Ligand-tuning copper in coordination polymers for efficient electrochemical C-C coupling.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39060325.
- Also identified by DOI 10.1038/s41467-024-50791-2 and PMC identifier 11282303.
- Licence recorded as CC BY-NC-ND.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
Cu catalyses electrochemical CO<sub>2</sub> 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 C<sub>2</sub> 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 CO<sub>2</sub> electrolysis and devises new catalyst design strategies appliable to other electrocatalysis.