Ligand-tuning copper in coordination polymers for efficient electrochemical C-C coupling.
Nat Commun
; 15(1): 6316, 2024 Jul 26.
Article
en En
| MEDLINE
| ID: mdl-39060325
ABSTRACT
Cu catalyses electrochemical CO2 reduction to valuable multicarbon products but understanding the structure-function relationship has remained elusive due to the active Cu sites being heterogenized and under dynamic re-construction during electrolysis. We herein coordinate Cu with six phenyl-1H-1,2,3-triazole derivatives to form stable coordination polymer catalysts with homogenized, single-site Cu active sites. Electronic structure modelling, X-ray absorption spectroscopy, and ultraviolet-visible spectroscopy show a widely tuneable Cu electronics by modulating the highest occupied molecular orbital energy of ligands. Using CO diffuse reflectance Fourier transform infrared spectroscopy, in-situ Raman spectroscopy, and density functional theory calculations, we find that the binding strength of *CO intermediate is positively correlated to highest occupied molecular orbital energies of the ligands. As a result, we enable a tuning of C-C coupling efficiency-a parameter we define to evaluate the efficiency of C2 production-in a broad range of 0.26 to 0.86. This work establishes a molecular platform that allows for studying structure-function relationships in CO2 electrolysis and devises new catalyst design strategies appliable to other electrocatalysis.
Texto completo:
1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
Nat Commun
Asunto de la revista:
BIOLOGIA
/
CIENCIA
Año:
2024
Tipo del documento:
Article
País de afiliación:
Australia