Dimethylsulfoxide as a modifier of platinum electrocatalytic activity toward oxygen reduction reaction in aqueous solutions: Combined theoretical and experimental study

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• 作者：Vladimir Tanaskovi膰 ; Igor A. Pa拧ti ; Nemanja Gavrilov ; Slavko V. Mentus
• 关键词：Adsorption ; Dimethylsulfoxide ; Oxygen reduction reaction ; Polycrystalline platinum ; Voltammetry
• 刊名：Journal of Electroanalytical Chemistry
• 出版年：1 February, 2014
• 年：2014
• 卷：714-715
• 期：Complete
• 页码：11-18
• 全文大小：2102 K

文摘

By both density functional theory calculations (DFT) and voltammetry on rotating polycrystalline platinum disc, dimethylsulfoxide (DMSO) was investigated as a modifier of platinum electrocatalytic activity toward oxygen reduction reaction in aqueous solutions. The DFT calculations evidenced that DMSO molecule interacts with Pt surface most strongly by the mediation of S atom in SO group, and the modification of the surface electronic structure of Pt is restricted to the Pt atom contacting directly with the S atom. The calculated adsorption energy on Pt surface (Pt(1 0 0)) amounted to 鈭?08 kJ mol^鈭?. The voltammetry with polycrystalline Pt disk electrode in mixed H2O-DMSO solutions supported by 0.1 mol dm^鈭? H₂SO₄ pointed out that DMSO adsorption suppressed oxide formation on Pt surface. In O₂-saturated solutions, in presence of 1 vol.% of DMSO, it was found that the rate of oxygen reduction reaction (ORR) was higher in comparison to the one measured in DMSO-free solution. It was also confirmed that adsorption of DMSO suppressed ethanol oxidation reaction in the entire potential window where ORR takes place.