Active Site Isolation and Enhanced Electron Transfer Facilitate Photocatalytic CO2 Reduction by A Multifunctional Metal–Organic Framework

We report a multifunctional metal–organic framework (MOF) photocatalyst for the CO2 reduction reaction (CO2RR) under visible light irradiation with high efficiency (turnover number = 2638) and CO selectivity (97.0%). The short distance (6.6 Å) between bipyridine sites in the MOF allows the integration of Ir photosensitizers and Ni catalysts in proximity, thereby enhancing their electron transfer for photocatalytic CO2RR. Isolation of these metal centers by the MOF structure prevents their deactivation, leading to 54 times higher CO2RR activity than the homogeneous system and allowing for easy recovery for use in five consecutive cycles of photocatalytic CO2RR without significant loss of catalytic activity.