Dynamic Restructuring of Coordinatively Unsaturated Copper Paddle Wheel Clusters to Boost Electrochemical CO2 Reduction to Hydrocarbons**
- 27 October 2021
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 61 (3) , e202112116
Abstract
The electrochemical reduction of CO2 to hydrocarbons involves a multistep proton‐coupled electron transfer (PCET) reaction. Second coordination sphere engineering is reported to be effective in the PCET process; however, little is known about the actual catalytic active sites under realistic operating conditions. We have designed a defect‐containing metal–organic framework, HKUST‐1, through a facile “atomized trimesic acid” strategy, in which Cu atoms are modified by unsaturated carboxylate ligands, producing coordinatively unsaturated Cu paddle wheel (CU−CPW) clusters. We investigate the dynamic behavior of the CU−CPW during electrochemical reconstruction through the comprehensive analysis of in situ characterization results. It is demonstrated that Cu2(HCOO)3 is maintained after electrochemical reconstruction and that is behaves as an active site. Mechanistic studies reveal that CU−CPW accelerates the proton‐coupled multi‐electron transfer (PCMET) reaction, resulting in a deep CO2 reduction reaction.Keywords
Funding Information
- National Natural Science Foundation of China (51872108, U20A20246)
- Fundamental Research Funds for the Central Universities (CCNU20TS006)
- China Postdoctoral Science Foundation (20201jb015)
- Postdoctoral Science Foundation of Hubei Province (20201jb013)
- National Key Research and Development Program of China (2017YFA0403400, 2020YFA0715000)
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