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We have developed a comprehensive strategy for quantitatively assessing the hydrophilicity/hydrophobicity of nanoporous materials by combining advanced adsorption studies, novel liquid intrusion techniques, and solid-state NMR spectroscopy. For this, we have chosen a well-defined system of model materials, i.e., the highly ordered mesoporous silica molecular sieve SBA-15 in its pristine state and functionalized with different amounts of trimethylsilyl (TMS) groups, allowing one to accurately tailor the surface chemistry while maintaining the well-defined pore structure. For an absolute quantification of the trimethylsilyl group density, quantitative 1 H solid-state NMR spectroscopy under magic angle spinning was employed. A full textural characterization of the materials was obtained by high-resolution argon 87 K adsorption, coupled with the application of dedicated methods based on nonlocal-density functional theory (NLDFT). Based on the known texture of the model materials, we developed a novel methodology allowing one to determine the effective contact angle of water adsorbed on the pore surfaces from complete wetting to nonwetting, constituting a powerful parameter for the characterization of the surface chemistry inside porous materials. The surface chemistry was found to vary from hydrophilic to hydrophobic as the TMS functionalization content was increased. For wetting and partially wetting surfaces, pore condensation of water is observed at pressures P smaller than the bulk saturation pressure p 0 (i.e., at p / p 0 < 1) and the effective contact angle of water on the pore walls could be derived from the water sorption isotherms. However, for nonwetting surfaces, pore condensation occurs at pressures above the saturation pressure (i.e., at p / p 0 > 1). In this case, we investigated the pore filling of water (i.e., the vapor-liquid phase transition) by the application of a novel, liquid water intrusion/extrusion methodology, allowing one to derive the effective contact angle of water on the pore walls even in the case of nonwetting. Complementary molecular simulations provide density profiles of water on pristine and TMS-grafted silica surfaces (mimicking the tailored, functionalized experimental silica surfaces), which allow for a molecular view on the water adsorbate structure. Summarizing, we present a comprehensive and reliable methodology for quantitatively assessing the hydrophilicity/hydrophobicity of siliceous nanoporous materials, which has the potential to optimize applications in heterogeneous catalysis and separation (e.g., chromatography).

Industrialization over the past two centuries has resulted in a continuous rise in global CO 2 emissions. These emissions are changing ecosystems and livelihoods. Therefore, methods are needed to capture these emissions from point sources and possibly from our atmosphere. Though the amount of CO 2 is rising, it is challenging to capture directly from air because its concentration in air is extremely low, 0.04%. In this study, amines installed inside metal-organic frameworks (MOFs) are investigated for the adsorption of CO 2 , including at low concentrations. The amines used are polyamidoamine dendrimers that contain many primary amines. Chemically reversible adsorption of CO 2 via carbamate formation was observed, as was enhanced uptake of carbon dioxide, likely via dendrimer-amide-based physisorption. Limiting factors in this initial study are comparatively low dendrimer loadings and slow kinetics for carbon dioxide uptake and release, even at 80 °C.

During the last decades, major progress was made concerning the understanding of subcritical low-pressure adsorption of fluids like nitrogen and argon at their boiling temperatures in nanoporous materials. It was possible to understand how structural properties affect the shape of the adsorption isotherms. However, within the context of gas storage applications, supercritical high-pressure gas adsorption is important. A key feature here is that the experimentally determined surface excess adsorption isotherm may exhibit a characteristic maximum at a certain pressure. For a given temperature and adsorptive/adsorbent system, the surface excess maximum (and the corresponding adsorbed amount) is related to the storage capacity of the adsorbent. However, there is still a lack of understanding of how key textural properties such as surface area and pore size affect details of the shape of supercritical high-pressure adsorption isotherms. To address these open questions, we have performed a systematic experimental study assessing the effect of pore size/structure on the supercritical adsorption isotherms of pure fluids such as C 2 H 4 , CO 2 , and SF 6 over a wider range of temperatures and pressures on a series of model materials exhibiting well-defined pore sizes, i.e., ordered micro- and mesoporous materials (e.g., NaY zeolite, KIT-6 silica, and MCM-48 silica). A fundamental result of our experiments is a unique fluid-independent correlation between the pressure of the surface excess maximum p max (at a given temperature) and the pore size (by taking into account the kinetic diameter of the fluid and the underlying effective attractive fluid-wall interaction). Summarizing, our results suggest important structure-property relationships, allowing one to determine, for given thermodynamic conditions, important information related to the optimal operating conditions for supercritical adsorption applications. The insights may also serve as a basis for optimizing and tailoring the properties of nanoporous adsorbent materials for gas storage applications.

