Effects of O2 addition on the plasma uniformity and reactivity of Ar DBD excited by ns pulsed and AC power supplies

Dielectric barrier discharges (DBDs) have been widely used in ozone synthesis, materials surface treatment, and plasma medicine for their advantages of uniform discharge and high plasma-chemical reactivity. To improve the reactivity of DBDs, in this work, the O₂ is added into Ar nanosecond (ns) pulsed and AC DBDs. The uniformity and discharge characteristics of Ar ns pulsed and AC DBDs with different O₂ contents are investigated with optical and electrical diagnosis methods. The DBD uniformity is quantitatively analyzed by gray value standard deviation method. The electrical parameters are extracted from voltage and current waveforms separation to characterize the discharge processes and calculate electron density n_e. The optical emission spectroscopy is measured to show the plasma reactivity and calculate the trend of electron temperature T_e with the ratio of two emission lines. It is found that the ns pulsed DBD has a much better uniformity than AC DBD for the fast rising and falling time. With the addition of O₂, the uniformity of ns pulsed DBD gets worse for the space electric field distortion by O₂⁻, which promotes the filamentary formation. While, in AC DBD, the added O₂ can reduce the intensity of filaments, which enhances the discharge uniformity. The ns pulsed DBD has a much higher instantaneous power and energy efficiency than AC DBD. The ratio of Ar emission intensities indicates that the T_e drops quickly with the addition of O₂ both ns pulsed and AC DBDs and the ns pulsed DBD has an obvious higher T_e and n_e than AC DBD. The results are helpful for the realization of the reactive and uniform low temperature plasma sources.     

Influence of Ti3C2Tx(MXene)on the generation of dielectric barrier discharge in air

The formation of homogeneous dielectric barrier discharge(DBD)in air is a key scientific problem and core technical problem to be solved for the application of plasmas.Here,we report the effect of two-dimensional(2D)nanomaterial Ti3C2Tx(Tx=-F,-O and/or-OH)on regulating the electrical discharge characteristics.The field emission and weak bound state property of Ti3C2Tx can effectively increase the seed electrons and contribute to the generation of atmospheric pressure homogeneous air DBD.The electron avalanche development for the uneven electrode structure is calculated,and the discharge mode transition is modeled.The comparative analyses of discharge phenomena validate the regulation of Ti3C2Tx on the discharge characteristics of DBD.The light emission capture and the voltage and current waveforms verify that the transition of Townsend discharge to streamer discharge is effectively inhibited.The optical emission spectra are used to characterize the plasma and confirm that it is in a non-equilibrium state and the gas temperature is at room temperature.This is the first exploration of Ti3C2Tx on the regulation of electrical discharge characteristics as far as we know.This work proves the feasibility of Ti3C2Tx as a source of seed electrons to form homogeneous DBD,establishing a preliminary foundation for promoting the application of atmospheric pressure non-equilibrium plasma.     

Influence of nitrogen impurities on the characteristics of a patterned helium dielectric barrier discharge at atmospheric pressure

In this paper, a two-dimensional axisymmetric fluid model was established to investigate the influence of nitrogen impurity content on the discharge pattern and the relevant discharge characteristics in an atmosphere pressure helium dielectric barrier discharge (DBD). The results indicated that when the nitrogen content was increased from 1 to 100 ppm, the discharge pattern evolved from a concentric-ring pattern into a uniform pattern, and then returned to the concentricring pattern. In this process, the discharge mode at the current peak moment transformed from glow mode into Townsend mode, and then returned to glow mode. Further analyses revealed that with the increase of impurity level, the rate of Penning ionization at the pre-ionization stage increased at first and decreased afterwards, resulting in a similar evolution pattern of seed electron level. This evolution trend was believed to be resulted from the competition between the N₂ partial pressure and the consumption rate of metastable species. Moreover, the discharge uniformity was found positively correlated with the spatial uniformity of seed electron density as well as the seed electron level. The reason for this correlation was explained by the reduction of radial electric field strength and the promotion of seed electron uniformity as pre-ionization level increases. The results obtained in this work may help better understand the pattern formation mechanism of atmospheric helium DBD under the variation of N₂ impurity level, thereby providing a possible means of regulating the discharge performance in practical application scenarios.     

