Sustainable ammonia synthesis:An in-depth review of non-thermal plasma technologies

Ammonia serves both as a widely used fertilizer and environmentally friendly energy source due to its high energy density,rich hydrogen content,and emissions-free combustion.Additionally,it offers convenient transportation and storage as a hydrogen carrier.The dominant method used for large-scale ammonia production is the Haber-Bosch process,which requires high temperatures and pressures and is energy-intensive.However,non-thermal plasma offers an eco-friendly alternative for ammonia synthesis,gaining significant attention.It enables ammonia production at lower temperatures and pressures using plasma technology.This review provides insights into the catalyst and reactor developments,which are pivotal for promoting ammonia efficiency and addressing existing challenges.At first,the reaction kinetics and mechanisms are introduced to gain a comprehensive understanding of the reaction pathways involved in plasma-assisted ammonia synthesis.Thereafter,the enhancement of ammonia synthesis efficiency is discussed by developing and optimizing plasma reactors and effective catalysts.The effect of other feeding sources,such as water and methane,instead of hydrogen is also presented.Finally,the challenges and possible solutions are outlined to facilitate energy-saving and enhance ammonia efficiency in the future.

Non-thermal plasma enhanced catalytic conversion of methane into value added chemicals and fuels

Plasma catalysis has recently gained increased attention for its application in gas conversion,notably in processes like the dry reforming of methane aimed at transforming them into valuable chemicals and fuels.As this field is still in its early developmental stages,there is a crucial necessity to explore the synergistic mechanism between plasma and catalysts.The optimization of catalysts is imperative to improve their selectivity and conversion rates for desired products in a plasma environment.Additionally,delving into microscale investigations of plasma characteristics,such as electron temperature and the density of energetic species,is essential to enhance the stability and activity of catalysts.This review examines recent advancements in various methane conversion techniques,encompassing Dry Reforming of Methane,Steam Methane Reforming,Pa rtial Oxidation of Metha ne,and Methane Decomposition utilizing non-thermal dielectric barrier discharge(DBD)plasma.The aim is to gain a deeper understanding of plasma-catalyst interactions and to refine catalyst selection strategies for maximizing the production of desired products such as syngas,oxygenates,or higher hydrocarbons.The review delves into the catalytic mechanisms that delineate the synergistic effects between DBD plasma and catalyst in each technology,shedding light on the role of diverse catalytic properties in activating methane molecules-a pivotal step in hybrid plasma-catalytic reactions.Various approaches employed by researchers in exploring suitable catalysts and optimal reaction conditions to bolster CH_(4) conversion rates and selectivity using DBD plasma are discussed.Additionally,the review identifies gaps in the realm of plasma catalysis,underscoring the necessity for further research to fully understand the underlying principles of plasma and catalyst which are not trivial to uncover.

Modulation of starch digestibility using non-thermal processing techniques:A review

Obesity and type 2 diabetes are widespread throughout the world, especially in developed countries. Starch is an important part of human staple food, the modulating of starch digestibility is conducive to reducing postprandial blood glucose levels and alleviating the chronic disease caused by high caloric intake. The digestion properties of starch are correlated with its structural features, including crystallization, amylose/amylopectin ratio, non-starch components, etc. Among the modified methods applied to regulate starch digestibility, non-thermal processing techniques(NTPT) receive extensive attention due to the characteristics of safety, environmental friendliness and high efficiency. The influence and mechanism of NTPT on the digestion properties of starch are discussed in this review, including ultrasounds, high pressure, γ-irradiation, etc. NTPT induces the alternation of morphological and structural characteristics of native starch, changing their sensitivity to enzymes. The effects of NTPT on the digestibility of starch are highly related to the processing parameters and structure characteristics of native starch. The review shows that NTPT is an effective way to modulate the digestion properties of starch and prevent people from suffering from chronic diseases such as obesity and type 2 diabetes.

