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.     

Investigation on discharge characteristics of a coaxial dielectric barrier discharge reactor driven by AC and ns power sources

A coaxial dielectric barrier discharge(DBD) reactor with double layer dielectric barriers has been developed for exhaust gas treatment and excited either by AC power or nanosecond(ns)pulse to generate atmospheric pressure plasma. The comparative study on the discharge characteristics of the discharge uniformity, power deposition, energy efficiency, and operation temperature between AC and ns pulsed coaxial DBD is carried out in terms of optical and electrical characteristics and operation temperature for optimizing the coaxial DBD reactor performance. The voltages across the air gap and dielectric layer and the conduction and displacement currents are extracted from the applied voltages and measured currents of AC and ns pulsed coaxial DBDs for the calculation of the power depositions and energy efficiencies through an equivalent electrical model. The discharge uniformity and operating temperature of the coaxial DBD reactor are monitored and analyzed by optical images and infrared camera. A heat conduction model is used to calculate the temperature of the internal quartz tube. It is found that the ns pulsed coaxial DBD has a much higher instantaneous power deposition in plasma, a lower total power consumption, and a higher energy efficiency compared with that excited by AC power and is more homogeneous and stable. The temperature of the outside wall of the AC and ns pulse excited coaxial DBD reaches 158 ℃ and 64.3 ℃ after 900 s operation, respectively.The experimental results on the comparison of the discharge characteristics of coaxial DBDs excited by different powers are significant for understanding of the mechanism of DBDs,reducing energy loss, and optimizing the performance of coaxial DBD in industrial applications.     

Effect of methane content and the oscillating electric field between electrodes on atmospheric Ar/methane plasma jet and DLC coating deposition

In this work, the effects of the methane gas flow and the internal oscillating electric field between electrodes on radio-frequency(RF) atmospheric pressure argon/methane plasma jet and process of diamond-like carbon(DLC) film deposition have been investigated. Properties of RF atmospheric Ar/methane plasma jet such as active species density, length, electron temperature,appearance and ionization process of argon/methane plasma jet are changed due to the changing of methane flow content and electric field vector and its gradient. With increasing methane flow,the formation of C2 hydrocarbon and CH band content is decreased because injected electrical energy to a mixture of Ar/methane gases is insufficient to stabilize the ionization process of methane gas and the electrical-chemical reaction rate is decreased. With shortening the gas gap between two electrodes, electric field strength and its gradient are increased leading to more energy injection to the electron. Electrical-chemical reactions are strengthened leading to increasing the CH band content. These phenomena introduce the Ar/methane plasma jet in different modes causing to deposit the DLC film with different structures and properties. With using quartz glass and alumina ceramic as dielectric barriers tubes, RF atmospheric pressure Ar/methane plasma jet has been used to deposit DLC coating in different modes. Increasing methane content and shortening the gas gap leads to decreasing sp3 bonded content and the quality of the deposited film.     

Methane Conversion to C2 Hydrocarbons by Abnormal Glow Discharge at Atmospheric Pressure

Methane conversion to C2 hydrocarbons has been investigated with the addition of hydrogen in a plasma reactor of abnormal glow discharge at atmospheric pressure. The aim of this experiment is to minimize coke formation and improve discharge stability. The typical conditions in the experiment are 300 ml of total feed flux and 400 W of discharge power. The experimental results show that methane conversion is from 91.6% to 35.2% in mol, acetylene selectivity is from 90.2% to 57.6%, and ethylene selectivity is approximately from 7.8% to 3.6%, where the coke increases gradually along with the increase of CH4/H2 from 2 ： 8 to 9 ： 1. A stable discharge for a considerable running time can be obtained only at a lower ratio of CH4/H2 = 2：8 or 3： 7. These phenomena indicate that the coke deposition during methane conversion is obviously reduced by adding a large amount of hydrogen during an abnormal glow discharge. A qualitative interpretation is presented, namely, with abundant hydrogen, the possibility that hydrogen molecules are activated to hydrogen radicals is increased with the help of the abnormal glow discharge. These hydrogen radicals react with carbon radicals to form C2 hydrocarbon products. Therefore, the deposition of coke is restrained.     

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.     

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.     

Study on the Enhancement Effect of Dielectric Barrier Discharge on the Premixed Methane/Oxygen/Helium Flame Velocity

Recently,plasma-assisted combustion has become a potentially applicable technology in many combustion scenarios.In this paper,a dielectric barrier discharge(DBD) plasma generator is designed to explore the effect of plasma on the CH4 oxidation process,and several properties of combustion are considered.First,in the presence or absence of plasma discharge,physical appearance of the flame is examined and analyzed.Second,the flame propagation velocity is calculated by the flame front extracted from the imaging data with the Bunsen burner method.Finally,the main molecular components and their intensity variation in the flame and the plasma zones are identified with an emission spectrograph to analyze the effect of active species on the combustion process.We also discuss the possible kinetic regime of plasma-assisted combustion.Experimental results imply that plasma discharge applied to the premixed CH_4/O_2/He mixture significantly raises the flame speed with equivalence ratios ranging from 0.85 to 1.10,with the flame speed improved by 17%to 35%.It can be seen that plasma can improve methane oxidation efficiency in the premixed fuel/oxidizer,especially at a low equivalence ratio.     

