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
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
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
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
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
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 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(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 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
Renewable energy driven N_(2) electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production.However,relevant out-lab research is still in its infancy.Herein,a novel S...Renewable energy driven N_(2) electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production.However,relevant out-lab research is still in its infancy.Herein,a novel Sn-based MXene/MAX hybrid with abundant Sn vacancies,Sn@Ti_(2)CTX/Ti_(2)SnC–V,was synthesized by controlled etching Sn@Ti_(2)SnC MAX phase and demonstrated as an efficient electrocatalyst for electrocatalytic N2 reduction.Due to the synergistic effect of MXene/MAX heterostructure,the existence of Sn vacancies and the highly dispersed Sn active sites,the obtained Sn@Ti2CTX/Ti_(2)SnC–V exhibits an optimal NH_(3) yield of 28.4μg h^(−1) mg_(cat)^(−1) with an excellent FE of 15.57% at−0.4 V versus reversible hydrogen electrode in 0.1 M Na_(2)SO_(4),as well as an ultra-long durability.Noticeably,this catalyst represents a satisfactory NH3 yield rate of 10.53μg h^(−1) mg^(−1) in the home-made simulation device,where commercial electrochemical photovoltaic cell was employed as power source,air and ultrapure water as feed stock.The as-proposed strategy represents great potential toward ammonia production in terms of financial cost according to the systematic technical economic analysis.This work is of significance for large-scale green ammonia production.展开更多
Ammonia-diesel dual fuel(ADDF)engines for transportation applications are an important way to reduce carbon emissions.In order to achieve better combustion of ammonia in diesel engines.A small-bore single-cylinder eng...Ammonia-diesel dual fuel(ADDF)engines for transportation applications are an important way to reduce carbon emissions.In order to achieve better combustion of ammonia in diesel engines.A small-bore single-cylinder engine was converted into an ADDF engine with the help of mature computational fluid dynamics(CFD)simulation software to investigate the performance of an engine with a high ammonia energy ratio(AER),and to study the effect of spray tilt angle on ADDF engine.The results showed that the increase in AER reduced nitric oxide(NO)and nitrogen dioxide(NO2)emissions but increased nitrous oxide(N2O)and unburned ammonia emissions.AER in the range of 50%-70%achieved lower greenhouse gases(GHG)emissions than the pure diesel mode.Relative to the pure diesel mode,when the AER was 60%,the indicated thermal efficiency(ITE)was increased by 0.2%and the GHG emissions were decreased by 22.3%,but carbon monoxide(CO)and Hydrocarbon(HC)emissions were increased.Increasing the in-cylinder combustion temperature or high-temperature region range of the ADDF engine could reduce GHG emissions.At an AER of 60%,an increase in the spray tilt angle helped the ammonia combustion in the residual gap to reduce the unburned ammonia emissions.Compared to the pure diesel mode with a spray tilt angle of 75°,an AER of 60%with a spray tilt angle of 77.5°improved the ITE by 1.5%,and reduced theGHGemissions by 25.7%.Adjusting the spray tilt angle of theADDFengine also reducedCOandHCemissions.This is an effective way to improve ADDF engine performance by adjusting the spray tilt angle.展开更多
Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such...Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.展开更多
