Redox property switching in MOFs with open metal sites for improved catalytic hydrogenation performance

Abstract

In this study, a decompression-thermalization strategy was utilized for a Cu-containing metal-organic framework (MOF) to tune its redox and catalytic hydrogenation properties. Remarkably, at just 120 °C, open metal sites (OMSs) were successfully constructed by removing coordinated solvent molecules to generate the daughter MOF-120. The tailored redox property of MOF-120 is correlated with the presence of OMSs. Compared with the pristine MOF where copper cations were capped by DMF, MOF-120 exhibited improved kinetics, showed a reduction of activation energy and outstanding recyclability in the hydrogenation of 4-nitrophenol under mild conditions (25 °C, 1 atm). Both experimental studies and theoretical calculation results reveal that the generation of OMSs endows the Cu species with unique electronic properties, which assist the adsorption and electron transfer between substrate molecules and is responsible for the enhanced performance in the hydrogenation process.