Light‐Assisted CO2 Hydrogenation over Pd3Cu@UiO‐66 Promoted by Active Sites in Close Proximity

Abstract CO 2 hydrogenation to methanol has attracted great interest while suffering from low conversion and high energy input. Herein, tiny Pd 3 Cu nanoparticles are confined into a metal–organic framework (MOF), UiO‐66, to afford Pd 3 Cu@UiO‐66 for CO 2 hydrogenation. Remarkably, it achieves a methanol production rate of 340 μmol g −1 h −1 at 200 °C and 1.25 MPa under light irradiation, far surpassing that in the dark. The photo‐generated electron transfer from the MOF to antibonding orbitals of CO 2 * promotes CO 2 activation and HCOO* formation. In addition, the Pd 3 Cu microenvironment plays a critical role in CO 2 hydrogenation. In contrast to the MOF‐supported Pd 3 Cu (Pd 3 Cu/UiO‐66), the Pd 3 Cu@UiO‐66 exhibits a much higher methanol production rate due to the close proximity between CO 2 and H 2 activation sites, which greatly facilitates their interaction and conversion. This work provides a new avenue to the integration of solar and thermal energy for efficient CO 2 hydrogenation under moderate conditions.