Atmospheric ammonia(NH_(3)) is a chemically active trace gas that plays an important role in the atmospheric environment and climate change. Satellite remote sensing is a powerful technique to monitor NH_(3) concentra...Atmospheric ammonia(NH_(3)) is a chemically active trace gas that plays an important role in the atmospheric environment and climate change. Satellite remote sensing is a powerful technique to monitor NH_(3) concentration based on the absorption lines of NH_(3) in the thermal infrared region. In this study, we establish a retrieval algorithm to derive the NH_(3)column from the Hyperspectral Infrared Atmospheric Sounder(HIRAS) onboard the Chinese Feng Yun(FY)-3D satellite and present the first atmospheric NH_(3) column global map observed by the HIRAS instrument. The HIRAS observations can well capture NH_(3) hotspots around the world, e.g., India, West Africa, and East China, where large NH_(3) emissions exist. The HIRAS NH_(3) columns are also compared to the space-based Infrared Atmospheric Sounding Interferometer(IASI)measurements, and we find that the two instruments observe a consistent NH_(3) global distribution, with correlation coefficient(R) values of 0.28–0.73. Finally, some remaining issues about the HIRAS NH_(3) retrieval are discussed.展开更多
Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum s...Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.展开更多
This study focused on the development and characterization of TiO<sub>2</sub>-PES composite fibers with varying TiO<sub>2</sub> loading amounts using a phase inversion process. The resulting co...This study focused on the development and characterization of TiO<sub>2</sub>-PES composite fibers with varying TiO<sub>2</sub> loading amounts using a phase inversion process. The resulting composite fibers exhibited a sponge-like structure with embedded TiO<sub>2</sub> nanoparticles within a polymer matrix. Their photocatalytic performance for ammonia removal from aqueous solutions under UV-A light exposure was thoroughly investigated. The findings revealed that PeTi8 composite fibers displayed superior adsorption capacity compared to other samples. Moreover, the study explored the impact of pH, light intensity, and catalyst dosage on the photocatalytic degradation of ammonia. Adsorption equilibrium isotherms closely followed the Langmuir model, with the results indicating a correlation between qm values of 2.49 mg/g and the porous structure of the adsorbents. The research underscored the efficacy of TiO<sub>2</sub> composite fibers in the photocatalytic removal of aqueous under UV-A light. Notably, increasing the distance between the photocatalyst and the light source resulted in de-creased hydroxyl radical concentration, influencing photocatalytic efficiency. These findings contribute to our understanding of TiO<sub>2</sub> composite fibers as promising photocatalysts for ammonia removal in water treatment applications.展开更多
Highly dispersed bimetallic alloy nanoparticle electrocatalysts have been demonstrated to exhibit exceptional performance in driving the nitrate reduction reaction(NO_(3)RR)to generate ammonia(NH_(3)).In this study,we...Highly dispersed bimetallic alloy nanoparticle electrocatalysts have been demonstrated to exhibit exceptional performance in driving the nitrate reduction reaction(NO_(3)RR)to generate ammonia(NH_(3)).In this study,we prepared mesoporous carbon nanofibers(mCNFs)functionalized with ordered PtFe alloys(O-PtFe-mCNFs)by a composite micelle interface-induced co-assembly method using poly(ethylene oxide)-block-polystyrene(PEO-b-PS)as a template.When employed as electrocatalysts,O-PtFe-mCNFs exhibited superior electrocatalytic performance for the NO_(3RR)compared to the mCNFs functionalized with disordered PtFe alloys(D-PtFe-mCNFs).Notably,the NH_(3)production performance was particularly outstanding,with a maximum NH_(3)yield of up to 959.6μmol/(h·cm~2).Furthermore,the Faraday efficiency(FE)was even 88.0%at-0.4 V vs.reversible hydrogen electrode(RHE).This finding provides compelling evidence of the potential of ordered PtFe alloy catalysts for the electrocatalytic NO_(3)RR.展开更多
Surface charge, secondary adsorption- desorption and form distribution of Cu2+ and Zn2+ in Ultisols and Alfisols having adsorbed phosphate were studied by potentiometric titration, adsorption equilibrium and sequentia...Surface charge, secondary adsorption- desorption and form distribution of Cu2+ and Zn2+ in Ultisols and Alfisols having adsorbed phosphate were studied by potentiometric titration, adsorption equilibrium and sequential extraction method, respectively. The soil surface negative charges increased whereas the amount of positive charges decreased with increase of P adsorbed. The soil secondary adsorption capacity for Cu2+ and Zn2+ was positively significantly correlated with the amount of P adsorbed by the soils, which could be described by the Langmuir equation. The amounts of Cu2+ and Zn2+ desorption from soils were decreased after P adsorption by the soils and the relationship between them was linear. After the soils adsorbed P, form distribution of Cu2+ and Zn2+ in soils changed remarforbly.展开更多
