Sustainable Ammonia Synthesis from Nitrogen and Water by One-Step Plasma Catalysis

Sustainable ammonia synthesis at ambient conditions that relies on renewable sources of energy and feedstocks is globally sought to replace the Haber-Bosch process.Here,using nitrogen and water as raw materials,a nonthermal plasma catalysis approach is demonstrated as an effective powerto-chemicals conversion strategy for ammonia production.By sustaining a highly reactive environment,successful plasma-catalytic production of NH_(3) was achieved from the dissociation of N_(2) and H_(2)O under mild conditions.Plasma-induced vibrational excitation is found to decrease the N_(2) and H_(2)O dissociation barriers,with the presence of matched catalysts in the nonthermal plasma discharge reactor contributing significantly to molecular dissociation on the catalyst surface.Density functional theory calculations for the activation energy barrier for the dissociation suggest that ruthenium catalysts supported on magnesium oxide exhibit superior performance over other catalysts in NH_(3) production by lowering the activation energy for the dissociative adsorption of N_(2) down to 1.07 eV.The highest production rate,2.67 mmol gcat.^(-1) h^(-1),was obtained using ruthenium catalyst supported on magnesium oxide.This work highlights the potential of nonthermal plasma catalysis for the activation of renewable sources to serve as a new platform for sustainable ammonia production.

Is a catalyst always beneficial in plasma catalysis? Insights from the many physical and chemical interactions

Plasma-catalytic dry reforming of CH_(4)(DRM) is promising to convert the greenhouse gasses CH_(4) and CO_(2) into value-added chemicals, thus simultaneously providing an alternative to fossil resources as feedstock for the chemical industry. However, while many experiments have been dedicated to plasma-catalytic DRM, there is no consensus yet in literature on the optimal choice of catalyst for targeted products,because the underlying mechanisms are far from understood. Indeed, plasma catalysis is very complex,as it encompasses various chemical and physical interactions between plasma and catalyst, which depend on many parameters. This complexity hampers the comparison of experimental results from different studies, which, in our opinion, is an important bottleneck in the further development of this promising research field. Hence, in this perspective paper, we describe the important physical and chemical effects that should be accounted for when designing plasma-catalytic experiments in general, high-lighting the need for standardized experimental setups, as well as careful documentation of packing properties and reaction conditions, to further advance this research field. On the other hand, many parameters also create many windows of opportunity for further optimizing plasma-catalytic systems.Finally, various experiments also reveal the lack of improvement in plasma catalysis compared to plasma-only, specifically for DRM, but the underlying mechanisms are unclear. Therefore, we present our newly developed coupled plasma-surface kinetics model for DRM, to provide more insight in the underlying reasons. Our model illustrates that transition metal catalysts can adversely affect plasmacatalytic DRM, if radicals dominate the plasma-catalyst interactions. Thus, we demonstrate that a good understanding of the plasma-catalyst interactions is crucial to avoiding conditions at which these interactions negatively affect the results, and we provide some recommendations for improvement. For instance, we believe that plasma-catalytic DRM may benefit more from higher reaction temperatures,at which vibrational excitation can enhance the surface reactions.

Application of in-plasma catalysis and post-plasma catalysis for methane partial oxidation to methanol over a Fe_2O_3-CuO/γ-Al_2O_3 catalyst

Methane partial oxidation to methanol （MPOM） using dielectric barrier discharge over a Fe2O3-CuO/γ-Al2O3 catalyst was performed.The multicomponent catalyst was combined with plasma in two different configurations,i.e.,in-plasma catalysis （IPC） and post-plasma catalysis （PPC）.It was found that the catalytic performance of the catalysts for MPOM was strongly dependent on the hybrid configuration.A better synergistic performance of plasma and catalysis was achieved in the IPC configuration,but the catalysts packed in the discharge zone showed lower stability than those connected to the discharge zone in sequence.Active species,such as ozone,atomic oxygen and methyl radicals,were produced from the plasma-catalysis process,and made a major contribution to methanol synthesis.These active species were identified by the means of in situ optical emission spectra,ozone measurement and FT-IR spectra.It was confirmed that the amount of active species in the IPC system was greater than that in the PPC system.The results of TG,XRD,and N2 adsorption-desorption revealed that carbon deposition on the spent catalyst surface was responsible for the catalyst deactivation in the IPC configuration.