Degradation of chlorobenzene by non-thermal plasma coupled with catalyst:influence of catalyst,interaction between plasma and catalyst

Non-thermal plasma(NTP)is considered to be a promising technology for the removal of volatile organic compounds;however,its application is limited by low CO_(2) selectivity and undesirable by-products.To overcome these issues,this paper discusses the degradation of chlorobenzene(CB)in systems of NTP coupled with catalysts,and the influence of catalyst locations in the NTP was investigated.In addition,the interaction between plasma and catalyst was also explored.The results indicated that the degradability of CB was remarkably improved through the combination of NTP with catalysts,and the formation of ozone was effectively inhibited.The degradation efficiency increased from 33.9%to 79.6%at 14 kV in the NTPcatalytic system,while the ozone concentration decreased from 437 to 237 mg m^(-3),and the degradation efficiency of in plasma catalysis(IPC)systems was superior to that of the post plasma catalysis system,while the inhibition ability of ozone exhibited an opposing trend.In the IPC system,the degradation efficiency was 87.7%at 14 k V,while the ozone concentration was151 mg m^(-3).Besides,the plasma did not destroy the pore structure and crystal structure of the catalyst,but affected the surface morphology and redox performance of the catalyst.Thus,NTP coupled catalytic system could improve the degradation performance of CB.Furthermore,the plasma discharge characteristics played a major role in the NTP synergistic catalytic degradation of CB.Finally,based on the experiment analysis results,the general reaction mechanism of CB degradation in an IPC reaction system was proposed.

Revisiting “Non-Thermal” Batch Microwave Oven Inactivation of Microorganisms

Over the last few decades there has been active discussion concerning the mechanisms involved in “non-thermal” microwave-assisted inactivation of microorganisms. This work presents a novel non-invasive acoustic measurement of a domestic microwave oven cavity-magnetron operating at fo = 2.45 ± 0.05 GHz (λo ~ 12.2 cm) that is modulated in the time-domain (0 to 2 minutes). The measurements reveal the cavity-magnetron cathode filament cold-start warm-up period and the pulse width modulation periods (time-on time-off and base-time period, where time-on minus base-time = duty cycle). The waveform information is used to reconstruct historical microwave “non-thermal” homogeneous microorganism inactivation experiments: where tap-water is used to mimic the microorganism suspension;and ice, crushed ice, and ice slurry mixture are used as the cooling media. The experiments are described using text, diagrams, and photographs. Four key experimental parameters are indentified that influence the suspension time-dependent temperature profile. First, where the selected process time > the time-base, the cavity-magnetron continuous wave rated power should be used for each second of microwave illumination. Second, external crushed ice and ice slurry baths induce different cooling profiles due to difference in their heat absorption rates. In addition external baths may shield the suspension resulting in a retarding of the time-dependent heating profile. Third, internal cooling systems dictate that the suspension is directly exposed to microwave illumination due to the absence of surrounding ice volume. Fourth, four separated water dummy-loads isolate and control thermal heat transfer (conduction) to and from the suspension, thereby diverting a portion of the microwave power away from the suspension. Energy phase-space projections were used to compare the “non-thermal” energy densities of 0.03 to 0.1 kJ·m-1 at 800 W with reported thermal microwave-assisted microorganism inactivation energy densities of 0.5 to 5 kJ·m-1 at 1050 ± 50 W. Estimations of the “non-thermal” microwave-assisted root mean square of the electric field strength are found to be in the range of 22 to 41.2 V·m-1 for 800 W.

Simultaneous removal of NO and SO_2 from dry gas stream using non-thermal plasma

In order to investigate the feasibility of sequential removal NO and SO2 using non-thermal plasma and adsorbent simultaneously, the removal of NO and SO2 from dry gas stream （NO/SO2/N2/O2） with very little O2 using non-thermal plasma was investigated using a coaxial dielectric barrier discharge. Comparative experiments were carried out in the dry gas stream with and without Ar respectively at O2 concentration of 0.1%. The results showed that NO could be removed remarkably and it would be enhanced in the presence of Ar in the dry gas stream. It seems that SO2 could not be removed unless there is Ar in the dry gas stream. The mechanism of removal of NO and SO2 in the dry gas stream was discussed.

