Improvement of the Derjaguin-Broekhoff-de Boer theory for capillary condensation/evaporation of nitrogen in mesoporous systems and its implications for pore size analysis of MCM-41 silicas and related materials

In this work, we propose an improvement of the classical Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in mesoporous systems. The primary idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the surface tension changes in mesopores. In addition, the statistical film thickness (so-called t-curve) evaluated accurately on the basis of the adsorption isotherms measured for the MCM-41 materials is used instead of the originally proposed t-curve (to take into account the excess of the chemical potential due to the surface forces). It is shown that the aforementioned modifications of the original DBdB theory have significant implications for the pore size analysis of mesoporous solids. To verify our improvement of the DBdB pore size analysis method (IDBdB), a series of the calcined MCM-41 samples, which are well-defined materials with hexagonally ordered cylindrical mesopores, were used for the evaluation of the pore size distributions. The correlation of the IDBdB method with the empirically calibrated Kruk-Jaroniec-Sayari (KJS) relationship is very good in the range of small mesopores. So, a major advantage of the IDBdB method is its applicability for small mesopores as well as for the mesopore range beyond that established by the KJS calibration, i.e., for mesopore radii greater than approximately 4.5 nm. The comparison of the IDBdB results with experimental data reported by Kruk and Jaroniec for capillary condensation/evaporation as well as with the results from nonlocal density functional theory developed by Neimark et al. clearly justifies our approach. Note that the proposed improvement of the classical DBdB method preserves its original simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the mean pore size by the powder X-ray diffraction method.     

Adsorption hysteresis in ordered mesoporous silicas

We review some recent progress in experimental studies of the adsorption hysteresis of simple molecules in ordered mesoporous silicas. We show that the nature of the adsorption hysteresis due to capillary condensation can be examined with less ambiguity by measuring the hysteresis loop for the ordered mesoporous silicas with three types of pore geometries (cylindrical, interconnected cylindrical, and interconnected spherical) over a wide temperature range. The adsorption hysteresis arises from the metastability of a confined phase and the temperature at which the hysteresis disappears is lower than the critical temperature of vapor-liquid equilibrium in pores. The hysteresis occurs mainly on the desorption rather than adsorption branch, irrespective of the pore geometries.     

Gas adsorption in mesoporous micelle-templated silicas: MCM-41, MCM-48, and SBA-15

This paper reports a molecular simulation and experimental study on the adsorption and condensation of simple fluids in mesoporous micelle-templated silicas MCM-41, MCM-48, and SBA-15. MCM-41 is described as a regular cylindrical silica nanopore, while SBA-15 is assumed to be made up of cylindrical nanopores that are connected through lateral channels. The 3D-connected topology of MCM-48 is described using a gyroid periodic minimal surface. Argon adsorption at 77 K is calculated for the three materials using Grand Canonical Monte Carlo simulations. Qualitative comparison with experiments for nitrogen adsorption in mesoporous micelle-templated silicas is made. The adsorption isotherm for SBA-15 resembles that for MCM-41. In particular, capillary condensation and evaporation are not affected by the presence of the connecting lateral channels. In contrast, the argon adsorption isotherm for MCM-48 departs from that for MCM-41 having the same pore size. While condensation in MCM-41 is a one-step process, filling of MCM-48 involves two successive jumps in the adsorbed amounts which correspond to condensation in different domains of the porosity. The condensation pressure for MCM-48 is larger than that for MCM-41. We attribute this result to the morphology of the MCM-48 surface (made up of both concave and convex regions) that differs from that for MCM-41 (concave only). Our results suggest that the pore connectivity affects pore filling when the size of the connections is comparable to that of the nanopores.     

Nitrogen adsorption on silica surfaces of nonporous and mesoporous materials

We present an accurate comparative analysis of N 2 adsorption at 77 K on nonporous silica and the pore wall surface of MCM-41 materials. The analysis shows that in the low-pressure region of N 2 adsorption obeys a peculiar mechanism governed by short-ranged forces, which makes the surface curvature effect on the N 2 adsorption in mesopores nearly negligible. We used this observation to define more exactly compared to the BET technique the specific surface area of the reference adsorption isotherm on nonporous silica basing on XRD data and linear sections of t-plots. Calculation of the capillary evaporation and condensation pressures seems to confirm our previous finding that the capillary condensation pressure corresponds to the equilibrium transition rather than spinodal condensation at least for pore sizes less than 7 nm. It allowed us to provide more reliable pore size distribution (PSD) analysis of mesoporous silica materials. For example, the PSDs of MCM-41 samples do not show artificial peaks in the micropore range that we obtained in our earlier publications.     

A New Method of Calculating Pore Size Distribution: Analysis of Adsorption Isotherms of N(2) and CCl(4) for a Series of MCM-41 Mesoporous Silicas

The adsorption isotherms of N(2) gas at 77 K and CCl(4) vapor at 283.1(5), 298.1(5), and 308.1(5) K were measured for six samples of the mesoporous silicas having uniform cylindrical pores (MCM-41). The pore radii of the six samples (r(p)), which were evaluated from the alpha(s) plots of the N(2) isotherms, were 1.13, 1.29, 1.50, 1.65, 1.90, and 2.53 nm. The CCl(4) adsorption isotherms show that the capillary condensation occurs at the very narrow P/P(0) range. The core radii of the six adsorbents (r(c)), which were estimated from a comparison plot of the CCl(4) isotherm, were 0.90, 1.01, 1.28, 1.37, 1.60, and 2.17 nm. In the comparison plot, the standard CCl(4) isotherm for nonporous silica was used as the reference isotherm. It has been clarified that the Polanyi adsorption potential of capillary condensation is proportional to the reciprocal of the core radii: RT ln(P(0)/P)=5.37r(c)(-1) nm(-1), ln(P(0)/P)=2.17r(c)(-1) nm(-1) at 298.1(5) K, [A]. The statistical thickness of adsorbed CCl(4) on the curved surface (t((pore))), which was estimated from the difference between the pore radii and the core radii, was given by Eq. [B]: t((pore))=0.188+0.336(P/P(0))+0.382(P/P(0))(2) nm [B], (0.08

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Benzene Adsorption Isotherms on MCM-41 and their Use for Pore Size Analysis

This work is focused on the elaboration of methodology for adsorption characterization of porous silicas by using benzene adsorption isotherms measured on good quality MCM-41 materials. Three MCM-41 samples were synthesized by using tetraethyl orthosilicate (TEOS) as silica source and surfactants, octyltrimethylammonium (C8), decyltrimethylammonium (C10) and cetyltrimethylammonium (C16) bromides as templates. A characteristic feature of this synthesis was relatively long hydrothermal treatment (5 days) at 373 K, which gave well ordered samples as evidenced by powder XRD analysis. Benzene adsorption isotherms measured on these MCM-41 samples were used to evaluate such standard quantities as the BET specific surface area, total pore volume, external surface area and the volume of ordered mesopores, and to obtain the statistical film thickness (t-curve) as well as the Kelvin-type relation, which describes the dependence between pore width and condensation pressure for benzene on silica at 298 K. The latter relations were incorporated into the Barrett-Joyner-Halenda algorithm to extend its applicability to calculate the pore size distributions from benzene adsorption data.     

Lower closure point of adsorption hysteresis in ordered mesoporous silicas

To examine the nature of the lower closure point of adsorption hysteresis in ordered mesoporous silicas, we measured the temperature dependence of the adsorption-desorption isotherm of nitrogen for three kinds of ordered silicas with cagelike pores and three kinds of ordered silicas with cylindrical pores. The lower closure point pressure of nitrogen in the cagelike pores with sufficiently small necks, that is, the cavitation pressure of a confined liquid, did not depend appreciably on the cage size in the temperature region far away from a hysteresis critical temperature (Tch) but its cage-size dependence was noticeable in the vicinity of Tch. The lower closure point in the cylindrical pores depended on the pore size, and its thermal behavior was totally different from that in the cagelike pores. Nevertheless, the hysteresis critical points of nitrogen in the ordered mesoporous silicas, which are defined as a threshold of temperatures (Tch) and pressure above which reversible capillary condensation takes place in a given size and shape of pores, fell on a common line in a temperature-pressure diagram regardless of the pore geometries. We consider this finding as evidence that capillary evaporation in the cylindrical pores follows a cavitation process in the vicinity of Tch in the same way as that in the cagelike pores and also that the low limit of the hysteresis loop that has been long recognized since 1965 is due to the occurrence of a vapor bubble in a stretched metastable liquid confined to the pores with decreasing pressure (cavitation).     

