The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for ...The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.展开更多
Reasonable nitrogen(N) application is a promising strategy for reducing crop cadmium(Cd) toxicity. However, the specific form of N and the required amount that affect Cd tolerance and accumulation in rice remain uncle...Reasonable nitrogen(N) application is a promising strategy for reducing crop cadmium(Cd) toxicity. However, the specific form of N and the required amount that affect Cd tolerance and accumulation in rice remain unclear. This study explored the influence of different N-fertilizer forms(NH_(4)NO_(3), NH_4Cl, and KNO_(3)) and dosages on Cd tolerance and uptake in Cd-stressed N-sensitive and N-insensitive indica rice accessions. The results indicated that the Cd tolerance of N-sensitive indica accessions is more robust than that of N-insensitive ones. Furthermore, the shoot Cd content and Cd translocation rate in both N-sensitive and N-insensitive indica accessions decreased with an appropriate supply of NH_(4)NO_(3) and NH_4Cl, whereas they were comparable or slightly increased with increased KNO_(3). Unfortunately, we did not find significant and regular differences in Cd accumulation or translocation between N-sensitive and N-insensitive rice accessions. Consistent with the reduction of shoot Cd content, the addition of NH_(4)NO_(3) and NH_4Cl also inhibited the instantaneous root Cd^(2+) uptake. The expression changes of Cd transport-related genes under different N forms and dosages suggested that the decreased shoot Cd content, caused by the increased supply of NH_(4)NO_(3) and NH_4Cl, is likely achieved by reducing the transcription of OsNRAMP1 and OsIRT1. In summary, our findings reveal that an appropriate supply of NH_(4)NO_(3) and NH_4Cl could reduce Cd uptake and transport in rice seedlings, suggesting that rational N management could reduce the Cd risk in rice production.展开更多
The nitrite(NO_(2)^(−))to ammonia(NH3)electroreduction reaction(NO_(2)^(−)RR)would be impeded by sluggish proton-coupled electron transfer kinetics and competitive hydrogen evolution reaction(HER).A key to improving t...The nitrite(NO_(2)^(−))to ammonia(NH3)electroreduction reaction(NO_(2)^(−)RR)would be impeded by sluggish proton-coupled electron transfer kinetics and competitive hydrogen evolution reaction(HER).A key to improving the NH_(3) selectivity is to facilitate adsorption and activation of NO_(2)^(−),which is generally undesirable in unitary species.In this work,an efficient NO_(2)^(−)RR catalyst is constructed by cooperating Pd with In2O3,in which NO_(2)^(−)could adsorb on interfacial dual-site through“Pd–N–O–In”linkage,leading to strengthened NO_(2)^(−)adsorption and easier N=O bond cleavage than that on unitary Pd or In2O3.Moreover,the Pd/In_(2)O_(3)composite exhibits moderate H^(*)adsorption,which may facilitate protonation kinetics while inhibiting competitive HER.As a result,it exhibits a fairly high NH_(3)yield rate of 622.76 mmol h^(−1)g^(−1)cat with a Faradaic efficiency(FE)of 95.72%,good selectivity of 91.96%,and cycling stability towards the NO_(2)^(−)RR,surpassing unitary In_(2)O_(3)and Pd/C electrocatalysts.Besides,computed results indicate that NH_(3)production on Pd/In_(2)O_(3)follows the deoxidation to hydrogenation pathway.This work highlights the significance of H^(*)and NO_(2)^(−)adsorption modulation and N=O activation in NO_(2)^(−)RR electrochemistry by creating synergy between a mediocre catalyst with an appropriate cooperator.展开更多
Lithium-sulfur(Li-S)batteries are one of the most promising modern-day energy supply systems because of their high theoretical energy density and low cost.However,the development of high-energy density Li-S batteries ...Lithium-sulfur(Li-S)batteries are one of the most promising modern-day energy supply systems because of their high theoretical energy density and low cost.However,the development of high-energy density Li-S batteries with high loading of flammable sulfur faces the challenges of electrochemical performance degradation owing to the shuttle effect and safety issues related to fire or explosion accidents.In this work,we report a three-dimensional(3D)conductive nitrogen-doped carbon foam supported electrostatic self-assembled MXene-ammonium polyphosphate(NCF-MXene-APP)layer as a heat-resistant,thermally-insulated,flame-retardant,and freestanding host for Li-S batteries with a facile and costeffective synthesis method.Consequently,through the use of NCF-MXene-APP hosts that strongly anchor polysulfides,the Li-S batteries demonstrate outstanding electrochemical properties,including a high initial discharge capacity of 1191.6 mA h g^(-1),excellent rate capacity of 755.0 mA h g^(-1)at 1 C,and long-term cycling stability with an extremely low-capacity decay rate of 0.12%per cycle at 2 C.More importantly,these batteries can continue to operate reliably under high temperature or flame attack conditions.Thus,this study provides valuable insights into the design of safe high-performance Li-S batteries.展开更多
Previous studies have revealed that ammonia nitrogen has several adverse effects on clam Ruditapes philippinarum.However,knowledge is lacking regarding the related proteins involved in the toxicological responses,whic...Previous studies have revealed that ammonia nitrogen has several adverse effects on clam Ruditapes philippinarum.However,knowledge is lacking regarding the related proteins involved in the toxicological responses,which is vital to elucidate the underlying mechanism of ammonia nitrogen.In this study,clams R.philippinarum were exposed to ammonia nitrogen for 21 d at two environmentally relevant concentrations.The tandem mass tags approach(TMT)was applied to assay the differentially expressed proteins(DEPs)in clam gill tissues on the 3 rd and 21 st day.Finally,a total of 7263 proteins were identified.Bioinformatics analyses revealed that clam protein profiles changed in dose-and time dependent manner after ammonia nitrogen exposure.We inferred that the clams may face heavy challenges after ammonia exposure,such as unbalanced gender ratio,lysosomal disease,energy lack,neurological disorders,altered glutamine metabolism,increased lipid synthesis,and impaired immunity.Variation profiles of enzyme activities of glutaminase and glutamine synthase provided direct evidence to verify the related inference from proteome data.Most of the inferred toxic effects merit further study.This study identified important proteins related to ammonia nitrogen toxicity in the clam and indicated the severe stress of marine ammonia pollution on the healthy development of mollusc aquaculture.展开更多