Through analysis of the statistical mechanical equations for a thin adsorbed film (gas, liquid, or solid) on a solid substrate or confined within a pore, it is possible to express the equilibrium thermodynamic properties of the film as a function of just two dimensionless parameters: a nanoscale wetting parameter, α w , and pore width, H* . The wetting parameter, α w , is defined in terms of molecular parameters for the adsorbed film and substrate and so is applicable at the nanoscale and for films of any phase. The main assumptions in the treatment are that (a) the substrate structure is not significantly affected by the adsorbed layer and (b) the diameter of the adsorbate molecules is not very small compared to the spacing of atoms in the solid substrate. We show that different surface geometries of the substrate (e.g., slit, cylindrical, and spherical pores) and various models of wall heterogeneity can be accounted for through a well-defined correction to the wetting parameter; no new dimensionless variables are introduced. Experimental measurements are reported for contact angles for various liquids on several planar substrates and are shown to be closely correlated with the nanoscale wetting parameter. We apply this approach to phase separation in nanopores of various geometries. Molecular simulation results for the phase diagram in confinement, obtained by the flat histogram Monte Carlo method, are reported and are shown to be closely similar to experimental results for capillary condensation, melting, and the triple point. The value of the wetting parameter, α w , is shown to determine the qualitative behavior (e.g., increase vs decrease in the melting temperature, capillary condensation vs evaporation), whereas the pore width determines the magnitude of the confinement effect. The triple point temperature and pressure for the confined phase are always lower than those for the bulk phase for all cases studied.

The reliable assessment of surface area is extremely important for many applications, e.g., catalysis, separation, and energy storage/conversion. Within this context, major progress has been made concerning the textural characterization of porous materials in the gas/dry state, e.g., gas physisorption and mercury porosimetry. However, these methods are not sufficient for the characterization of wet materials utilized in liquid-phase processes. For this, the application of nuclear magnetic resonance (NMR) relaxometry has been considered, but a systematic and rigorous assessment of the applicability of NMR relaxometry for reliable surface and pore size characterization of nanoporous materials is missing. Hence, we present a systematic study in which we assess the applicability of NMR relaxometry for reliable surface area assessment utilizing for the first time true surface area benchmark data based on argon 87 K adsorption on nonporous particles (silica and carbon black) coupled with the development of an advanced methodology including the investigation of the choice of the probe molecule and the effect of its accessibility to the pore network. Our results show that the method provides a fast (a few minutes per measurement) and reliable surface area of silica and carbon black model materials immersed in a liquid phase. In addition, our work clearly demonstrates the potential of NMR relaxometry for the targeted surface area assessment of defined pore classes (here ultramicropores) and suggests a new methodology for the characterization of pore entrances (pore window size). Furthermore, we investigate the effect of wettability and suggest that NMR relaxometry could be developed into a unique tool for assessing the wetting characteristics of adsorbate phases on pore surfaces. This fundamental study can be considered a first major step in enabling NMR relaxometry for reliable surface area assessment for wet materials, particularly relevant for materials used in processes occurring in a liquid phase.

In disordered mesopore networks, the size distribution and connection between adjacent pores control desorption. How network characteristics can be extracted from corresponding physisorption isotherms is still a matter of research. To elucidate this, we study krypton physisorption (117.8 K) in the mesopore networks of "Nakanishi"-type monolithic silica. Combining physisorption in scanning acquisition mode with synchrotron-based in-situ SAXS provides complementary information on pore-filling states. These data reveal a mean pore size gradient in which pores grow smaller towards the material's network center. This structural motif cannot be derived through conventional isotherm analysis, but it is clearly exposed through scanning desorption curves which do not quite converge but merge individually with the main desorption isotherm before the lower hysteresis closing point. Hence, our findings provide the basis to build advanced models for analyzing scanning isotherms and extracting network characteristics through new descriptors, such as pore size and connectivity distributions as a function of the distance from the network center.