Improvement of the Derjaguin-Broekhoff-de Boer theory for the capillary condensation/evaporation of nitrogen in spherical cavities and its application for the pore size analysis of silicas with ordered cagelike mesopores

In a previous work, we proposed an improvement of the Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in open-ended cylindrical mesopores. In this paper, we report a further extension of this approach to the capillary condensation/evaporation of nitrogen in siliceous spherical cavities. The main idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the variation of the surface tension in spherical mesopores. In addition, the statistical film thickness (the so-called t-curve), which is evaluated accurately on the basis of adsorption isotherms measured for MCM-41 materials, is used instead of the originally proposed t-curve to take into account the excess chemical potential due to the surface forces. It is shown that the aforementioned modifications of the original DBdB theory that was refined by Ravikovitch and Neimark have significant implications for the pore size analysis of cagelike mesoporous silicas. To verify the proposed improvement of the DBdB pore size analysis (IDBdB), two series of FDU-1 samples, which are well-defined cagelike mesoporous materials (composed of siliceous spherical cavities interconnected by short necks), were used for the evaluation of the pore size distributions (PSDs). The correlation between the spinodal condensation point in the spherical pores predicted by the nonlocal density functional theory (NDFT) developed by Ravikovitch and Neimark and that predicted by the IDBdB theory is very good in the whole range of mesopores. This feature is mirrored to the realistic PSD characterized by the bimodal structure of pores computed from the IDBdB theory. As in the case of open-ended cylindrical pores, the improvement of the classical DBdB theory preserves its simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the average pore size by the NDFT and the powder X-ray diffraction method.     

单壁碳纳米管中甲烷吸附的分子模拟

采用巨正则系统MonteCarlo方法研究了甲烷在单壁碳纳米管(Singlewallcarbonnanotube,SWNT)中于低温74.05K下的吸附等温线及吸附机理,发现在两个较小的孔径(1.225nm和1.632nm)下单壁碳纳米管中甲烷的吸附有着明显的微孔所独有的“填充效应”,而在2.04nm以上的孔的吸附中会出现毛细凝聚现象。通过模拟知道发生毛细凝聚的必要条件是孔内能至少容纳下两层粒子,此外还导出在恒定温度下毛细凝聚吸附量与SWNT孔径关系。本文还模拟了常温300K下甲烷在SWNT内的吸附,对比了2.04nm和4.077nm两种孔径的SWNT吸附甲烷的等温线,推荐在4.077nm孔中的适宜吸附存储压力为5.0～6.0MPa,吸附质量分数可达16%～19%.     

Synthesis of ordered and disordered silicas with uniform pores on the border between micropore and mesopore regions using short double-chain surfactants.

Silica molecular sieves with uniform pores on the borderline between micropore (diameter <2 nm) and mesopore (from 2 to 50 nm) ranges were synthesized by a novel method using judiciously chosen mixtures of short double-chain alkylammonium surfactants. These silicas were characterized using X-ray diffraction (XRD), thermogravimetry, and nitrogen and argon adsorption. The calcined materials exhibited either 2-dimensional (2-D) hexagonal or disordered structures with XRD interplanar spacing from 2.51 to 2.93 nm, including the value of as small as 2.69 nm for highly ordered 2-D hexagonal silica. The dependence of the pore size and surfactant content on the surfactant chain length provided strong evidence for supramolecular templating being operative in the formation of small-pore silicas, even for the surfactant chain length of six carbon atoms. Both hexagonally ordered and disordered calcined samples were shown to exhibit narrow pore size distributions with maxima in the range from 1.96 to 2.61 nm (reliably evaluated on the basis of the unit-cell dimension and pore volume for 2-D hexagonal materials, and calculated using a properly calibrated procedure), tailored by the surfactant chain length. The samples exhibited primary pore volumes from 0.28 to 0.54 cm(3) g(-1) and specific surface areas from 730 to 930 m(2) g(-1). Because of their small yet uniform pore size and large specific surface area, the silicas reported herein promise to be useful in applications in adsorption and catalysis. Adsorption studies of these materials provided a unique new insight into the pore-filling mechanism for small-pore materials. Moreover, the approach proposed herein is expected to facilitate the synthesis of not only small-pore silicas but also materials with other framework compositions, thus largely contributing to bridging the gap in attainable pore sizes between micropore and mesopore ranges.     