For the deep understanding on combustion of ammonia/diesel,this study develops a reduced mechanism of ammonia/diesel with 227 species and 937 reactions.The sub-mechanism on ammonia/interactions of N-based and C-based ...For the deep understanding on combustion of ammonia/diesel,this study develops a reduced mechanism of ammonia/diesel with 227 species and 937 reactions.The sub-mechanism on ammonia/interactions of N-based and C-based species(N—C)/NOx is optimized using the Non-dominated Sorting Genetic Algorithm II(NSGA-II)with 200 generations.The optimized mechanism(named as 937b)is validated against combustion characteristics of ammonia/methane(which is used to examine the accuracy of N—C interactions)and ammonia/diesel blends.The ignition delay times(IDTs),the laminar flame speeds and most of key intermediate species during the combustion of ammonia/methane blends can be accurately simulated by 937b under a wide range of conditions.As for ammonia/diesel blends with various diesel energy fractions,reasonable predictions on the IDTs under pressures from 1.0 MPa to5.0 MPa as well as the laminar flame speeds are also achieved by 937b.In particular,with regard to the IDT simulations of ammonia/diesel blends,937b makes progress in both aspects of overall accuracy and computational efficiency,compared to a detailed ammonia/diesel mechanism.Further kinetic analysis reveals that the reaction pathway of ammonia during the combustion of ammonia/diesel blend mainly differs in the tendencies of oxygen additions to NH_2 and NH with different equivalence ratios.展开更多
For carbon-free electrochemical fuel formation,the electrochemical cell must be powered by renewable energy.Obtaining solar-powered H_(2) fuel from water typically requires multiple photovoltaic cells and/or junctions...For carbon-free electrochemical fuel formation,the electrochemical cell must be powered by renewable energy.Obtaining solar-powered H_(2) fuel from water typically requires multiple photovoltaic cells and/or junctions to drive the water splitting reaction.Because of the lower thermodynamic requirements to oxidize ammonia compared to water,solar cells with smaller open circuit voltages can provide the required potential for ammonia splitting.In this work,a single perovskite solar cell with an open-circuit potential of 1.08 V is coupled to a 2-electrode electrochemical cell employing hybrid electroanodes functionalized with Ru-based molecular catalysts.The device is active for more than 30 min,producing N_(2) and H_(2) in a 1:2.9 ratio with 89%faradaic efficiency with no external applied bias.This work illustrates that hydrogen production from ammonia can be driven by conventional semiconductors.展开更多
Ammonium dinitramide(ADN)is a new type of green energetic oxidizer with excellent energy density and low pollution combustion characteristics.However,the strong hygroscopicity has a significant impact on its practical...Ammonium dinitramide(ADN)is a new type of green energetic oxidizer with excellent energy density and low pollution combustion characteristics.However,the strong hygroscopicity has a significant impact on its practical application.To assist in the research on moisture-proof modification of ADN materials,an innovative hygroscopic modeling approach was proposed to evaluate the hygroscopicity of ADN at various temperatures and humidities.By investigating the diffusion coefficient of water molecules in molecular dynamics processes,a visual insight into the hygroscopic process of ADN was gained.Furthermore,analyzing the non-covalent interactions between ADN and water molecules,the hygroscopicity of ADN could be evaluated qualitatively and quantitatively.The energy analysis revealed that electrostatic forces play a dominant role in the process of water adsorption by ADN,whereas van der Waals forces impede it.As a whole,the simulation results show that ADN presents the following hygroscopic law:At temperatures ranging from 273 K to 373 K and relative humidity(RH)from 10%to 100%,the hygroscopicity of ADN generally shows an increasing trend with the rise in temperature and humidity based on the results of three simulations.According to the non-hygroscopic point(298 K,52%RH)of ADN obtained by experiment in the literature,a non-hygroscopic range of temperature and humidity for ADN can be depicted when the simulation results in relative hygroscopicity is less than or equal to 17%.This study can provide effective strategies for screening anti-hygroscopic modified materials of ADN.展开更多
This study aimed to investigate the effects of ammonia addition on ethylene counter-flow diffusion flames with different diluents on the fuel or oxidizer side,using kinetic analyses.A special emphasis was put on asses...This study aimed to investigate the effects of ammonia addition on ethylene counter-flow diffusion flames with different diluents on the fuel or oxidizer side,using kinetic analyses.A special emphasis was put on assessing the coupled chemical effects of NH_(3) and CO_(2) on C2H4 combustion chemistry.The chemical effects could be evaluated by comparing fictitious inert NH_(3) or CO_(2) with normal active NH_(3) or CO_(2).The results revealed that the addition of NH_(3) decreased the mole fractions and production rates of key soot precursors,such as acetylene,propynyl,and benzene.When CO_(2) was used as the dilution gas,the coupled chemical effects of NH_(3) and CO_(2) were affected by the chemical effects of CO_(2) to varying degrees.With the oxidizer-side CO_(2) addition,the coupled chemical effects of NH_(3) and CO_(2) reduced the mole fractions of H,O,OH radicals,acetylene,propynyl,and benzene,while the effects differed from the fuel-side CO_(2) addition.The coupled chemical effects of NH_(3) and CO_(2) also promoted the formation of aldehyde contaminants,such as acetaldehyde,to some extent,particularly with CO_(2) addition on the oxidizer side.展开更多
Electrochemical corrosion of AZ31 magnesium alloy in the NH_(4)^(+)-SO_(4)2−-Cl−environment is studied.Effect of NH_(4)^(+)overshadows that of Cl−as the(NH_(4))_(2)SO_(4) concentration is 0.005 M or higher,yielding an...Electrochemical corrosion of AZ31 magnesium alloy in the NH_(4)^(+)-SO_(4)2−-Cl−environment is studied.Effect of NH_(4)^(+)overshadows that of Cl−as the(NH_(4))_(2)SO_(4) concentration is 0.005 M or higher,yielding an evolution from localized corrosion to uniform corrosion.Acceleration effect of NH_(4)^(+)can be attributed to that(i)NH_(4)^(+)dissolves the inner MgO and hinders the precipitation of Mg(OH)_(2) and(ii)the buffering ability of NH_(4)^(+)provides H+,enhances the hydrogen evolution,and expedites the corrosion process.The latter is demonstrated as the dominant factor with the results in unbuffered and buffered environments.The severe corrosion and hydrogen process in NH_(4)^(+)-containing solution results in a high Hads coverage and yields an inductive loop within the low frequency.Meanwhile,SO_(4)^(2−)is helpful in generating cracked but partially protective corrosion products,while Cl−could broaden the corrosion area beneath the corrosion product.展开更多
