Unraveling the Mechanism of Water-Mediated Sulfur Tolerance via Operando Surface-Enhanced Raman Spectroscopy

While several proton-conducting anode materials have shown excellent tolerance to sulfur poisoning, the mechanism is still unclear due largely to the inability to probe miniscule amounts of sulfur-containing species using conventional surface characterization techniques. Here we present our findings in unraveling the mechanism of water-mediated sulfur tolerance of a proton conductor under operating conditions empowered by surface-sensitive, operando surface-enhanced Raman spectroscopy (SERS) coupled with impedance spectroscopy. Contrary to the conventional view that surface-adsorbed sulfur is removed mainly by oxygen anions, it is found that −SO4 groups on the surface of the proton conductor are converted to SO2 by a water-mediated process, as confirmed by operando SERS analysis and density functional theory (DFT)-based calculations. The combination of operando SERS performed on a model electrode and theoretical computation offers an effective approach to investigate into complex mechanisms of electrode p...