Gennady Y. Gor

Adsorption-Induced Deformation of Mesoporous Solids

The Derjaguin-Broekhoff-de Boer theory of capillary condensation is employed to describe deformation of mesoporous solids in the course of adsorption-desorption hysteretic cycles. We suggest a thermodynamic model, which relates the mechanical stress induced by the adsorbed phase to the adsorption isotherm. Analytical expressions are derived for the dependence of the solvation pressure on the vapor pressure. The proposed method provides a description of nonmonotonic hysteretic deformation during capillary condensation without invoking any adjustable parameters. The method is showcased drawing on the examples of literature experimental data on adsorption deformation of porous glass and SBA-15 silica.

Characterization of the Pore Structure of Three-Dimensionally Ordered Mesoporous Carbons Using High Resolution Gas Sorption

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.

Adsorption-Induced Deformation of Mesoporous Solids: Macroscopic Approach and Density Functional Theory

We present a theoretical study of the deformation of mesoporous solids during adsorption. The proposed thermodynamic model allows one to link the mechanical stress and strain to the solvation pressure exerted by the adsorbed molecules on the pore wall. Two approaches are employed for calculation of solvation pressure as a function of adsorbate pressure: the macroscopic Derjaguin-Broekhoff-de Boer theory of capillary condensation, and the microscopic density functional theory. We revealed that the macroscopic and microscopic theories are in quantitative agreement for the pores >8 nm diameter within the whole range of adsorbate pressures. For smaller pores, the macroscopic theory gradually deteriorates, and the density functional theory extends the thermodynamic model of adsorption-induced deformation to the nanometer scales.

Elastic response of mesoporous silicon to capillary pressures in the pores

We study water adsorption-induced deformation of a monolithic, mesoporous silicon membrane traversed by independent channels of ∼8 nm diameter. We focus on the elastic constant associated with the Laplace pressure-induced deformation of the membrane upon capillary condensation, i.e., the pore-load modulus. We perform finite-element method (FEM) simulations of the adsorption-induced deformation of hexagonal and square lattices of cylindrical pores representing the membrane. We find that the pore-load modulus weakly depends on the geometrical arrangement of pores, and can be expressed as a function of porosity. We propose an analytical model which relates the pore-load modulus to the porosity and to the elastic properties of bulk silicon (Youngs modulus and Poissons ratio), and provides an excellent agreement with FEM results. We find good agreement between our experimental data and the predictions of the analytical model, with the Youngs modulus of the pore walls slightly lower than the bulk value. This...

Adsorption of n-Pentane on Mesoporous Silica and Adsorbent Deformation

Development of quantitative theory of adsorption-induced deformation is important, e.g., for enhanced coalbed methane recovery by CO2 injection. It is also promising for the interpretation of experimental measurements of elastic properties of porous solids. We study deformation of mesoporous silica by n-pentane adsorption. The shape of experimental strain isotherms for this system differs from the shape predicted by thermodynamic theory of adsorption-induced deformation. We show that this difference can be attributed to the difference of disjoining pressure isotherm, responsible for the solid-fluid interactions. We suggest the disjoining pressure isotherm suitable for n-pentane adsorption on silica and derive the parameters for this isotherm from experimental data of n-pentane adsorption on nonporous silica. We use this isotherm in the formalism of macroscopic theory of adsorption-induced deformation of mesoporous materials, thus extending this theory for the case of weak solid-fluid interactions. We employ the extended theory to calculate solvation pressure and strain isotherms for SBA-15 and MCM-41 silica and compare it with experimental data obtained from small-angle X-ray scattering. Theoretical predictions for MCM-41 are in good agreement with the experiment, but for SBA-15 they are only qualitative. This deviation suggests that the elastic modulus of SBA-15 may change during pore filling.