Charge characteristics and Cu2+ adsorption-desorption of soils with variable charge (latosol) and permanent charge (brown soil) and the relationship between them were studied by means of back-titration and adsorption ...Charge characteristics and Cu2+ adsorption-desorption of soils with variable charge (latosol) and permanent charge (brown soil) and the relationship between them were studied by means of back-titration and adsorption equilibrium respectively. The amount of variable negative charge was much less in variable-charge soil than in permanent-charge soil and increased with the pH in the system, but the opposite trend occurred in the points of zero charge (PZCs). The amount of Cu2+ ions sorbed by permanent-charge soil was more than that by variable-charge soil and increased with the increase of Cu2+ concentration within a certain range in the equilibrium solution. The amount of Cu2+ ions desorbed with KC1 from permanent-charge soil was more than that from variable-charge soil, but the amount of Cu2+ ions desorbed with de-ionized water from permanent-charge soil was extremely low whereas there was still a certain amount of desorption from variable-charge soil. The increase of PZC of soils with variable or permanent charge varied with the increment of Cu2+ ions added. When the same amount of Cu2+ ions was added, the increments of PZC and variable negative surface charge of permanent-charge soil were different from those of variable-charge soil.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 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 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.
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This work was supported by the National Natural Science Foundation of China(Nos.22308139,52071171,52202248)Natural Science Foundation of Liaoning Province(2023-MS-140)+11 种基金Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Shenyang Science and Technology Project(21-108-9-04)Young Scientific and Technological Talents Project of the Department of Education of Liaoning Province(LQN202008)Key Research Project of Department of Education of Liaoning Province(LJKZZ20220015)Foundation of State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology(MJNYSKL202301)Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(KF2023006)Anhui Province Key Laboratory of Coal Clean Conversion and High Valued Utilization,Anhui University of Technology(CHV22-05)Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)Linkage Project(LP210100467,LP210200504,LP210200345,LP220100088)Industrial Transformation Training Centre(IC180100005)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077).
文摘Renewable energy driven N_(2) electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production.However,relevant out-lab research is still in its infancy.Herein,a novel Sn-based MXene/MAX hybrid with abundant Sn vacancies,Sn@Ti_(2)CTX/Ti_(2)SnC–V,was synthesized by controlled etching Sn@Ti_(2)SnC MAX phase and demonstrated as an efficient electrocatalyst for electrocatalytic N2 reduction.Due to the synergistic effect of MXene/MAX heterostructure,the existence of Sn vacancies and the highly dispersed Sn active sites,the obtained Sn@Ti2CTX/Ti_(2)SnC–V exhibits an optimal NH_(3) yield of 28.4μg h^(−1) mg_(cat)^(−1) with an excellent FE of 15.57% at−0.4 V versus reversible hydrogen electrode in 0.1 M Na_(2)SO_(4),as well as an ultra-long durability.Noticeably,this catalyst represents a satisfactory NH3 yield rate of 10.53μg h^(−1) mg^(−1) in the home-made simulation device,where commercial electrochemical photovoltaic cell was employed as power source,air and ultrapure water as feed stock.The as-proposed strategy represents great potential toward ammonia production in terms of financial cost according to the systematic technical economic analysis.This work is of significance for large-scale green ammonia production.
