Semiconductive Copper(I)–Organic Frameworks for Efficient Light‐Driven Hydrogen Generation Without Additional Photosensitizers and Cocatalysts

Abstract As the first example of a photocatalytic system for splitting water without additional cocatalysts and photosensitizers, the comparatively cost‐effective Cu 2 I 2 ‐based MOF, Cu‐I‐bpy (bpy=4,4′‐bipyridine) exhibited highly efficient photocatalytic hydrogen production (7.09 mmol g −1 h −1 ). Density functional theory (DFT) calculations established the electronic structures of Cu‐I‐bpy with a narrow band gap of 2.05 eV, indicating its semiconductive behavior, which is consistent with the experimental value of 2.00 eV. The proposed mechanism demonstrates that Cu 2 I 2 clusters of Cu‐I‐bpy serve as photoelectron generators to accelerate the copper(I) hydride interaction, providing redox reaction sites for hydrogen evolution. The highly stable cocatalyst‐free and self‐sensitized Cu‐I‐bpy provides new insights into the future design of cost‐effective d 10 ‐based MOFs for highly efficient and long‐term solar fuels production.