RE-NiO_(x)(RE=Ce,Y,La)composite oxides coupled plasma catalysis for benzene oxidation and by-product ozone removal

Plasma-coupled catalysis is a promising volatile organic co mpounds(VOCs) removal technology because of its interactional principles of plasma decomposition and catalytic oxidation.However,the problem of harmful by-products is still in trouble.A series of rare earth doped RE-NiO_(x)(RE=Ce,Y,La) composite oxides were synthesized by metal organic frameworks(MOFs)-derived method for coupled plasma oxidation of benzene and by-product ozone removal.Compared with plasma alone,the 1%La-NiO_(x)catalyst shows the best enhancement of 50% for benzene conversion with complete removal of a maximum of 800 ppm ozone.The energy consumption for 90% benzene removal efficiency(η90%) is also reduced from 3600 to 1200 J/L.Characterization re sults of RE-NiO_(x) catalysts indicate that the doping of La causes interaction and synergistic effect between La and Ni,and the surface oxygen and lattice oxygen with defects play crucial roles in benzene oxidation and ozone decomposition,respectively.In addition,the decomposition mechanism of benzene and ozone under plasma is proposed.Plasma is responsible for the indiscriminate bond breaking in benzene and oxygen to form a variety of organic intermediates and ozone,while the La-NiO_(x) catalyst selectively oxidizes the intermediates to CO_(x)/H2O and decomposes the ozone into oxygen.

Generation of air discharge plasma in the cavities of porous catalysts:a modeling study

A study of the behaviors of air discharge plasma inside a catalyst’s pores is important to understand the plasma catalysis mechanism;however,few articles have reported the generation characteristics of air plasma in the pores of catalysts.The production of air microdischarge in a pore was studied by a two-dimensional fluid model,mainly focusing on the effect of pore size and applied voltage.The results show that an increase in the pore size in the range of 20–100μm facilitates the occurrence of microdischarge in the pore.In addition,at an applied voltage of 9 kV,the ionization of air mainly occurs near the topside of the pore when the pore diameter is less than 20μm,leading to a low plasma density in the pore,but the time-averaged plasma density in the pore reaches a maximum value at a 70μm pore diameter.Moreover,the applied voltage also has an important effect on the production of air microdischarge in the pore.The existence of a pore of 80μm diameter on the dielectric has no obvious influence on the plasma density in the pore at 2 kV applied voltage,but the plasma density in the pore begins to sharply rise when the voltage exceeds 3 kV due to the enhanced air ionization at higher applied voltage.The study indicates that microdischarge can be generated in a pore with a size of tens of micrometers,and the microdischarge in porous catalysts will affect the catalytic degradation efficacy of gaseous pollutants.

Charge transfer in plasma assisted dry reforming of methane using a nanosecond pulsed packed-bed reactor discharge

This paper is aimed to investigate the effect of packing material on plasma characteristic from the viewpoint of charge transfer process.Both the charge accumulation and release processes in the dielectric barrier discharge reactor and packed-bed reactor were investigated by measuring voltage and current waveforms and taking ICCD images.The packing material was ZrO2 pellets and the reactors were driven by a parameterized nanosecond pulse source.The quantity of transferred charges in the dielectric barrier discharge reactor was enhanced when decreasing pulse rise time or increasing pulse width(within 150 ns),but reduced when the gas gap was packed with pellets.The quantity of accumulated charges in the primary discharge was larger than the quantity of released charges in the secondary discharges in the dielectric barrier discharge reactor,but they were almost equal in the packed-bed reactor.It indicates that the discharge behavior has been changed from the view of charge transfer process once the gas gap was packed with pellets,and the ICCD images confirmed it.

