Enhanced CO monolayer electro-oxidation reaction on sulfide-adsorbed Pt nanoparticles: A combined electrochemical and in situ ATR-SEIRAS spectroscopic study

The influence of adsorbed sulfide (S2−ads) on CO monolayer electro-oxidation reaction (CMOR with M for monolayer to emphasize that oxidation always starts with a saturated CO coverage) on carbon-supported Pt nanoparticles (Pt/C NPs) was investigated using electrochemical and in situ ATR-SEIRAS (attenuated total reflection-surface enhanced IR absorption spectroscopy) techniques. An enhanced kinetics of CMOR on the S2−ads-Pt/C was observed by potentiodynamic CO stripping and potentiostatic CO oxidation analyses. Electrochemical impedance measurements revealed a weakened bonding of oxygen-containing species with the S2−ads-Pt/C surface as compared with the clean Pt/C surface, which we believe was the main reason for the observed enhanced CMOR by the S2−ads. The in situ SEIRAS data showed the existence of both linear- and bridge-bonded CO (COL and COB respectively) in all samples and that the sulfide adsorption increased substantially the fraction of the former on the available Pt sites and facilitated the conversion between them. Our results also indicate that the frequently observed pre-CMOR current arises most likely from oxidation of weakly-bonded CO rather than from reactions taking place at defect sites.

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► Activity enhancement on CO monolayer electro-oxidation reaction (CMOR) by adsorbed sulfide was observed.
► Weakened PtOHads bonding interaction by adsorbed sulfide bears major responsibility for the enhanced CMOR.
► Weakly-bonded CO was identified as being responsible for the ubiquitously observed pre-CMOR currents.