Zhuo Tian-Ci, Song Yang, Zhuang Gui-Lin, Chang Lu-Ping, Yao Shuang, Zhang Wei, Wang Ye, Wang Ping, Lin Wenbin, Lu Tong-Bu, Zhang Zhi-Ming
Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science & Engineering, School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China.
Department of Chemistry, University of Chicago, 929 East 57th Street, Chicago, Illinois 60637, United States.
J Am Chem Soc. 2021 Apr 28;143(16):6114-6122. doi: 10.1021/jacs.0c13048. Epub 2021 Apr 19.
It is highly desirable to achieve solar-driven conversion of CO 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 CO to formate (99.7%) was achieved with a high yield of 3040 μmol g 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. Systematic investigations revealed that the catalytic process is mediated by the H-bond synergy between Cu-bound X and CO-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 CO photoreduction.
非常希望能实现太阳能驱动的一氧化碳向有价值燃料的转化，并具有可控的选择性。现有的催化剂主要用于一氧化碳的生产，而很少用于甲酸盐的生成。在此，通过将光敏剂和单金属[bpy-Cu/ClX]（X = Cl或腺嘌呤）催化剂分层整合到稳定的Eu-bpy金属有机框架中，实现了一氧化碳向甲酸盐的高选择性光还原（99.7%），在10小时内产率高达3040 μmol g。然而，在[bpy-CuCl/X]中用吡啶取代X会显著降低甲酸盐产量，同时将一氧化碳产率提高到960 μmol g。系统研究表明，催化过程由铜结合的X与一氧化碳衍生物种之间的氢键协同作用介导，并且通过简单地取代配位配体就可以控制甲酸盐的选择性。这项工作提供了一个分子精确的结构模型，为一氧化碳光还原的选择性控制提供了机理见解。
