pH Variation in the Acidic Electrochemical CO2 Reduction Process

To address the carbonate problem in the alkaline electrochemical CO2 reduction reaction (CO2RR), more attention has been paid to the CO2RR conducted in acidic electrolytes. The pH stability of such an acidic electrolyte is vital to make sure that the conclusion made in the so-called acidic CO2RR is reliable. Herein, based on reported model electrocatalysts for acidic CO2RR, by monitoring the varying of pH and alkali cation (K+) concentration along with the CO2RR performance in initially acidic electrolyte solution (K2SO4 with pH = 3.5), we unveil their remarkable CO2RR performance along with the rapid pH increase up to 9.5 in the cathode chamber and decrease down to 2.4 in the anode chamber due to the diffusion of K+ along with protons through the proton exchange membrane from the anode to the cathode chamber. We further reveal the rapid collapse of their CO2RR performance in a constant acid solution. This means that some previously reported "remarkable acidic CO2RR performances" actually originate from the alkaline rather than acidic electrolyte, and the conclusions made in such work need to be reconsidered. We also summarize the actual relationship between the CO2RR performance and catholyte pH in widely used Bi- and Sn-based catalysts. This work provides deeper insights into the stability of acidity and the pH effect on electrocatalysts for the CO2RR.