Study on purification technology of polyacrylamide wastewater by non-thermal plasma

In this work, non-thermal plasma has been applied to treat polyacrylamide（PAM） wastewater.We have investigated the influence of the rule of PAM wastewater initial pH, solution concentration and discharge time, discharge voltage on chemical oxygen demand（COD）degradation rate. At the same time, the effect of pH and discharge time on the viscosity removal rate of PAM solution was also studied. Then, the effect of pH on the viscosity removal rate of1.0 gl-1 PAM solution was studied separately. Through orthogonal test, the factors affecting the COD degradation rate of PAM wastewater were determined as follows: discharge time > discharge voltage > solution concentration > wastewater initial pH. The COD highest removal rate of PAM wastewater reached 85.74%, when the optimal conditions are as follows:discharge voltage 40 k V, discharge time 5 h, solution concentration 1.0 gl-1, pH 1.5. This research provides some basic data and new theoretical basis for PAM wastewater purification.

Synergistic removal of nitrogen monoxide by non-thermal plasma and catalyst simultaneously

An experimental system of De-NO with plasma-catalyst（Cu zeolite） was established to investigate the differences between De- NO with plasma-catalyst and De-NO only with plasma, to provide the instruction for selecting appropriate catalyst and operating condition, The characteristics of De-NO with plasma and De-NO with plasma-catalyst were investigated comparatively by experiments. The experimental results show that De-NO with plasma-catalyst has high NO removal rate; Cu zeolite is an effective catalyst which can promote NO removal rate in plasma remarkably; De-NO with plasma-catalyst should be operated at low temperature and the temperature has opposite effects on the function of catalvst and plasma; water vapor and O2 can increase the NO removal rate.

Non-thermal ablation of rabbit liver VX2 tumor by pulsed high intensity focused ultrasound with ultrasound contrast agent:Pathological characteristics

AIM： To investigate the pathological characteristics of non-thermal damage induced by pulsed high intensity focused ultrasound （PHIFU） combined with ultrasound contrast agent （UCA）, SonoVue （Bracco SpA, Milan, Italy） in rabbit liver VX2 tumor. METHODS： Liver VX2 tumor models were established in 20 rabbits, which were divided randomly into PHIFU combined with ultrasound contrast agent group （PHIFU ＋ UCA group） and sham group. In the PHIFU ＋ UCA group, 0.2 mL of SonoVue was injected intravenously into the tumor, followed by ultrasound exposure of Isp 5900 W/cm^2. The rabbits were sacrificed one day after ultrasound exposure. Specimens of the exposed tumor tissues were obtained and observed pathologically under light microscope and transmission electron microscope. The remaining tumor tissues were sent for 2,3,5-Triphenyltetrazolium chloride （TTC） staining. RESULTS： Before Trc staining, tumor tissues in both the sham and the PHIFU ＋ UCA groups resembled gray fish meat, After TIC staining, the tumor tissues were uniformly stained red, with a clear boundary between tumor tissue and normal tissue, Histological examination showed signs of tumor cell injury in PHIFU ＋ UCA group, with cytoplasmic vacuoles of various sizes, chromatin margination and karyopyknosis. Electron microscopic examination revealed tumor cell volume reduction, karyopyknosis, chromatin margination, intercellular space widening, the presence of high electro＇n-density apoptotic bodies and vacuoles in cytoplasm. CONCLUSION： The non-thermal effects of PHIFU combined with UCA can be used to ablate rabbit liver VX2 tumors.