Defect engineering is an effective strategy for modifying the energy storage materials to improve their electrochemical performance.However,the impact of oxygen defect and its content on the electrochemical performanc...Defect engineering is an effective strategy for modifying the energy storage materials to improve their electrochemical performance.However,the impact of oxygen defect and its content on the electrochemical performances in the burgeoning aqueous NH_(4)^(+)storage field remains explored.Therefore,for the first time in this work,an oxygen-defective ammonium vanadate[(NH_(4))_(2)V_(10)O_(25)·8H_(2)O,denoted as Od-NHVO]with a novel 3D porous flower-like architecture was achieved via the reduction of thiourea in a mild reaction condition,which is a facile method that can realize the intention to regulate the oxygen defect content,with the capability of mass-production.The as-prepared Od_M-NHVO with moderate oxygen defect content can deliver a stable specific capacitance output(505 F g^(-1),252 mAh g^(-1)at 0.5 A g^(-1)with~80% capacitance retention after 10,000 cycles),which benefits from extra active sites,unimpeded NH_(4)^(+)-migration path and relatively high structure integrity.In contrast,low oxygen defect content will lead to the torpid electrochemical reaction kinetics while too high content of it will reduce the chargestorage capability and induce structural disintegration.The superior NH_(4)^(+)-storage behavior is achieved with the reversible intercalation/deintercalation process of NH_(4)^(+)accompanied by forming/breaking of hydrogen bond.As expected,the assembled flexible OdM-NHVO//PTCDI quasi-solid-state hybrid supercapacitor(FQSS HSC)also exhibits high areal capacitance,energy density and reliable flexibility.This work provides a new avenue for developing materials with oxygen-deficient structure for application in various aqueous non-metal cation storage systems.展开更多
Vanadium-based cathode materials are attractive for aqueous zinc-ion batteries(AZIBs)owing to the high capacity from their open frameworks and multiple valences.However,the cycle stability and rate capability are stil...Vanadium-based cathode materials are attractive for aqueous zinc-ion batteries(AZIBs)owing to the high capacity from their open frameworks and multiple valences.However,the cycle stability and rate capability are still restricted by the low electrical conductivity and trapped diffusion kinetics.Here,we propose an organic-inorganic co-intercalation strategy to regulate the structure of ammonium vanadate(NH_(4)V_(4)O_(10),NVO).The introduction of Al^(3+)and polyaniline(PANI)induces the optimized layered structure and generation of urchin-like hierarchical construction(AP-NVO),based on heterogeneous nucleation and dissolution-recrystallization growth mechanism.Owing to these favorable features,the AP-NVO electrode delivers a desirable discharge capacity of 386 mA h g^(-1) at 1.0 A g^(-1),high-rate capability of 263 mA h g^(-1 )at 5.0 A g^(-1) and excellent cycling stability with 80.4%capacity retention over 2000 cycles at 5.0 A g^(-1).Such satisfactory electrochemical performance is believed to result from the enhanced reaction kinetics provided by the stable layered structure and a high intercalation pseudo-capacitance reaction.These results could provide enlightening insights into the design of layered vanadium oxide cathodematerials.展开更多
The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia syn...The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia synthesis.While the process is thermodynamically feasible at ambient temperature and pressure,challenges such as the competing hydrogen evolution reaction,low nitrogen solubility in electrolytes,and the activation of inert dinitrogen(N_(2))gas adversely affect the performance of ammonia production.These hurdles result in low Faradaic efficiency and low ammonia production rate,which pose obstacles to the commercialisation of the process.Researchers have been actively designing and proposing various electrocatalysts to address these issues,but challenges still need to be resolved.A key strategy in electrocatalyst design lies in understanding the underlying mechanisms that govern the success or failure of the electrocatalyst in driving the electrochemical reaction.Through mechanistic studies,we gain valuable insights into the factors affecting the reaction,enabling us to propose optimised designs to overcome the barriers.This review aims to provide a comprehensive understanding of the various mechanisms involved in eNRR on the electrocatalyst surface.It delves into the various mechanisms such as dissociative,associative,Mars-van Krevelen,lithium-mediated nitrogen reduction and surface hydrogenation mechanisms of nitrogen reduction.By unravelling the intricacies of eNRR mechanisms and exploring promising avenues,we can pave the way for more efficient and commercially viable ammonia synthesis through this sustainable electrochemical process by designing an efficient electrocatalyst.展开更多
The quality upgrading and deashing of inferior coal by chemical method still faces great challenges.The dangers of strong acid,strong alkali,waste water and exhaust gas as well as high cost limit its industrial produc...The quality upgrading and deashing of inferior coal by chemical method still faces great challenges.The dangers of strong acid,strong alkali,waste water and exhaust gas as well as high cost limit its industrial production.This paper systematically investigates the ash reduction and desilicification of two typical inferior coal utilizing ammonium fluoride roasting method.Under the optimal conditions,for fat coal and gas coal,the deashing rates are 69.02%and 54.13%,and the desilicification rates are 92.64%and 90.27%,respectively.The molar dosage of ammonium fluoride remains consistent for both coals;however,the gas coal,characterized by a lower ash and silica content(less than half that of the fat coal),achieves optimum deashing effect at a reduced time and temperature.The majority of silicon in coal transforms into gaseous ammonium fluorosilicate,subsequently preparing nanoscale amorphous silica with a purity of 99.90%through ammonia precipitation.Most of the fluorine in deashed coal are assigned in inorganic minerals,suggesting the possibility of further fluorine and ash removal via flotation.This research provides a green and facile route to deash inferior coal and produce nano-scale white carbon black simultaneously.展开更多
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 transport...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.展开更多
Ammonia allows storage and transport of hydrogen over long distances and is an attractive potential hydrogen carrier.Electrochemical decomposition has recently been used for the conversion of ammonia to hydrogen and i...Ammonia allows storage and transport of hydrogen over long distances and is an attractive potential hydrogen carrier.Electrochemical decomposition has recently been used for the conversion of ammonia to hydrogen and is regarded as a future technology for production of CO_(2)-free pure hydrogen.Herein,a heterostructural Pt-Ir dual-layer electrode is developed and shown to achieve successful long-term operation in an ammonia electrolyzer with an anion exchange membrane(AEM).This electrolyzer consisted of eight membra ne electrode assemblies(MEAs)with a total geometric area of 200 cm~2 on the anode side,which resulted in a hydrogen production rate of 25 L h~(-1).We observed the degradation in MEA performance attributed to changes in the anode catalyst layer during hydrogen production via ammonia electrolysis.Furthermore,we demonstrated the relationship between the ammonia oxidation reaction(AOR)and the oxygen evolution reaction(OER).展开更多
