Postsynthetic Modification of UIO-Type Metal-Organic Frameworks (MOFS) for Advanced Heterogeneous Catalysis

Abstract

Metal-organic frameworks are an emerging class of porous materials over last decades. The building units, rather organic linkers or inorganic clusters are highly tailorable, in which the desired coordination moieties, functional groups, length and geometries can be rationally functionalized to build target MOFs for proper application. Especially for research on heterogeneous catalysis, the high surface area, high stability, and tunability on molecular level have made MOFs of interest candidates on the development of advanced heterogeneous catalysts. Bearing these advantages, several methods of post-synthetic modification on UiO-type MOFs were conducted and applied to a variety of reactions:

(1) In-situ metal immobilization on an azobenzene MOF (PCN-160) to get cyclopalladated complex in the MOF pore for continuous Suzuki cross coupling reaction.

(2) Through ligand exchange, functionalize UiO-66 with monophosphine complex for Heck reaction and N-alkylation reaction.

(3) Functionalization of UiO-66 with bis(diphenylphosphino)amine type ligand for continuous gas phase ethylene dimerization reaction and systemic ligand tunning for reaction optimization.