Non-thermal Plasma Suppresses Bacterial Colonization on Skin Wound and Promotes Wound Healing in Mice

The present study evaluated the effect of non-thermal plasma on skin wound healing in BalB/c mice.Two 6-mm wounds along the both sides of the spine were created on the back of each mouse（n=80） by using a punch biopsy.The mice were assigned randomly into two groups,with 40 animals in each group：a non-thermal plasma group in which the mice were treated with the non-thermal plasma;a control group in which the mice were left to heal naturally.Wound healing was evaluated on postoperative days（POD） 4,7,10 and 14（n=5 per group in each POD） by percentage of wound closure.The mice was euthanized on POD 1,4,7,10,14,21,28 and 35（n=1 in each POD）.The wounds were removed,routinely fixed,paraffin-embedded,sectioned and HE-stained.A modified scoring system was used to evaluate the wounds.The results showed that acute inflammation peaked on POD 4 in non-thermal plasma group,earlier than in control group in which acute inflammation reached a peak on POD 7,and the acute inflammation scores were much lower in non-thermal group than in control group on POD 7（P0.05）.The amount of granular tissue was greater on POD 4 and 7 in non-thermal group than in control group（P0.05）.The re-epithelialization score and the neovasularization score were increased significantly in non-thermal group when compared with control group on POD 7 and 10（P0.05 for all）.The count of bacterial colonies was 103 CFU/mL on POD 4 and 20 CFU/mL on POD 7,significantly lower than that in control group（109 CFU/mL on POD 4 and 1012 CFU/mL on the POD 7）（P0.05）.It was suggested that the non-thermal plasma facilitates the wound healing by suppressing bacterial colo-nization.

Recent advances in non-thermal plasma(NTP)catalysis towards C1 chemistry

C1 chemistrymainly involves the catalytic transformation of C1molecules(i.e.,CO,CO2,CH4 and CH3OH),which usually encounters thermodynamic and/or kinetic limitations.To address these limitations,non-thermal plasma(NTP)activated heterogeneous catalysis offers a number of advantages,such as relatively mild reaction conditions and energy efficiency,in comparison to the conventional thermal catalysis.This review presents the state-of-the-art for the application of NTP-catalysis towards C1 chemistry,including the CO2 hydrogenation,reforming of CH4 and CH3OH,and water-gas shift(WGS)reaction.In the hybrid NTP-catalyst system,the plasma-catalyst interactions aremultifaceted.Accordingly,this reviewalso includes a brief discussion on the fundamental research into themechanisms of NTP activated catalytic C1 chemistry,such as the advanced characterisation methods(e.g.,in situ diffuse reflectance infrared Fourier transform spectroscopy,DRIFTS),temperatureprogrammed plasma surface reaction(TPPSR),kinetic studies.Finally,prospects for the future research on the development of tailor-made catalysts for NTP-catalysis systems(which will enable the further understanding of its mechanism)and the translation of the hybrid technique to practical applications of catalytic C1 chemistry are discussed.

Recent progress on non-thermal plasma technology for high barrier layer fabrication

This review describes the application of non-thermal plasma（NTP） technology for high barrier layer fabrication in packaging area.NTP technology is considered to be the most prospective approaches for the barrier layer fabrication over the past decades due to unpollution,high speed,low-costing.The applications of NTP technology have achieved numerous exciting results in high barrier packaging area.Now it seemly demands a detailed review to summarize the past works and direct the future developments.This review focuses on the different NTP resources applied in the high barrier area,the role of plasma surface modification on packaging film surface properties,and the deposition of different barrier coatings based on NTP technology.In particular,this review emphasizes the cutting-edge technologies of NTP on interlayer deposition with organic,inorganic for multilayer barriers fabrication.The future prospects of NTP technology in high barrier film areas are also described.

Sterilization of Staphylococcus Aureus by an Atmospheric Non-Thermal Plasma Jet

An atmospheric non-thermal plasma jet was developed for sterilizing the Staphylococcus aureus （S. aureus）. The plasma jet was generated by dielectric barrier discharge （DBD）, which was characterized by electrical and optical diagnostics. The survival curves of the bacteria showed that the plasma jet could effectively inactivate 10 6 cells of S. aureus within 120 seconds and the sterilizing efficiency depended critically on the discharge parameter of the applied voltage. It was further confirmed by scanning electron microscopy （SEM） that the cell morphology was seriously damaged by the plasma treatment. The plasma sterilization mechanism of S. aureus was attributed to the active species of OH, N 2 ＋ and O, which were generated abundantly in the plasma jet and characterized by OES. Our findings suggest a convenient and low-cost way for sterilization and inactivation of bacteria.

