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

Tian-Ci Zhuo; Yang Song; Gui-Lin Zhuang; Lu-Ping Chang; Shuang Yao; Wei Zhang; Ye Wang; Ping Wang; Wenbin Lin; Tong-Bu Lu; Zhi-Ming Zhang

doi:10.1021/jacs.0c13048

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

J Am Chem Soc. 2021 Apr 28;143(16):6114-6122. doi: 10.1021/jacs.0c13048. Epub 2021 Apr 19.

Authors

Affiliations

¹ 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.
² Department of Chemistry, University of Chicago, 929 East 57th Street, Chicago, Illinois 60637, United States.
³ Institute of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China.

PMID: 33871997
DOI: 10.1021/jacs.0c13048

Abstract

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.