Dual Regulation of Interfacial OH − Enrichment and d ‐Orbital Engineering in S‐Doped Ni(OH) 2 for Enhanced Electrocatalytic Methanol Oxidation to Formate

The electrocatalytic methanol (MeOH) selective oxidation reaction (MSOR) offers a promising strategy for H 2 production and value‐added chemical synthesis, yet its efficiency is often limited by insufficient interfacial OH − supply and competing oxygen evolution reaction (OER) at Ni‐based electrocatalysts. Herein, we demonstrate that S incorporation into nickel hydroxide (Ni(OH)S) simultaneously regulates the interfacial reaction environment and the electronic structure of Ni active sites, thereby accelerating the turnover of NiOOH during MeOH electrooxidation. Experimental and theoretical calculations reveal that S doping strengthens interfacial OH − enrichment, which facilitates the rapid electrochemical reconstruction of Ni(OH) 2 into NiOOH under anodic polarization. More importantly, the modified electronic configuration promotes the subsequent chemical reaction between NiOOH and MeOH, preventing excessive NiOOH accumulation and suppressing the competing OER. The resulting Ni(OH)S electrocatalyst achieves 100 mA·cm −2 at only 1.40 V and maintains >90 % Faradaic efficiency of formate over a broad potential window (1.40–1.80 V) with long‐term stability exceeding 60 h. This work demonstrates an effective strategy to simultaneously enhance interfacial OH − availability and mitigate competitive OER in Ni‐based MSOR electrocatalysts.