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.