Self-Organizing Sub-µm Surface Structures Stimulated by Microplasma Generated Reactive Species and Short-Pulsed Laser Irradiation.

Catalysts are critical components for chemical reactions in industrial applications. They are able to optimize selectivity, efficiency, and reaction rates, thus enabling more environmentally friendly processes. This work presents a novel approach to catalyst functionalization for the CO2 reduction reaction by combining the reactive species of an atmospheric pressure plasma jet with the electric fields and energy input of a laser. This leads to both a nanoscale structuring as well as a controllable chemical composition of the surface, which are important parameters for optimizing catalyst performance. The treatment is conducted on thin copper layers deposited by high power pulsed magnetron sputtering on silicon wafers. Because atomic oxygen plays a key role in oxidizing copper, two photon absorption fluorescence is used to investigate the atomic oxygen density in the interaction zone of the COST plasma jet and a copper surface. The used atmospheric pressure plasma jet provides an atomic oxygen density at the surface in a distance of 8 mm to the jet nozzle of approximately or a flux of . Pulsed laser-induced dewetting is used to form nanoparticles from the deposited copper layer to enhance catalytic performance. Varying the layer thickness allows control of the size of the particles. A gas flow directed on the sample during the combined treatment disturbs the particle formation. This can be prevented by increasing the laser energy to compensate for the cooling effect of the gas flow. Investigating the surface using X-ray photoemission spectroscopy reveals that the untreated copper layer surface consists mostly of metallic copper and Cu(I) oxide. Irradiating the sample only with the laser did not change the composition. The combination of plasma and laser treatment is able to produce Cu(II) species such as CuO, whose concentration increases with treatment time. The presented process allows the tuning of the ratio of C2O/CuO, which is an interesting parameter for further studies on copper catalyst performance.

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.

Gas Flow-Dependent Modification of Plasma Chemistry in µAPP Jet-Generated Cold Atmospheric Plasma and Its Impact on Human Skin Fibroblasts.

The micro-scaled Atmospheric Pressure Plasma Jet (µAPPJ) is operated with low carrier gas flows (0.25-1.4 slm), preventing excessive dehydration and osmotic effects in the exposed area. A higher yield of reactive oxygen or nitrogen species (ROS or RNS) in the µAAPJ-generated plasmas (CAP) was achieved, due to atmospheric impurities in the working gas. With CAPs generated at different gas flows, we characterized their impact on physical/chemical changes of buffers and on biological parameters of human skin fibroblasts (hsFB). CAP treatments of buffer at 0.25 slm led to increased concentrations of nitrate (~352 µM), hydrogen peroxide (H2O2; ~124 µM) and nitrite (~161 µM). With 1.40 slm, significantly lower concentrations of nitrate (~10 µM) and nitrite (~44 µM) but a strongly increased H2O2 concentration (~1265 µM) was achieved. CAP-induced toxicity of hsFB cultures correlated with the accumulated H2O2 concentrations (20% at 0.25 slm vs. ~49% at 1.40 slm). Adverse biological consequences of CAP exposure could be reversed by exogenously applied catalase. Due to the possibility of being able to influence the plasma chemistry solely by modulating the gas flow, the therapeutic use of the µAPPJ represents an interesting option for clinical use.

Treating Surfaces with a Cold Atmospheric Pressure Plasma using the COST-Jet.

In recent years, non-thermal atmospheric pressure plasmas have been used extensively for surface treatments, in particular, due to their potential in biological applications. However, the scientific results often suffer from reproducibility problems due to unreliable plasma conditions as well as complex treatment procedures. To address this issue and provide a stable and reproducible plasma source, the COST-Jet reference source was developed. In this work, we propose a detailed protocol to perform reliable and reproducible surface treatments using the COST reference microplasma jet (COST-Jet). Common issues and pitfalls are discussed, as well as the peculiarities of the COST-Jet compared to other devices and its advantageous remote character. A detailed description of both solid and liquid surface treatment is provided. The described methods are versatile and can be adapted for other types of atmospheric pressure plasma devices.