary as follows: ACs 4 ARb 4 AK 4 ANa 4 ALi (Table 1). Gelation time was considered to be25 when the solution was unable to ow inside the moulds when they were inclined at an angle of 451. After gelation, gels were transparent except in the case of ACs, which was opaque. After completing the cure cycle all the samples were opaque. ALi showed the most intense orange colour, and as the cation size increased, this colour became progressively paler down to ACs, which was white-pink. The structures of the aerogels were studied at a microscopic scale by FE-SEM. Representative micrographs are shown in Fig. 1; all of them have a magnication of 150 K for comparison purposes. In all cases the aerogels are made up of a three-dimensional network of nearly spherical particles forming a coral-like structure.3,7,8 However, the aggregation and packing of these primary particles is clearly dierent. ALi has a uniform and continuous structure of linked primary particles, while the structure of ACs is formed by the aggregation of particle clusters. The structures of the other samples fall somewhere in between these two extremes. The structure of the organic aerogels becomes progressively less compact as the cationic radius increases. This is because, the overlapping of primary particles and the formation of particle clusters becomes more favourable, leaving greater voids between the clusters. These structures are maintained after carbonization and consequently, the morphology and porosity of the carbon aerogels are dened during the gelation process. However, a signicant shrinkage and the development of necks between primary particles can be observed. A more open structure formed by overlapping particle clusters was again observed for ACs900. We evaluated the chemical nature and the degree of crosslinking of the organic aerogels using TG and FTIR (Fig. 2a and b). The weight loss (WL) by carbonization was around 55% in all cases, and the TG prole was independent of the
Table 1 Sample ALi ANa AK ARb ACs
a

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Five organic aerogels were prepared by polymerization of RF in aqueous solution using alkali carbonates (M2CO3; M = Li, Na, K, Rb and Cs) as basication agents. The molar ratios used were: R/F = 0.5, R/C = 300 and R/W = 0.07. The initial pH = 5.5. After mixing, the homogeneous solutions were cast into glass moulds (0.5 cm internal diameter), and these were sealed in order to prevent evaporation. The cure process involves 1 day at 30 1C, 1 day at 50 1C and 5 days at 80 1C. After curing, samples were cut into pellets of around 5 mm long, exchanged with acetone for 2 days, and nally, dried in supercritical CO2. Carbon aerogels were prepared from these organic precursors by carbonization in a 100 cm3 min1 N2 ow at 900 1C with a soak time of 5 h, and a heating rate of 1.5 1C min1. Organic aerogels will be referred to as AM (M = alkali metal) and carbon aerogels as AM900 (we have added the carbonization temperature to the name of the aerogel). 2.2 Characterization methods

The chemical nature of the organic aerogels was analysed using TG and FTIR. TG-DTG experiments were carried out with a Shimadzu TGA-50H thermobalance with a heating rate of 10 1C min1 up to 900 1C in N2 ow. FTIR spectra were recorded with a NICOLET 20SXB FTIR spectrophotometer from 4000 to 400 cm1. XPS measurements of the pretreated catalysts were made with an Escalab 200R system (VG Scientic Co.) equipped with a Mg Ka X-ray source (hv = 1253.6 eV) and a hemispherical electron analyzer. The spectra obtained after background signal correction were tted to Lorentzian and Gaussian curves in order to obtain the number of components, the position of each peak and the peak areas. The morphology of the aerogels was analyzed by SEM with a LEO (Carl Zeiss) GEMINI-1530 microscope. The textural characterization was carried out by N2 and CO2 adsorption at 196 1C and 0 1C, respectively, and by mercury porosimetry. The BET and DubininRaduskevich22,23 equations were applied to determine the apparent surface area and the micropore volume. In the absence of restriction, W0 (N2) yields the total micropore volume23 while W0 (CO2) estimates the narrow microporosity (micropores smaller than 0.7 nm). The BJH method24 was applied to the desorption branch of the N2 adsorption isotherms (software AS1WIN-1.52 of Quantachrome) to obtain the mesopore volume (VBJH) and PSD curves. Mercury porosimetry was performed up to a pressure of 345 MPa using Quantachrome Autoscan 60 equipment, obtaining the volume of pores, V2 (4.3 nm o dpore o 50 nm), the macropore volume, V3 for pores with dpore 4 50 nm and their surface area (Sext) values. The mechanical properties of the pellets were also determined by compression experiments using a Shimazdu AGS-J 10 kN
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Gelation time and mechanical properties of organic aerogels tgelation/mina 75 80 90 110 115 E/MPa 92.8 100.3 107.8 121.2 222.9 smax/MPa 52.5 31.4 32.3 20.5 18.2 ebreak (%) 54.4 42.9 41.7 33.1 16.3

Gelation time at 50 1C after 1 day at room temperature. E = Young modulus. smax = maximum strength. ebreak = deformation capacity.

