Spontaneous Neutral‐pH Organic Oxidation on Trivalent Nickel Enables Spatially Separated H2 and Organic Products

Water electrolysis faces critical efficiency and cost challenges, primarily due to the high energy demand and low economic value of the oxygen evolution reaction (OER). To overcome this limitation, we introduce an innovative electrochemical-chemical sequential strategy that replaces OER with methanol oxidation (MOR). Our decoupled process comprises cathodic hydrogen evolution reaction (HER) paired with anodic Ni(OH)₂ oxidation to NiOOH in 1 M KOH electrolyte, followed by spontaneous NiOOH reduction via MOR, selectively generating formic acid (HCOOH) with 95% formic acid Faraday efficiency in neutral electrolyte. Crucially, we developed a scalable bottom-up method to electrochemically prepare the active NiOOH catalyst directly from Ni(OH)₂ particles. This catalyst achieved a HCOOH yield of 48.25 mmol per kg catalyst. Collectively, this strategy establishes an efficient and recyclable pathway for alkaline hydrogen production integrated with high-value formic acid synthesis in neutral media.