Electrochemical reactions are normally initiated in solution by metal electrodes such as Pt, which are expensive and limited in supply. In this Communication, we demonstrate that an atmospheric-pressure microplasma can act as a gaseous, metal-free electrode to mediate electron-transfer reactions in aqueous solutions. Ferricyanide is reduced to ferrocyanide by plasma electrons, and the reduction rate is found to depend on discharge current. The ability to initiate and control electrochemical reactions at the plasma-liquid interface opens a new direction for electrochemistry based on interactions between gas-phase electrons and ionic solutions.

Plasmas (gas discharges) formed at the surface of liquids can promote a complex mixture of reactions in solution. Here, we decouple two classes of reactions, those initiated by electrons (electrolysis) and those initiated by gaseous neutral species, by examining an atmospheric-pressure microplasma formed in different ambients at the surface of aqueous saline (NaCl) solutions. Electrolytic reactions between plasma electrons and aqueous ions yield an excess of hydroxide ions (OH(-)), making the solution more basic, while reactions between reactive neutral species formed in the plasma phase and the solution lead to nitrous acid (HNO2), nitric acid (HNO3), and hydrogen peroxide (H2O2), making the solution more acidic. The relative importance of either reaction path is quantified by pH measurements, and we find that it depends directly on the composition of the ambient background gas. With a background gas of oxygen or argon, electron transfer reactions yielding excess OH(-) dominate, while HNO2 and HNO3 formed in the plasma and by the dissolution of nitrogen oxide (NOx) species dominate in the case of air and nitrogen. For pure nitrogen (N2) gas, we observe a unique coupling between both reactions, where oxygen (O2) gas formed via water electrolysis reacts in the bulk of the plasma to form NOx, HNO2, and HNO3.

The formation of atmospheric-pressure plasmas with liquid electrodes holds great importance for a number of emerging technologies and applications, yet fundamental questions remain about the nature of the interactions at the plasma/liquid interface. In particular, when the liquid serves as the anode, the plasma supplies gas-phase electrons to the liquid surface, and how these electrons interact with the liquid has not been fully explained. In this work, we present experimental evidence that in the case of water, plasma electrons are involved in electrolytic reactions leading to the conversion of protons (H +) to hydrogen gas. Reactions associated with water electrolysis are indirectly characterized by pH measurements that show qualitatively and quantitatively that the liquid at the plasma interface increases in basicity, consistent with the reduction of protons by plasma electrons. Mass spectrometry measurements confirm the evolution of hydrogen gas, directly providing evidence of water electrolysis. This work highlights the critical role that plasma electrons can play in plasma/liquid interactions with broad implications for any plasma system involving an aqueous electrode, including emerging applications in plasma medicine and plasma-liquid materials synthesis.

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