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Fig. 1

SEM microphotographs: inuence of alkali cations on the morphology of organic aerogels and carbon aerogels.

alkali cation. The TG curves show two main slope changes associated with the release of water and other reactants at low temperature, and the breaking of CO and CH bonds during carbonization26 respectively. The main gases evolved were H2O, CO, CO2 and CH4 formed from the decomposition of the aliphatic bridges between the aromatic rings.9 The FTIR bands at 1460 and 1260 cm1 are associated respectively in the literature25,27 with the formation of methylene and methylene ether bridges between the aromatic rings. These bands correspond to the CH bending and CO stretching vibrations in COC structures respectively. The main band in the region of 1600 cm1 is due to the CQC stretching in aromatic rings. After carbonization, the intensity of the FTIR bands decreases signicantly (spectra not shown), as a consequence of the release of gases and only the band corresponding to the aromatic rings is clearly observed. The surface chemistry of carbon xerogels was also studied by XPS. The C, O and alkali M spectral region of interest was scanned several times to obtain good signal-to-noise ratios and the deconvolution of each spectrum was performed according to previous work.28 As observed in the FTIR and TG experiments, the XPS analysis also showed that they had a very similar chemical nature and composition. As expected, a high C content, around 9596 wt%, was observed in all samples, and the B.E. of the dierent C1s components was also similar. However, the corresponding alkali metal was not detected, except in the case of ACs900. The band at 725.2 eV corresponding to the Cs 3d5/2 denotes the presence of CsO bonds. In addition, if we take into account the amount of reactants (R+F) and Cs2CO3 in the initial solution, and the weight loss that takes place during carbonization, the concentration of Cs in the carbon bulk should be less than 1 wt%, however, the XPS analysis showed a Cs content of 3.8 wt%, which clearly indicates a concentration of Cs on the external surface of the sample.
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Fig. 2 (a) TG and (b) FTIR proles of organic aerogels.

The mechanical properties of the samples (Table 1) were determined by compression experiments. We observed that
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aerogels became progressively more rigid on a scale ranging from ALi to ACs, although the greatest dierence was observed for ACs. The Young modulus (E) increases and both the maximum strength (s) and deformation capacity (e) decrease over this range. Some of the stressstrain curves are shown in Fig. 3 as examples. The deformation capacity was considered to be the point at which the rst crack appeared in the pellets. The deformation of ALi was about 54% at breaking point, while in the case of ACs it was only 16%. However, the E modulus for ACs is more than twice that for ALi. After carbonization, samples became more rigid, but also more fragile, with E values increasing while both e and smax fell. This behaviour of RF aerogels after carbonization agrees with previous ndings.6 Fig. 3b shows the proles of the se curves for some of the carbon aerogels. The dierences observed for the organic aerogels disappeared, and all the carbon aerogels showed similar mechanical properties. The E modulus increased to around 750 MPa but smax fell to 20 MPa and e dropped below 4%. Previous researchers6 found that the E modulus of carbon aerogels is a function of density (E = crn), and is therefore also related to the porous texture of the samples. Textural characterization was carried out using mercury porosimetry and gas adsorption. Mercury porosimetry is a powerful tool for analysing macro/mesoporosity. The cumulative intrusion/extrusion curves are depicted in Fig. 4a

and the results are summarized in Table 2, where VHg is the total mercury volume intruded, VHg ext is the volume of mercury that remains inside the pores after extrusion, and V* is the volume of mercury that remains inside the pores Hg calculated by weighing the pellets before and after the experiments. The ALiARb cumulative curves are very similar. In the case of the ACs aerogel, the slope of the curve is more pronounced and starts at higher pressure, although the maximum VHg is lower. During the pressure decrease, the variation in VHg for ACs is however much greater than for the other samples. As commented, the aerogel pellets were weighed before and after the porosimetry experiments. The weight variation (Dm) indicated the volume of Hg that remained inside the pores (V* = Dm/rHg). We observed (Table 2) that ALiARb Hg samples do not show any mass gain, V* = 0, in spite of Hg the fact that the porosimetry curves show that V* E VHg ext. Hg These results indicate that these organic aerogels were isostatically compressed and only a slight elastic recovery took place when the pressure decreased, i.e, VHg does not show a real mercury intrusion inside the pores, and is due instead to the crushing of the pellets. This nding was conrmed by carrying out two consecutive porosimetry runs (Fig. 4b) in which VHg fell sharply in the second run compared to the rst one. The ACs aerogel seems to suer less crushing. This behaviour is related to the mechanical properties of the

Fig. 3 Compression stressstrain curves of (a) organic and (b) carbon aerogels.