Adsorption-induced deformation of nanoporous materials—A review

When a solid surface accommodates guest molecules, they induce noticeable stresses to the surface and cause its strain. Nanoporous materials have high surface area and, therefore, are very sensitive to this effect called adsorption-induced deformation. In recent years, there has been significant progress in both experimental and theoretical studies of this phenomenon, driven by the development of new materials as well as advanced experimental and modeling techniques. Also, adsorption-induced deformation has been found to manifest in numerous natural and engineering processes, e.g., drying of concrete, water-actuated movement of non-living plant tissues, change of permeation of zeolite membranes, swelling of coal and shale, etc. In this review, we summarize the most recent experimental and theoretical findings on adsorption-induced deformation and present the state-of-the-art picture of thermodynamic and mechanical aspects of this phenomenon. We also reflect on the existing challenges related both to the f...

Monte Carlo simulation of cavitation in pores with nonwetting defects.

We investigate the onset of cavitation in a metastable fluid confined to nanoscale pores with nonwetting defects present. Using grand canonical and gauge cell mesocanonical Monte Carlo simulations, we study the degree of metastability (relative vapor pressure), at which the critical bubble forms in a spherical pore with a circular nonwetting defect. It is shown that an increase of the defect size leads to a transition from homogeneous to heterogeneous nucleation of critical bubbles formed at the defect site. In this case, the desorption process may be initiated at larger relative vapor pressures than those predicted by the theories of homogeneous cavitation.

Capillary condensation hysteresis in overlapping spherical pores: a Monte Carlo simulation study.

The mechanisms of hysteretic phase transformations in fluids confined to porous bodies depend on the size and shape of pores, as well as their connectivity. We present a Monte Carlo simulation study of capillary condensation and evaporation cycles in the course of Lennard-Jones fluid adsorption in the system of overlapping spherical pores. This model system mimics pore shape and connectivity in some mesoporous materials obtained by templating cubic surfactant mesophases or colloidal crystals. We show different mechanisms of capillary hysteresis depending on the size of the window between the pores. For the system with a small window, the hysteresis cycle is similar to that in a single spherical pore: capillary condensation takes place upon achieving the limit of stability of adsorption film and evaporation is triggered by cavitation. When the window is large enough, the capillary condensation shifts to a pressure higher than that of the isolated pore, and the possibility for the equilibrium mechanism of desorption is revealed. These finding may have important implications for practical problems of assessment of the pore size distributions in mesoporous materials with cagelike pore networks.

Relation Between Pore Size and the Compressibility of a Confined Fluid

When a fluid is confined to a nanopore, its thermodynamic properties differ from the properties of a bulk fluid, so measuring such properties of the confined fluid can provide information about the pore sizes. Here, we report a simple relation between the pore size and isothermal compressibility of argon confined in such pores. Compressibility is calculated from the fluctuations of the number of particles in the grand canonical ensemble using two different simulation techniques: conventional grand-canonical Monte Carlo and grand-canonical ensemble transition-matrix Monte Carlo. Our results provide a theoretical framework for extracting the information on the pore sizes of fluid-saturated samples by measuring the compressibility from ultrasonic experiments.

Adsorption stress changes the elasticity of liquid argon confined in a nanopore.

Knowledge of the elastic properties of a fluid is crucial for predicting its flow under high pressure, particularly in porous media. However, when a fluid is confined to a nanopore, many of its thermodynamic properties change as compared to bulk. Here we study the effect of confinement on the bulk modulus of liquid argon adsorbed in mesopores using classical density functional theory. We show that, at pressures lower than the saturation pressure, high adsorption stress in the pore causes the lowering of the fluid bulk modulus, a phenomenon which was recently observed experimentally [ Schappert, K.; Pelster, R. Europhys. Lett. 2014 , 105 , 5600 ]. Furthermore, we find that the pore size has a strong effect on the fluid bulk modulus, so that even at saturation, the elastic properties of nanoconfined fluid differ from the bulk values. We show that this difference is also due to the adsorption stress. Our results provide a basis for a new method for characterization of porous materials and have implications for modeling fluids in nanoporous geological formations, such as coal or shale.