Mechanistic insights into CO2 conversion chemistry of copper bis-(terpyridine) molecular electrocatalyst using accessible operando spectrochemistry

Huihui Zhang, Chang Xu, Xiaowen Zhan (), Yu Yu, Kaifu Zhang, Qiquan Luo (), Shan Gao (), Jinlong Yang and Yi Xie ()
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Huihui Zhang: Anhui University
Chang Xu: Anhui University
Xiaowen Zhan: Anhui University
Yu Yu: Anhui University
Kaifu Zhang: Anhui University
Qiquan Luo: Anhui University
Shan Gao: Anhui University
Jinlong Yang: University of Science and Technology of China
Yi Xie: University of Science and Technology of China

Nature Communications, 2022, vol. 13, issue 1, 1-11

Abstract: Abstract The implementation of low-cost transition-metal complexes in CO2 reduction reaction (CO2RR) is hampered by poor mechanistic understanding. Herein, a carbon-supported copper bis-(terpyridine) complex enabling facile kilogram-scale production of the catalyst is developed. We directly observe an intriguing baton-relay-like mechanism of active sites transfer by employing a widely accessible operando Raman/Fourier-transform infrared spectroscopy analysis coupled with density functional theory computations. Our analyses reveal that the first protonation step involves Cu-N bond breakage before the *COOH intermediate forms exclusively at the central N site, followed by an N-to-Cu active site transfer. This unique active site transfer features energetically favorable *CO formation on Cu sites, low-barrier CO desorption and reversible catalyst regeneration, endowing the catalyst with a CO selectively of 99.5 %, 80 h stability, and a turn-over efficiency of 9.4 s−1 at −0.6 V vs. the reversible hydrogen electrode in an H-type cell configuration. We expect that the approach and findings presented here may accelerate future mechanistic studies of next-generation CO2RR electrocatalysts.

Date: 2022
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DOI: 10.1038/s41467-022-33689-9

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