Understanding how the electrolyte pH affects electrocatalytic activity is a topic of crucial importance in a large variety of systems. However, unraveling the origin of the pH effects is complicated often by the fact that both the reaction driving forces and reactant concentrations in the electric double layer (EDL) change simultaneously with the pH value. Herein, we employ the hydrogen evolution reaction (HER) at Au(111)-aqueous solution interfaces as a model system to disentangle different pH-dependent factors. In 0.1 M NaOH, the HER current density at Au(111) in the potential range of −0.4 V < ERHE < 0 V is up to 60 times smaller than that in 0.1 M HClO4. A reaction model with proper consideration of the local reaction conditions within the EDL is developed. After correcting for the EDL effects, the rate constant for HER is only weakly pH-dependent. Our analysis unambiguously reveals that the observed pH effects are mainly due to the pH-dependent reorganization free energy, which depends on the electrostatic potential and the local reaction conditions within the EDL. Possible origins of the pH and temperature dependence of the activation energy and the electron transfer coefficients are discussed. This work suggests that factors influencing the intrinsic pH-dependent kinetics are easier to understand after proper corrections of EDL effects.

Disentangling Multiple pH-Dependent Factors on the Hydrogen Evolution Reaction at Au(111)