Porous materials are characterized by the pore surface area (
S) and volume (
V) accessible to a confined fluid. For mesoporous materials NMR measurements of diffusion are used to assess the
S/
V ratio, because at short times, only
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Porous materials are characterized by the pore surface area (
S) and volume (
V) accessible to a confined fluid. For mesoporous materials NMR measurements of diffusion are used to assess the
S/
V ratio, because at short times, only the diffusivity of molecules in the adsorbed layer is affected by confinement and the fractional population of these molecules is proportional to the
S/
V ratio. For materials with sub-nanometer pores, this might not be true, as the adsorbed layer can encompass the entire pore volume. Here, using molecular simulations, we explore the role played by
S and
S/
V in determining the dynamical behavior of two carbon-bearing fluids—CO
2 and ethane—confined in sub-nanometer pores of silica.
S and
V in a silicalite model representing a sub-nanometer porous material are varied by selectively blocking a part of the pore network by immobile methane molecules. Three classes of adsorbents were thus obtained with either all of the straight (labeled ‘S-major’) or zigzag channels (‘Z-major’) remaining open or a mix of a fraction of both types of channel blocked, resulting in half of the total pore volume being blocked (‘Half’). While the adsorption layers from opposite surfaces overlap, encompassing the entire pore volume for all pores except the intersections, the diffusion coefficient is still found to be reduced at high
S/
V, especially for CO
2, albeit not so strongly as would be expected in the case of wider pores. This is because of the presence of channel intersections that provide a wider pore space with non-overlapping adsorption layers.
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