Discharge Modes Suggested by Emission Spectra of Nitrogen Dielectric Barrier Discharge with Wire-Cylinder Electrodes

In this paper,nitrogen dielectric barrier discharge(DBD) plasma was generated in a quartz tube with coaxial wire-cylinder electrodes at atmospheric pressure.By varying the nitrogen gas flow(FN) in the range of 0-1 m3/h,the plasma optical emission spectra(OES) were measured and studied.The vibration(T_(vib)) and rotation temperature(T_(rot)) of nitrogen were obtained,by fitting the rovibronic bands of N_2(C~3∏_u-B~3∏_g,0-1),and by the Boltzmann plot method for purposes of comparison.T_(vib) increased up to 2481 K with increasing nitrogen flow till0.2 m3/h,and then decreased with further increasing FN,while Trot decreased monotonously and approached to-350 K for FN ≥ 0.6 m~3/h.The intensity of N_2(C~3∏_u-B~3∏_g,0-0,1-0,0-3) and N_2~+(B~2∑_u~+-X~2Σ_g~+,0-0) exhibited similar evolution with increasing FN to those of the T_(vib) and Trot,respectively.The discharge photos revealed that the discharge filaments gradually decreased with increasing FN,and eventually disappeared,which implied that a discharge mode transition emerged with increasing FN.The possible mechanism for the discharge mode transition is studied in detail according to the vibration(T_(vib)) and rotation temperature(T_(rot)) of nitrogen.     

Influence of non-uniform electric field distribution on the atmospheric pressure air dielectric barrier discharge

The dielectric barrier discharge(DBD) in air at atmospheric pressure is not suitable for industrial applications due to its randomly distributed discharge filaments. In this paper, the influence of the electric field distribution on the uniformity of DBD is theoretically analyzed and experimentally verified. It is found that a certain degree of uneven electric field distributions can control the development of electron avalanches and regulate their transition to streamers in the gap. The discharge phenomena and electrical characteristics prove that an enhanced Townsend discharge can be formed in atmospheric-pressure air with a curved-plate electrode. The spectral analysis further confirms that the gas temperature of the plasma produced by the curved-plate electrode is close to room temperature, which is beneficial for industrial applications. This paper presents the relationship between the electron avalanche transition and the formation of a uniform DBD, which can provide some references for the development and applications of the DBD in the future.     

Evaluation on a double-chamber gas-liquid phase discharge reactor for benzene degradation

A double-chamber gas-liquid phase DBD reactor (GLDR), consisting of a gas-phase discharge chamber and a gas-liquid discharge chamber in series, was designed to enhance the degradation of benzene and the emission of NOx. The performance of the GLDR on discharge characteristics, reactive species production and benzene degradation was compared to that of the single-chamber gas phase DBD reactor (GPDR). The effects of discharge gap, applied voltage, initial benzene concentration, gas flow rate and solution conductivity on the degradation and energy yield of benzene in the GLDR were investigated. The GLDR presents a higher discharge power, higher benzene degradation and higher energy yield than that of the GPDR. NO₂ emission was remarkably inhibited in the GLDR, possibly due to the dissolution of NO₂ in water. The benzene degradation efficiency increased with the applied voltage, but decreased with the initial concentration, gas flow rate, and gas discharge gap, while the solution conductivity presented less influence on benzene degradation. The benzene degradation efficiency and the energy yield reached 61.11% and 1.45 g kWh^–1 at 4 mm total gas discharge gap, 15 kV applied voltage, 200 ppm benzene concentration, 0.2 L min⁻¹ gas flow rate and 721 μS cm⁻¹ water conductivity. The intermediates and byproducts during benzene degradation were detected by FT-IR, GC-MS and LC-MS primarily, and phenols, CO_x, and other aromatic substitutes, O₃, NO_x, etc, were determined as the main intermediates. According to these detected byproducts, a possible benzene degradation mechanism was proposed.     

