X-ray Diffraction and Molecular Simulations in the Study of Metal–Organic Frameworks for Membrane Gas Separation

For more than a decade, researchers have been developing metal–organic frameworks (MOFs) in the form of pure MOF membranes as well as MOF-containing mixed-matrix membranes. MOF membranes have been used for H 2 /CO 2 or C 3 H 6 /C 3 H 8 separation, but relatively few MOF membranes enable the high-performance separation of CO 2 /N 2, CO 2 /CH 4, or N 2 /CH 4 . This article describes the use of in situ XRD analysis and molecular simulation to elucidate gas transport within MOFs and derivative membranes at the molecular level. In a review of recent studies by the authors and other research groups, this article examines the flexibility of MOFs initiated by activation, gas adsorption, and aging effects during gas permeation. This article also discusses the application of XRD analysis in conjunction with computational methods to investigate the CO 2 –MOF Coulombic interaction and its effects on CO 2 separation. Note that this combined analysis approach is also useful in studying the effects of linker rotation on N 2 /CH 4 separation. This article also examines the use of computational tools in identifying new MOFs for gas separation and, more importantly, in elaborating the relationship between the structure of MOFs and their corresponding gas transport properties.