Promoting CO2 Electroreduction Kinetics on Atomically Dispersed Monovalent ZnI Sites by Rationally Engineering Proton-Feeding Centers

Jiayi Chen; Zhongjian Li; Xinyue Wang; Xiahan Sang; Sixing Zheng; Shoujie Liu; Bin Yang; Qinghua Zhang; Lecheng Lei; Liming Dai; Yang Hou

doi:10.1002/anie.202111683

Promoting CO₂ Electroreduction Kinetics on Atomically Dispersed Monovalent Zn^I Sites by Rationally Engineering Proton-Feeding Centers

Angew Chem Int Ed Engl. 2022 Feb 7;61(7):e202111683. doi: 10.1002/anie.202111683. Epub 2021 Dec 27.

Authors

Jiayi Chen¹, Zhongjian Li^{1

2}, Xinyue Wang¹, Xiahan Sang³, Sixing Zheng¹, Shoujie Liu⁴, Bin Yang^{1

2}, Qinghua Zhang^{1

2}, Lecheng Lei^{1

2}, Liming Dai⁵, Yang Hou^{1

2}

Affiliations

¹ Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China.
² Institute of Zhejiang University-Quzhou, Quzhou, 324000, China.
³ Nanostructure Research Center, Wuhan University of Technology, Wuhan, 430070, China.
⁴ Chemistry and Chemical Engineering Guangdong Laboratory, Shantou, 515031, China.
⁵ Australian Carbon Materials Centre(A-CMC), School of Chemical Engineering, University of New South Wales, Sydney, NSW, 2052, Australia.

PMID: 34608726
DOI: 10.1002/anie.202111683

Abstract

Electrocatalytic reduction of CO₂ (CO₂ RR) to value-added chemicals is of great significance for CO₂ utilization, however the CO₂ RR process involving multi-electron and proton transfer is greatly limited by poor selectivity and low yield. Herein, We have developed an atomically dispersed monovalent zinc catalyst anchored on nitrogenated carbon nanosheets (Zn/NC NSs). Benefiting from the unique coordination environment and atomic dispersion, the Zn/NC NSs exhibit a superior CO₂ RR performance, featuring a high current density up to 50 mA cm^-2 with an outstanding CO Faradaic efficiency of ≈95 %. The center Zn^I atom coordinated with three N atoms and one N atom that bridges over two adjacent graphitic edges (Zn-N₃₊₁ ) is identified as the catalytically active site. Experimental results reveal that the twisted Zn-N₃₊₁ structure accelerates CO₂ activation and protonation in the rate-determining step of *CO₂ to *COOH, while theoretical calculations elucidate that atomically dispersed Zn-N₃₊₁ moieties decrease the potential barriers for intermediate COOH* formation, promoting the proton-coupled CO₂ RR kinetics and boosting the overall catalytic performance.

Keywords: atomic dispersion; electroreduction; molten salt-assisted synthesis; monovalent ZnI sites; proton-feeding.

Abstract

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