Electronic metal-support interaction modulates Cu electronic structures for CO2 electroreduction to desired products
Yong Zhang, Feifei Chen, Xinyi Yang, Yiran Guo, Xinghua Zhang, Hong Dong, Weihua Wang, Feng Lu, Zunming Lu, Hui Liu, Hui Liu, Yao Xiao, Yahui Cheng
Abstract
In this work, the Cu single-atom catalysts (SACs) supported by metal-oxides (Al2O3-CuSAC, CeO2-CuSAC, and TiO2-CuSAC) are used as theoretical models to explore the correlations between electronic structures and CO2RR 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 3dyz orbital of Al2O3-CuSAC enhances the adsorption strength of CO and weakens C-O bonds through 3dyz-π* electron back-donation. This reduces the energy barrier for C-C coupling, thereby promoting multicarbon formation on Al2O3-CuSAC. The highest occupied 3dz2 orbital of TiO2-CuSAC accelerates the H2O activation, and lowers the reaction energy for forming CH4. This over activated H2O, in turn, intensifies competing hydrogen evolution reaction (HER), which hinders the high-selectivity production of CH4 on TiO2-CuSAC. CeO2-CuSAC with highest occupied 3dx2-y2 orbital promotes CO2 activation and its localized electronic state inhibits C-C coupling. The moderate water activity of CeO2-CuSAC facilitates *CO deep hydrogenation without excessively activating HER. Hence, CeO2-CuSAC exhibits the highest CH4 Faradaic efficiency of 70.3% at 400 mA cm−2. Rational regulation of electronic structures to control CO2 electroreduction pathways is challenging. Here, the authors report modulating the highest occupied orbital of Cu single-sites via electronic metal-support interaction, enabling switchable selectivity between multicarbons and methane.