Glow discharge plasma formed in solution under atmospheric pressure has been expected to provide reaction fields with characteristic physical and chemical properties owing to the frequent collisions and reactions of reactive particles inside and the rapid quenching of the products by the surrounding cold solutions. In particular, when an aqueous solution is utilized as the surrounding solution, the atmospheric-pressure in-solution glow (ASG) plasma contains hydrogen and hydroxyl radicals showing large activities for reduction and oxidation, respectively. In addition, because the ASG plasma is formed under atmospheric pressure, the collision frequencies between the particles contained in the plasma are higher than those in other plasmas ordinarily formed under low pressure. This feature should result in rapid energy redistribution among particles contained in the plasma. In the present study, time-resolved optical emission spectroscopy with nanosecond time resolution was applied for the diagnostics of the ASG plasma with chemical species selectivity. The time-resolved measurements revealed that the temporal evolutions of the temperatures of blackbody, hydrogen radical, and hydroxyl radical contained in the ASG plasma consist of two stages: initial rise within 0.15 µs (rising stage) and fluctuation around certain values for about 1 µs (fluctuating stage). In the time region corresponding to the rising stage, the electron number density is about ten times larger than the value temporally averaged during the plasma emission. The initial rise should result from frequent collisions between charged particles accelerated by the applied voltage and unexcited particles. In the fluctuating stage, the electron number density strongly correlates with the increase in the radical temperatures. It is concluded that the electron number density, rather than the electron temperature, is a key parameter determining the temperatures of reactive species in the ASG plasma.

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By applying a high pulsed voltage to a gap between two electrodes placed in a solution, an atmosphericpressure in-solution glow (ASG) plasma is generated. The ASG plasma is applied in a new material processing method, called solution plasma processing (SPP). In order to accelerate the reaction and to add functions to the synthesized materials, it is important to alter the gas content in the ASG plasma. We developed a direct gas injection system for an ASG discharge cell. When O 2 , CO 2 , N 2 and Ar gases were injected into the ASG plasma, emission bands due to the derivatives of the injected gases were observed in the emission spectra from the ASG plasma. The electron number density in the ASG plasma was increased by the O 2 , CO 2 , and N 2 injections, probably due to the enhancements of the a and g processes by the larger molecular weights than H 2 O. In addition, the first dielectric breakdown of the solution and the formation of the gas bubble processes gradually disappeared due to the gas injection.When O 2 was injected, the amount of $OH generation was increased. By the enhancement of the $OH generation, the degradation speed of rhodamine B in the ASG plasma was increased by a factor of two. When Au nanoparticles were synthesized utilizing the ASG plasma, the zeta potential of the Au nanoparticles was increased by about 30% by the O 2 injection. The plasma parameters and the reactivity of the ASG plasma can be altered more widely by changing the kind of injected gas and the flow rate.

Discharge plasma formed in aqueous solutions has attracted much attention for its applications in environmental purification and material syntheses. The onset and evolution of the discharge plasma in an aqueous solution and transient reactive species formed in it are successfully monitored with micrometer spatial resolution and nanosecond temporal resolution. The combination of a custom-made microscopic discharge system and a high-speed camera provides direct evidence that water vapor bubbles form before the discharge with the thermal phase transition of aqueous solution at the electrode tip. The water vapor bubbles, i.e., locally formed space in the gas phase, connect the gap between the tips of the opposed electrodes. The local gas area formed in aqueous solution plays a crucial role in the ignition and continuance of the discharge plasma. It is also found that the initially formed plasma lasts for under 100 ns and quenches rapidly. However, plasma regenerates in the water vapor bubble and successively bridges the opposing electrodes during the pulsed-voltage application (ca. 1 μs). These two temporally distinct generations of plasma, i.e., the initial plasma (IP) and the following successive plasma (SP), can be seen to correspond to the dielectric breakdown and glow-like plasma, respectively. These results provide an important picture for the proposed mechanism for plasma evolution in water and also important information for the efficient control of the discharge plasma with its applications in waste-water treatments, nanomaterial syntheses with plasma oxidation–reduction reactions, and the chemical modification of the material surfaces in aqueous solutions as a form of “green chemistry.”