Abstract
Nitrate anion (NO3–) oxidation to nitrate radical (NO3•) is chemically irreversible in acetonitrile (MeCN) solvent due to solvent-based hydrogen-atom transfer (HAT). Introducing benzyl alcohol (PhCH2OH) leads to competition with MeCN for electrochemically generated NO3• and affords benzaldehyde (PhCHO) product with ∼80% faradaic efficiency (FE) in 250 mM PhCH2OH. Stoichiometric HNO3 forms during HAT reactions (observed by UV–vis spectroscopy) and exists as an electrochemically inert and weak electrolyte; this off-cycle form of nitrate can be reintroduced to the catalytic cycle upon deprotonation by 2,6-lutidine while maintaining the base-free FE. Oxygen reduction complements nitrate oxidation during catalysis and reduced oxygen species (ROS) generated during proton-coupled oxygen reduction are identified through rotating ring-disk electrochemistry; proton-coupled oxygen reduction indicates ROS are capable of rendering NO3– catalytic when collocal. Directly observing ROS as the stoichiometric base generated during nitrate anion oxidation resolves differences in photocatalytic vs photoelectrochemical reactivity of NO3– in base-free conditions and points toward HAT as the general mode of reactivity for nitrate radical in acetonitrile solutions.
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