Electrochemical water splitting represents a highly promising technology for high-purity hydrogen production. By replacing the kinetically sluggish anodic oxygen evolution reaction (OER) with a thermodynamically more favorable oxidation reaction, energy-efficient hydrogen generation can be achieved. This thermodynamic superiority provides the fundamental driving force for energy saving. Significant research efforts have been devoted to designing advanced electrocatalysts for small-molecule oxidation that not only improve reaction kinetics but, more fundamentally, optimize the adsorption free energy of reactive intermediates to minimize the practical overpotential. To gain deeper insights into the current progress and future directions of small-molecule electrochemical oxidation reaction (SMOR) assisted hydrogen production, this review systematically summarizes optimization strategies for electrocatalysts, spanning active sites, electrochemical interfaces, electron transfer pathways and d-band center modulation to maximize their catalytic performance in small-molecule oxidation reactions. Moreover, this review highlights innovative design strategies for high-performance SMOR electrocatalysts, addressing the distinct challenges associated with different reaction systems. It further outlines future research directions for catalyst development and identifies key areas requiring deeper investigation.

Rational design and synthesis of bifunctional oxygen electrocatalysts with high activity and stability are key challenges in the development of rechargeable Zn-air batteries (ZABs). In this paper, tungsten carbide (WC) and Co₇Fe₃ embedded in N,P co-doped hierarchical carbon (WC/Co₇Fe₃-NPHC) was prepared by using zeolite imidazolate frameworks as precursor. Density functional theory demonstrates that the mutual adjustment among the WC, Co₇Fe₃, and N,P co-doped carbon at the three-phase heterojunction interface makes the catalyst possess moderate adsorption strength, and greatly improves the conductivity and electron transfer rate of the catalyst. As a result, the WC/Co₇Fe₃-NPHC exhibits a low overall oxygen redox potential difference of 0.72 V, while the ZAB assembled by WC/Co₇Fe₃-NPHC as an air cathode exhibits ultra-long cycle stability of over 550 h. Futhermore, WC/Co₇Fe₃-NPHC can keep good charge and discharge stability at different bending angles when applied to flexible solid ZAB.