p–d Orbital Hybridization Induced by p‑Block Metal-Doped Cu Promotes the Formation of C₂₊ Products in Ampere-Level CO₂ Electroreduction

Large-current electrolysis of CO₂ to multi-carbon (C₂₊) products is critical to realize the industrial application of CO₂ conversion. However, the poor binding strength of *CO intermediates on the catalyst surface induces multiple competing pathways, which hinder the C₂₊ production. Herein, we report that p–d orbital hybridization induced by Ga-doped Cu (CuGa) could promote efficient CO₂ electrocatalysis to C₂₊ products at ampere-level current density. It was found that CuGa exhibited the highest C₂₊ productivity with a remarkable Faradaic 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 V versus reversible hydrogen electrode. At 1.1 A/cm², the catalyst still maintained a high C₂₊ 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 CO₂ electroreduction for C₂₊ production. As far as we know, this is the first work to promote electrochemical CO₂ reduction reaction to generate the C₂₊ product by p–d orbital hybridization interaction using a p-block metal-doped Cu catalyst.