Mechanistic insights into CO2 conversion chemistry of copper bis-(terpyridine) molecular electrocatalyst using accessible operando spectrochemistry
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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. Transition metal complexes are potential low-cost electrocatalysts for CO2 reduction. Here, using accessible spectrochemistry, the authors observe an intriguing baton relay-like mechanism of active site transfer during CO2 reduction to CO on a carbon-supported copper bis-(terpyridine) complex.
SUBMITTER: Zhang H
PROVIDER: S-EPMC9561705 | biostudies-literature | 2022 Jan
REPOSITORIES: biostudies-literature
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