文摘Ammonia-diesel dual fuel(ADDF)engines for transportation applications are an important way to reduce carbon emissions.In order to achieve better combustion of ammonia in diesel engines.A small-bore single-cylinder engine was converted into an ADDF engine with the help of mature computational fluid dynamics(CFD)simulation software to investigate the performance of an engine with a high ammonia energy ratio(AER),and to study the effect of spray tilt angle on ADDF engine.The results showed that the increase in AER reduced nitric oxide(NO)and nitrogen dioxide(NO2)emissions but increased nitrous oxide(N2O)and unburned ammonia emissions.AER in the range of 50%-70%achieved lower greenhouse gases(GHG)emissions than the pure diesel mode.Relative to the pure diesel mode,when the AER was 60%,the indicated thermal efficiency(ITE)was increased by 0.2%and the GHG emissions were decreased by 22.3%,but carbon monoxide(CO)and Hydrocarbon(HC)emissions were increased.Increasing the in-cylinder combustion temperature or high-temperature region range of the ADDF engine could reduce GHG emissions.At an AER of 60%,an increase in the spray tilt angle helped the ammonia combustion in the residual gap to reduce the unburned ammonia emissions.Compared to the pure diesel mode with a spray tilt angle of 75°,an AER of 60%with a spray tilt angle of 77.5°improved the ITE by 1.5%,and reduced theGHGemissions by 25.7%.Adjusting the spray tilt angle of theADDFengine also reducedCOandHCemissions.This is an effective way to improve ADDF engine performance by adjusting the spray tilt angle.
基金financial support from the Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX24_0690)financial support from the National Natural Science Foundation of China (Project No. 22275088, 52101260)+4 种基金the Project of Shuangchuang Scholar of Jiangsu Province (Project No. JSSCBS20210212)the Fundamental Research Funds for the Central Universities (Project No. 30921011203)the Start-Up Grant (Project No. AE89991/340) from Nanjing University of Science and Technologyfinancial support from the Foundation of Jiangsu Educational Committee (22KJB310008)the Senior Talent Program of Jiangsu University (20JDG073)
文摘Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.
基金supported by the Feng Yun Application Pioneering Project (FY-APP-2022.0502)the National Natural Science Foundation of China (Grant No. 42205140)。
文摘Atmospheric ammonia(NH_(3)) is a chemically active trace gas that plays an important role in the atmospheric environment and climate change. Satellite remote sensing is a powerful technique to monitor NH_(3) concentration based on the absorption lines of NH_(3) in the thermal infrared region. In this study, we establish a retrieval algorithm to derive the NH_(3)column from the Hyperspectral Infrared Atmospheric Sounder(HIRAS) onboard the Chinese Feng Yun(FY)-3D satellite and present the first atmospheric NH_(3) column global map observed by the HIRAS instrument. The HIRAS observations can well capture NH_(3) hotspots around the world, e.g., India, West Africa, and East China, where large NH_(3) emissions exist. The HIRAS NH_(3) columns are also compared to the space-based Infrared Atmospheric Sounding Interferometer(IASI)measurements, and we find that the two instruments observe a consistent NH_(3) global distribution, with correlation coefficient(R) values of 0.28–0.73. Finally, some remaining issues about the HIRAS NH_(3) retrieval are discussed.
基金supported by is supported by the Shanghai Municipal Science and Technology Major Projectthe support from Shanghai Super Postdoctoral Incentive Program
文摘Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.
文摘This study focused on the development and characterization of TiO<sub>2</sub>-PES composite fibers with varying TiO<sub>2</sub> loading amounts using a phase inversion process. The resulting composite fibers exhibited a sponge-like structure with embedded TiO<sub>2</sub> nanoparticles within a polymer matrix. Their photocatalytic performance for ammonia removal from aqueous solutions under UV-A light exposure was thoroughly investigated. The findings revealed that PeTi8 composite fibers displayed superior adsorption capacity compared to other samples. Moreover, the study explored the impact of pH, light intensity, and catalyst dosage on the photocatalytic degradation of ammonia. Adsorption equilibrium isotherms closely followed the Langmuir model, with the results indicating a correlation between qm values of 2.49 mg/g and the porous structure of the adsorbents. The research underscored the efficacy of TiO<sub>2</sub> composite fibers in the photocatalytic removal of aqueous under UV-A light. Notably, increasing the distance between the photocatalyst and the light source resulted in de-creased hydroxyl radical concentration, influencing photocatalytic efficiency. These findings contribute to our understanding of TiO<sub>2</sub> composite fibers as promising photocatalysts for ammonia removal in water treatment applications.
