Insight into the Change in Local pH near the Electrode Surface Using Phosphate Species as the Probe

The difference between solution pH and local pH near an electrode surface greatly determines the electrocatalytic performance. However, there is still a lack of a facile and universal method for the local pH detection of various electrode reactions, leaving the origin of local pH changes unclear. Herein, by using phosphate species in phosphate buffer solution (PBS) as the pH probe, we demonstrate a universal local pH detection strategy through in situ Raman spectroscopy for various electrode reactions. Oxygen evolution is chosen as the example to detect the potential-dependent local pH change. Then the strategy extends to nitrate reduction, nitrobenzene reduction, and benzylamine oxidation. By comparing the local pH changes in different reactions, we reveal that the local pH change is strongly dependent on the reaction current, the ability of the system to replenish the local H⁺/OH^–, and the number of H⁺/OH^– per electron transfer of the electrode reaction.