A numerical simulation study on active species production in dense methane-air plasma discharge

Recently, low-temperature atmospheric pressure plasmas have been proposed as a potential type of ‘reaction carrier' for the conversion of methane into value-added chemicals. In this paper, the multi-physics field coupling software of COMSOL is used to simulate the detailed discharge characteristics of atmospheric pressure methane-air plasma. A two-dimensional axisymmetric fluid model is constructed, in which 77 plasma chemical reactions and 32 different species are taken into account. The spatial density distributions of dominant charged ions and reactive radical species, such as CH_4~+CH_3~+N_2~+O_2~+H, O, CH_3, and CH_2, are presented, which is due to plasma chemical reactions of methane/air dissociation(or ionization) and reforming of small fragment radical species. The physicochemical mechanisms of methane dissociation and radical species recombination are also discussed and analyzed.     

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.     

CO2 Reforming of CH4 by Atmospheric Pressure Abnormal Glow Plasma

A novel plasma atmospheric pressure abnormal glow discharge was used to investigate synthesis gas production from reforming methane and carbon dioxide. Special attentions were paid to the discharge characteristics and CH4, CO2 conversion, H2, CO selectivity, and ratio of H2/CO varied with the changing of discharging power, the total flux, and the ratio of CH4/CO2. Experiments were performed in wider operation variables, the discharging power of 240 to 600 W, the CH4/CO2 of 0.2 to 1.0 and the total flux of 140 to 500mL/min. The experiments showed that the conversion of CH4 and CO2 was up to 91.9% and 83.2%, the selectivity of CO and H2 was also up to 80% and 90% and H2/CO mole ratio was 0.2 to 1.2, respectively. A brief analysis for discharge characteristics and the experimental results were given.     

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.     

High concentration xylene decomposition and diagnostic analysis by non-thermal plasma in a DBD reactor

Dielectric barrier discharge (DBD) is utilized to decompose xylene vapor in mobile gas under normal atmospheric pressure.The plasma is generated by an AC power source with a frequency of 6 kHz.In the experiment,the discharge power on the DBD reactor was calculated by a Lissajous figure,and the specific input energy (SIE) of different discharge voltage or residence time was obtained.The concentrations of xylene,carbon monoxide and carbon dioxide in the gas were analyzed by gas chromatography.The spectra of DBD were diagnosed using a spectrometer.We calculated the conversion rate (CR),mineralization rate (MR) and carbon dioxide selectivity.The relationship between these quantities and the SIE was analyzed.The experimental results show that high concentration xylene can be decomposed mostly by DBD plasma.The CR can reach as high as 90％ with the main product of carbon dioxide.     

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.     

Numerical study of the influence of dielectric tube on propagation of atmospheric pressure plasma jet based on coplanar dielectric barrier discharge

A 2D fluid model was employed to simulate the influence of dielectric on the propagation of atmospheric pressure helium plasma jet based on coplanar dielectric barrier discharge (DBD). The spatio-temporal distributions of electron density, ionization rate, electrical field, spatial charge and the spatial structure were obtained for different dielectric tubes that limit the helium flow. The results show that the change of the relative permittivity of the dielectric tube where the plasma jet travels inside has no influence on the formation of DBD itself, but has great impact on the jet propagation. The velocity of the plasma jet changes drastically when the jet passes from a tube of higher permittivity to one of lower permittivity, resulting in an increase in jet length,ionization rate and electric field, as well as a change in the distribution of space charges and discharge states. The radius of the dielectric tube has a great influence on the ring-shaped or solid bullet structure. These results can well explain the behavior of the plasma jet from the dielectric tube into the ambient air and the hollow bullet in experiments.     

Conversion of NO with a catalytic packed-bed dielectric barrier discharge reactor

This paper discusses the conversion of nitric oxide (NO) with a low-temperature plasma induced by a catalytic packed-bed dielectric barrier discharge (DBD) reactor.Alumina oxide (Al2O3),glass (SiO2) and zirconium oxide (ZrO2),three different spherical packed materials of the same size,were each present in the DBD reactor.The NO conversion under varying input voltage and specific energy density,and the effects of catalysts (titanium dioxide (TiO2) and manganese oxide (MnOx) coated on Al2O3) on NO conversion were investigated.The experimental results showed that NO conversion was greatly enhanced in the presence of packed materials in the reactor,and the catalytic packed bed of MnOx/Al2O3 showed better performance than that of TiO2/Al2O3.The surface and crystal structures of the materials and catalysts were characterized through scanning electron microscopy analysis.The final products were clearly observed by a Fourier transform infrared spectrometer and provided a better understanding of NO conversion.     

