Production and transport of plasma-generated hydrogen peroxide from gas to liquid.

In this work, the transport of hydroxyl radicals and hydrogen peroxide from a humid atmospheric pressure plasma jet into plasma-treated liquids is analysed. The concentration of H2O2 was measured by a spectrophotometric approach using the reagent ammonium metavanadate. OH was measured by the terephthalic acid dosimeter and the chemiluminescence of luminol. The plasma jet used is based on the design of the well-investigated COST reference jet and is extended by a capillary between the two electrodes. In addition to the experiments, the 0-dimensional plasma-chemical kinetics code GlobalKin was used to analyse the plasma chemistry in the gas phase in more detail. After 5 min plasma treatment, a maximum H2O2 concentration of 1 mM was found in the liquid, while the OH concentration was a factor 50 lower. The concentrations of both species in the liquid increased with plasma power, and the H2O2 concentration also increased with the humidity concentration of the feed gas, while the OH concentration first increased with humidity admixture and then decreased. The transport of both species could be controlled by the treatment distance, the gas flow rate and low frequency pulsing of the RF jet in such a way that the selectivity towards the long-lived species H2O2 was increased. Qualitative trends in the simulated number densities of gas phase H2O2 and OH at the location of the gas-liquid interface fit relatively well to the experimental measurements in the liquid.

Vibrational kinetics in repetitively pulsed atmospheric pressure nitrogen discharges: average-power-dependent switching behaviour.

Characterisation of the vibrational kinetics in nitrogen-based plasmas at atmospheric pressure is crucial for understanding the wider plasma chemistry, which is important for a variety of biomedical, agricultural and chemical processing applications. In this study, a 0-dimensional plasma chemical-kinetics model has been used to investigate vibrational kinetics in repetitively pulsed, atmospheric pressure plasmas operating in pure nitrogen, under application-relevant conditions (average plasma powers of 0.23-4.50 W, frequencies of 1-10 kHz, and peak pulse powers of 23-450 W). Simulations predict that vibrationally excited state production is dominated by electron-impact processes at lower average plasma powers. When the average plasma power increases beyond a certain limit, due to increased pulse frequency or peak pulse power, there is a switch in behaviour, and production of vibrationally excited states becomes dominated by vibrational energy transfer processes (vibration-vibration (V-V) and vibration-translation (V-T) reactions). At this point, the population of vibrational levels up to v ⩽ 40 increases significantly, as a result of V-V reactions causing vibrational up-pumping. At average plasma powers close to where the switching behaviour occurs, there is potential to control the energy efficiency of vibrational state production, as small increases in energy deposition result in large increases in vibrational state densities. Subsequent pathways analysis reveals that energy in the vibrational states can also influence the wider reaction chemistry through vibrational-electronic (V-E) linking reactions (N + N 2 ( 40 ⩽ v ⩽ 45 ) → N ( 2 D ) + N 2 ( A ) and N + N 2 ( 39 ⩽ v ⩽ 45 ) → N + N 2 ( a ' ) ), which result in increased Penning ionisation and an increased average electron density. Overall, this study investigates the potential for delineating the processes by which electronically and vibrationally excited species are produced in nitrogen plasmas. Therefore, potential routes by which nitrogen-containing plasma sources could be tailored, both in terms of chemical composition and energy efficiency, are highlighted.

Disrupting the spatio-temporal symmetry of the electron dynamics in atmospheric pressure plasmas by voltage waveform tailoring.

Single frequency, geometrically symmetric Radio-Frequency (rf) driven atmospheric pressure plasmas exhibit temporally and spatially symmetric patterns of electron heating, and consequently, charged particle densities and fluxes. Using a combination of phase-resolved optical emission spectroscopy and kinetic plasma simulations, we demonstrate that tailored voltage waveforms consisting of multiple rf harmonics induce targeted disruption of these symmetries. This confines the electron heating to small regions of time and space and enables the electron energy distribution function to be tailored.

Chemical kinetics in an atmospheric pressure helium plasma containing humidity.

Atmospheric pressure plasmas are sources of biologically active oxygen and nitrogen species, which makes them potentially suitable for the use as biomedical devices. Here, experiments and simulations are combined to investigate the formation of the key reactive oxygen species, atomic oxygen (O) and hydroxyl radicals (OH), in a radio-frequency driven atmospheric pressure plasma jet operated in humidified helium. Vacuum ultra-violet high-resolution Fourier-transform absorption spectroscopy and ultra-violet broad-band absorption spectroscopy are used to measure absolute densities of O and OH. These densities increase with increasing H2O content in the feed gas, and approach saturation values at higher admixtures on the order of 3 × 1014 cm-3 for OH and 3 × 1013 cm-3 for O. Experimental results are used to benchmark densities obtained from zero-dimensional plasma chemical kinetics simulations, which reveal the dominant formation pathways. At low humidity content, O is formed from OH+ by proton transfer to H2O, which also initiates the formation of large cluster ions. At higher humidity content, O is created by reactions between OH radicals, and lost by recombination with OH. OH is produced mainly from H2O+ by proton transfer to H2O and by electron impact dissociation of H2O. It is lost by reactions with other OH molecules to form either H2O + O or H2O2. Formation pathways change as a function of humidity content and position in the plasma channel. The understanding of the chemical kinetics of O and OH gained in this work will help in the development of plasma tailoring strategies to optimise their densities in applications.