Fig. 4 Cumulative mercury porosimetry curves (a) inuence of the alkali cation (b) eect of two consecutive runs.

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Textural characteristics of organic aerogels r/g cm3 0.55 0.56 0.56 0.57 0.59 VHg/cm3 g1 1.20 1.20 1.26 1.24 1.05 VHg 1.09 1.09 1.14 1.11 0.73
3 ext/cm

Table 2 Sample ALi ANa AK ARb ACs

g1

V* /cm3 g1 Hg 0.00 0.00 0.00 0.00 0.47

SBET/m2 g1 324 389 347 314 210

VBJH/cm3 g1 1.06 1.24 1.23 1.22 0.00

r = Bulk density. VHg=Cumulative mercury volume. VHg ext = Cumulative mercury volume after extrusion. V* =Total mercury volume inside Hg the pores after experiments, determined by weighing. SBET = BET surface area. VBJH = Pore volume determined by application of the BJH equation to the desorption branch of the N2 adsorption isotherms.

organic aerogels described above. The more rigid character of ACs prevents crushing and permits Hg intrusion inside the pores. Thus, V* can be measured by weighing, although VHg Hg * ext was larger than VHg (Table 2). The crushing of RF organic aerogels has been reported in previous studies,29,30 and the consequence of this behaviour is that Washburns equation cannot be used to determine the corresponding PSD. It is however noteworthy that VBJH and VHg show similar values, except in the case of ACs. After carbonization, the samples were mechanically reinforced, as previously commented. The extrusion curves for these samples do not fall away, which indicates that mercury remains inside the pores, but in this case, this behaviour was veried by the similar values of VHg ext and V*Hg. This means that crushing is avoided, the intrusion of Hg inside the pores is irreversible, and Washburns equation can be applied to determine the macro and mesopore volume of these samples. The results obtained are summarized in Table 3, and Fig. 5 shows the corresponding PSD. A monomodal PSD is observed in all cases, but the mean pore size shifted progressively upwards to large pores over the range Li to Cs. Fig. 5b shows the PSD for ACs and ACs900. As expected, both are macroporous materials, although narrower macropores are observed after carbonization as a consequence of shrinkage. The rest of the carbon aerogels are highly mesoporous materials with a large external surface area (Table 3). The mesopore volume also increases on a scale from ALi900 to ARb900. The cumulative pore volume (VHg = V2 + V3) is smaller in the case of macroporous samples, leading to a slight increase in density. This fact also favours the mechanical behaviour of these samples, as previously explained. The organic aerogels have type-IV N2 adsorption isotherms (Fig. 6), typical of mesoporous materials, except in the case of ACs, which has a type-I isotherm, typical of microporous materials. Thus, while for ACs adsorption only occurs at low pressure as a result of micropore lling, the other samples show signicant N2 adsorption at higher pressures indicating adsorption in large micropores and mesopores. The mesopore volume was calculated by the BJH method (Table 2) and the adsorption in this porosity range leads to the mesoporous ALiARb organic aerogels having higher SBET values than ACs. The N2 adsorption isotherms for carbon aerogels had a similar shape to those for organic aerogels, which conrms the mesoporous character of carbon aerogels, except for ACs900, in which adsorption only occurs into micropores. Some of the PSDs obtained from N2 adsorption by the BJH method are presented in Fig. 7. There is a progressive shift in mesopore
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Fig. 5 (a) Comparison of the pore size distribution, PSD, of carbon aerogels determined by mercury porosimetry. (b) Eect of carbonization: PSD of samples ACs an ACs900.

size distributions to larger pores, as the size of the cations increases. However, a certain degree of shrinkage occurs during carbonization. These results coincide closely with those obtained by mercury porosimetry (Fig. 5 and Table 3). The dierent properties of the carbon aerogels are therefore clearly dened during the gelation process. Carbon aerogels present a morphology and porous texture that is clearly determined by their corresponding raw organic aerogels. As regards microporosity and surface area, both the micropore volume (W0) and the BET surface area increase in all the samples after carbonization (Tables 2 and 4), reaching SBET values of over 1300 m2 g1. The smallest dierences between the results obtained from N2 and CO2 isotherms were for ACs900, which indicates that in this sample both molecules are adsorbed within the same pore range. In the rest of the
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External surface area and macro and mesopore volumes of carbon aerogels Sext/m2 g1 191 186 218 218 59 VHg/cm3 g1 1.06 1.23 1.31 1.67 1.27 V2/cm3 g1 1.06 1.16 1.27 1.67 0.07 V3/cm3 g1 0.00 0.07 0.04 0.00 1.20 VBJH/cm3 g1 1.06 1.23 1.32 1.29 0.00

Table 3 Sample ALi900 ANa900 AK900 ARb900 ACs900

Fig. 6 N2 adsorption isotherms of organic aerogels.

