On-Chip in Situ Monitoring of Competitive Interfacial Anionic Chemisorption as a Descriptor for Oxygen Reduction Kinetics

[Image: see text] The development of future sustainable energy technologies relies critically on our understanding of electrocatalytic reactions occurring at the electrode–electrolyte interfaces, and the identification of key reaction promoters and inhibitors. Here we present a systematic in situ nanoelectronic measurement of anionic surface adsorptions (sulfates, halides, and cyanides) on ultrathin platinum nanowires during active electrochemical processes, probing their competitive adsorption behavior with oxygenated species and correlating them to the electrokinetics of the oxygen reduction reaction (ORR). The competitive anionic adsorption features obtained from our studies provide fundamental insight into the surface poisoning of Pt-catalyzed ORR kinetics by various anionic species. Particularly, the unique nanoelectronic approach enables highly sensitive characterization of anionic adsorption and opens an efficient pathway to address the practical poisoning issue (at trace level contaminations) from a fundamental perspective. Through the identified nanoelectronic indicators, we further demonstrate that rationally designed competitive anionic adsorption may provide improved poisoning resistance, leading to performance (activity and lifetime) enhancement of energy conversion devices.