Zhicheng Wei, Obeylaw Moyo, Jiaqiao Yang, Yu Zhang, J Zhang, Hainan Sun
ABSTRACT Hydrogen is emerging as a crucial clean energy carrier, but its large‐scale production through conventional water electrolysis is limited by the high overpotential and sluggish kinetics of the anodic oxygen evolution reaction (OER). Small‐molecule oxidation reactions provide attractive alternative anodic pathways, enabling lower cell voltages while simultaneously co‐producing value‐added chemicals. The effectiveness of such systems strongly depends on catalyst design, particularly strategies that minimize noble‐metal usage while maintaining high catalytic activity and durability. This review highlights recent advances in transition‐metal‐based catalysts promoted by low‐loading noble metals (e.g., Pt, Pd, Ru, and Ir) for small‐molecule‐oxidation‐assisted hydrogen production. Special emphasis is placed on the underlying promotion mechanisms, including electronic modulation of the d‐band center, geometric effects that generate highly active sites, and synergistic stabilization against dissolution and oxidation. Key design strategies, such as alloying and doping, single‐atom or cluster incorporation, surface functionalization, heterointerface engineering, and in situ catalyst reconstruction, are systematically discussed. Insights from advanced in situ/operando characterization techniques and theoretical calculations are integrated to clarify structure‐activity relationships and catalytic mechanisms. Finally, current challenges and future perspectives are outlined to guide the development of efficient, durable, and cost‐effective catalysts for sustainable hydrogen production.