Conceptual and Practical Aspects of Metal-Organic Frameworks for Solid-Gas Reactions.

The presence of site-isolated and well-defined metal sites has enabled the use of metal-organic frameworks (MOFs) as catalysts that can be rationally modulated. Because MOFs can be addressed and manipulated through molecular synthetic pathways, they are chemically similar to molecular catalysts. They are, nevertheless, solid-state materials and therefore can be thought of as privileged solid molecular catalysts that excel in applications involving gas-phase reactions. This contrasts with homogeneous catalysts, which are overwhelmingly used in the solution phase. Herein, we review theories dictating gas phase reactivity within porous solids and discuss key catalytic gas-solid reactions. We further treat theoretical aspects of diffusion within confined pores, the enrichment of adsorbates, the types of solvation spheres that a MOF might impart on adsorbates, definitions of acidity/basicity in the absence of solvent, the stabilization of reactive intermediates, and the generation and characterization of defect sites. The key catalytic reactions we discuss broadly include reductive reactions (olefin hydrogenation, semihydrogenation, and selective catalytic reduction), oxidative reactions (oxygenation of hydrocarbons, oxidative dehydrogenation, and carbon monoxide oxidation), and C-C bond forming reactions (olefin dimerization/polymerization, isomerization, and carbonylation reactions).