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Abstract: Equilibrium and nonequilibrium transport properties of adsorbates in mesoporous Vycor porous glass have been experimentally studied using nuclear magnetic resonance techniques. With the known geometrical characteristics of porous glass and with measured self-diffusivities, transient sorption curves have been quantitatively compared to those predicted within a Fick''s law model. This model correctly describes data outside a hysteresis region. In contrast, in the hysteresis region, a two-step mechanism of density relaxation is required to explain the behavior. These two mechanisms are identified as diffusion at early stages and activated density redistribution at later stages of adsorption. The latter mechanism, being intrinsically slow in nature, is anticipated to prevent the system from reaching equilibrium. [Copyright &y& Elsevier]

Abstract: The pulsed-field gradient NMR method has been applied to study self-diffusion of liquids in mesoporous materials with different pore sizes and morphologies as a function of pore loading. It is found that the effective diffusivities of adsorbate molecules in mesopores at partial loadings are related to two mechanisms, the Knudsen diffusion through the gaseous phase in the pore space and the diffusion within the layer of molecules adsorbed on the pore walls. The relative contributions of these modes, which are determined by the details of the interphase equilibrium, change with variation of the pore loading, leading to a complex behavior of the effective self-diffusion coefficient. The impact of the pore size and the adsorbate–surface interaction on self-diffusion is elucidated. Possible reasons for an experimentally obtained hysteresis in the diffusivities measured on adsorption and desorption in mesopores are discussed. [Copyright &y& Elsevier]

The application of nuclear magnetic resonance magnetization transfer experiments to probe the surface-to-volume ratio and pore morphology of porous materials with characteristic pore sizes of 1-100 nm is described. The method is based on the phenomenon of incomplete freezing of liquids in small pores where a few monolayers adjacent to the pore walls remain liquid. Sufficient difference between the transverse relaxation times in the solid frozen core and liquid surface layer allows the initial preparation and subsequent re-equilibration of a solid-liquid magnetization grating. The method is demonstrated using model nanoporous materials with known characteristics. The ensuing problems of the mechanism of the magnetization transfer through the interface and within the frozen core are discussed and elucidated by pulsed-field-gradient NMR experiments. [Copyright &y& Elsevier]