Engineering an Artificial Metalloenzyme for Efficient Photo‐Enzymatic CO 2 Conversion

ABSTRACT Integrated photo‐enzymatic catalysis combines the merits of both photocatalytic and enzymatic systems; however, the spatial separation of photocatalysts and enzymes in conventional one‐pot setups often limits overall efficiency due to sluggish electron transfer. To address this, we constructed a light‐driven artificial metalloenzyme (Rh‐L6‐FDH) featuring dual catalytic centers by covalently conjugating formate dehydrogenase (FDH) with a tailored rhodium complex (Rh‐L6), thereby facilitating synergistic NADH regeneration and CO 2 conversion. Screening nine synthesized Rh complexes with structurally diverse ligands revealed that Rh‐L6 exhibited the highest efficiency for light‐driven NADH regeneration. Consequently, the resulting Rh‐L6‐FDH conjugate yielded formate with a 2.31‐fold increase compared to the physical mixture of free FDH and Rh‐L6. The enhancement is mechanistically linked to the combined effects of a narrowed bandgap, diminished activation energy, and the proximity between catalytic centers, which synergistically promote charge separation and CO 2 activation. To overcome the inherent instability of the conjugate, Rh‐L6‐FDH was immobilized within a ZIF‐67 framework. This strategy markedly improved catalytic robustness, boosting formate conversion to 98.4%—a 16.68‐fold improvement over the free component system. This work demonstrates the potential of integrating molecular metal complexes with enzymes into a unified architecture, offering a promising pathway for sustainable cofactor regeneration and efficient carbon sequestration.