ABSTRACT Coupling methanol electrooxidation with water electrolysis offers a promising alternative to oxygen evolution, significantly reducing energy input while generating value‐added chemicals. In this work, we report a hexagonal NiS electrocatalyst synthesized via a rapid fuel‐assisted redox route, delivering bifunctional activity toward both the methanol electrooxidation reaction (MEOR) and the hydrogen evolution reaction (HER). The NiS/NF electrode achieves a current density of 100 mA cm −2 at only 1.37 V for MEOR in 1 M KOH with methanol, substantially lower than the 1.68 V required for conventional OER, while simultaneously producing formate as a selective anodic product. For HER, NiS/NF requires just 90 mV to reach 100 mA cm −2 , demonstrating excellent hydrogen evolution kinetics. Gas–liquid product analysis confirms high Faradaic efficiencies of 90% for H 2 and 93% for formate. A symmetric NiS||NiS two‐electrode cell delivers 10 mA cm −2 at 1.57 V, which is further reduced to 1.48 V in a single‐stack configuration. Density functional theory (DFT) calculations on the NiS (101) surface reveal Ni sites as the dominant active centers, facilitating a CO‐free reaction pathway toward formate. This study establishes hexagonal NiS as an efficient earth‐abundant catalyst for integrated hydrogen and chemical cogeneration, advancing sustainable electrolysis strategies beyond conventional OER‐limited systems.
H.M et al. (Sun,) studied this question.