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Locke, Bruce R.

Publications and source records attributed to Locke, Bruce R..

Recent Insights Into Interfacial Transport and Chemical Reactions of Plasma–Generated Species in Liquid

The chemistry of plasma–liquid interactions involves a complex interplay of physical and chemical processes at the plasma–liquid interface. These interactions give rise to the generation, transport, and transformation of various reactive species. Since the publication of the Lorenz Roadmap in 2016, significant progress has been made in understanding the interfacial transport and coupled reactions of plasma-generated species with inorganic and organic compounds. However, critical aspects of plasma–liquid chemistry and mass transfer still require further investigation. Here, this review summarizes recent work on processes at the plasma–liquid interface and the coupled reactions in the liquid phase. We highlight key findings related to the involvement of O atoms, H radicals, solvated electrons, photons, and nitrogen-derived species at the interface and within the bulk liquid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Collaborative Research Proposal: Time Resolved Optical Emissions Spectroscopy and Laser Induced Fluorescence Spectroscopy of Nanosecond Pulsed Discharges in a Gas-Liquid Water Film Reactor

Electrical discharge plasma formed in contact with liquid water is of interest for a wide range of applications in chemical, biomedical, agricultural, electrical, and materials science and engineering. Such plasma reactors are of very timely importance since they also have significant disinfection capability by inactivating bacteria, viruses and other pathogens. Many types of plasma sources including those driven by AC, DC, RF, microwave, and pulsed electrical power supplies coupled to a wide range of different electrode configurations and reactor designs have been developed and explored which contact the plasma with liquid water. Recent roadmaps have recommended that further work is needed to develop our understanding of the fundamental chemical and physical process which occur at the interface of non-thermal plasma with liquid water solutions in order to advance this large diversity of applications which ultimately depend upon efficient production of key reactive chemical species. There is a wide range of interacting factors that affect the chemical reactions that occur in the plasma, in the liquid phase, and at the interface. These factors ultimately govern the key reactive chemical species formed and used in the various applications and they include a) the reactor design and input parameters, b) the discharge and transport processes, c) the plasma properties, and d) the resulting chemical reactions. For pulsed discharges, the power supply design and output parameters control the applied voltage, frequency, rise time, and width (duration) of the applied pulses. The reactor design involves specification of the gas-liquid contacting methods, electrode gap distance, reactor volume and shape, and gas and liquid flow rates achievable. The gas and liquid compositions as well as the liquid properties such as pH and conductivity are also of key importance in determination of the resulting chemical reactions. In addition, the important plasma properties include plasma gas temperature, electron density, electron energy (distribution), and size of the plasma channels which are all affected by the discharge and transport properties. Many studies have focused on specific aspects of these various processes. Of particular important and relevance to the proposed work is the utilization of nanosecond pulses to generate plasma in gas-liquid systems, liquid bubbles, underwater, and in gases. Recent advances in nanosecond pulses provide significant advantages in utilization with liquid water. For example, fast rise time and short pulses are less sensitive to water conductivity, such short pulses may provide advantages in fast temporal quenching of the plasma, and fundamental analysis of pulse properties, including pulse shape and width, may be facilitated by investigation of single filamentary fast pulses. Many studies have also dealt with the role of the gas composition on formation of reactive oxygen species (ROS) (i.e., hydroxyl radicals – ·OH, hydrogen peroxide – H 2 O 2 , various atomic oxygen species, ozone-O 3 , hydroperoxyl radicals HO 2 ·) and reactive nitrogen species (RNS) (i.e., nitrogen oxides – NO, NO 2 , N 2 O - collectively termed NO X , nitrite-NO 2 - , nitrate-NO 3 - , peroxynitrite-ONOO - ). The hydroxyl radical is the critical species in many chemical oxidation reactions for chemical degradation of toxic compounds in water and gases and for synthesis of some compounds. The mixture of various nitrogen oxide species is important for many biochemical and biological processes involved in biomedical and agricultural applications including disinfection and fertilizer production. The present proposal focuses on determination of the effects of time resolved electron density and hydroxyl radicals on plasma chemical reactions through collaboration with the Princeton Collaborative Low Temperature Plasma Research Facility (PCRF) at the Princeton Plasma Physics Laboratory (PPPL). In order to further investigate the role of the plasma generated electrons and hydroxyl radicals on the overall formation of the key species including hydrogen peroxide, hydroxyl radicals, and nitrogen oxides, the proposed work, thus seeks to determine high resolution time resolved electron density by optical emissions spectroscopy and time resolved hydroxyl radicals using laser induced fluorescence in the nanosecond discharge reactor. The combination of data on electron density and hydroxyl radical concentration will be utilized in the present work to more fully characterize the chemical reaction processes in this system and to advance the design, development, and operation of such chemical reactors for a wide range of applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Gas–Liquid Chemical Reactions with Nanosecond Pulses: Role of Frequency and Pulse Delivery Modes

The effects of changes in the mode of delivery of nanosecond pulses in a gas-liquid plasma reactor on the formation of hydrogen peroxide, H 2 O 2 , and, as an indicator for ·OH radicals, the decoloration of methylene blue, MB, were determined for pulse delivery by a) increasing frequency with uniform pulses (5-50 kHz), b) variation of the time between bursts of pulses (burst period), c) changing the inner burst frequency (1 over the time between the pulses in the burst), and d) variation of number of pulses in a burst (N-cycles). H 2 O 2 peroxide formation was not affected by the method of pulse delivery in the range of parameters studied here and all data followed an approximately linear increase in H 2 O 2 production rate with discharge power. In contrast, the MB decoloration rate was affected by the burst modes. In terms of discharge power, the MB decoloration rate was highest for the uniform pulse mode; however, the linear trend in increase of MB decoloration with power when the burst period was varied, suggest that at higher power the burst mode may be more effective than the uniform pulsing. Consideration of the per pulse decoloration with energy per pulse and with number of pulses suggest that the burst mode can affect reactions differently from applying a uniform pulse.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Effects of frequency and pulse width on electron density, hydrogen peroxide generation, and perfluorooctanoic acid mineralization in a nanosecond pulsed discharge gas-liquid plasma reactor

Plasma electron density and temperature were characterized in a continuous flowing gas-liquid film reactor with argon carrier gas by time-resolved optical emission spectroscopy. The plasma parameters were studied as a function of time for varying pulse widths and frequencies. Pulse frequency was varied between 1 and 10 kHz at 16 kV (input voltage) and 40 ns (pulse width) using an Eagle Harbor Technologies, Inc. (EHT) power supply and 5–100 kHz using an Airity Technologies, LLC (AT) power supply. The pulse width was varied between 40 and 200 ns at 16 kV, 2 kHz with the EHT power supply. Optimal frequencies of 5 and 20 kHz were observed for peak electron density with EHT and AT power supplies, respectively. The peak electron density increased with increasing pulse width between 40 and 200 ns using the EHT power supply. Hydrogen peroxide exiting the reactor in the liquid phase increased with discharge power irrespective of the power supply or pulse parameters. Mineralization of 12.5, 50, and 200 ppm perfluorooctanoic acid (PFOA) dissolved in DI water to fluoride (F - ) correlated to the peak electron density. Glycerol, a liquid-phase hydroxyl radical scavenger, depleted hydrogen peroxide but did not affect PFOA mineralization. CO, a gas-phase hydroxyl radical scavenger, led to a reduction in the formation of F - production, suggesting hydroxyl radicals in the gas-liquid film play a necessary, but not singular, role in mineralization of PFOA.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