Fig. 7 Inuence of the alkali cation and carbonization treatment on the PSD obtained by application of the BJH method to the N2 adsorption isotherms.

samples, W0 (N2) is always larger than W0 (CO2), which indicates the contribution of wider micropores and mesopores to the N2 adsorption capacity. Although the objective of this paper is not to determine the mechanism by which the cations modify the nal texture of the gels, the results obtained are in perfect agreement with
Table 4 Sample ALi900 ANa900 AK900 ARb900 ACs900 BET surface area and micropore volume of carbon aerogels SBET/m2 g1 902 1071 1345 859 758 W0 (N2)/cm3 g1 0.37 0.44 0.55 0.35 0.30 W0 (CO2)/cm3 g1 0.25 0.28 0.32 0.25 0.27

previous studies. As described in the Introduction, the role of carbonate anions is to favour proton abstraction to generate resorcinol anions, which are more active than uncharged resorcinol molecules in the addition of formaldehyde reaction. The hydroxymethyl derivatives formed by this reaction are really the critical monomers for further condensation reactions, in this way, the RF clusters grow into colloidal particles, which in the end form the RF hydrogel.31 The size and arrangement of these primary particles dene the textural properties of the hydrogels because the meso and macropores are located between them. However the microporosity is mainly generated during pyrolysis by the release of gases.4,9,32 Thus, the growth of RF gels occurs through the formation of anionic species induced by weak bases like carbonates. This implies that there are electrostatic interactions with the other charged species. On this basis, surfactants are a powerful tool to help control the gel properties. Nishiyama33 describes the formation of RF-surfactant copolymers by electrostatic interactions, where the cationic heads of surfactant molecules are combined with anionic functional groups of the RF chains forming layered composites. In our case, the cationic species only correspond to the alkali cations added as carbonate counter-ions. In the bibliography, there are also several references to the dierent interaction of alkali cations with the environment. It was pointed out for example that dierent interactions occur between alkali cations and solvents34 and that the ligand binding energies of M+ to oxygenated functional groups of organic compounds such as aminoacids decreases as cation size increases.35 Alkali metals also modify the activity of heterometallic lanthanide catalysts in methyl methacrylate polymerization.36 Cezard34 noted that the most important parameter controlling these interactions is the polarizing power of the cations, which, is in turn the only variable in our synthesis process. Due to the fact that in this work, the only variable is the nature of the alkali cations, the dierences between the samples described above should be related in some way to this fact. Alkali cations are poorly active in the hydrolysis process; they do not modify the solution pH, which remains constant. The concentration of species in solution was also established a priori at a constant level in all cases. Thus, taking into account that the electrostatic interactions depend on the charge of the ions (which remain constant), and also on the distance between them by an inverse square law, we can conclude that the interactions between anionic RF chains and alkali cations become progressively weaker as the cation size increases (as the polarizing power decreases). After establishing the nature and the strength of interactions, one can assume that the stronger interactions of the
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smaller cations with oxygenated functionalities of the RF clusters can provoke a quicker stabilization of the primary particles, decreasing gelation time, while a slow gelation process favours the aggregation and the formation of particle clusters. The progressive overlapping of the primary particles into clusters is responsible for the mechanical reinforcement we observed and generates progressively larger pores and larger pore volumes in the aerogel structure as shown by SEM and textural characterization. This leads to mesopore coarsening, in such a way that in the case of ACs, macropores can be formed from adjacent mesopores. Very recently, Reu and Ratke37 prepared RF aerogels catalyzed by ammonium carbonate. The morphology and porosity of these aerogels depends largely on the gelation temperature and the catalyst concentration. They found larger particles at high R/C ratios (slow gelation process) connected by compact necks that are formed by the reaction between the particles, the free resorcinol and formaldehyde still remaining in solution after rst gel formation (aging and coarsening). The average particle diameter grows considerably with decreasing quantities of catalyst, while the opposite occurs with the specic surface. Saliger et al.38 also described similar eects when the gelation time was changed by varying R/C or the gelation temperature. When the gelation time increased they obtained paler gels and their structures became coarser as a result of the formation of particle clusters, which produced macroporous materials with reinforced elastic modulus. They proposed that prolonged aging processes (long gelation times at room temperature) favour the dissolution of monomers at the concave part of particles in contact and the re-agglomeration of materials at the necks, producing a similar eect to sintering in other materials such as silica aerogels. This hypothesis also has to be considered in our case. It should be noted that the solubility of organic alkali salts (e.g. alkali benzoates) increases with cation size. Thus the solubility/mobility of chemical species will increase over the range ALi to ACs, which together with long gelation times, favour the formation of particle clusters. Job et al.21 showed that the eect of alkali earth cations and alkali cations on the pore texture of RF xerogels depended on electrostatic interactions. These authors proposed that stronger electrostatic interactions favoured microphase separation during RF polymerization. In conrmation of these results, we found that gelation time decreases as electrostatic interactions increase, i.e. as the cation polarizing power increases. The increase in the molecular weight of the polymerizing species reduces their solubility in water, which eventually triggers a phase separation, according to the model proposed by Pekala.6 Our results are therefore in agreement with both the colloidal aggregation model31,37,38 and the microphase separation model.6 This is probably because, as suggested by Gommes,39 they are two idealizations of the same complex physical process, although even SAXS data do not enable discrimination between the two mechanisms of gel formation. We can therefore conclude that the dierent interaction strengths between cations and RF chains determines the morphology of RF gels (particle size, degree of overlapping,
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etc.) during the polymerization stage. The morphology in turn, determines parameters such as macro/mesoporosity, sample density and mechanical properties. After drying and carbonization the macro/mesopore structure of the aerogels is maintained, although it undergoes a certain degree of shrinkage. Chemically, carbon aerogels are very similar, as shown by FTIR and XPS analysis. The main dierence is the high Cs content observed on the carbon aerogel surface, while the concentration of the other alkali cations remains below the detection limit. This is probably due to the long gelation time of this sample and the weaker CsRF interaction. In this way, the Cs cations can remain in solution for a long time, before nally being deposited on the outer surface of the gel particles in the nal gelation steps or curing, as described by Reu37 for the formation of the necks between particles. Carbonization strongly develops the micropore volume due to the release of gases. In our sample series the BET surface area reached values of over 1300 m2 g1. However, the values of W0 (CO2) for the dierent samples are quite similar, because they undergo similar pyrolysis processes, as denoted by the TG proles. In the case of ACs 900, W0 (CO2) E W0 (N2), which conrms the macroporous character of this sample as compared to the mesoporous character of ALi900ARb900. Carbonization also induces an increase in the elastic modulus again favoured by the appearance of necks between the primary particles, but the development of microporosity makes the carbon aerogels brittle. The rst cracks appear at less than 3% of deformation. Nevertheless, the high E values of carbon aerogels prevent crushing during mercury porosimetry experiments and the PSD can be determined with accuracy. We were therefore able to conrm that PSD moves to larger pores as the size of the counter-ion increases.