An Experimental Study on Atmospheric Pressure Glow Discharge in Different Gases

Usually,the electrical breakdown of dielectric barrier discharge(DBD) at atmospheric pressure leads to a filamentary non-homogeneous discharge,However,it is also possible to obtain a diffuse DBD in homogeneous form,called atmospheric pressure glow discharge(APGD).We obtained a uniform APGD in helium and in the mixture of argon with alcohol,and studied the electrical characteristics of helium APGD.It if found that the relationship between discharge current and source frequency is different depending on the difference in gas gap when the applied voltage is kept constant.The discharge current shows an increasing trend with the increased frequency when gas gap is 0.8cm ,but the discharge current tends to decrease with the increased frequency when the gas gap increases.The discharge current always increases with the increased applied voltage when the source frequency is kept constant.We also observed a glow-like discharge in nitrogen at atmospheric pressure.     

Effect of insulating oil covering electrodes on the characteristics of a dielectric barrier discharge

In this study, the effects of the fluid cooling and electric field line deformation were investigated in a dielectric barrier discharge (DBD) plasma source. The DBD plasma jet is improved by covering the ground electrode and a power electrode with insulating oil. We obtained positive results as insulating oil prevents arc formation, while it improved the supplied power and plasma jet length, and increased radical production. Radical production of this nonthermal plasma jet is studied with polyvinyl alcohol–potassium iodide liquid.     

Effects of Dielectric Barrier Discharge Plasma Treatment on Pentachlorophenol Removal of Granular Activated Carbon

The pentachlorophenol(PCP)adsorbed granular activated carbon(GAC)was treated by dielectric barrier discharge(DBD)plasma.The effects of DBD plasma on the structure of GAC and PCP decomposition were analyzed by N_2 adsorption,thermogravimetric,scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS)and gas chromatographymass spectrometry(GC-MS).The experimental data of adsorption kinetics and thermodynamics of PCP on GAC were fitted with different kinetics and isotherm models,respectively.The results indicate that the types of N_2 adsorption isotherm of GAC are not changed by DBD plasma,while the specific surface area and pore volume increase after DBD plasma treatment.It is found that the weight loss of the saturated GAC is the highest,on the contrary,the weight loss of DBD treated GAC is the least because of reduced PCP residue on the GAC.The XPS spectra and SEM image suggest that some PCP on the GAC is removed by DBD plasma,and the surface of GAC treated by DBD plasma presents irregular and heterogeneous morphology.The GC-MS identification of by-products shows that two main dechlorination intermediate products,tetrachlorophenol and trichlorophenol,are distinguished.The fitting results of experimental data of adsorption kinetics and thermodynamics indicate that the pseudo-first-order and pseudo-second order models can be used for the prediction of the kinetics of virgin GAC and DBD treated GAC for PCP adsorption,and the Langmuir isotherm model fits better with the data of adsorption isotherm than the Freundlich isotherm in the adsorption of PCP on virgin GAC and DBD treated GAC.     

Exploration to generate atmospheric pressure glow discharge plasma in air

Atmospheric pressure glow discharge (APGD) plasma in air has high application value.In this paper,the methods of generating APGD plasma in air are discussed,and the characteristics of dielectric barrier discharge (DBD) in non-uniform electric field are studied.It makes sure that APGD in air is formed by DBD in alternating current electric field with using the absorbing electron capacity of electret materials to provide initial electrons and to end the discharge progress.Through designing electric field to form two-dimensional space varying electric field and three-dimensional space varying electric field,the development of electron avalanches in airgap is suppressed effectively and a large space of APGD plasma in air is generated.Further,through combining electrode structures,a large area of APGD plasma in air is generated.On the other hand,by using the method of increasing the density of initial electrons,millimeter-gap glow discharge in atmospheric pressure air is formed,and a maximum gap distance between electrodes is 8 ram.By using the APGD plasma surface treatment device composed of contact electrodes,the surface modification of high polymer materials such as aramid fiber and polyester are studied and good effect of modifications is obtained.The present paper provides references for the researchers of industrial applications of plasma.     

Conversion from Dimethyl Ether to Dimethoxymethane and Dimethoxyethane Using Dielectric-Barrier Discharge Plasma

Experimental investigation was conducted to convert dimethyl ether (DME) in the presence of steam using dielectric barrier discharge (DBD) at atmospheric pressure and 373 K.The flow rate of DME was 20 ml/min. The introduction of steam resulted in an increase in the DME conversion and the selectivity of oxygenates. Plasma steam-enhanced dimethyl ether (DME)conversion led to a direct synthesis of DMMT and DMET, with a high selectivity of 5.78% and 17.99%, respectively. The addition of steam promoted the formation of ““plasma aerosol““ that was favored for the formation of liquid oxygenates. The reaction pathway of plasma DME conversion was proposed.