Equilibrium adsorption in cylindrical mesopores: a modified Broekhoff and de Boer theory versus density functional theory

This paper presents a thermodynamic analysis of capillary condensation phenomena in cylindrical pores. Here, we modified the Broekhoff and de Boer (BdB) model for cylindrical pores accounting for the effect of the pore radius on the potential exerted by the pore walls. The new approach incorporates the recently published standard nitrogen and argon adsorption isotherm on nonporous silica LiChrospher Si-1000. The developed model is tested against the nonlocal density functional theory (NLDFT), and the criterion for this comparison is the condensation/evaporation pressure versus the pore diameter. The quantitative agreement between the NLDFT and the refined version of the BdB theory is ascertained for pores larger than 2 nm. The modified BdB theory was applied to the experimental adsorption branch of adsorption isotherms of a number of MCM-41 samples to determine their pore size distributions (PSDs). It was found that the PSDs determined with the new BdB approach coincide with those determined with the NLDFT (also using the experimental adsorption branch). As opposed to the NLDFT, the modified BdB theory is very simple in its utilization and therefore can be used as a convenient tool to obtain PSDs of all mesoporous solids from the analysis of the adsorption branch of adsorption isotherms of any subcritical fluids.     

Does water condense in carbon pores?

Using grand canonical Monte Carlo (GCMC) simulations of molecular models, we investigate the nature of water adsorption and desorption in slit pores with graphitelike surfaces. Special emphasis is placed on the question of whether water exhibits capillary condensation (i.e., condensation when the external pressure is below the bulk vapor pressure). Three models of water have been considered. These are the SPC and SPC/E models and a model where the hydrogen bonding is described by tetrahedrally coordinated square-well association sites. The water-carbon interaction was described by the Steele 10-4-3 potential. In addition to determining adsorption/desorption isotherms, we also locate the states where vapor-liquid equilibrium occurs for both the bulk and confined states of the models. We find that for wider pores (widths >1 nm), condensation does not occur in the GCMC simulations until the pressure is higher than the bulk vapor pressure, P0. This is consistent with a physical picture where a lack of hydrogen bonding with the graphite surface destabilizes dense water phases relative to the bulk. For narrow pores where the slit width is comparable to the molecular diameter, strong dispersion interactions with both carbon surfaces can stabilize dense water phases relative to the bulk so that pore condensation can occur for P < P0 in some cases. For the narrowest pores studied--a pore width of 0.6 nm--pore condensation is again shifted to P > P0. The phase-equilibrium calculations indicate vapor-liquid coexistence in the slit pores for P < P0 for all but the narrowest pores. We discuss the implications of our results for interpreting water adsorption/desorption isotherms in porous carbons.     

Correct form of the equation of capillary condensation in porous bodies in application to the separation of adsorption and capillary condensation in slits and porous bodies of known structure and determination of their structure by adsorption and sorption isotherms

A line of thermodynamic reasoning of a very general nature is presented. It does not depend on any special pore shape or any pore width distribution. It does not require the use of the ‘disjoining pressure’ but leads to the precise equation of capillary condensation in porous bodies of any kind, applicable for any adsorption isotherm in the simplest case when the influence of the pore wall curvature on the adsorption equilibrium may be neglected.     

Distribution of carbon nanotube sizes from adsorption measurements and computer simulation