Non-thermal effects of 0.1 THz radiation on intestinal alkaline phosphatase activity and conformation

Alkaline phosphatase(ALP) plays an integral role in the metabolism of liver and development of the skeleton in humans. To date, the interactions between different-duration terahertz(THz) radiation and ALP activities, as well as the influence mechanism are still unclear. In this study, using the para-nitro-phenyl-phosphate(p NPP) method, we detect changes in ALP activities during 40-minute THz radiation(0.1 THz, 13 m W/cm^2). It is found that the activity of ALP decreases in the first 25 min, and subsequently increases in the later 15 min. Compared with the activity of ALP being heated, the results suggest that short-term terahertz radiation induces a decrease in enzyme activity through the non-thermal mechanism. In order to explore the non-thermal effects of THz radiation on ALP, we focus on the impacts of 0.1 THz radiation for 20 min on the activity of ALP in different concentrations. The results reveal that the activity of ALP decreases significantly after exposure to THz radiation. In addition, it could be deduced from fluorescence, ultraviolet-visible(UV-vis), and THz spectra results that THz radiation has induced changes in ALP structures. Our study unlocks non-thermal interactions between THz radiation and ALP, as well as suggests that THz spectroscopy is a promising technique to distinguish ALP structures.

Characteristics of non-thermal AC arcs in multi-arc generator

To obtain large-volume non-thermal arc plasma(NTAP), a multiple NTAP generator with three pairs of electrodes has been developed. The arc plasma characteristics, including dynamic process, spatial distribution, and rotation velocity in the discharge zone, were investigated by high speed photograph and image processing methods. The results showed that the dynamic behaviors and spatial distribution of the arc plasma were strongly related to the electrode configuration.A swirl flow of multi-arc plasma was formed by adjusting the electrode configuration, and a steady luminance area was clearly observed in the center of the discharge zone. Moreover, the size of the luminance area increased by decreasing the gas flow rate. The electrical connection in series could be formed between/among these arc columns with their respective driving power supplies in the multi-arc dynamic evolution process. An approximately periodical process of acceleration and deceleration of the arc rotation velocity was observed in the multi-arc generator with swirl flow configuration. In general, the mean velocity of arc rotation was higher in the multi-arc generator with swirl flow configuration when a pair of electrodes driven by a power supply were opposite to each other rather than adjacent.

Investigation of non-thermal atmospheric plasma for the degradation of avermectin solution

Increasing concern with regard to food safety in the presence of pesticide residues(PRs) on the surface of agricultural products has resulted in the rapid development of practical degrading technologies for corresponding PRs. In this paper, an unconventional method of degrading pesticides, non-thermal atmospheric plasma(NTAP), was proposed to degrade the avermectin(AVM) in aqueous solution. Optical emission spectroscopy shows that NTAP, consisting of filamentary streamers, contains a variety of reactive oxygen species(ROS) that may interact with AVM. The high-performance liquid chromatography(HPLC)-MS/MS results indicate that the efficiency of AVM degradation seriously depends on multiple operation parameters of the NTAP,including the applied voltage, treatment time and gas flow rate. The maximum degradation rate of AVM was observed to be 97.47% after 240 s exposure under NTAP with an applied voltage of 18 kV and gas flow rate of 1 l min-1. Molecular dynamics simulation based on a reactive force field for the interaction between O(ground state atomic oxygen) and AVM was performed to analyze the underpinning mechanisms. The simulation result shows the possible pathways of the NTAPgenerated O degrading AVM by destroying the glycosyl group or fracturing the ester group.

