p–d Orbital Hybridization Induced by p-Block Metal-Doped Cu Promotes the Formation of C<sub>2+</sub> Products in Ampere-Level CO<sub>2</sub> Electroreduction
Pengsong Li, Jiahui Bi, Jiyuan Liu, Yong Wang, Xinchen Kang, Xiaofu Sun, Jianling Zhang, Zhimin Liu, Qinggong Zhu, Buxing Han
Abstract
Large-current electrolysis of CO 2 to multi-carbon (C 2+ ) products is critical to realize the industrial application of CO 2 conversion. However, the poor binding strength of *CO intermediates on the catalyst surface induces multiple competing pathways, which hinder the C 2+ production. Herein, we report that p–d orbital hybridization induced by Ga-doped Cu (CuGa) could promote efficient CO 2 electrocatalysis to C 2+ products at ampere-level current density. It was found that CuGa exhibited the highest C 2+ productivity with a remarkable Faradaic efficiency (FE) of 81.5% at a current density of 0.9 A/cm 2, and the potential at such a high current density was −1.07 V versus reversible hydrogen electrode. At 1.1 A/cm 2, the catalyst still maintained a high C 2+ productivity with an FE of 76.9%. Experimental and theoretical studies indicated that the excellent performance of CuGa results from the p–d hybridization of Cu and Ga, which not only enriches reactive sites but also enhances the binding strength of the *CO intermediate and facilitates C–C coupling. The p–d hybridization strategy can be extended to other p-block metal-doped Cu catalysts, such as CuAl and CuGe, to boost CO 2 electroreduction for C 2+ production. As far as we know, this is the first work to promote electrochemical CO 2 reduction reaction to generate the C 2+ product by p–d orbital hybridization interaction using a p-block metal-doped Cu catalyst.