photocatalytic system based on rh-functionalized metal-organic framework

Abstract

SSCI-VIDE+ING+JEC:DFAInternational audienceMetal-Organic-Frameworks appear to be appealing platforms for immobilization of single-site organometallic catalysts. The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Through post-synthetic ligand exchange methodology, we successfully proceeded to the heterogenization of this molecular catalyst via the synthesis of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and more selective for formate. Through the study of the behaviour of MOF systems having a controlled Rh loading, competitive catalytic reaction occurring inside the Cp*Rh@UiO-67 framework are postulated. Finally, a combined computational-experimetnal methodology allowed unravelling the band-gap as a new descriptor of the chemical compostion of the hybrid material, to assess ultimately the covalent incorporation of the organometallic catalyst within the framework