Water Dissociation: A New Dimension for Understanding and Designing Aqueous Electrocatalysts

ABSTRACT Water dissociation plays a central role in key electrocatalytic reactions—including hydrogen evolution, oxygen evolution, CO ₂ reduction, and nitrogen reduction—by serving as the essential proton or hydroxyl source that fundamentally governs reaction pathways and product selectivity. However, its mechanism has long been oversimplified as an isolated chemical step occurring at a single active “dissociation” site, neglecting the profound influence of the interfacial microenvironment between catalyst and electrolyte. Recent advances reveal that water dissociation is dynamically coupled with, and actively reshapes, the interfacial microenvironment, thereby enabling performance breakthroughs across diverse reactions. This review systematically analyzes the multiscale mechanisms underlying this coupling, surveys advanced characterization techniques for probing dynamic interfaces, and discusses rational strategies—including catalyst engineering, molecular modification, and electrolyte design—for actively tuning the microenvironment to accelerate water dissociation and direct reaction pathways. This interfacial‐system perspective offers a transformative framework for designing next‐generation electrocatalysts, with broad implications for sustainable energy technologies such as water electrolyzers, fuel cells, and carbon/nitrogen reduction systems.