Impact of solute concentration on the electrocatalytic conversion of dissolved gases in buffered solutions

To maintain local pH levels near the electrode during electrochemical reactions, the use of buffer solutions is effective. Nevertheless, the critical effects of the buffer concentration on electrocatalytic performances have not been discussed in detail. In this study, two fundamental electrochemical reactions, oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR), on a platinum rotating disk electrode are chosen as model gas-related aqueous electrochemical reactions at various phosphate concentrations. Our detailed investigations revealed that the kinetic and limiting diffusion current densities for both the ORR and HOR logarithmically decrease with increasing solute concentration (log|jORR|=−0.39c+0.92,log|jHOR|=−0.35c+0.73). To clarify the physical aspects of this phenomenon, the electrolyte characteristics are addressed: with increasing phosphate concentration, the gas solubility decrease, the kinematic viscosity of the solution increase and the diffusion coefficient of the dissolved gases decrease. The simulated limiting diffusion currents using the aforementioned parameters match the measured ones very well (log|jORR|=−0.43c+0.99,log|jHOR|=−0.40c+0.54), accurately describing the consequences of the electrolyte concentration. These alterations of the electrolyte properties associated with the solute concentration are universally applicable to other aqueous gas-related electrochemical reactions because the currents are purely determined by mass transfer of the dissolved gases.