For the synthesis of metal nanoparticles in aqueous solution, we propose dual plasma electrolysis, which consists of a Hoffman electrolysis apparatus with two atmospheric glow discharge plasmas as electrodes instead of conventional metal electrodes immersed in a liquid. The plasma anode irradiates positive ions to the solution surface while the plasma cathode irradiates electrons to the solution surface. The dual plasma electrolysis system enables us to simultaneously investigate the influence of electron and positive ion irradiation to a solution surface on metal nanoparticle generation at the same current. In this work, we used aqueous solutions of AgNO3, HAuCl4, and their mixture. In dual plasma electrolysis with AgNO3, Ag nanoparticles were only synthesized on the plasma cathode side. This means that Ag nanoparticles are generated via the reduction of Ag+ by electrons. With HAuCl4 solution, Au nanoparticles were synthesized on both the plasma anode and plasma cathode sides. Ion irradiation with the plasma anode is more effective than electron irradiation for Au nanoparticle synthesis. This finding suggests that positive ions from the plasma trigger the dissociative reaction of AuCl4 − at the plasma–liquid interface. When a AgNO3–HAuCl4 mixture was used, the synthesized nanoparticles have a structure consisting of a Au core covered with a Ag shell.

We experimentally investigated some of the initial reactions in a liquid induced by electron or positive-ion irradiation from an atmospheric-pressure dc glow discharge in contact with the liquid. Aqueous solutions of NaCl, AgNO 3 , and HAuCl 4 are used as the electrolyte. We measured the pH and conductivity in the liquid at approximately 1 cm below the solution surfaces. OH radical generation in the liquid was observed by a chemical probe method. Experimental results showed that electron irradiation of the liquid surface generates OH % in water and that positive-ion irradiation of the liquid surface generates H + in water even without the dissolution of gas-phase nitrogen oxide. A possible reaction process is qualitatively discussed. In particular, the contribution of charge transfer collision between impinging low-energy positive ions and water molecules to the ionic species in the liquid is used to explain the overall tendency of the experimental results.

Self-organized luminous pattern formation is observed in the liquid surface of an atmospheric dc glow discharge using a liquid electrode with a miniature helium flow. The factors affecting pattern formation are the gap length, discharge current, helium mass flow rate and polarity. The pattern shape depends on the conductivity and temperature of the liquid electrode. A variety of patterns were observed by changing the conductivity and temperature of the liquid. We clarified that the self-organized pattern formation depends on the amount of electronegative gas, such as oxygen, in the gas in the electrode gap. When an oxygen gas flow was fed to the liquid surface from the outside in an obliquely downward direction, namely, the amount of oxygen gas on the liquid surface was increased locally, self-organized pattern formation was observed in the region with the increased amount of oxygen gas. When the amount of oxygen in the gas in the gap was changed by using a sheath flow system, the appearance of the pattern changed. The presence of oxygen gas strongly affected the self-organized pattern formation of the atmospheric dc discharge using a liquid anode.

An atmospheric dc glow discharge using a liquid cathode and an axial miniature helium flow was generated stably between a nozzle anode and an electrolyte cathode (NaCl solution) in ambient air. Under low-current operation, the typical structure of dc glow discharges, i.e. a negative glow, a Faraday dark space and positive column, was observed. With increasing discharge current, the visible negative glow became weak and was replaced by an intense yellow-light emission, which was considered to originate from sodium atoms vaporized from the electrolyte surface by local heating due to ion bombardment from the glow discharge. To examine the effect of the liquid electrode temperature on the discharge characteristics, we controlled the electrolyte cathode temperature using an injection-type cooler or heater. The intensity of the sodium emission decreased when the electrolyte cathode was cooled, while it increased when the electrolyte cathode was heated. When a pulse-modulated dc voltage was applied, the sodium emission appeared with a delay relative to the inception of discharge, while nitrogen molecular lines appeared in the emission spectra and reached their peak intensities immediately. The temperature of the liquid cathode is an important factor in controlling the plasma-liquid interaction from the discharge and in resolving the detailed mechanism of the electrolyte cathode discharge.

Atmospheric-pressure helium glow discharge at 100 kHz between parallel plate dielectric electrodes is studied experimentally and theoretically. Experimental work was carried out by spatiotemporal optical emission spectroscopy to examine the behavior of electrons. The emission from helium atoms revealed the behavior of high-energy electrons (above 22 eV), while the emission from the second positive band of nitrogen revealed the behavior of medium-energy electrons (11–20 eV). Theoretical work was carried out using a one-dimensional fluid model with local field approximation under the same discharge conditions as the experimental one. It was clarified that i) the discharge structure is essentially the same as that in low-pressure glow discharge, ii) ionization by secondary electrons from the cathode is essential for sustaining the discharge, and iii) ionization occurs at low electric field (about 30 Td). This last property is important for conducting “moderate” ionization for stable glow discharge at atmospheric pressure in the absence of localized discharge columns.