4. Conclusions
Five organic aerogels were prepared in identical experimental conditions using the dierent alkali carbonates (M2CO3, M = Li, Na, K, Rb and Cs) as basication agents. The gelation time increases with the cation size and this favours the aggregation of primary particles into clusters. The progressive overlapping of primary particles also generates larger pores and larger pore volumes, as was shown by the PSD obtained from N2 adsorption isotherms. This leads to pore coarsening in such a way that in the case of ACs the mesoporosity disappears forming macropores. The overlapping of particles also favours the mechanical properties. The Young modulus of organic aerogels increases over the range ALiACs. After carbonization, the Young modulus increases but the maximum strain and the deformation capacity decrease; samples became stier, but more fragile. This increased rigidity prevents crushing during the mercury porosimetry experiments. A narrow mesopore PSD was obtained by mercury porosimetry and N2 adsorption, and there is a clear shift to larger pores over the range ALiARb. The ACs900 carbon aerogel is macroporous, as is its organic parent aerogel. Carbonization mainly increases the microporosity of the samples, reaching surface areas of over 1300 m2g1.
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Therefore, alkali cations signicantly inuence the characteristics of the nal carbon aerogels from the RF polymerization process. The eect of the alkali cations on the polymerization of RF seems to be related to their polarizing power. The larger cations induce the larger gelation times because interactions with the organic polymer are weaker. The longer gelation times favour the overlapping of primary particles, leading to both mechanical reinforcement and the progressive displacement of the PSD to the larger pores.

Acknowledgements
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This work was supported by the Spanish MEC; Project CTQ-2007-61324. A.F. Perez-Cadenas and S. Morales-Torres also acknowledge the Spanish MEC for a Ramon y Cajal research contract and for a F.P.U research fellowship, respectively.

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