p–d Orbital\nHybridization Induced by p‑Block\nMetal-Doped Cu Promotes the Formation of C2+ Products in\nAmpere-Level CO2 Electroreduction

Large-current electrolysis of CO2 to multi-carbon\n(C2+) products is critical to realize the industrial application\nof CO2 conversion. However, the poor binding strength of\n*CO intermediates on the catalyst surface induces multiple competing\npathways, which hinder the C2+ production. Herein, we report\nthat p–d orbital hybridization induced by Ga-doped Cu (CuGa)\ncould promote efficient CO2 electrocatalysis to C2+ products at ampere-level current density. It was found that CuGa\nexhibited the highest C2+ productivity with a remarkable\nFaradaic efficiency (FE) of 81.5% at a current density of 0.9 A/cm2, and the potential at such a high current density was −1.07\nV versus reversible hydrogen electrode. At 1.1 A/cm2, the\ncatalyst still maintained a high C2+ productivity with\nan FE of 76.9%. Experimental and theoretical studies indicated that\nthe excellent performance of CuGa results from the p–d hybridization\nof Cu and Ga, which not only enriches reactive sites but also enhances\nthe binding strength of the *CO intermediate and facilitates C–C\ncoupling. The p–d hybridization strategy can be extended to\nother p-block metal-doped Cu catalysts, such as CuAl and CuGe, to\nboost CO2 electroreduction for C2+ production.\nAs far as we know, this is the first work to promote electrochemical\nCO2 reduction reaction to generate the C2+ product\nby p–d orbital hybridization interaction using a p-block metal-doped\nCu catalyst.