Ammonium dinitramide(ADN),which has the advantages of high energy density,no halogen and low characteristic signal,is not only considered as a new high-energy oxidizer that is expected to replace the traditional oxidi...Ammonium dinitramide(ADN),which has the advantages of high energy density,no halogen and low characteristic signal,is not only considered as a new high-energy oxidizer that is expected to replace the traditional oxidizer ammonium perchlorate(AP)in solid propellants,but also a good performance explosive in itself.However,due to the strong hygroscopicity of ADN,its application in solid propellants and explosives is greatly limited.Solving the hygroscopicity of ADN is the key to realize the wide application of ADN.In this paper,we systematically review the research progress of anti-hygroscopic strategies of ADN coating.The surface coating methods are focusing on solvent volatilization,solvent-non-solvent,melt crystallization and atomic layer deposition technology.The characteristics of the different methods are compared and analyzed,and the basis for the classification and selection of the coating materials are introduced in detail.In addition,the feasibility of material for surface coating of ADN is evaluated by several compatibility analysis methods.It is highly expected that the liquid phase method(solvent volatilization method,solvent-non-solvent method)would be the promising method for future ADN coating because of its effective,safety and facile operation.Furthermore,polymer materials,are the preferred coating materials due to their high viscosity,easy adhesion,good anti-hygroscopic effect,and heat resistance,which make ADN weak hygroscopicity,less sensitive,easier to preserve and good compatibility.展开更多
Ammonia(NH_(3))is a multifunctional compound that is an important feedstock for the agricultural and pharmaceutical industries and attractive energy storage medium.At present,NH_(3)synthesis is highly dependent on the...Ammonia(NH_(3))is a multifunctional compound that is an important feedstock for the agricultural and pharmaceutical industries and attractive energy storage medium.At present,NH_(3)synthesis is highly dependent on the conventional Haber–Bosch process that operates under harsh conditions,which consumes large quantities of fossil fuels and releases a large amount of carbon dioxide.As an alternative,electrosynthesis is a prospective method for producing NH_(3)under normal temperature and pressure conditions.Although electrocatalytic nitrogen reduction to ammonia has attracted considerable attentions,the low solubility of N_(2)and high N≡N cracking energy render the achievements of high NH_(3) yield rate and Faradaic efficiency difficult.Nitrate and nitrite(NO_(x)^(-))are common N-containing pollutants.Due to their high solubilities and low dissociation energy of N=O,NO_(x)^(-)−are ideal raw materials for NH_(3) production.Therefore,electrocatalytic NO_(x)^(-)−reduction to NH_(3)(eNO_(x)RR)is a prospective strategy to simultaneously realise environmental protection and NH_(3) synthesis.This review offers a comprehensive understanding of the thriving eNO_(x)RR under ambient conditions.At first,the popular theory and mechanism of eNO_(x)RR and a summary of the measurement system and evaluation criteria are introduced.Thereafter,various strategies for developing NO_(x)−reduction catalysts are systematically presented and discussed.Finally,the challenges and possible prospects of electrocatalytic NO_(x)^(-1) reduction are outlined to facilitate energy-saving and environmentally friendly large-scale synthesis of NH_(3) in the future.展开更多
Ammonia is one of the most important chemical raw materials in both manufacture and life of human.Traditionally Haber-Bosch method for ammonia synthesis involves high temperature and high pressure conditions,leading t...Ammonia is one of the most important chemical raw materials in both manufacture and life of human.Traditionally Haber-Bosch method for ammonia synthesis involves high temperature and high pressure conditions,leading to significant energy consumption and environmental pollution.Non-thermal plasma(NTP) is a promising alternative approach to ammonia synthesis at low temperature and atmospheric pressure.In this study,the synergistic effect of nanosecond pulsed dielectric barrier discharge(np-DBD) and Ni-MOF-74 catalyst was investigated in ammonia synthesis by utilizing nitrogen and hydrogen as feedstock.The results demonstrated that the plasma catalytic-synthesis process parameters play a crucial role in the synthesis process of ammonia.The highest ammonia synthesis rate of 5145.16 μmol·g^(-1)·h^(-1)with an energy efficiency of 1.27 g·kWh^(-1)was observed in the presence of the Ni-MOF-74 catalyst,which was3.7 times higher than that without Ni-MOF-74 catalyst.The synergistic effect of Ni-MOF-74catalyst and nanosecond pulsed plasma was explored by in-situ plasma discharge diagnostics.展开更多
Ammonia is gaining increasing attention as a green alternative fuel for achieving large-scale carbon emission reduction. Despite its potential technical prospects, the harsh ignition conditions and slow flame propagat...Ammonia is gaining increasing attention as a green alternative fuel for achieving large-scale carbon emission reduction. Despite its potential technical prospects, the harsh ignition conditions and slow flame propagation speed of ammonia pose significant challenges to its application in engines. Non-equilibrium plasma has been identified as a promising method, but current research on plasma-enhanced ammonia combustion is limited and primarily focuses on ignition characteristics revealed by kinetic models. In this study, low-temperature and low-pressure chemistry in plasma-assisted ammonia oxidative pyrolysis is investigated by integrated studies of steady-state GC measurements and mathematical simulation. The detailed kinetic mechanism of NH_(3) decomposition in plasma-driven Ar/NH_(3) and Ar/NH_(3)/O_(2) mixtures has been developed. The numerical model has good agreements with the experimental measurements in NH_(3)/O_(2) consumption and N_(2)/H_(2) generation, which demonstrates the rationality of modelling. Based on the modelling results, species density profiles, path flux and sensitivity analysis for the key plasmaproduced species such as NH_(2), NH, H_(2), OH, H, O, O(^(1)D), O_(2)(a^(1)△_(g)), O_(2)(b^(1)∑_(g)^(+)), Ar^(*), H^(-), Ar^(+), NH_(3)^(+), O_(2)^(-) in the discharge and afterglow are analyzed in detail to illustrate the effectiveness of the active species on NH_(3) excitation and decomposition at low temperature and relatively higher E/N values. The results revealed that NH_(2), NH, H as well as H_(2) are primarily generated through the electron collision reactions e + NH_(3)→ e + NH_(2)+ H, e + NH_(3)→ e + NH + H_(2) and the excited-argon collision reaction Ar^(*) + NH_(3)+ H → Ar + NH_(2)+ 2H, which will then react with highly reactive oxidative species such as O_(2)^(*), O^(*), O, OH, and O_(2) to produce stable products of NOx and H_(2)O. NH_(3)→ NH is found a specific pathway for NH_(3) consumption with plasma assistance, which further highlights the enhanced kinetic effects.展开更多
基金supported by the National Natural Science Foundation of China(22108238,21878259)the Zhejiang Provincial Natural Science Foundation of China(LR18B060001)+5 种基金Anhui Provincial Natural Science Founda-tion(1908085QB68)the Natural Science Foundation of the Anhui Higher Education Institutions of China(KJ2020A0275)Major Science and Technology Project of Anhui Province(201903a05020055)Foundation of Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology(ZJKL-ACEMT-1802)China Postdoctoral Science Foundation(2019M662060,2020T130580)Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology(BM2012110).
文摘The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.