Enhanced effect of plasma on catalytic reduction of CO2 to CO with hydrogen over Au/CeO2 at low temperature

In terms of the reaction of COreduction to CO with hydrogen, COconversion is very low at low temperature due to the limitation of thermodynamic equilibrium（TE）. To overcome this limitation, plasma catalytic reduction of COto CO in a catalyst-filled dielectric barrier discharge（DBD） reactor is studied. An enhanced effect of plasma on the reaction over Au/CeOcatalysts is observed. For both the conventionally catalytic（CC） and plasma catalytic（PC, Pin= 15 W） reactions under conditions of 400 °C, H/CO= 1,200 SCCM, GHSV = 12,000 mL·gcat·h, COconversions over Au/CeOreach 15.4% and 25.5% due to the presence of Au, respectively, however, those over CeOare extremely low and negligible. Moreover,COconversion over Au/CeOin the PC reaction exceeds 22.4% of the TE conversion. Surface intermediate species formed on the catalyst samples during the reactions are determined by in-situ temperatureprogrammed decomposition（TPD） technique. Interestingly, it disclosed that in the PC reaction, the formation of formate intermediate is enhanced by plasma, and the acceleration by plasma in the decomposition of formate species is much greater than that in the formation of formate species on Au/CeO. Enhancement factor is introduced to quantify the enhanced effect of plasma. Lower reactor temperature, higher gas hourly space velocity（GHSV）, and lower molar ratio of H/COwould be associated with larger enhancement factor.

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

In this work,a single Al_(2)O_(3) 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.

The Catalytic Effect of Metal Ions on the Degradation of 4-Chlorophenol Induced by an Aqueous Pulsed Discharge Plasma

The influence of metal ions, such as Fe^2＋, Fe^3＋, Cu^2＋ and Mn^2＋, on 4-CP degrada-tion was investigated in an aqueous pulsed discharge plasma system with or without the addition of a TiO2 photo-catalyst. From an analysis of the pseudo first-order rate constant （kcp） and energy efficiency （G50%） for 4-CP degradation, the experimental results show that the degrada- tion of 4-CP is much enhanced in the presence of ferrous ions at the optimal concentration of 0.2-0.8 mmol/L or 0.2 mmol/L in an aqueous pulsed discharge plasma without or with the TiO2 system, respectively, and the enhancement is ascribed to plasma induced Fenton and photo-Fenton reactions. Meanwhile, the rank of such metal ions for catalytic effect on 4-CP degradation was Fe^2＋〉 Fe^3＋ 〉 Cu^2＋ 〉 Mn^2＋ and Fe^2＋ 〉 Fe^3＋ 〉 Mn^2＋ 〉 Cu^2＋ for the former and the latter systems, respectively, and the reasons behind this were discussed through the analysis of active species, especially hydrogen peroxide.

Simultaneous catalytic removal of NOx and diesel PM over La_(0.9) K_(0.1) CoO_3 catalyst assisted by plasma

The simultaneous removal of NOx and particulate matter(PM) from diesel exhaust is investigated over a mixed metal oxide catalyst of La 0.9 K 0.1 CoO 3 loaded on γ-Al 2O 3 spherules with the assistant of plasma. It was found that NOx was reduced by PM in oxygen rich atmosphere, the CO 2 and N 2 were produced in the same temperature window without considering the N 2 formed by plasma decomposition. As a result, the temperature for the PM combustion decreases and the reduction efficiency of NOx to N 2 increases during the plasma process, which indicated that the activity of the catalyst can be improved by plasma. The NOx is decomposed by plasma at both low temperature and high temperature. Therefore, the whole efficiency of NOx conversion is enhanced.

Catalytic technology for water treatment by micro arc oxidation on Ti-AI alloy

The feasibility of the formation of a liquid plasma catalysis system through micro arc oxidation（MAO） under AC power with titanium-aluminum alloy electrodes was investigated.In the decolorization of organic dyeing wastewater simulated with Rhodamine B,Ti-Al alloy electrodes were superior over Ti electrodes and Al electrodes.The optimal molar percentage of Ti in alloy electrodes was 70%and the optimal decolorization rate was up to 88.9%if the additive suitable for Al was added into the solution to be treated.The decolorization rates were the same in the case of the alloy-alloy electrodes and alloy-Al electrodes.The proportion of the effects of plasma,TiO2 catalyzer during MAO and H2O2 after MAO in decolorization has been obtained.With the catalysis of TiO2 formed on the electrodes,the reaction rate was improved by a maximum of 95%and the decolorization rate was improved by a maximum of 71.6%.Based on the spectral analysis,the plasma catalysis mechanism has been studied.

