Bioinspired Metalation of the Metal‐Organic Framework MIL‐125‐NH2for Photocatalytic NADH Regeneration and Gas‐Liquid‐Solid Three‐Phase Enzymatic CO2Reduction

Abstract Coenzyme NADH regeneration is crucial for sustained photoenzymatic catalysis of CO 2 reduction. However, light‐driven NADH regeneration still suffers from the low regeneration efficiency and requires the use of a homogeneous Rh complex. Herein, a Rh complex‐based electron transfer unit was chemically attached onto the linker of the MIL‐125‐NH 2 . The coupling between the light‐harvesting iminopyridine unit and electron‐transferring Rh‐complex facilitated the photo‐induced electron transfer for the NADH regeneration with the yield of 66.4 % in 60 mins for 5 cycles. The formate dehydrogenase was further deposited onto the hydrophobic layer of the membrane by a reverse filtering technique, which forms the gas‐liquid‐solid reaction interface around the enzyme site. It gave an enhanced formic acid yield of 9.5 mM in 24 hours coupled with the in situ regenerated NADH. The work could shed light on the construction of integrated inorganic‐enzyme hybrid systems for artificial photosynthesis.