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

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 forma

SUBMITTER: Zhang H 

PROVIDER: S-EPMC9561705 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature