Optical and Chemical Measurements of Solvated Electrons Produced in Plasma Electrolysis with a Water Cathode.

It is known that glow discharges with a water anode inject and form solvated electrons at the plasma-liquid interface, driving a wide variety of reduction reactions. However, in systems with a water cathode, the production and role of solvated electrons are less clear. Here, we present evidence for the direct detection of solvated electrons produced at the interface of an argon plasma and a water cathode via absorption spectroscopy. We further quantify their yield using the dissociative electron attachment of chloroacetate, measuring a yield of 1.04 ± 0.59 electrons per incident ion, corresponding to approximately 100% faradaic efficiency. Additionally, we estimate a yield of 2.09 ± 0.93 hydroxyl radicals per incident ion. Comparison of this yield with other findings in the literature supports that these hydroxyl radicals are likely formed directly in the liquid phase rather than by diffusion from the vapor phase.

Chemical Analysis of Secondary Electron Emission from a Water Cathode at the Interface with a Nonthermal Plasma.

When a nonthermal plasma and a liquid form part of the same circuit, the liquid may function as a cathode, in which case electrons are emitted from the liquid into the gas to sustain the plasma. As opposed to solid electrodes, the mechanism of this emission has not been established for a liquid, even though various theories have attempted to explain it via chemical processes in the liquid phase. In this work, we tested the effects of the interfacial chemistry on electron emission from water, including the role of pH as well as the hydroxyl radical, the hydrogen atom, the solvated electron, and the presolvated electron; it was found that none of these species are critical to sustain the plasma. We propose an emission mechanism where electrons, generated from ionized water molecules in the uppermost monolayers of solution, are emitted into the plasma directly from the conduction band of the water.

Total Internal Reflection Absorption Spectroscopy (TIRAS) for the Detection of Solvated Electrons at a Plasma-liquid Interface.

The total internal reflection absorption spectroscopy (TIRAS) method presented in this article uses an inexpensive diode laser to detect solvated electrons produced by a low-temperature plasma in contact with an aqueous solution. Solvated electrons are powerful reducing agents, and it has been postulated that they play an important role in the interfacial chemistry between a gaseous plasma or discharge and a conductive liquid. However, due to the high local concentrations of reactive species at the interface, they have a short average lifetime (~1 µs), which makes them extremely difficult to detect. The TIRAS technique uses a unique total internal reflection geometry combined with amplitude-modulated lock-in amplification to distinguish solvated electrons' absorbance signal from other spurious noise sources. This enables the in situ detection of short-lived intermediates in the interfacial region, as opposed to the bulk measurement of stable products in the solution. This approach is especially attractive for the field of plasma electrochemistry, where much of the important chemistry is driven by short-lived free radicals. This experimental method has been used to analyze the reduction of nitrite (NO2-(aq)), nitrate (NO3-(aq)), hydrogen peroxide (H2O2(aq)), and dissolved carbon dioxide (CO2(aq)) by plasma-solvated electrons and deduce effective rate constants. Limitations of the method may arise in the presence of unintended parallel reactions, such as air contamination in the plasma, and absorbance measurements may also be hindered by the precipitation of reduced electrochemical products. Overall, the TIRAS method can be a powerful tool for studying the plasma-liquid interface, but its effectiveness depends on the particular system and reaction chemistry under study.

Electrostatic Debye layer formed at a plasma-liquid interface.

We construct an analytic model for the electrostatic Debye layer formed at a plasma-liquid interface by combining the Gouy-Chapman theory for the liquid with a simple parabolic band model for the plasma sheath. The model predicts a nonlinear scaling between the plasma current density and the solution ionic strength, and we confirmed this behavior with measurements using a liquid-anode plasma. Plots of the measured current density as a function of ionic strength collapse the data and curve fits yield a plasma electron density of ∼10^{19}m^{-3} and an electric field of ∼10^{4}V/m on the liquid side of the interface. Because our theory is based firmly on fundamental physics, we believe it can be widely applied to many emerging technologies involving the interaction of low-temperature, nonequilibrium plasma with aqueous media, including plasma medicine and various plasma chemical synthesis techniques.

The solvation of electrons by an atmospheric-pressure plasma.

Solvated electrons are typically generated by radiolysis or photoionization of solutes. While plasmas containing free electrons have been brought into contact with liquids in studies dating back centuries, there has been little evidence that electrons are solvated by this approach. Here we report direct measurements of solvated electrons generated by an atmospheric-pressure plasma in contact with the surface of an aqueous solution. The electrons are measured by their optical absorbance using a total internal reflection geometry. The measured absorption spectrum is unexpectedly blue shifted, which is potentially due to the intense electric field in the interfacial Debye layer. We estimate an average penetration depth of 2.5 ± 1.0 nm, indicating that the electrons fully solvate before reacting through second-order recombination. Reactions with various electron scavengers including H(+), NO2(-), NO3(-) and H2O2 show that the kinetics are similar, but not identical, to those for solvated electrons formed in bulk water by radiolysis.

Decoupling interfacial reactions between plasmas and liquids: charge transfer vs plasma neutral reactions.

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.