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

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• 作者：In-Su Park^a ; ^b ; De-Jun Chen^a ; Dianne O. Atienza^a ; YuYe J. Tong^a ; ^{yyt@georgetown.edu}
• 关键词：Adsorbed sulfide S2&minus ; CO monolayer electro-oxidation reaction (CMOR) ; Carbon-supported Pt nanoparticles ; ATR-SEIRAS ; Electrochemical impedance analysis
• 刊名：Catalysis Today
• 出版年：2013
• 出版时间：15 March, 2013
• 年：2013
• 卷：202
• 期：Complete
• 页码：175-182
• 全文大小：1598 K

文摘

The influence of adsorbed sulfide (S^2?_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 S^2?_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 S^2?_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 S^2?_ads. The in situ SEIRAS data showed the existence of both linear- and bridge-bonded CO (CO_L and CO_B 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.