Unlocking Efficient Hydrogen Production: Nucleophilic Oxidation Reactions Coupled with Water Splitting

Electrocatalytic water splitting driven by sustainable energy is a clean and promising water‐chemical fuel conversion technology for the production of high‐purity green hydrogen. However, the sluggish kinetics of anodic oxygen evolution reaction (OER) pose challenges for large‐scale hydrogen production, limiting its efficiency and safety. Recently, the anodic OER has been replaced by a nucleophilic oxidation reaction (NOR) with biomass as the substrate and coupled with a hydrogen evolution reaction (HER), which has attracted great interest. Anode NOR offers faster kinetics, generates high‐value products, and reduces energy consumption. By coupling NOR with hydrogen evolution reaction, hydrogen production efficiency can be enhanced while yielding high‐value oxidation products or degrading pollutants. Therefore, NOR‐coupled HER hydrogen production is another new green electrolytic hydrogen production strategy after electrolytic water hydrogen production, which is of great significance for realizing sustainable energy development and global decarbonization. This review explores the potential of nucleophilic oxidation reactions as an alternative to OER and delves into NOR mechanisms, guiding future research in NOR‐coupled hydrogen production. It assesses different NOR‐coupled production methods, analyzing reaction pathways and catalyst effects. Furthermore, it evaluates the role of electrolyzers in industrialized NOR‐coupled hydrogen production and discusses future prospects and challenges. This comprehensive review aims to advance efficient and economical large‐scale hydrogen production. Nucleophilic oxidation (NOR) has great potential as an alternative to OER. NOR offers faster kinetics, generates high‐value products, and reduces energy consumption. By coupling NOR with hydrogen evolution reaction, hydrogen production efficiency can be enhanced while yielding valuable by‐products or degrading pollutants. Focusing on the reaction mechanisms and reaction paths of different NORs in anodic oxidation reactions. The review is intended to provide theoretical guidance for future research on NOR‐coupled HER hydrogen production.