Electronic metal-support interaction modulates Cu electronic structures for CO<sub>2</sub> electroreduction to desired products.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 40000632.
- Also identified by DOI 10.1038/s41467-025-57307-6 and PMC identifier 11861622.
- 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
In this work, the Cu single-atom catalysts (SACs) supported by metal-oxides (Al<sub>2</sub>O<sub>3</sub>-Cu<sub>SAC</sub>, CeO<sub>2</sub>-Cu<sub>SAC</sub>, and TiO<sub>2</sub>-Cu<sub>SAC</sub>) are used as theoretical models to explore the correlations between electronic structures and CO<sub>2</sub>RR performances. For these catalysts, the electronic metal-support interaction (EMSI) induced by charge transfer between Cu sites and supports subtly modulates the Cu electronic structure to form different highest occupied-orbital. The highest occupied 3d<sub>yz</sub> orbital of Al<sub>2</sub>O<sub>3</sub>-Cu<sub>SAC</sub> enhances the adsorption strength of CO and weakens C-O bonds through 3d<sub>yz</sub>-π* electron back-donation. This reduces the energy barrier for C-C coupling, thereby promoting multicarbon formation on Al<sub>2</sub>O<sub>3</sub>-Cu<sub>SAC</sub>. The highest occupied 3d<sub>z2</sub> orbital of TiO<sub>2</sub>-Cu<sub>SAC</sub> accelerates the H<sub>2</sub>O activation, and lowers the reaction energy for forming CH<sub>4</sub>. This over activated H<sub>2</sub>O, in turn, intensifies competing hydrogen evolution reaction (HER), which hinders the high-selectivity production of CH<sub>4</sub> on TiO<sub>2</sub>-Cu<sub>SAC</sub>. CeO<sub>2</sub>-Cu<sub>SAC</sub> with highest occupied 3d<sub>x2-y2</sub> orbital promotes CO<sub>2</sub> activation and its localized electronic state inhibits C-C coupling. The moderate water activity of CeO<sub>2</sub>-Cu<sub>SAC</sub> facilitates *CO deep hydrogenation without excessively activating HER. Hence, CeO<sub>2</sub>-Cu<sub>SAC</sub> exhibits the highest CH<sub>4</sub> Faradaic efficiency of 70.3% at 400 mA cm<sup>-2</sup>.