Electrochemical characterization and regeneration of sulfur poisoned Pt catalysts in aqueous media

Understanding the poisoning and recovery of precious metal catalysts is greatly relevant for the chemical industry dealing with the synthesis of organic compounds. For example, hydrogenation reactions typically use platinum catalysts and sulfuric acid media, leading to poisoning by sulfur-containing species. In this work, we have applied electrochemical methods to understand the status and recovery of Pt catalysts by studying the electro-oxidation of a family of sulfur-containing species adsorbed at several types of Pt electrodes: (i) polycrystalline Pt foil; (ii) Pt single-crystal electrodes; and (iii) Pt nanoparticles supported on Vulcan carbon. The results obtained from polycrystalline Pt electrodes and Pt nanoparticles supported on Vulcan carbon demonstrate that all sulfur-containing species with different oxidation states (2-, 3+ and 4+) lead to the poisoning of Pt active sites. X-ray photoelectron spectroscopy (XPS) analysis was employed to elucidate the chemical state of sulfur species during the recovery process. The degree of poisoning decreased with increased sulfur oxidation state, while the rate of regeneration of the Pt surfaces generally increases with the oxidation state of the sulfur species. Finally, the use of Pt single-crystal electrodes reveals the surface-structure sensitivity of the oxidation of the sulfur species. This information could be useful in designing catalysts that are less susceptible to poisoning and/or more easily regenerated. These studies demonstrate voltammetry to be a powerful method for assessing the status of platinum surfaces and for recovering catalyst activity, such that electrochemical methods could find applications as sensors in catalysis and for catalyst recovery in-situ.