Journal
ANALYTICAL CHEMISTRY
Volume 86, Issue 21, Pages 10917-10924Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ac503176d
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Funding
- National Science Foundation [CHE-1214151]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1214151] Funding Source: National Science Foundation
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Glassy carbon (GC) electrodes are well-known to contain oxygenated functional groups such as phenols, carbonyls, and carboxylic acids on their surface. The effects of these groups on voltammetry in aqueous solution are well-studied, but there has been little discussion of their possible effects in nonaqueous solution. In this study, we show that the acidic functional groups, particularly phenols, are likely causes of anomalous features often seen in the voltammetry of quinones in nonaqueous solution. These features, a too small second cyclic voltammetric wave and extra current between the two waves that sometimes appears to be a small, broad third voltammetric wave, have previously been attributed to different types of dimerization. In this work, concentration-dependent voltammetry in acetonitrile rules out dimerization with a series of alkyl-benzoquinones because the anomalous features get larger as the concentration decreases. At low concentrations, solution bimolecular reactions will be relatively less important than reactions with surface groups. Addition of substoichiometric amounts of naphthol at higher quinone concentrations produces almost identical behavior as seen at low quinone concentrations with no added naphthol. This implicates hydrogen bonding and proton transfer from the surface phenolic groups as the cause of the anomalous features in quinone voltammetry at GC electrodes. This conclusion is supported by the perturbation of surface oxide coverage on GC electrodes through different electrode pretreatments.
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