Study of Non-Thermal DC Arc Plasma of CH_4/Ar at Atmospheric Pressure Using Optical Emission Spectroscopy and Mass Spectrometry

Non-thermal C/H/Ar plasmas are widely applied to carbonaceous material production and processing.In this work,plasma parameters and gaseous species of the atmospheric non-thermal C/H/Ar plasmas produced by an atmospheric-pressure DC arc discharge generator in CH_4/Ar were investigated.The voltage-current characteristics were measured for different CH_4/Ar ratios.Optical emission spectroscopy was employed to analyze the electron excitation temperature,gas temperature and electron density under various discharge conditions.The hydrocarbon molecules produced in the CH4/Ar plasmas were detected with photoionization mass spectrometry.The optical spectral results demonstrated that the electron excitation temperature was 0.4-1 eV,the gas temperature was 2800-4200 K and the electron density was in the range of（5-20）×10^15 cm^-3.The mass spectrum indicated that a variety of unsaturated hydrocarbons（C2H4,C3H6,C6H6,etc.） and several highly unsaturated hydrocarbons（C4H2,C5H6,etc.） were produced in the non-thermal arc plasmas.

Non-Thermal Radio Frequency Stimulation of Tubulin Polymerization in Vitro: A Potential Therapy for Cancer Treatment

The use of radio frequency energy is an established technology for certain oncology therapies. Direct inputs of radio frequency (RF) energy as thermal energy are applied to ablate tumors or catalyze secondary reactions in adjunct treatments against certain tumor types. Yet, other applications are being developed which take advantage of properties of RFs that impinge on biological proteins and cells without thermal effects. Here we report a proof-of-concept application of specific, digitally encoded, low power (non-thermal) radio frequency energy in an in vitro preparation of a tubulin polymerization assay. The radio frequency energy signal, designated M2(3), was applied to the tubulin polymerization assay samples during spectrophotometric measurements to assess the effectiveness for enhancing tubulin polymerization. A commercially available taxane (paclitaxel) that promotes tubulin polymerization was used as a control to assess the effectiveness of the M2(3) radio frequency energy signal on tubulin polymerization rates. A low power, specific, digital radio frequency energy signal is capable of promoting tubulin polymerization as effectively as a commercially available taxane.

Mechanism and Kinetics Analysis of NO/SO_2/N_2/O_2 Dissociation Reactions in Non-Thermal Plasma

The kinetics mechanism of the dissociation reactions in a NO/SO2/N2/O2 system was investigated in consideration of energetic electrons＇ impacts on a non-thermal plasma. A model was derived from the Boltzmann equation and molecule collision theory to predict the dissociation reaction rate coefficients. Upon comparison with available literature, the model was confirmed to be acceptably accurate in general. Several reaction rate coefficients of the NO/SO2/N2/O2 dissociation system were derived according to the Arrhenius formula. The activation energies of each plasma reaction were calculated by quantum chemistry methods. The relation between the dissociation reaction rate coefficient and electron temperature was established to describe the importance of each reaction and to predict relevant processes of gaseous chemical reactions. The sensitivity of the mechanism of NO/SO2/N2/O2 dissociation reaction in a non-thermal plasma was also analysed.

Improvement of Polytetrafluoroethylene Surface Energy by Repetitive Pulse Non-Thermal Plasma Treatment in Atmospheric Air

Improvement of polytetrafluoroethylene surface energy by non-thermal plasma treatment is presented, using a nanosecond-positive-edge repetitive pulsed dielectric barrier discharge generator in atmospheric air. The electrical parameters including discharging power, peak and density of micro-discharge current were calculated, and the electron energy was estimated. Surface treatment experiments of polytetrafluoroethylene films were conducted for both different applied voltages and different treating durations. Results show that the surface energy of polytetrafluoroethylene film could be improved to 40 mJ/m2 or more by plasma treatment. Surface roughness measurement and surface X-ray photoelectron spectroscopy analysis indicate that there are chemical etching and implantation of polar oxygen groups in the sample surface treating process, resulting in the improvement of the sample surface energy. Compared with an AC source of 50 Hz, the dielectric barrier discharges generated by a repetitive pulsed source could provide higher peak power, lower mean power, larger micro-discharge current density and higher electron energy. Therefore, with the same applied peak voltage and treating duration, the improvement of polytetrafluoroethylene surface energy using repetitive pulsed plasma is more effective, and the plasma treatment process based on repetitive pulsed dielectric barrier discharges in air is thus feasible and applicable.