Ligand-tuning copper in coordination polymers for efficient electrochemical C–C coupling.

Autor: Yang, Yu, Zhang, Cheng, Zhang, Chengyi, Shi, Yaohui, Li, Jun, Johannessen, Bernt, Liang, Yongxiang, Zhang, Shuzhen, Song, Qiang, Zhang, Haowei, Huang, Jialei, Ke, Jingwen, Zhang, Lei, Song, Qingqing, Zeng, Jianrong, Zhang, Ying, Geng, Zhigang, Wang, Pu-Sheng, Wang, Ziyun, Zeng, Jie
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Zdroj: Nature Communications; 7/26/2024, Vol. 15 Issue 1, p1-11, 11p
Abstrakt: 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. Understanding the structure-function relationship in Cu-catalyzed CO2 reduction is challenging due to dynamic active sites. This study introduces stable coordination polymer catalysts with homogenized, single-site Cu, enabling the study and tuning of C–C coupling efficiency in CO2 electroreduction. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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