Ligand‐Hybridization Engineering Enabling Stable Cu δ + for Durable CO 2 Electroreduction to C 2+ Products

Abstract Electrocatalytic carbon dioxide reduction reaction (CO 2 RR) offers a sustainable route to convert CO 2 into value‐added multi‐carbon (C 2+ ) chemicals using renewable electricity. Copper (Cu) is considered as the promising catalyst for generating C 2+ products, but suffers from low Faradaic efficiency (FE) and poor stability. Herein, a ligand‐hybridization strategy on Cu 2 (OH) 3 NO 3 (CuON) to precisely regulate the coordination environment of Cu sites by partially substituting hydroxyl or nitrate with acetate ligands is demonstrated. The ligand hybridization facilitates the electron delocalization across Cu sites and the coordinated acetate ligands, and induces the formation and stabilization of active Cu δ + species, thereby boosting efficient and stable C‐C coupling for selective C 2+ production. Impressively, acetate‐hybridized CuON catalyst (AH‐CuON) exhibits superior FE up to 74.7% at a high current density of 400 mA cm −2 toward C 2+ products, while maintaining stability for 20 h toward CO 2 RR. Significantly, this study offers a new strategy for designing highly efficient and stable Cu‐based CO 2 RR catalysts toward C 2+ products.