Carbon dioxide adsorption on micro- and mesoporous carbonaceous materials in a wide range of temperatures and pressures is of great importance for the problems of gas separations, greenhouse gas capture and sequestration, enhanced hydrocarbon recovery from shales and coals, as well as for the characterization of nanoporous materials using CO 2 as a molecular probe. We investigate the influence of temperature on CO 2 adsorption focusing on the capillary condensation and hysteresis phenomena. We present experimental data on the adsorption of CO 2 on CMK-3, ordered carbon with mesopores of ∼5-6 nm, at various temperatures (185-273 K) and pressures (up to 35 bars). Using Monte Carlo (MC) simulations in the grand canonical and mesocanonical ensembles, we attempt to predict the transition from reversible capillary condensation to hysteretic adsorption-desorption cycles that is experimentally observed with the decrease of temperature. We show that although the desorption at all temperatures occurs at the conditions of pore vapor-liquid equilibrium, the capillary condensation is a nucleation-driven process associated with an effective energy barrier of ∼43 kT, specific to the sample used in this work. This barrier can be overcome at the equilibrium conditions in the region of reversible condensation at temperatures higher than 240 K. At lower temperatures, the regime of developing hysteresis is observed with progressively widening hysteresis loops. The position of capillary condensation transition is estimated using the pressure dependence of the energy barrier calculated by the thermodynamic integration of the van der Waals-type continuous canonical isotherm simulated with the gauge cell MC method. These findings lay the foundation for developing kernels of CO 2 adsorption and desorption isotherm for calculating the pore size distribution in the entire range of micropore and mesopore sizes from one high-pressure experimental isotherm.

The texture of mesoporous FAU-Y (FAUmes) prepared by surfactant-templating in basic media is a subject of debate. It is proposed that mesoporous FAU-Y consists of: (1) ordered mesoporous zeolite networks formed by a surfactant-assisted zeolite rearrangement process involving local dissolution and reconstruction of the crystalline framework, and (2) ordered mesoporous amorphous phases as Al-MCM-41, which coexist with zeolite nanodomains obtained by a dissolution-reassembly process. By the present systematic study, performed with FAU-Y (Si/Al = 15) in the presence of octadecyltrimethylammonium bromide and 0 < NaOH/Si ratio < 0.25 at 115 °C for 20 h, we demonstrate that mesoporous FAU zeolites consist, in fact, of a complex family of materials with textural features strongly impacted by the experimental conditions. Two main families have been disclosed: (1) for 0.0625 < NaOH/Si < 0.10, FAUmes are ordered mesoporous materials with zeolite walls, which coexist with zeolite nanodomains (100-200 nm) and (2) for 0.125 < NaOH/Si < 0.25, FAUmes are ordered mesoporous materials with amorphous walls as Al-MCM-41, which coexist with zeolite nanodomains (5-100 nm). The zeolite nanodomains decrease in size with the increase of NaOH/Si ratio. Increasing NaOH/Si ratio leads to an increase of mesopore volume, while the total surface area remains constant, and to a decrease of strong acidity in line with the decrease of micropore volume. The ordered mesoporous materials with zeolite walls feature the highest acidity strength. The ordered mesoporous materials with amorphous walls present additional large pores (50-200 nm), which increase in size and amount with the increase of NaOH/Si ratio. This alkaline treatment of FAU-Y represents a way to obtain ordered mesoporous materials with zeolite walls with high mesopore volume for NaOH/Si = 0.10 and a new way to synthesize mesoporous Al-MCM-41 materials containing extralarge pores (50-200 nm) ideal for optimal diffusion (NaOH/Si = 0.25).

Carbon dioxide was shown to identify surface basic properties of nitrogen-substituted microporous and mesoporous silicas, in addition to conventional basic oxides, by a detailed study using isotherm and heat of adsorption measurements as well as by infrared spectroscopy. A hydrogen-bonded weak interaction was primarily observed between CO 2 and silanol (Si-OH) and silamine (Si-NH-Si) groups. The heat of adsorption of CO 2 demonstrated that the latter adspecies were formed preferentially over the former, although a much higher amount of linear CO 2 adspecies were found on SBA-15 mesoporous silica because of the presence of a large quantity of silanol groups on its surface. Carbamate-type chemisorbed adspecies were not detected on silamino sites, whereas carbonate-type adspecies were formed on alkali ion-exchanged zeolites and also residual sodium ions on the surface of silicalite-1. CO 2 was shown to be a successful probe molecule for identifying weakly interactive hydrogen-bonding sites, and it has potential as a surface probe for strongly interactive nucleophilic sites derived from alkaline ions or a methylated silamino group, Si-N(CH 3 )-Si.

