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

By Tanasković, Vladimir; Pašti, Igor A.; Gavrilov, Nemanja & Mentus, Slavko V.
Published in Journal of Electroanalytical Chemistry NULL 2014

Abstract

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 -108 kJ mol-1. The voltammetry with polycrystalline Pt disk electrode in mixed H2O-DMSO solutions supported by 0.1 mol dm-3 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.

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