Online Monitoring of Electrochemical Carbon Corrosion in Alkaline Electrolytes by Differential Electrochemical Mass Spectrometry

Abstract Carbon corrosion at high anodic potentials is a major source of instability, especially in acidic electrolytes and impairs the long‐term functionality of electrodes. In‐depth investigation of carbon corrosion in alkaline environment by means of differential electrochemical mass spectrometry (DEMS) is prevented by the conversion of CO 2 into CO 3 2− . We report the adaptation of a DEMS system for online CO 2 detection as the product of carbon corrosion in alkaline electrolytes. A new cell design allows for in situ acidification of the electrolyte to release initially dissolved CO 3 2− as CO 2 in front of the DEMS membrane and its subsequent detection by mass spectrometry. DEMS studies of a carbon‐supported nickel boride (Ni x B/C) catalyst and Vulcan XC 72 at high anodic potentials suggest protection of carbon in the presence of highly active oxygen evolution electrocatalysts. Most importantly, carbon corrosion is decreased in alkaline solution.