The mechanism of dibromomethane (DBM) sorption in mesoporous silica was investigated by in situ small-angle X-ray scattering (SAXS). Six different samples of commercial porous silica particles used for liquid chromatography were studied, featuring a disordered mesoporous structure, with some of the samples being functionalized with alkyl chains. SAXS curves were recorded at room temperature at various relative pressures P/P0 during adsorption of DBM. The in situ SAXS experiment is based on contrast matching between silica and condensed DBM with regard to X-ray scattering. One alkyl-modified silica sample was evaluated in detail by extraction of the chord-length distribution (CLD) from SAXS data obtained for several P/P0. On the basis of this analytical approach and by comparison with ex situ obtained data of nitrogen and DBM adsorption, the mechanism of DBM uptake was studied. Results of average mesopore sizes obtained with the CLD method were compared with pore size analysis using nitrogen physisorption (77 K) with advanced state-of-the-art nonlocal density functional theory (NLDFT) evaluation. The dual SAXS/physisorption study indicates that microporosity is negligible in all silica samples and that surface functionalization with a hydrophobic ligand has a major influence upon the process of DBM adsorption. Also, all of the mesopores are accessible as evidenced by in situ SAXS. The data suggest that no multilayer adsorption occurs on C18-(octadecyl-)modified silica surfaces using DBM as adsorptive, and it is possibly also negligible on bare silica surfaces.

Ordered mesoporous CMK carbons and periodic mesoporous organosilica (PMO) materials have been characterized by combining nitrogen (77.4 K) and argon (87.3 K) adsorption with recently developed quenched solid density functional theory (QSDFT). Systematic, high-resolution water adsorption experiments have been performed in the temperature range from 298 to 318 K in order to ascertain the effect of surface chemistry (using periodic mesoporous organosilicas (PMOs) of given pore size) and pore size/pore geometry (using CMK-3, CMK-8 carbons) on the adsorption, pore filling, condensation and hysteresis behavior. These data reveal how the interplay between confined geometry effects and the strength of the adsorption forces influence the adsorption, wetting, and phase behavior of pore fluids. Further, our results indicate that water adsorption is quite sensitive to both small changes in pore structure and surface chemistry, showing the potential of water adsorption as a powerful complementary tool for the characterization of nanoporous solids.

The use of colloidal crystals with various primary particle sizes as templates leads to the formation of three-dimensionally ordered mesoporous (3DOm) carbons containing spherical pores with tailorable pore size and extremely high pore volumes. We present a comprehensive structural characterization of these novel carbons by using nitrogen (77.4 K) and argon (87.3 K) adsorption coupled with the application of novel, dedicated quenched solid density functional theory (QSDFT) methods which assume correctly the underlying spherical pore geometry and also the underlying adsorption mechanism. The observed adsorption isotherms are of Type IV with Type H1-like hysteresis, despite the fact that pore blocking affects the position of the desorption branch. This follows also from detailed, advanced scanning hysteresis experiments which not only allow one to identify the underlying mechanisms of hysteresis, but also provide complementary information about the texture of these unique porous materials. This work addresses the problem of pore size analysis of novel, ordered porous carbons and highlights the importance of hysteresis scanning experiments for textural analysis of the pore network.

