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

Angewandte Chemie - International Edition

4 years ago

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

Ming-Jun Sun, Rui Zheng, Junwei Zhao, Dongying Shi, Chun-Sen Liu, Chao-Jie Cui, Miao Du, Chun-Xiao Sun, Xinrui Cao

As the first example of a photocatalytic system for splitting water without additional cocatalysts and photosensitizers, the comparatively cost-effective Cu2I2-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 Cu2I2 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 d10-based MOFs for highly efficient and long-term solar fuels production. No additives required: A low-cost Cu2I2-based MOF exhibits efficient photocatalytic H2 production without additional photosensitizers and cocatalysts. DFT calculations reveal a good band alignment with the water redox energy levels. The proposed mechanism demonstrates that Cu2I2 clusters in Cu-I-bpy (bpy=4,4′-bipyridine) serve as photoelectron generators to accelerate copper(I) hydride interaction for hydrogen evolution.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201709869