A Simplified Numerical Study of the Kr/Cl2 Plasma Chemistry in Dielectric Barrier Discharge

In this paper, the generation of excimers and exciplexe radiation in mixtures of rare gas with halogen by homogeneous dielectric barrier discharge （DBD） is investigated. The typical characteristics of an excilamp based on KrCl exciplexe molecules and the kinetic processes for the formation and the decay of this molecules in the Kr/Cl₂ mixture are studied. The computer model developed is based on the Kr/Cl₂ mixture chemistry, the equivalent electric circuit and the Boltzmann equations. The importance in the kinetic processes of some species such as the metastable state of Krypton （Kr（3P0,2）） and the negative ion of chloride （Cl） is considered. The results illustrate the time variations of charged species （ne,Kr+,Cl,Cl+,Cl+2,Kr+2）, excited atoms and molecules （Kr（3P0,2）, Kr（3P1）, Cl, Cl2）, the excimers （Kr2,KrCl（B）,KrCl（C）,Kr2Cl） and the UV photon concentrations （in 222nm,235nm,258nm and 325nm range）. The effects of chlorine concentration and the total gas pressure in the Kr-Cl₂ discharge on the electric parameters and radiation emissions are investigated.     

Enhancing toluene removal in a plasma photocatalytic system through a black TiO_2 photocatalyst

An efficient toluene removal in air using a plasma photocatalytic system(PPS) not only needs favorable surface reactions over photocatalysts under the action of plasma,but also requires the photocatalysts to efficiently absorb light emitted from the discharge for driving the photocatalytic reactions. We report here that the PPS constructed by integrating a black titania(B-TiO_2)photocatalyst with a dielectric barrier discharge(DBD) can effectively remove toluene with above 70% CO_2 selectivity and remarkably reduced the concentration of secondary pollutants of ozone and nitrogen oxides at a specific energy input of 1500 J·l~(-1),while exhibiting good stability. Photocatalyst characterizations suggest that the B-TiO_2 provides a high concentration of oxygen vacancies for the surface oxidation of toluene in DBD,and efficiently absorbs ultraviolet–visible light emitted from the discharge to induce plasma photocatalytic oxidation of toluene. The presence of B-TiO_2 in the plasma region also results in a high discharge efficiency,facilitating the generation of large numbers of reactive species and thus the oxidation of toluene towards CO_2. The greatly enhanced performance of the PPS integrated with B-TiO_2 in toluene removal offers a promising approach to efficiently remove refractory volatile organic compounds from air at low temperatures.     

Plasma-assisted Ru/Zr-MOF catalyst for hydrogenation of CO2 to methane

As an important type of metal–organic framework (MOF), Zr-MOF shows excellent CO₂ adsorption performance. In this work, a Zr-MOF was synthesized by a solvothermal method and adopted to support Ru through simple incipient-wetness impregnation. Then the Ru/Zr-MOF was applied for CO₂ hydrogenation (V_H2 : V_CO2= 4:1) with the assistance of dielectric barrier discharge (DBD) plasma. The hydrogenation of CO₂ results showed that methane was produced selectively under the synergistic effect between plasma and the Ru/Zr-MOF catalyst, and the selectivity and yield of methane reached 94.6% and 39.1%, respectively. The XRD and SEM analyses indicate that the basic crystalline phase structure and morphology of the Zr-MOF and Ru/Zr-MOF remained the same after DBD plasma treatment, suggesting that the catalysts are stable in plasma. The guest molecules in the pores of the Zr-MOF are removed and the Ru³⁺ ions are reduced to metallic Ru⁰ in the reduction atmosphere according to the BET and XPS results, which are responsible for the high performance of plasma with the Ru/Zr-MOF catalyst. In situ optical emission spectra of pure plasma, plasma with Zr-MOF, and plasma with Ru/Zr-MOF were measured, and the active species of C, H and CH for CO₂ hydrogenation were detected. The plasma-assisted Ru/Zr-MOF exhibited high catalytic activity and stability in CO₂ hydrogenation to methane, and it has great guiding significance for CO₂ hydrogenation by using plasma and MOF materials.     

