H‑Bond-Mediated Selectivity Control of Formate versus CO during CO₂ Photoreduction with Two Cooperative Cu/X Sites

It is highly desirable to achieve solar-driven conversion of CO₂ to valuable fuels with controlled selectivity. The existing catalysts are mainly explored for CO production but rarely for formate generation. Herein, highly selective photoreduction of CO₂ to formate (99.7%) was achieved with a high yield of 3040 μmol g^–1 in 10 h by hierarchical integration of photosensitizers and monometallic [bpy-Cu/ClX] (X = Cl or adenine) catalysts into a stable Eu-bpy metal–organic framework. However, replacing X with pyridine in [bpy-CuCl/X] significantly reduced formate production while increasing the CO yield to 960 μmol g^–1. Systematic investigations revealed that the catalytic process is mediated by the H-bond synergy between Cu-bound X and CO₂-derived species, and the selectivity of HCOO^– can be controlled by simply replacing the coordination ligands. This work provides a molecularly precise structural model to provide mechanistic insights for selectivity control of CO₂ photoreduction.