• • The electric double layer (EDL) extends to the inner Helmholtz plane (IHP), outer Helmholtz plane (OHP), and diffuse layer; reactant adsorption and product desorption occur on the IHP, where surface charge and field intensity changes alter solvent molecule concentration and arrangement in the OHP, directly impacting proton-coupled electron transfer (PCET) kinetics.
• • Alkali metal cations act as homogeneous cocatalysts for the oxygen reduction reaction (ORR) in aqueous electrolytes, as demonstrated by Ji et al. (Nat Catal, 2024, 7: 1330–1338), providing a pathway to enhance ORR activity without noble metals.
• • Interfacial cation enrichment enables carbon- and energy-efficient ethanol electrosynthesis, achieving high selectivity and reduced energy input (Shayesteh Zeraati et al., Nat Synth, 2025, 4: 75–83), which is critical for industrial-scale CO2 conversion.
• • pH effects in a model electrocatalytic reaction were disentangled by Zhu et al. (JACS Au, 2023, 3: 1052–1064), revealing that local pH shifts, not intrinsic kinetics, dominate the bell-shaped vs. volcano-shaped pH-dependent kinetics of formic acid and formate oxidation, with direct implications for catalyst layer design.