Volume added surface barrier discharge plasma excited by bipolar nanosecond pulse power in atmospheric air: optical emission spectra influenced by gap distance

In this paper, volume barrier discharge with different gap distances is added on the discharge border of high-voltage electrode of annular surface barrier discharge for generating volume added surface barrier discharge (V-SBD) excited by bipolar nanosecond high-voltage pulse power in atmospheric air. The excited V-SBDs consist of surface barrier discharge (d=0 mm) and volume added surface barrier discharges (d=2 mm and 3 mm). The optical emission spectra are recorded for calculating emission intensities of N₂ (C ³Ⅱ_u →B³Π_g ) and N₂⁺ (B ²Σ_u⁺ → X ²Σ_g⁺ ), and simulating rotational and vibrational temperatures. The influences of gap distance of V-SBD on emission intensity and plasma temperature are also investigated and analyzed. The results show that d=0 mm structure can excite the largest emission intensity of N ₂ (C ³ Π_u →B ³Π_g ), while the existence of volume barrier discharge can delay the occurrence of the peak value of the emission intensity ratio of N₂⁺ (B ²Σ_u⁺ → X ²Σ_g⁺ )/N ₂(C³Π_u →B³Π_g ) during the rising period of the applied voltage pulse and weaken it during the end period. The increasing factor of emission intensity is effected by the pulse repetition rate. The d=3 mm structure has the highest threshold voltage while it can maintain more emission intensity of N₂(C³ Π _u →B ³Π_g ) than that of d=2 mm structure. The structure of d=2 mm can maintain more increasing factor than that of the d=3 mm structure with varying pulse repetition rate. Besides, the rotational temperatures of three V-SBD structures are slightly affected when the gap distance and pulse repetition rate vary. The vibrational temperatures have decaying tendencies of all three structures with the increasing pulse repetition rate.     

Spectroscopic diagnosis of plasma in atmospheric pressure negative pulsed gasliquid discharge with nozzle-cylinder electrode

The plasma characteristics of a gas-liquid phase discharge reactor were investigated by optical and electrical methods.The nozzle-cylinder electrode in the discharge reactor was supplied witha negative nanosecond pulsed generator.The optical emission spectrum diagnosis revealed that OH(A~2∑~+?→?X~2Π,306–309 nm),N~3_2(CΠ→B~3Π_g,337 nm),O(3p~5p→3s~5s~0,777.2 nm)and O(3p~3p→3s~3s~0,844.6 nm)were produced in the discharge plasma channels.The electron temperature(T_e)was calculated from the emission relative intensity ratio between the atomic O 777.2 nm and 844.6 nm,and it increased with the applied voltage and the pulsed frequency and fell within the range of 0.5–0.8 e V.The gas temperature(T_g)that was measured by Lifbase was in a range from 400 K to 600 K.     

DBD coupled with MnOx/γ-Al2O3 catalysts for the degradation of chlorobenzene

This paper investigates the degradation of chlorobenzene by dielectric barrier discharge(DBD)coupled with MnOx/γ-Al2O3 catalysts.MnOx/γ-Al2O3 catalysts were prepared using the impregnation method and were characterized in detail by N2 adsorption/desorption,x-ray diffraction and x-ray photoelectron spectroscopy.Compared with the single DBD reactor,the coupled reactor has a better performance on the removal rate of chlorobenzene,the selectivity of COx,and the inhibition of ozone production,especially at low discharge voltages.The degradation rate of chlorobenzene and selectivity of COx can reach 96.3%and 53.0%,respectively,at the specific energy density of 1350 J l-1.Moreover,the ozone concentration produced by the discharge is significantly reduced because the MnOx/Al2O3 catalysts contribute to the decomposition of ozone to form oxygen atoms for the oxidation of chlorobenzene.In addition,based on analysis of the byproducts,the decomposition mechanism of chlorobenzene in the coupled reactor is also discussed.     

Plasma-catalytic degradation of tetracycline hydrochloride over Mn/γ-Al2O3 catalysts in a dielectric barrier discharge reactor

A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series ofMn/γ-Al₂O₃ catalysts prepared by the incipient wetness impregnation method. The combination of plasma and theMn/γ-Al₂O₃ catalysts significantly enhanced the degradation efficiency of tetracycline hydrochloride compared to the plasma process alone, with the 10%Mn/γ-Al₂O₃ catalyst exhibiting the best tetracycline hydrochloride degradation efficiency. A maximum degradation efficiency of 99.3% can be achieved after 5 min oxidation and a discharge power of 1.3 W, with only 69.7% by a single plasma process. The highest energy yield of the plasma-catalytic process is 91.7 gkWh⁻¹. Probable reaction mechanisms of the plasma-catalytic removal of tetracycline hydrochloride were also proposed.     