The method for the evaluation of the distribution of carbon nanotube sizes from the static adsorption measurements and computer simulation of nitrogen at 77 K is developed. We obtain the condensation/evaporation pressure as a function of pore size of a cylindrical carbon tube using Gauge Cell Monte Carlo Simulation (Gauge Cell MC). To obtain the analytical form of the relationships mentioned above we use Derjaguin-Broekhoff-deBoer theory. Finally, the pore size distribution (PSD) of the single-walled carbon nanohorns (SWNHs) is determined from a single nitrogen adsorption isotherm measured at 77 K. We neglect the conical part of an isolated SWNH tube and assume a structureless wall of a carbon nanotube. We find that the distribution of SWNH sizes is broad (internal pore radii varied in the range 1.0-3.6 nm with the maximum at 1.3 nm). Our method can be used for the determination of the pore size distribution of the other tubular carbon materials, like, for example, multiwalled or double-walled carbon nanotubes. Besides the applicable aspect of the current work the deep insight into the problem of capillary condensation/evaporation in confined carbon cylindrical geometry is presented. As a result, the critical pore radius in structureless single-walled carbon tubes is determined as being equal to three nitrogen collision diameters. Below that size the adsorption-desorption isotherm is reversible (i.e., supercritical in nature). We show that the classical static adsorption measurements combined with the proper modeling of the capillary condensation/evaporation phenomena is a powerful method that can be applied for the determination of the distribution of nanotube sizes.     

Accurate relations between pore size and the pressure of capillary condensation and the evaporation of nitrogen in cylindrical pores

To examine the theoretical and semiempirical relations between pore size and the pressure of capillary condensation or evaporation proposed so far, we constructed an accurate relation between the pore radius and the capillary condensation and evaporation pressure of nitrogen at 77 K for the cylindrical pores of the ordered mesoporous MCM-41 and SBA-15 silicas. Here, the pore size was determined from a comparison between the experimental and calculated X-ray diffraction patterns due to X-ray structural modeling recently developed. Among the many theoretical relations that differ from each other in the degree of theoretical improvements, a macroscopic thermodynamic approach based on Broekhoff-de Boer equations was found to be in fair agreement with the experimental relation obtained in the present study.     

Nature of adsorption and desorption branches in cylindrical pores

To examine the nature of the adsorption and desorption branches in hysteretic adsorption isotherms of gases on mesoporous materials, we measured the temperature dependence of the adsorption and desorption isotherms of argon, oxygen, and carbon dioxide onto MCM-41 with a pore diameter of 4.4 nm. The results clearly show that in the open-ended cylindrical pores of MCM-41, capillary condensation rather than evaporation takes place near a thermodynamical equilibrium transition, as opposed to the general statement that capillary evaporation can occur via a meniscus formed at the pore mouth, and, thus, takes place at equilibrium.     

Adsorption hysteresis of nitrogen and argon in pore networks and characterization of novel micro- and mesoporous silicas

We report results of nitrogen and argon adsorption experiments performed at 77.4 and 87.3 K on novel micro/mesoporous silica materials with morphologically different networks of mesopores embedded into microporous matrixes: SE3030 silica with worm-like cylindrical channels of mode diameter of approximately 95 angstroms, KLE silica with cage-like spheroidal pores of ca. 140 angstroms, KLE/IL silica with spheroidal pores of approximately 140 angstroms connected by cylindrical channels of approximately 26 angstroms, and, also for a comparison, on Vycor glass with a disordered network of pores of mode diameter of approximately 70 angstroms. We show that the type of hysteresis loop formed by adsorption/desorption isotherms is determined by different mechanisms of condensation and evaporation and depends upon the shape and size of pores. We demonstrate that adsorption experiments performed with different adsorptives allow for detecting and separating the effects of pore blocking/percolation and cavitation in the course of evaporation. The results confirm that cavitation-controlled evaporation occurs in ink-bottle pores with the neck size smaller than a certain critical value. In this case, the pressure of evaporation does not depend upon the neck size. In pores with larger necks, percolation-controlled evaporation occurs, as observed for nitrogen (at 77.4 K) and argon (at 87.3 K) on porous Vycor glass. We elaborate a novel hybrid nonlocal density functional theory (NLDFT) method for calculations of pore size distributions from adsorption isotherms in the entire range of micro- and mesopores. The NLDFT method, applied to the adsorption branch of the isotherm, takes into account the effect of delayed capillary condensation in pores of different geometries. The pore size data obtained by the NLDFT method for SE3030, KLE, and KLE/IL silicas agree with the data of SANS/SAXS techniques.     

