Impact of Anodic Oxidation Reactions in the Performance Evaluation of High-Rate CO 2 /CO Electrolysis.

The membrane-electrode assembly (MEA) approach appears to be the most promising technique to realize the high-rate CO 2 /CO electrolysis, however there are major challenges related to the crossover of ions and liquid products from cathode to anode via the membrane and the concomitant anodic oxidation reactions (AORs). In this perspective, by combining experimental and theoretical analyses, several impacts of anodic oxidation of liquid products in terms of performance evaluation are investigated. First, the crossover behavior of several typical liquid products through an anion-exchange membrane is analyzed. Subsequently, two instructive examples (introducing formate or ethanol oxidation during electrolysis) reveals that the dynamic change of the anolyte (i.e., pH and composition) not only brings a slight shift of anodic potentials (i.e., change of competing reactions), but also affects the chemical stability of the anode catalyst. Anodic oxidation of liquid products can also cause either over- or under-estimation of the Faradaic efficiency, leading to an inaccurate assessment of overall performance. To comprehensively understand fundamentals of AORs, a theoretical guideline with hierarchical indicators is further developed to predict and regulate the possible AORs in an electrolyzer. The perspective concludes by giving some suggestions on rigorous performance evaluations for high-rate CO 2 /CO electrolysis in an MEA-based setup.