We studied cavitation in metastable fluids drawing on the example of liquid nitrogen confined to spheroidal pores of specially prepared well-characterized mesoporous silica materials with mean pore diameters ranging from approximately 6 to approximately 35 nm. Cavitation was monitored in the process of evaporation/desorption from fully saturated samples with gradually decreasing vapor pressure at the isothermal conditions. The onset of cavitation was displayed by a sharp step on the desorption isotherm. We found that the vapor pressure at the onset of cavitation depended on the pore size for the samples with pores smaller than approximately 11 nm and remained practically unchanged for the samples with larger pores. We suggest that the observed independence of the cavitation pressure on the size of confinement indicates that the conditions of bubble nucleation in pores larger than approximately 11 nm approach the nucleation conditions in the bulk metastable liquid. To test this hypothesis and to evaluate the nucleation barriers, we performed grand canonical and gauge cell Monte Carlo simulations of nitrogen adsorption and desorption in spherical silica pores ranging from 5.5 to 10 nm in diameter. Simulated and experimental adsorption isotherms were in good agreement. Exploiting the correlation between the experimental cavitation pressure and the simulated nucleation barrier, we found that the nucleation barrier increased almost linearly from approximately 40 to approximately 70 k(B)T in the range of pores from approximately 6 to approximately 11 nm, and varied in diapason of 70-75 k(B)T in larger pores, up to 35 nm. We constructed the dependence of the nucleation barrier on the vapor pressure, which asymptotically approaches the predictions of the classical nucleation theory for the metastable bulk liquid at larger relative pressures (>0.6). Our findings suggest that there is a limit to the influence of the confinement on the onset of cavitation, and thus, cavitation of nanoconfined fluids may be employed to explore cavitation in macroscopic systems.

The glancing angle deposition (GLAD) technique is used to fabricate nanostructured thin films with high surface area. Quantifying this property is important for optimizing GLAD-based device performance. Our group has used high-sensitivity krypton gas adsorption and the complementary technique of cyclic voltammetry to measure surface area as a function of deposition angle, thickness, and morphological characteristics for several metal oxide thin films. In this work, we studied amorphous titanium dioxide (TiO(2)), amorphous silicon dioxide (SiO(2)), and polycrystalline indium tin oxide (ITO) nanostructures with vertical and helical post morphologies over a range of oblique deposition angles from 0 to 86 degrees. Krypton gas sorption isotherms, evaluated using the Brunauer-Emmettt-Teller (BET) method, revealed maximum surface area enhancements of 880 +/- 110, 980 +/- 125, and 210 +/- 30 times the footprint area (equivalently 300 +/- 40, 570 +/- 70, and 50 +/- 6 m(2) g(-1)) for vertical posts TiO(2), SiO(2), and ITO. We also applied the cyclic voltammetry technique to these ITO films and observed the same overall trends as seen with the BET method. In addition, we applied the BET method to the measurement of helical films and found that the surface area trend was shifted with respect to that of vertical post films. This revealed the important influence of the substrate rotation rate and film morphology on surface properties. Finally, we showed that the surface area scales linearly with film thickness, with slopes of 730 +/- 35 to 235 +/- 10 m(2) m(-2) microm(-1) found for titania vertical post films deposited at angles from 70 to 85 degrees. This characterization effort will allow for the optimization of solar, photonic, and sensing devices fabricated from thin metal oxide films using GLAD.

The combination of physisorption experiments with simultaneous in situ small-angle X-ray and neutron scattering (SAXS/SANS) was used to elucidate the porosity in mesoporous silica with a trimodal pore structure. The material ("KLE-IL") contains spherical mesopores of 14 nm in diameter, worm-like mesopores (2-3 nm), and micropores, templated by a block copolymer and an ionic liquid surfactant, while the micropores originate from the hydrophilic block of the block copolymer. The main objective of the study was the quantification of the microporosity and the small mesopores and to find out if they are indeed located between the larger, spherical mesopores. Our in situ SAXS/SANS experiments took advantage of contrast matching of nitrogen (SANS, T = 77 K) and dibromomethane (SAXS, T = 290 K). By using the latter gas with a slightly larger kinetic diameter, it was possible to judge the accessibility of the pores under ambient conditions. The in situ experiments were supported by high-precision ex situ physisorption. Using suitable approaches for the SAXS/SANS analysis, it was possible to separate the content of the micropores and small mesopores.

The aim of the present study was to characterize pegylated nanoparticles (NPs) for their microporosity and study the effect of microporosity on drug release kinetics. Blank and drug-loaded NPs were prepared from three different pegylated polymers, namely, poly(ethylene glycol)1%-graft-poly(D,L)-lactide, poly(ethylene glycol)5%-graft-poly(D,L)-lactide, and the multiblock copolymer (poly(D,L)-lactide-block-poly(ethylene glycol)-block-poly(D,L)-lactide)n. These NPs were characterized for their microporosity using nitrogen adsorption isotherms. NPs of the multiblock copolymer showed the least microporosity and Brunauer-Emmett-Teller (BET) surface area, and that of PEG1%-g-PLA showed the maximum. Based on these results, the structural organization of poly(D,L)-lactide (PLA) and poly(ethylene glycol) (PEG) chains inside the NPs was proposed and was validated with differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS) surface analysis. An in vitro drug release study revealed that PEG1%-g-PLA NPs exhibited slower release despite their higher surface area and microporosity. This was attributed to the presence of increased microporosity forming tortuous internal structures, thereby hindering drug diffusion from the matrix. Thus, it was concluded that the microporous structure of NPs, which is affected by the molecular architecture of polymers, determines the release rate of the encapsulated drug.