Degradation of o-dichlorobenzene by DBD-NTP co-modified titanium gel catalyst

In order to study the degradation process of dioxins in industrial flue gas,the decomposition of o-dichlorobenzene(o-DCB)in a DBD plasma catalytic reactor was investigated.The results showed that an NTP-catalyzed system,especially using the Cu Mn Ti Oxcatalyst,had better o-DCB degradation performance compared to plasma alone.The combination of the Cu Mn Ti Oxcatalyst with NTP can achieve a degradation efficiency of up to 97.2%for o-DCB;the selectivity of CO and CO_(2)and the carbon balance were 40%,45%,and 85%,respectively.The dielectric constant and electrical property results indicated that the surface discharge capacity of the catalysts played a major role in the degradation of o-DCB,and a higher dielectric constant could suppress the plasma expansion and enhance the duration of the plasma discharge per discharge cycle.According to the O1s XPS and O_(2)-TPD results,the conversion of CO to CO_(2)follows the M-v-K mechanism;thus,the active species on the catalyst surface play an important role.Moreover,the Cu Mn Ti Oxand NTP mixed system exhibited excellent stability,which is probably because Cu doping improved the lifetime of the catalyst.This work can provide an experimental and theoretical basis for research in the degradation of o-DCB by plasma catalyst systems.

Efficient degradation of chlorobenzene in a non-thermal plasma catalytic reactor supported on CeO_2/HZSM-5 catalysts

Chlorobenzene removal was investigated in a non-thermal plasma reactor using CeO2/HZSM-5catalysts.The performance of catalysts was evaluated in terms of removal and energy efficiency.The decomposition products of chlorobenzene were analyzed.The results show that CeO2/HZSM-5 exhibited a good catalytic activity,which resulted in enhancements of chlorobenzene removal,energy efficiency,and the formation of lower amounts of by-products.With regards to CO2 selectivity,the presence of catalysts favors the oxidation of by-products,leading to a higher CO2 selectivity.With respect to ozone,which is considered as an unavoidable by-product in air plasma reactors,a noticeable decrease in its concentration was observed in the presence of catalysts.Furthermore,the stability of the catalyst was investigated by analyzing the evolution of conversion in time.The experiment results indicated that CeO2/HZSM-5 catalysts have excellent stability：chlorobenzene conversion only decreased from 78%to 60%after 75 hr,which means that the CeO2/HZSM-5 suffered a slight deactivation.Some organic compounds and chlorinated intermediates were adsorbed or deposited on the catalysts surface as shown by the results of Fourier Transform Infrared（FT-IR） spectroscopy,scanning electron microscope（SEM） and energy dispersive X-ray spectroscopy（EDS） analyses of the catalyst before and after the reaction,revealing the cause of catalyst deactivation.

Plasma-enhanced catalytic activation of CO_(2) in a modified gliding arc reactor

For the first time,this paper demonstrates a synergistic effect from the combination of a gliding arc discharge plasma with a photocatalyst TiO_(2) for CO_(2) dissociation.The effects of adding a tray downstream the discharge and the combination of the catalyst with plasma have been investigated.Two different combination modes of plasma catalysis,i.e.,in-plasma catalysis and post-plasma catalysis,have been evaluated with the emphasis on the analysis of potential mechanisms.The results show that modifying the gliding arc reactor by the addition of a tray can enhance the fraction of gas treated by plasma,thus improv-ing the reaction performance.An exceptional synergistic effect of combining the gliding arc discharge with TiO_(2) for CO_(2) activation forms in the in-plasma catalysis mode.The presence of TiO_(2) significantly enhances the CO_(2) conversion by 138% and the energy efficiency by 133%at a flow rate of 2 L/min.The plasma activation effect,which produces energetic electrons that can create the electron-hole pairs on the catalyst surface,is believed to be the major contributor to the generation of the plasma catalysis synergy.This mechanism has been further evidenced by the negligible influence of the post-plasma catalysis on the reaction performance.