Evaluation of pore size distribution in boundary region of micropore and mesopore using gas adsorption method

This paper discusses an accurate method of pore size distribution evaluation in boundary regions of micropores and mesopores using the gas adsorption process on the basis of the capillary condensation theory, which is liable to be underestimated with the existing BJH and DH methods. A typical nitrogen adsorption isotherm for highly ordered mesoporous silica, which has cylindrical pores with diameter smaller than 4 nm, is considered to be type IV and it is well known for the steep increase of the amount adsorbed through capillary condensation in the region of the relative pressure P/P0 smaller than 0.4. In calculating the distribution of the pore size from the change of the amount adsorbed due to capillary condensation, it is important to accurately predict both the multilayer thickness t of the adsorbed nitrogen molecules and the critical radius rc where capillary condensation occurs. It is necessary to consider the curvature of the adsorption layer-gas phase interface when predicting the multilayer thickness t of nitrogen adsorbed within the pore of highly ordered mesoporous silica. Revision of the Kelvin equation is also required when rc is to be predicted. While the predicted value of t based on the Broekhoff and de Boer theory is matched well with the value of t which is actually measured using highly ordered mesoporous silica, and the predicted value of rc based on the GTKB-Kelvin-cylindrical equation that has been revised considering the effect of the interfacial curvature on the interfacial tension of the adsorption layer-gas phase interface is matched with the value of rc which is actually measured using highly ordered mesoporous silica. A combination method of the Broekhoff and de Boer equation and the GTKB-Kelvin-cylindrical equation is proposed as a means of accurately evaluating, from the nitrogen adsorption isotherm, the pore size distribution in the highly ordered mesoporous silica in boundary region of micropore and mesopore. The proposed new method of pore size evaluation features high accuracy and offers the convenience of obtaining the pore size distribution without repeated calculations by employing the same algorithm as DH method. The pore size predicted by the Halsey equation and the Kelvin equation of the conventional DH method is about 20% smaller than the pore size predicted by the newly proposed evaluation method.     

Argon and krypton adsorption on templated mesoporous silicas: molecular simulation and experiment

In this work we report molecular simulation results for argon and krypton adsorption on atomistic models of templated mesoporous silica materials. These models add atomistic levels of detail to mesoscale representations of these porous materials, which were originally generated from lattice Monte Carlo simulations mimicking the synthesis process of templated mesoporous silicas. We generate our atomistic pore models by carving out of a silica block a ‘mathematically-smooth’ representation of the pores from lattice MC simulations. Following that procedure, we obtain a model material with mean mesopore and micropore diameters of 5.4 nm and 1.1 nm, respectively (model A). Two additional model materials were considered: one with no microporosity, and with mesopores similar to those of model A (model B), and a regular cylindrical pore (model C). Simulation results for Ar and Kr adsorption on these model materials at 77 K and 87 K shows that model A provides the best agreement with experimental data; however, our results suggest that fine-tuning the microporosity and/or the surface chemistry (i.e., by decreasing the density of OH groups at the pore surface) of model A can lead to better agreement with experiments. The filling of the mesopores in model materials A and B proceeded via a classical capillary condensation mechanism, where the pores fill at slightly different pressures. This observation contrasts with what was observed in our previous study (Coasne, et al. in Langmuir 22:194–202, 2006), where we considered atomistic silica mesopores with an important degree of surface roughness at length scales below 10 Å, for which we observed a quasi-continuous mesopore filling involving intermediate phases with liquid-like “bridges” and gas-like regions. These results suggest that pore surface roughness, and other morphological features such as constrictions, play an important role in the mechanism of adsorption and filling of the mesopores.     

Effect of pore structure in mesoporous silicas on VOC dynamic adsorption/desorption performance

The dynamic adsorption/desorption behavior of volatile organic compounds (VOCs) such as toluene (C7H8) and benzene (C6H6) was evaluated for three kinds of mesoporous silicas of SBA-15, all having almost the same mesopore size of ca. 5.7 nm, and a MCM-41 silica with a smaller pore size of 2.1 nm using a continuous three-step test. The fiberlike SBA-15 silica exhibited exceptionally good breakthrough behavior, a higher VOC capacity, and easier desorption. The fiberlike silica was composed through the catenation of rodlike particles. The rodlike silicas, by comparison, were proven to be less useful in dynamic adsorption processes because of lower dynamic VOC capacities despite having comparative porous parameters with the fiberlike silica. The large dynamic VOC capacity of the fiberlike silica was attributed to the presence of a bimodal pore system consisting of longer, one-dimensional mesopore channels connected by complementary micropores.