The pore hierarchy of a hierarchical porous SiO2 with 14 nm spherical mesopores and 3 nm worm-like pores (KLE1C16) is studied by small-angle neutron scattering (SANS) in combination with in-situ nitrogen sorption at 77 K. A novel setup is used developed at Hahn-Meitner Institute, Berlin. It is demonstrated that in these materials indeed all of the large mesopores are connected through the smaller ones, thus providing invaluable insights into the general phenomenon of pore connectivity in mesoporous materials.

We present results from experiments and molecular modeling of mercury porosimetry into mesoporous Vycor and controlled pore glass (CPG) solid materials. The experimental intrusion/extrusion curves show a transition from a type H2 hysteresis for the Vycor glass to a type H1 hysteresis for the CPG. Mercury entrapment is observed in both materials, but we find that the amount of entrapped mercury depends on the chosen experimental relaxation time. No additional entrapment is found in a second intrusion/extrusion cycle, but hysteresis is still observed. This indicates that hysteresis and entrapment are of different origin. The experimental observations are qualitatively reproduced in theoretical calculations based on lattice models, which provide significant insights of the molecular mechanisms occurring during mercury porosimetry experiments in these porous glasses.

The generation of porous silica with hierarchically organized bimodal mesoporosity of adjustable size and well-defined shape was investigated by using surfactant mixtures and the nanocasting procedure (liquid crystalline templating). A systematic study of combinations of various block copolymers (Pluronics F127, KLE (poly(omega-hydroxypoly(ethylene-co-butylene)-co-poly(ethylene oxide))) and SE (PS-co-PEO)) with smaller surfactants (Pluronics P123, C16mimCl, and CTAB) revealed that hierarchical bimodal mesopore architectures could only be obtained by the usage of block copolymers with a strong hydrophilic-hydrophobic contrast, such as KLE and SE, giving rise to pores between 6 and 22 nm. Furthermore, the ionic liquid (IL) C16mimCl appeared to have advantageous templating properties, resulting in 2-3-nm pores being located between the block copolymer mesopores, whereas phase separation was observed for Pluronics and CTAB as small templates. Thereby, the study provided also general insights into the mixing and co-self-assembly behavior of block copolymers and ionic surfactants in water and confirmed the special templating properties of ILs, as recently proposed. In addition to the bimodal mesoporosity, additional tunable macroporosity was created by the presence of poly(styrene) or poly(methyl methacrylate) spheres, leading to well-defined trimodal hierarchical pore architectures with the small pores being located in the walls of the respective larger pores. As a major improvement, due to the pore hierarchy, these large-pore materials showed relatively large surface areas and pore volumes, and the size of densely packed macropores could even be decreased down to 90 nm. The materials were characterized by electron microscopy, small-angle X-ray scattering, and nitrogen sorption using a proper NLDFT (nonlocal density functional theory) approach for calculations of the pore size distribution in the entire range of micro- and mesopores.

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.

We consider mercury porosimetry from the perspective of the statistical thermodynamics of penetration of a nonwetting liquid into a porous material under an external pressure. We apply density functional theory to a lattice gas model of the system and use this to compute intrusion/extrusion curves. We focus on the specific example of a Vycor glass and show that essential features of mercury porosimetry experiments can be modeled in this way. The lattice model exhibits a symmetry that provides a direct relationship between intrusion/extrusion curves for a nonwetting fluid and adsorption/desorption isotherms for a wetting fluid. This relationship clarifies the status of methods that are used for transforming mercury intrusion/extrusion curves into gas adsorption/desorption isotherms. We also use Monte Carlo simulations to investigate the nature of the intrusion and extrusion processes., (Copyright 2004 American Chemical Society)