Self‐Supported Bimetallic Nickel Catalyst for High‐Efficiency Urea Electrocatalytic Oxidation

Abstract The electrocatalytic oxidation of urea (UOR) at near‐theoretical potentials presents a promising approach for efficient urea energy conversion. A critical challenge lies in enhancing the compatibility between the active sites and the multiple intermediates of UOR to accelerate urea dehydrogenation kinetics, thereby overcoming the high overpotential barrier of urea oxidation. Herein, we propose a strategy to enhance d–p orbital hybridization via bimetallic doping and develop a silver/cobalt (ACO/NS) co‐doped nickel sulfide‐based self‐supporting composite catalyst. The synergistic interaction between the bimetallic oxide and nickel sulfide heterojunction regulates d–p orbital hybridization, redistributes charge, and optimizes the adaptability of the Ni site energy levels to better match urea and various intermediates. This promotes efficient electron coupling and dehydrogenation processes with OH⁻. Experimental results demonstrate that ACO/NS exhibits outstanding urea oxidation activity, achieving a current density of 10 mA cm −2 at a potential of 1.04 V (versus RHE) and maintaining stable activity over 168 h. Theoretical analysis combined with experimental findings reveals a microscopic reaction mechanism at low potentials: the enhanced d–p hybridization induced by bimetallic doping modulates the adsorption strength of OH* and urea, thereby accelerating the dehydrogenation kinetics of urea oxidation. This work highlights the feasibility of achieving near‐theoretical potential urea oxidation through the systematic modulation and optimization of catalysts, providing valuable insights for the development of high‐performance catalytic systems.