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- W2056116934 abstract "Recent studies of anion adsorption on Pt have shown that trifluoromethane sulfonic acid (TFMSA) is a non-adsorbing electrolyte. Previous comparisons of the kinetics of oxygen reduction on Pt in TFMSA to the kinetics in H3PO4 show qualitatively that better kinetics were obtained in TFMSA electrolyte, but these studies were not done in a manner in which the effect of specific adsorption by H2PO4− anion was apparent. The effect is shown directly in this study by adding small aliquots of H3PO4 to 0.1 M TFMSA while determining the oxygen reduction kinetics with a Pt rotating disc electrode. The range of H2PO4− concentrations was varied by nearly four orders of magnitude, from 2.9×10−5 M to 7.3×10−2 M. The H2PO4− had a dramatically negative effect on the kinetics. Based on H2PO4− coverage data reported in the literature, the decrease in rate observed was greater than expected from just a site blocking effect. A small [<1 kCal/mol (4 kJ/mol)] increase in activation energy occurs in addition to the steric effect. Finite rates are observed even at saturation coverage due to either of two possible factors: (i) a close-packed overlayer of very large ions leaves “holes” large enough for oxygen molecule penetration; (ii) coulombic repulsion of like-ions prohibits the formation of a close-packed overlayer. The kinetic effect due to poisoning of the surface by specifically adsorbed H2PO4− anion at saturation coverage is about a factor of 15 relative to the rate in a non-adsorbing electrolyte." @default.
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- W2056116934 date "1983-09-01" @default.
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- W2056116934 title "The effect of H2PO4− anion on the kinetics of oxygen reduction on Pt" @default.
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- W2056116934 doi "https://doi.org/10.1016/s0022-0728(83)80542-7" @default.
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