Catalytic inorganic membranes are among the most challenging and intriguing porous materials. Consisting of a thin film of mesoporous or microporous inorganic material deposited on a macroporous material, catalytic membranes are multifunctional materials that must be engineered for both chemical and physical properties. New approaches to carrying out chemical reactions are possible by tailoring the membrane catalytic activity and selectivity, permselectivity, and other thin film properties. Readers are referred to several recent reviews of inorganic membranes, in particular, Zaspalis and Burggraaf, Armor, Gellings and Bouwmeister, Hsieh, Stoukides, and Tsotsis et al.
Inorganic membranes are most conveniently classified according to pore size (see introductory article). Of particular importance is the ratio of the pore size to the molecular mean free path (MFP). Decreasing pore dimensions lead to increased selectivity with corresponding loss of permeability. Macroporous membranes have a pore size much larger than the MFP, leading to molecular (bulk) diffusion or viscous flow. Knudsen diffusion dominates in the mesoporous regime, where the pore size is comparable to the MFP. In addition, surface diffusion of the molecules along the pore walls may contribute, leading to an enhanced flux of the adsorbed species along the walls. The microporous regime is encountered when the pore size is comparable to the molecules. This regime makes possible much higher permselectivities, which depend on both molecular size and specific interactions with the solid. Finally, in dense membranes, molecular transport occurs through a solution-diffusion mechanism, which also involves specific interactions between the solute and membrane.