Multimodal In Situ Characterization Uncovers Unexpected Stability of a Cobalt Electrocatalyst for Acidic Sustainable...

An accelerated development of durable and affordable sustainable energy technologies is often hindered by a limited understanding of how nonprecious materials within these systems degrade. In acidic proton exchange membrane fuel cells and water electrolyzers, metallic cobalt (Co) is considered an unstable component that is often combined with precious metals or other stabilizers. To understand the mechanisms behind Co instability, we employ an experimental platform that quantifies dissolution with on-line inductively coupled plasma mass spectrometry and product formation with electrochemical mass spectrometry during electrochemical testing, along with ex situ characterization. Under varied conditions (electrocatalysis, time, gas-type saturation, and ion concentration), windows of Co stability are observed that are different than predicted with classical chemical thermodynamics, suggesting new stabilization and degradation mechanisms than previously understood. Notably, Co is active for the hydrogen evolution reaction (HER), with prolonged stability that is ∼300 mV greater than thermodynamically projected. Additionally, in an oxygenated environment, Co concurrently performs the HER and the oxygen reduction reaction (ORR) yet undergoes different morphology changes and dissolution mechanisms. Interestingly, at open-circuit voltage, there is a 22× decrease in dissolution in an oxygen-free environment, proposing a route to decrease Co losses during device shutdown protocols. Lastly, under more extreme operating conditions, Co becomes stable after a substantial amount of dissolution, suggesting that high concentrations of Co²⁺ ions in the microenvironment induce the formation of a stable CoHO₂ surface. Altogether, these results can be leveraged to improve the design and development of more robust and cost-effective sustainable energy technologies, as well as promote strategic strategies for prolonged material utilization.