Surface Modification of Fluororubber Using Atmospheric Pressure Dielectric Barrier Discharge （DBD）

Fluoride rubber F2311 film, an alternating copolymer of CF2-CFC1 （CTFE） and CH2-CF2 （VF2） components, was treated by atmospheric pressure dielectric barrier discharge （DBD） in air. The surface structure, topography and surface chemistry of the treated F2311 films were characterized by contact angle measurement, atomic force microscopy （AFM）, and X-ray photoelectron spectroscopy （XPS）, respectively. The experimental results showed that a short time air plasma treatment led to morphological, wettability and chemical changes in the F2311 films. The surface hydrophilicity increased greatly after the plasma treatment, the static water contact angle decreased from 98.6° to 32°, and oxygen containing groups （C=O, O-C=O, etc. ） were introduced. Atomic force microscopy revealed that plasma produced by DBD etched F2311 films obviously. The roughness of the samples increased remarkably with the formation of peaks and valleys on the treated surfaces. The increased surface wettability may be correlated with both the introduction of hydrophilic groups due to air plasma oxidation of the surface and the change in surface morphology etched by DBD.     

Measurement ofHe2* density with an auxiliary measuring electrode in atmospheric pressure plasma jet

In this study, the density of metastable He₂* in an atmospheric-pressure plasma jet operating in helium with 0.001% nitrogen has been measured using an auxiliary measuring electrode technique. In the glow discharge mode, waveforms from two grounding electrodes, including one main discharge electrode and one auxiliary electrode, are captured. The isolated current peak formed by Penning ionization in waveforms from the auxiliary measuring electrode is identified to calculate the density of metastable He₂*. In our discharge environment, the helium metastable densities along the jet axis direction are between 2.26× 10¹³ and 1.74× 10¹³ cm^-3, which is in good agreement with the results measured by other techniques. This measurement technique can be conveniently applied to the diagnosis of metastableHe₂* in an atmospheric-pressure plasma jet array.     

Analysis of the critical active species for methylene blue decoloration in a dielectric barrier discharge plasma system

In the paper, a hybrid gas–liquid dielectric barrier discharge (DBD) plasma system was set up to treat a methylene blue (MB) solution. The effects of the change of the carrier gas, the gas bubbling rate and different kinds of scavenger addition, including sodium carbonate (Na₂CO₃), para benzoquinone (p-BQ), triethylenediamine and sodium dihydrogen phosphate (NaH₂PO₄), on the MB decoloration were reviewed to clarify the critical active species for the dye decoloration in the DBD plasma system. The obtained results show that higher decoloration of the MB solution could be achieved when O₂ was used as the carrier gas, which could be 100% after 20 min discharge treatment, and the result confirmed the crucial effect of O₃ in the MB decoloration. Based on the experiments of the scavenger addition, it could be concluded that O₂⁻ and ¹O₂ were two other important reactive oxygen species (ROS) for the MB decoloration. The results of the higher chemical oxygen demand removal and faster disappearance of the characteristic peak of the MB from the UV–vis analysis under O₂ bubbling conditions also proved the critical effect of the ROS formed by O₂ on the MB decoloration.     

Numerical simulation of plasma-assisted combustion of methane-air mixtures in combustion chamber

A two-dimensional mathematical model was developed to investigate the effects of dielectric barrier discharge (DBD) plasma on CH₄-air mixtures combustion at atmospheric pressure. Considering the physical and chemical processes of plasma-assisted combustion (PAC), plasma discharge, heat transfer and turbulent were simultaneously coupled into simulation of PAC. This coupling model consists of DBD kinetic model and methane combustion model. By comparing simulations and the original reference’s results, a high-accuracy of this model was validated. In addition, the effects of PAC actuation parameters on combustion characteristics were studied. Numerical simulations show that with an inlet airflow velocity of 10 ms ^-1, a CH₄-air mixtures’ equivalence ratio of 0.5, an applied voltage of 10 kV, a frequency of 1200 kHz, compared to conventional combustion (CC), the highest flame temperature rises by 32 K; outlet temperature distribution coefficient drops by 2.3%; the maximum net reaction rate of CH₄ and H₂O increase by 11.22% and 12.80% respectively; the maximum CO emission index decreases by 14.61%; the mixing region turbulence mixing time reduces by 89 ms.     

