Affiliation:
1. School of Chemical Engineering and Light Industry Guangdong University of Technology Guangzhou Guangdong 510006 P. R. China
2. Department of Applied Biology and Chemical Technology and Research Institute for Smart Energy The Hong Kong Polytechnic University Hung Hom Hong Kong, SAR Kowloon 999077 P. R. China
3. Guangdong Provincial Laboratory of Chemistry and Fine Chemical Engineering Jieyang Center Jieyang 515200 P. R. China
Abstract
AbstractAdapting the coordination environment to influence the electronic configuration of active sites represents an efficient approach for improving the photocatalytic performance of the CO2 reduction reaction (CO2RR) but how to execute it precisely remains challenging. Herein, heteroatom‐substitution in Ni‐porphyrin to break the coordination symmetry of Ni center is proposed to be an effective solution. Based on this, two symmetry‐breaking Ni‐porphyrins, namely Ni(Cl)ON3Por and Ni(Cl)SN3Por, are designed and successfully prepared. By theoretical calculation, it is found that symmetry‐breaking efficiently regulates the 3d orbital energy levels of Ni center. Furthermore, experimental and theoretical findings jointly revealed that coordination symmetry‐breaking of Ni‐porphyrins facilitates the generation of highly reactive NiI species during the catalytic process, effectively stabilizing and reducing the energy barrier of formation of the key *COOH intermediate. As a result, Ni(Cl)ON3Por and Ni(Cl)SN3Por gave CO production rates of 24.7 and 38.8 mmol g−1 h−1 as well as selectivity toward CO of 94.0% and 96.4%, respectively, outperforming that of symmetric NiN4Por (CO production rate of 6.6 mmol g−1 h−1 and selectivity of 82.8%). These findings offer microscopic insights into how to modulate the catalytic activity by precisely tuning the coordination environment of active sites and rational design of competent catalyst for CO2RR photocatalysis.
Funder
National Natural Science Foundation of China
Cited by
3 articles.
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