基金supported by the National Natural Science Foundation of China (Grant No.31971872)the Open Research Fund of State Key Laboratory of Hybrid Rice, China (Grant No.2022KF02)+3 种基金the National Natural Science Foundation of China (Grant Nos.32101755 and 32188102)the Zhejiang Provincial Natural Science Foundation, China (Grant No.LY22C130005)the Key Research and Development Program of Zhejiang Province, China (Grant No.2021C02056)the ‘Pioneer’ and ‘Leading Goose’ R&D Program of Zhejiang, China (Grant No.2023C02014)。
文摘Reasonable nitrogen(N) application is a promising strategy for reducing crop cadmium(Cd) toxicity. However, the specific form of N and the required amount that affect Cd tolerance and accumulation in rice remain unclear. This study explored the influence of different N-fertilizer forms(NH_(4)NO_(3), NH_4Cl, and KNO_(3)) and dosages on Cd tolerance and uptake in Cd-stressed N-sensitive and N-insensitive indica rice accessions. The results indicated that the Cd tolerance of N-sensitive indica accessions is more robust than that of N-insensitive ones. Furthermore, the shoot Cd content and Cd translocation rate in both N-sensitive and N-insensitive indica accessions decreased with an appropriate supply of NH_(4)NO_(3) and NH_4Cl, whereas they were comparable or slightly increased with increased KNO_(3). Unfortunately, we did not find significant and regular differences in Cd accumulation or translocation between N-sensitive and N-insensitive rice accessions. Consistent with the reduction of shoot Cd content, the addition of NH_(4)NO_(3) and NH_4Cl also inhibited the instantaneous root Cd^(2+) uptake. The expression changes of Cd transport-related genes under different N forms and dosages suggested that the decreased shoot Cd content, caused by the increased supply of NH_(4)NO_(3) and NH_4Cl, is likely achieved by reducing the transcription of OsNRAMP1 and OsIRT1. In summary, our findings reveal that an appropriate supply of NH_(4)NO_(3) and NH_4Cl could reduce Cd uptake and transport in rice seedlings, suggesting that rational N management could reduce the Cd risk in rice production.
基金supported by the National Key R&D Program of China(Nos.2022YFA1503104 and 2022YFA1503102)the Natural Science Foundation of Shandong Province(No.2022HWYQ-009)+2 种基金the Natural Science Foundation of Jiangsu Province(No.BK20230243)Taishan Scholars Project(No.tspd20230601)Qilu Young Scholars Program of Shandong University.
文摘The nitrite(NO_(2)^(−))to ammonia(NH3)electroreduction reaction(NO_(2)^(−)RR)would be impeded by sluggish proton-coupled electron transfer kinetics and competitive hydrogen evolution reaction(HER).A key to improving the NH_(3) selectivity is to facilitate adsorption and activation of NO_(2)^(−),which is generally undesirable in unitary species.In this work,an efficient NO_(2)^(−)RR catalyst is constructed by cooperating Pd with In2O3,in which NO_(2)^(−)could adsorb on interfacial dual-site through“Pd–N–O–In”linkage,leading to strengthened NO_(2)^(−)adsorption and easier N=O bond cleavage than that on unitary Pd or In2O3.Moreover,the Pd/In_(2)O_(3)composite exhibits moderate H^(*)adsorption,which may facilitate protonation kinetics while inhibiting competitive HER.As a result,it exhibits a fairly high NH_(3)yield rate of 622.76 mmol h^(−1)g^(−1)cat with a Faradaic efficiency(FE)of 95.72%,good selectivity of 91.96%,and cycling stability towards the NO_(2)^(−)RR,surpassing unitary In_(2)O_(3)and Pd/C electrocatalysts.Besides,computed results indicate that NH_(3)production on Pd/In_(2)O_(3)follows the deoxidation to hydrogenation pathway.This work highlights the significance of H^(*)and NO_(2)^(−)adsorption modulation and N=O activation in NO_(2)^(−)RR electrochemistry by creating synergy between a mediocre catalyst with an appropriate cooperator.
基金supported by the National Research Foundation of Korea(NRF-2021R1A2C1008272)supported by the Institute of Information&communications Technology Planning&Evaluation(IITP)grant funded by the Korean government(MSIT)(No.2021-0-00259,Development of a Fast Wireless Charging System for Portable Terminals with improved heat dissipation and shielding performance)supported by the Applied Basic Research Program of Changzhou City(CJ20220030).
文摘Lithium-sulfur(Li-S)batteries are one of the most promising modern-day energy supply systems because of their high theoretical energy density and low cost.However,the development of high-energy density Li-S batteries with high loading of flammable sulfur faces the challenges of electrochemical performance degradation owing to the shuttle effect and safety issues related to fire or explosion accidents.In this work,we report a three-dimensional(3D)conductive nitrogen-doped carbon foam supported electrostatic self-assembled MXene-ammonium polyphosphate(NCF-MXene-APP)layer as a heat-resistant,thermally-insulated,flame-retardant,and freestanding host for Li-S batteries with a facile and costeffective synthesis method.Consequently,through the use of NCF-MXene-APP hosts that strongly anchor polysulfides,the Li-S batteries demonstrate outstanding electrochemical properties,including a high initial discharge capacity of 1191.6 mA h g^(-1),excellent rate capacity of 755.0 mA h g^(-1)at 1 C,and long-term cycling stability with an extremely low-capacity decay rate of 0.12%per cycle at 2 C.More importantly,these batteries can continue to operate reliably under high temperature or flame attack conditions.Thus,this study provides valuable insights into the design of safe high-performance Li-S batteries.
基金Supported by the Natural Science Foundation of Shandong Province(No.ZR 2023 MD 059)the National Natural Science Foundation of China(No.41876135)。
文摘Previous studies have revealed that ammonia nitrogen has several adverse effects on clam Ruditapes philippinarum.However,knowledge is lacking regarding the related proteins involved in the toxicological responses,which is vital to elucidate the underlying mechanism of ammonia nitrogen.In this study,clams R.philippinarum were exposed to ammonia nitrogen for 21 d at two environmentally relevant concentrations.The tandem mass tags approach(TMT)was applied to assay the differentially expressed proteins(DEPs)in clam gill tissues on the 3 rd and 21 st day.Finally,a total of 7263 proteins were identified.Bioinformatics analyses revealed that clam protein profiles changed in dose-and time dependent manner after ammonia nitrogen exposure.We inferred that the clams may face heavy challenges after ammonia exposure,such as unbalanced gender ratio,lysosomal disease,energy lack,neurological disorders,altered glutamine metabolism,increased lipid synthesis,and impaired immunity.Variation profiles of enzyme activities of glutaminase and glutamine synthase provided direct evidence to verify the related inference from proteome data.Most of the inferred toxic effects merit further study.This study identified important proteins related to ammonia nitrogen toxicity in the clam and indicated the severe stress of marine ammonia pollution on the healthy development of mollusc aquaculture.