Plasma propagation in single-particle packed dielectric barrier discharges: joint effects of particle shape and discharge gap

In this work, a single Al₂O₃ particle packed dielectric barrier discharge (DBD) reactor with adjustable discharge gap is built, and the influences of the particle shape (ball and column) and the residual gap between the top electrode and particle on the electrical and optical characteristics of plasma are studied. Our research confirms that streamer discharge and surface discharge are the two main discharge patterns in the single-particle packed DBD reactor. The strong electric field distortion at the top of the ball or column caused by the dielectric polarization effect is an important reason for the formation of streamer discharge. The length of streamer discharge is proportional to the size of the residual gap, but the number of discharge times of a single voltage cycle shows an opposite trend. Compared to the column, a smooth spherical surface is more conducive to the formation of large and uniform surface discharges. The surface discharge area and the discharge intensity reach a maximum when the gap is equal to the diameter of the ball. All in all, the results of this study will provide important theoretical support for the establishment of the synergistic characteristics of discharge and catalysis in plasma catalysis.     

Electrical characters and optical emission spectra of VBD coupled SBD excited by sine AC voltage in atmospheric air

In this paper,volume coupled surface barrier discharge(V-SBD) with three structures possessing different volumes is excited by sine AC power in atmospheric air.Discharge images,waveforms of applied voltage and discharge current,and optical emission spectra simulating rotational and vibrational temperatures are recorded and analyzed.The effects of applied voltage on emission intensities of N_2(C~3Π_u→ B~3Π_g) and N_2~+(B~2∑_u~+ → X~2E_g~+),and rotational and vibrational temperatures are investigated.The results show that as applied voltage rises,emission intensities and rotational temperatures increase while vibrational temperatures decrease.In addition it is found that,as applied voltage varies,the rotational temperature of surface discharge changes faster than that of volume discharge.     

Generation of reactive atomic species of positive pulsed corona discharges in wetted atmospheric flows of nitrogen and oxygen

The emission spectra of excited radicals(OH(A~2E),O(3p~3 P),H_α(3P)) and emissive species(N_2~+(B~2∑_u~+),N_2(C_3Π_u)) produced by positive pulsed high-voltage needle-plane corona discharges in atmospheric N_2 and O_2 flows wetted with 10%H_2O at 80 ℃ are used to investigate the relative concentrations of the produced radicals.The results indicate that the tendencies of the concentrations of radicals with discharge conditions are similar to each other due to their similar excitation processes by electron collision.The influence of oxygen flow mixed with the nitrogen flow on the emission intensities of O(3p~5P → 3s~5S_2~.),H_α(3P → 2S),N_2_+(B~2∑_u~+ → X~2∑_g+0-0),and N_2(C~3Π_u → B~3Π_g 1-0) is presented.When the flow rate of oxygen addition is varied from 0-30 ml min~(-1),the emission intensities of O(3p~5P → 3s~5S_2~0.),H_α(3P → 2s),and N_2~+(B~2∑_u~+ →X~2∑_g 0-0) increase and reach a maximum.Then,if the oxygen flow rate increases further,the emission intensities tend to decrease.However,the intensity of N_2(C~3Π_u → B~3Π_g1-0) decreases monotonously with the increasing oxygen flow,which indicates that the electron density decreases with the increasing oxygen flow.By the tendencies of the relative intensities to N_2(C~3Π_u → B~3Π_g 1-0),the concentrations of the total produced O,H,and N_2~+ are shown to increase with the oxygen flow.Based on the reactions for the production of H and O without and with the addition of O_2,the analytic solutions for H and O production are derived in accordance with the experimental results.