Mechanistic Insights Into Interfacial Hydrogen Bond Network‐Mediated Mass Transport for Aqueous Electrocatalysis

ABSTRACT The synergistic design combining thermodynamic and kinetic factors is critical for breaking bottlenecks in achieving both high efficiency and selectivity in electrocatalytic reactions. However, hindered by characterization limits, the interfacial supply and migration of reactants and products kinetically promoted by the interfacial hydrogen bond network are usually neglected. Owing to recent technological breakthroughs, there are significant progress in hydrogen‐bond‐network‐regulated electrocatalysis, heralding a new era of hydrogen‐bond‐directed electrocatalysis. This review first presents the fundamentals of interfacial hydrogen bond networks with an emphasis on the Grotthuss mechanism for proton (H + ) /hydroxide (OH − ) transfer and water (H 2 O) supply. Then it elucidates mass transport mechanisms of key species directly involved in the rate‐determining steps of many vital reactions through a hydrogen bond network. The key factors governing the efficient regulation of hydrogen bond networks, such as electronic structure, surface functionalization, and electrolyte composition, have been systematically sorted out for electrocatalytic reactions including the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), carbon dioxide reduction reaction (CO 2 RR), and nitrate reduction reaction (NO 3 − RR). Finally, future research focused on modulating interfacial hydrogen bond network under industrial operating conditions are outlooked, aiming to advance the field of aqueous electrocatalysis for a sustainable future driven by renewable‐energy‐driven green resource cycling.