基金the National Natural Science Foundation of China(project code:52202470)Jilin Province Natural Science Foundation(project codes:20220101205JC,20220101212JC)+2 种基金Jilin Province Specific Project of Industrial Technology Research&Development(project code:2020C025-2)2021 Interdisciplinary Integration and Innovation Project of Jilin University(project code:XJRCYB07)Free Exploration Project of Changsha Automotive Innovation Research Institute of Jilin University(project code:CAIRIZT20220202)。
文摘For the deep understanding on combustion of ammonia/diesel,this study develops a reduced mechanism of ammonia/diesel with 227 species and 937 reactions.The sub-mechanism on ammonia/interactions of N-based and C-based species(N—C)/NOx is optimized using the Non-dominated Sorting Genetic Algorithm II(NSGA-II)with 200 generations.The optimized mechanism(named as 937b)is validated against combustion characteristics of ammonia/methane(which is used to examine the accuracy of N—C interactions)and ammonia/diesel blends.The ignition delay times(IDTs),the laminar flame speeds and most of key intermediate species during the combustion of ammonia/methane blends can be accurately simulated by 937b under a wide range of conditions.As for ammonia/diesel blends with various diesel energy fractions,reasonable predictions on the IDTs under pressures from 1.0 MPa to5.0 MPa as well as the laminar flame speeds are also achieved by 937b.In particular,with regard to the IDT simulations of ammonia/diesel blends,937b makes progress in both aspects of overall accuracy and computational efficiency,compared to a detailed ammonia/diesel mechanism.Further kinetic analysis reveals that the reaction pathway of ammonia during the combustion of ammonia/diesel blend mainly differs in the tendencies of oxygen additions to NH_2 and NH with different equivalence ratios.
基金Financial support from Ministerio de Ciencia e Innovación through projects PID2022-140143OB-I00(MCIN/AEI/10.13039/501100011033)and SO-CEX2019-000925-S(MCIN/AEI/10.13039/5011000110)supported by Marie Sk?odowska-Curie Actions Individual Fellowship grant funding to AMB,grant 101031365-SolTIMEthe support from the MSCA-COFUND I2:ICIQ Impulsion(GA 801474)。
文摘For carbon-free electrochemical fuel formation,the electrochemical cell must be powered by renewable energy.Obtaining solar-powered H_(2) fuel from water typically requires multiple photovoltaic cells and/or junctions to drive the water splitting reaction.Because of the lower thermodynamic requirements to oxidize ammonia compared to water,solar cells with smaller open circuit voltages can provide the required potential for ammonia splitting.In this work,a single perovskite solar cell with an open-circuit potential of 1.08 V is coupled to a 2-electrode electrochemical cell employing hybrid electroanodes functionalized with Ru-based molecular catalysts.The device is active for more than 30 min,producing N_(2) and H_(2) in a 1:2.9 ratio with 89%faradaic efficiency with no external applied bias.This work illustrates that hydrogen production from ammonia can be driven by conventional semiconductors.
基金supported by the National Natural Science Foundation of China(Grant Nos.22375098,21805139 and 12102194)the Joint Funds of the National Natural Science Foundation of China(Grant No.U2141202)Young Elite Scientists Sponsorship Program by CAST(Grant No.2021QNRC001).
文摘Ammonium dinitramide(ADN)is a new type of green energetic oxidizer with excellent energy density and low pollution combustion characteristics.However,the strong hygroscopicity has a significant impact on its practical application.To assist in the research on moisture-proof modification of ADN materials,an innovative hygroscopic modeling approach was proposed to evaluate the hygroscopicity of ADN at various temperatures and humidities.By investigating the diffusion coefficient of water molecules in molecular dynamics processes,a visual insight into the hygroscopic process of ADN was gained.Furthermore,analyzing the non-covalent interactions between ADN and water molecules,the hygroscopicity of ADN could be evaluated qualitatively and quantitatively.The energy analysis revealed that electrostatic forces play a dominant role in the process of water adsorption by ADN,whereas van der Waals forces impede it.As a whole,the simulation results show that ADN presents the following hygroscopic law:At temperatures ranging from 273 K to 373 K and relative humidity(RH)from 10%to 100%,the hygroscopicity of ADN generally shows an increasing trend with the rise in temperature and humidity based on the results of three simulations.According to the non-hygroscopic point(298 K,52%RH)of ADN obtained by experiment in the literature,a non-hygroscopic range of temperature and humidity for ADN can be depicted when the simulation results in relative hygroscopicity is less than or equal to 17%.This study can provide effective strategies for screening anti-hygroscopic modified materials of ADN.
基金National Natural Science Foundation of China(52076110,52106160)Jiangsu Provincial Natural Science Foundation of China(BK20200490,BK20220955)Fundamental Research Funds for the Central Universities(30923010208 and 30920031103).
文摘This study aimed to investigate the effects of ammonia addition on ethylene counter-flow diffusion flames with different diluents on the fuel or oxidizer side,using kinetic analyses.A special emphasis was put on assessing the coupled chemical effects of NH_(3) and CO_(2) on C2H4 combustion chemistry.The chemical effects could be evaluated by comparing fictitious inert NH_(3) or CO_(2) with normal active NH_(3) or CO_(2).The results revealed that the addition of NH_(3) decreased the mole fractions and production rates of key soot precursors,such as acetylene,propynyl,and benzene.When CO_(2) was used as the dilution gas,the coupled chemical effects of NH_(3) and CO_(2) were affected by the chemical effects of CO_(2) to varying degrees.With the oxidizer-side CO_(2) addition,the coupled chemical effects of NH_(3) and CO_(2) reduced the mole fractions of H,O,OH radicals,acetylene,propynyl,and benzene,while the effects differed from the fuel-side CO_(2) addition.The coupled chemical effects of NH_(3) and CO_(2) also promoted the formation of aldehyde contaminants,such as acetaldehyde,to some extent,particularly with CO_(2) addition on the oxidizer side.
基金support of National Natural Science Foundation of China(No.U2106216)the National Science and Technology Resources Investigation Program of China(No.2019FY101400)the Youth Innovation Plan of Shandong Province(2019KJD001).
文摘Electrochemical corrosion of AZ31 magnesium alloy in the NH_(4)^(+)-SO_(4)2−-Cl−environment is studied.Effect of NH_(4)^(+)overshadows that of Cl−as the(NH_(4))_(2)SO_(4) concentration is 0.005 M or higher,yielding an evolution from localized corrosion to uniform corrosion.Acceleration effect of NH_(4)^(+)can be attributed to that(i)NH_(4)^(+)dissolves the inner MgO and hinders the precipitation of Mg(OH)_(2) and(ii)the buffering ability of NH_(4)^(+)provides H+,enhances the hydrogen evolution,and expedites the corrosion process.The latter is demonstrated as the dominant factor with the results in unbuffered and buffered environments.The severe corrosion and hydrogen process in NH_(4)^(+)-containing solution results in a high Hads coverage and yields an inductive loop within the low frequency.Meanwhile,SO_(4)^(2−)is helpful in generating cracked but partially protective corrosion products,while Cl−could broaden the corrosion area beneath the corrosion product.
