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• W2323168422 abstract "The mechanism by which pyridinium (pyrH+) is reduced at a Pt electrode is a matter of recent controversy. The quasireversible cyclic voltammetric wave observed at −0.58 V vs SCE at a Pt electrode was originally proposed to correspond to reduction of pyrH+ to pyridinyl radical (pyrH•). This mechanistic explanation for the observed electrochemistry seems unlikely in light of recent quantum mechanical calculations that predict a very negative reduction potential (−1.37 V vs SCE) for the formation of pyrH•. Several other mechanisms have been proposed to account for the discrepancy in calculated and observed reduction potentials, including surface adsorption of pyrH•, reduction of pyrH+ by two electrons rather than one, and reduction of the pyrH+ proton to a surface hydride rather than a π-based radical product. This final mechanism, which can be described as inner-sphere reduction of pyrH+ to form a surface hydride, is consistent with experimental observations." @default.
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• W2323168422 date "2013-09-17" @default.
• W2323168422 modified "2023-09-26" @default.
• W2323168422 title "Electrochemistry of Aqueous Pyridinium: Exploration of a Key Aspect of Electrocatalytic Reduction of CO₂ to Methanol" @default.
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• W2323168422 doi "https://doi.org/10.1021/ja4064052" @default.
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