The highly efficient and stable electrolysis needs the rational control of the catalytically active interface during the reactions. Here we report a new operando surface restructuring pathway activated by pairing catalyst and electrolyte ions. Using SrCoO_3-δ-based perovskites as model catalysts, we unveil the critical role of matching the catalyst properties with the electrolyte conditions in modulating catalyst ion leaching and steering surface restructuring processes toward efficient oxygen evolution reaction catalysis in both pH-neutral and alkaline electrolytes. Our results regarding multiple perovskites show that the catalyst ion leaching is controlled by catalyst ion solubility and anions of the electrolyte. Only when the electrolyte cations are smaller than catalyst's leaching cations, the formation of an outer amorphous shell can be triggered via backfilling electrolyte cations into the cationic vacancy at the catalyst surface under electrochemical polarization. Consequently, the current density of reconstructed SrCoO_3-δ is increased by 21 folds compared to the pristine SrCoO_3-δ at 1.75 V vs reversible hydrogen electrode and outperforms the benchmark IrO₂ by 2.1 folds and most state-of-the-art electrocatalysts in the pH-neutral electrolyte. Our work could be a starting point to rationally control the electrocatalyst surface restructuring via matching the compositional chemistry of the catalyst with the electrolyte properties.

Understanding the relationship between gas diffusion electrode (GDE) structures and the performance of electrochemical CO₂ reduction reaction (CO₂RR) is crucial to developing industrial-scale technologies to convert CO₂ to valuable products. We studied how the microporous layer (MPL) on GDE's coated with silver nanoparticle catalysts affects the electrochemical CO₂ conversion to CO in a flow cell electrolyser. We demonstrate a convenient method to measure the rate of catholyte seepage through a GDE during CO₂RR experiments and used this method to show how the MPL thickness affects flooding of the GDE. We found the GDE with the thickest MPL (39BB) had the best selectivity for CO and stability at current densities above 100 mA cm⁻² as the thick MPL minimized flooding. However, at low current densities the 39BB electrode achieved a lower CO selectivity than the GDE with thinner MPL. These results suggest opportunities to improve CO₂ electrolyser performances at high current by optimisation of the MPL structure and wettability.