基金partially supported by the Large Instrument and Equipment Open Foundation of Dalian University of Technology and Fundamental Research Funds for the Central Universities(DUT21LK34)。
文摘Defect engineering is an effective strategy for modifying the energy storage materials to improve their electrochemical performance.However,the impact of oxygen defect and its content on the electrochemical performances in the burgeoning aqueous NH_(4)^(+)storage field remains explored.Therefore,for the first time in this work,an oxygen-defective ammonium vanadate[(NH_(4))_(2)V_(10)O_(25)·8H_(2)O,denoted as Od-NHVO]with a novel 3D porous flower-like architecture was achieved via the reduction of thiourea in a mild reaction condition,which is a facile method that can realize the intention to regulate the oxygen defect content,with the capability of mass-production.The as-prepared Od_M-NHVO with moderate oxygen defect content can deliver a stable specific capacitance output(505 F g^(-1),252 mAh g^(-1)at 0.5 A g^(-1)with~80% capacitance retention after 10,000 cycles),which benefits from extra active sites,unimpeded NH_(4)^(+)-migration path and relatively high structure integrity.In contrast,low oxygen defect content will lead to the torpid electrochemical reaction kinetics while too high content of it will reduce the chargestorage capability and induce structural disintegration.The superior NH_(4)^(+)-storage behavior is achieved with the reversible intercalation/deintercalation process of NH_(4)^(+)accompanied by forming/breaking of hydrogen bond.As expected,the assembled flexible OdM-NHVO//PTCDI quasi-solid-state hybrid supercapacitor(FQSS HSC)also exhibits high areal capacitance,energy density and reliable flexibility.This work provides a new avenue for developing materials with oxygen-deficient structure for application in various aqueous non-metal cation storage systems.
基金financially supported by the National Natural Science Foundation of China(U21A2077)the Taishan Scholar Project Foundation of Shandong Province(ts20190908)the Natural Science Foundation of Shandong Province(ZR2022MB084 and ZR2021ZD05).
文摘Vanadium-based cathode materials are attractive for aqueous zinc-ion batteries(AZIBs)owing to the high capacity from their open frameworks and multiple valences.However,the cycle stability and rate capability are still restricted by the low electrical conductivity and trapped diffusion kinetics.Here,we propose an organic-inorganic co-intercalation strategy to regulate the structure of ammonium vanadate(NH_(4)V_(4)O_(10),NVO).The introduction of Al^(3+)and polyaniline(PANI)induces the optimized layered structure and generation of urchin-like hierarchical construction(AP-NVO),based on heterogeneous nucleation and dissolution-recrystallization growth mechanism.Owing to these favorable features,the AP-NVO electrode delivers a desirable discharge capacity of 386 mA h g^(-1) at 1.0 A g^(-1),high-rate capability of 263 mA h g^(-1 )at 5.0 A g^(-1) and excellent cycling stability with 80.4%capacity retention over 2000 cycles at 5.0 A g^(-1).Such satisfactory electrochemical performance is believed to result from the enhanced reaction kinetics provided by the stable layered structure and a high intercalation pseudo-capacitance reaction.These results could provide enlightening insights into the design of layered vanadium oxide cathodematerials.
基金the Science and Engineering Research Board(SERB),Government of India for funding this work(Sanction No.EEQ/2021/001116)。
文摘The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia synthesis.While the process is thermodynamically feasible at ambient temperature and pressure,challenges such as the competing hydrogen evolution reaction,low nitrogen solubility in electrolytes,and the activation of inert dinitrogen(N_(2))gas adversely affect the performance of ammonia production.These hurdles result in low Faradaic efficiency and low ammonia production rate,which pose obstacles to the commercialisation of the process.Researchers have been actively designing and proposing various electrocatalysts to address these issues,but challenges still need to be resolved.A key strategy in electrocatalyst design lies in understanding the underlying mechanisms that govern the success or failure of the electrocatalyst in driving the electrochemical reaction.Through mechanistic studies,we gain valuable insights into the factors affecting the reaction,enabling us to propose optimised designs to overcome the barriers.This review aims to provide a comprehensive understanding of the various mechanisms involved in eNRR on the electrocatalyst surface.It delves into the various mechanisms such as dissociative,associative,Mars-van Krevelen,lithium-mediated nitrogen reduction and surface hydrogenation mechanisms of nitrogen reduction.By unravelling the intricacies of eNRR mechanisms and exploring promising avenues,we can pave the way for more efficient and commercially viable ammonia synthesis through this sustainable electrochemical process by designing an efficient electrocatalyst.
文摘The quality upgrading and deashing of inferior coal by chemical method still faces great challenges.The dangers of strong acid,strong alkali,waste water and exhaust gas as well as high cost limit its industrial production.This paper systematically investigates the ash reduction and desilicification of two typical inferior coal utilizing ammonium fluoride roasting method.Under the optimal conditions,for fat coal and gas coal,the deashing rates are 69.02%and 54.13%,and the desilicification rates are 92.64%and 90.27%,respectively.The molar dosage of ammonium fluoride remains consistent for both coals;however,the gas coal,characterized by a lower ash and silica content(less than half that of the fat coal),achieves optimum deashing effect at a reduced time and temperature.The majority of silicon in coal transforms into gaseous ammonium fluorosilicate,subsequently preparing nanoscale amorphous silica with a purity of 99.90%through ammonia precipitation.Most of the fluorine in deashed coal are assigned in inorganic minerals,suggesting the possibility of further fluorine and ash removal via flotation.This research provides a green and facile route to deash inferior coal and produce nano-scale white carbon black simultaneously.
基金the financial support provided by the Canada Research Chair program and the Natural Science and Engineering Research Council of Canada (NSERC)
文摘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.
基金supported by the research program funded by the TKG Huchemssupported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)granted financial resources from the Ministry of Trade,Industry&Energy,Republic of Korea(20213030040590)supported by a National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(2021R1A5A1028138)。
文摘Ammonia allows storage and transport of hydrogen over long distances and is an attractive potential hydrogen carrier.Electrochemical decomposition has recently been used for the conversion of ammonia to hydrogen and is regarded as a future technology for production of CO_(2)-free pure hydrogen.Herein,a heterostructural Pt-Ir dual-layer electrode is developed and shown to achieve successful long-term operation in an ammonia electrolyzer with an anion exchange membrane(AEM).This electrolyzer consisted of eight membra ne electrode assemblies(MEAs)with a total geometric area of 200 cm~2 on the anode side,which resulted in a hydrogen production rate of 25 L h~(-1).We observed the degradation in MEA performance attributed to changes in the anode catalyst layer during hydrogen production via ammonia electrolysis.Furthermore,we demonstrated the relationship between the ammonia oxidation reaction(AOR)and the oxygen evolution reaction(OER).
