Doping Mo Triggers Charge Distribution Optimization and P Vacancy of Ni ₂ P@Ni ₁₂ P ₅ Heterojunction for Industrial Electrocatalytic Production of Adipic Acid and H ₂

Abstract Synchronous electrosynthesis of value‐added adipic acid (AA) and H ₂ is extremely crucial for carbon neutrality. However, accomplishing the preparation of AA and H ₂ at large current density with high selectivity is still challenging. Herein, a robust Mo‐doped Ni ₂ P@Ni ₁₂ P ₅ heterojunction with more P vacancies on Ni foam is proposed for accomplishing simultaneous electrooxidation of cyclohexanol (CHAOR) to AA and hydrogen evolution reaction (HER) at large current density. Combined X‐ray photoelectron spectroscopy, X‐ray absorption fine structure, and electron spin resonance confirm that Mo incorporation induces the charge redistribution of Ni ₂ P@Ni ₁₂ P ₅ , where Mo adjusts electrons from Ni to P, and triggers more P vacancies. Further experimental and theoretical investigations reveal that the d‐band center is upshifted, optimizing adsorption energies of water and hydrogen on electron‐rich P site for boosting HER activity. Besides, more Ni ³⁺ generated from electron‐deficient Ni induced by Mo, alongside more OH* triggered from more P vacancies concurrently promote CHA dehydrogenation and C─C bond cleavage, decreasing energy barrier of CHAOR. Consequently, a two‐electrode flow electrolyzer achieves industrial current density (>230 mA cm ⁻² ) with 85.7% AA yield, 100% Faradaic efficiency of H ₂ production. This study showcases an industrial bifunctional electrocatalyst for AA and H ₂ production with high productivity.