基金National Natural Science Foundation of China(Nos.52225204,52173233 and 52202085)Innovation Program of Shanghai Municipal Education Commission,China(No.2021-01-07-00-03-E00109)+3 种基金Natural Science Foundation of Shanghai,China(No.23ZR1479200)“Shuguang Program”Supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission,China(No.20SG33)Fundamental Research Funds for the Central Universities,China(No.2232024Y-01)DHU Distinguished Young Professor Program,China(Nos.LZA2022001 and LZB2023002)。
文摘Highly dispersed bimetallic alloy nanoparticle electrocatalysts have been demonstrated to exhibit exceptional performance in driving the nitrate reduction reaction(NO_(3)RR)to generate ammonia(NH_(3)).In this study,we prepared mesoporous carbon nanofibers(mCNFs)functionalized with ordered PtFe alloys(O-PtFe-mCNFs)by a composite micelle interface-induced co-assembly method using poly(ethylene oxide)-block-polystyrene(PEO-b-PS)as a template.When employed as electrocatalysts,O-PtFe-mCNFs exhibited superior electrocatalytic performance for the NO_(3RR)compared to the mCNFs functionalized with disordered PtFe alloys(D-PtFe-mCNFs).Notably,the NH_(3)production performance was particularly outstanding,with a maximum NH_(3)yield of up to 959.6μmol/(h·cm~2).Furthermore,the Faraday efficiency(FE)was even 88.0%at-0.4 V vs.reversible hydrogen electrode(RHE).This finding provides compelling evidence of the potential of ordered PtFe alloy catalysts for the electrocatalytic NO_(3)RR.
基金Project (No. 49871043) supported by the National Natural Science Foundation of China.
文摘Surface charge, secondary adsorption- desorption and form distribution of Cu2+ and Zn2+ in Ultisols and Alfisols having adsorbed phosphate were studied by potentiometric titration, adsorption equilibrium and sequential extraction method, respectively. The soil surface negative charges increased whereas the amount of positive charges decreased with increase of P adsorbed. The soil secondary adsorption capacity for Cu2+ and Zn2+ was positively significantly correlated with the amount of P adsorbed by the soils, which could be described by the Langmuir equation. The amounts of Cu2+ and Zn2+ desorption from soils were decreased after P adsorption by the soils and the relationship between them was linear. After the soils adsorbed P, form distribution of Cu2+ and Zn2+ in soils changed remarforbly.
基金Project (Nos.49831005 and 49871043) supported by the National Natural Science Foundation of China.
文摘Charge characteristics and Cu2+ adsorption-desorption of soils with variable charge (latosol) and permanent charge (brown soil) and the relationship between them were studied by means of back-titration and adsorption equilibrium respectively. The amount of variable negative charge was much less in variable-charge soil than in permanent-charge soil and increased with the pH in the system, but the opposite trend occurred in the points of zero charge (PZCs). The amount of Cu2+ ions sorbed by permanent-charge soil was more than that by variable-charge soil and increased with the increase of Cu2+ concentration within a certain range in the equilibrium solution. The amount of Cu2+ ions desorbed with KC1 from permanent-charge soil was more than that from variable-charge soil, but the amount of Cu2+ ions desorbed with de-ionized water from permanent-charge soil was extremely low whereas there was still a certain amount of desorption from variable-charge soil. The increase of PZC of soils with variable or permanent charge varied with the increment of Cu2+ ions added. When the same amount of Cu2+ ions was added, the increments of PZC and variable negative surface charge of permanent-charge soil were different from those of variable-charge soil.