Efficient Visible‐Light‐Driven Carbon Dioxide Reduction by a Single‐Atom Implanted Metal–Organic Framework

作者：Huabin Zhang, Jing Wei, Juncai Dong, Guigao Liu, Li Shi, Pengfei An, Guixia Zhao, Jin-Tao Kong, Xiaojun Wang, Xianguang Meng, Jing Zhang, Jinhua Ye · 发表于：Angewandte Chemie International Edition · 年份：2016 · DOI：10.1002/anie.201608597 · 被引用次数：761 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Advanced Photocatalysis Techniques、CO2 Reduction Techniques and Catalysts

Abstract Modular optimization of metal–organic frameworks (MOFs) was realized by incorporation of coordinatively unsaturated single atoms in a MOF matrix. The newly developed MOF can selectively capture and photoreduce CO 2 with high efficiency under visible‐light irradiation. Mechanistic investigation reveals that the presence of single Co atoms in the MOF can greatly boost the electron–hole separation efficiency in porphyrin units. Directional migration of photogenerated excitons from porphyrin to catalytic Co centers was witnessed, thereby achieving supply of long‐lived electrons for the reduction of CO 2 molecules adsorbed on Co centers. As a direct result, porphyrin MOF comprising atomically dispersed catalytic centers exhibits significantly enhanced photocatalytic conversion of CO 2 , which is equivalent to a 3.13‐fold improvement in CO evolution rate (200.6 μmol g −1 h −1 ) and a 5.93‐fold enhancement in CH 4 generation rate (36.67 μmol g −1 h −1 ) compared to the parent MOF.