基金financially supported by the National Natural Science Foundation of China(Grant Nos.21805139,12102194 and 22005144)the Joint Funds of the National Natural Science Foundation of China(Grant No.U2141202)+1 种基金the Fundamental Research Funds for the Central Universities(Grant No.30921011203)the Young Elite Scientists Sponsorship Program by CAST(YESS Program,2021QNRC001)。
文摘Ammonium dinitramide(ADN),which has the advantages of high energy density,no halogen and low characteristic signal,is not only considered as a new high-energy oxidizer that is expected to replace the traditional oxidizer ammonium perchlorate(AP)in solid propellants,but also a good performance explosive in itself.However,due to the strong hygroscopicity of ADN,its application in solid propellants and explosives is greatly limited.Solving the hygroscopicity of ADN is the key to realize the wide application of ADN.In this paper,we systematically review the research progress of anti-hygroscopic strategies of ADN coating.The surface coating methods are focusing on solvent volatilization,solvent-non-solvent,melt crystallization and atomic layer deposition technology.The characteristics of the different methods are compared and analyzed,and the basis for the classification and selection of the coating materials are introduced in detail.In addition,the feasibility of material for surface coating of ADN is evaluated by several compatibility analysis methods.It is highly expected that the liquid phase method(solvent volatilization method,solvent-non-solvent method)would be the promising method for future ADN coating because of its effective,safety and facile operation.Furthermore,polymer materials,are the preferred coating materials due to their high viscosity,easy adhesion,good anti-hygroscopic effect,and heat resistance,which make ADN weak hygroscopicity,less sensitive,easier to preserve and good compatibility.
基金supported by the National Natural Science Foundation of China[Nos.U21A20332,52103226,52202275,52203314,and 12204253]the Distinguished Young Scholars Fund of Jiangsu Province[No.BK20220061]the Fellowship of China Postdoctoral Science Foundation[No.2021M702382]。
文摘Ammonia(NH_(3))is a multifunctional compound that is an important feedstock for the agricultural and pharmaceutical industries and attractive energy storage medium.At present,NH_(3)synthesis is highly dependent on the conventional Haber–Bosch process that operates under harsh conditions,which consumes large quantities of fossil fuels and releases a large amount of carbon dioxide.As an alternative,electrosynthesis is a prospective method for producing NH_(3)under normal temperature and pressure conditions.Although electrocatalytic nitrogen reduction to ammonia has attracted considerable attentions,the low solubility of N_(2)and high N≡N cracking energy render the achievements of high NH_(3) yield rate and Faradaic efficiency difficult.Nitrate and nitrite(NO_(x)^(-))are common N-containing pollutants.Due to their high solubilities and low dissociation energy of N=O,NO_(x)^(-)−are ideal raw materials for NH_(3) production.Therefore,electrocatalytic NO_(x)^(-)−reduction to NH_(3)(eNO_(x)RR)is a prospective strategy to simultaneously realise environmental protection and NH_(3) synthesis.This review offers a comprehensive understanding of the thriving eNO_(x)RR under ambient conditions.At first,the popular theory and mechanism of eNO_(x)RR and a summary of the measurement system and evaluation criteria are introduced.Thereafter,various strategies for developing NO_(x)−reduction catalysts are systematically presented and discussed.Finally,the challenges and possible prospects of electrocatalytic NO_(x)^(-1) reduction are outlined to facilitate energy-saving and environmentally friendly large-scale synthesis of NH_(3) in the future.
基金the financial support from the Beijing Municipal Natural Science Foundation (No. 1242015)National Undergraduate Innovation and Entrepreneurship Training Program of China (No. 202310015019)Discipline Construction of Material Science and Engineering(Nos. 21090122014 and 21090123007)。
文摘Ammonia is one of the most important chemical raw materials in both manufacture and life of human.Traditionally Haber-Bosch method for ammonia synthesis involves high temperature and high pressure conditions,leading to significant energy consumption and environmental pollution.Non-thermal plasma(NTP) is a promising alternative approach to ammonia synthesis at low temperature and atmospheric pressure.In this study,the synergistic effect of nanosecond pulsed dielectric barrier discharge(np-DBD) and Ni-MOF-74 catalyst was investigated in ammonia synthesis by utilizing nitrogen and hydrogen as feedstock.The results demonstrated that the plasma catalytic-synthesis process parameters play a crucial role in the synthesis process of ammonia.The highest ammonia synthesis rate of 5145.16 μmol·g^(-1)·h^(-1)with an energy efficiency of 1.27 g·kWh^(-1)was observed in the presence of the Ni-MOF-74 catalyst,which was3.7 times higher than that without Ni-MOF-74 catalyst.The synergistic effect of Ni-MOF-74catalyst and nanosecond pulsed plasma was explored by in-situ plasma discharge diagnostics.
基金the grant support from the National Natural Science Foundation of China (No. 21975018, 22278032)。
文摘Ammonia is gaining increasing attention as a green alternative fuel for achieving large-scale carbon emission reduction. Despite its potential technical prospects, the harsh ignition conditions and slow flame propagation speed of ammonia pose significant challenges to its application in engines. Non-equilibrium plasma has been identified as a promising method, but current research on plasma-enhanced ammonia combustion is limited and primarily focuses on ignition characteristics revealed by kinetic models. In this study, low-temperature and low-pressure chemistry in plasma-assisted ammonia oxidative pyrolysis is investigated by integrated studies of steady-state GC measurements and mathematical simulation. The detailed kinetic mechanism of NH_(3) decomposition in plasma-driven Ar/NH_(3) and Ar/NH_(3)/O_(2) mixtures has been developed. The numerical model has good agreements with the experimental measurements in NH_(3)/O_(2) consumption and N_(2)/H_(2) generation, which demonstrates the rationality of modelling. Based on the modelling results, species density profiles, path flux and sensitivity analysis for the key plasmaproduced species such as NH_(2), NH, H_(2), OH, H, O, O(^(1)D), O_(2)(a^(1)△_(g)), O_(2)(b^(1)∑_(g)^(+)), Ar^(*), H^(-), Ar^(+), NH_(3)^(+), O_(2)^(-) in the discharge and afterglow are analyzed in detail to illustrate the effectiveness of the active species on NH_(3) excitation and decomposition at low temperature and relatively higher E/N values. The results revealed that NH_(2), NH, H as well as H_(2) are primarily generated through the electron collision reactions e + NH_(3)→ e + NH_(2)+ H, e + NH_(3)→ e + NH + H_(2) and the excited-argon collision reaction Ar^(*) + NH_(3)+ H → Ar + NH_(2)+ 2H, which will then react with highly reactive oxidative species such as O_(2)^(*), O^(*), O, OH, and O_(2) to produce stable products of NOx and H_(2)O. NH_(3)→ NH is found a specific pathway for NH_(3) consumption with plasma assistance, which further highlights the enhanced kinetic effects.