The electrocatalytic reduction of nitric oxide for ammonia synthesis(NORR)is a key green energy conversion technology.Its efficiency relies on high-performance electrocatalysts to enhance both ammonia yield(Y_(NH3))an...The electrocatalytic reduction of nitric oxide for ammonia synthesis(NORR)is a key green energy conversion technology.Its efficiency relies on high-performance electrocatalysts to enhance both ammonia yield(Y_(NH3))and Faradaic efficiency(F_(NH3)).However,conventional experimental methods for screening high-activity NORR catalysts often entail high resource consumption and time costs.Machine learning combined with SHAP feature analysis was employed to establish a stacked ensemble model that integrates multiple algorithms,to allow for a systematic investigation of the key descriptors governing NORR performance based on an experimental dataset.Evaluation of eight model algorithms revealed that the Stacked-SVR model achieved an R^(2)of 0.9223 and an RMSE of 0.0608 for predicting on the test set,whereas the Stacked-RF model achieved an R^(2)of 0.9042 and an RMSE of 0.0900 for predicting.The stacked ensemble model integrates the strengths of individual algorithms and demonstrates strong NORR prediction performance while avoiding overfitting.SHAP feature analysis results revealed that the Cu content in the catalyst composition has the most significant impact on catalytic performance.Moreover,the combination of the wet chemical reduction synthesis,a carbon fiber(CF)conductive substrate,and HCl electrolyte is more favorable for enhancing catalytic activity.Additionally,moderately lowering the working potential,controlling the electrolyte volume at low to medium levels,reducing catalyst loading,and increasing electrolyte concentration were found to synergistically enhance both and.展开更多
The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexit...The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexity of NO_(3)^(−)RR,yet challenges remain in optimizing performance and elucidating tandem mechanisms.Herein,we report a Cu@Co/CoFe-P tandem electrocatalyst featuring a phosphorus-doped heterostructure with dual active sites(Cu-P and Co/CoFe-P).This catalyst achieves an exceptional NH_(3)yield of 175.40 mg h^(−1)cm^(−2)and a record-high current density exceeding 2 A cm^(−2),with the electro-synthesized NH3 directly converted into NH4Cl.In situ spectroscopic analysis and density functional theory(DFT)calculations reveal a novel desorption-reactivation tandem mechanism:(1)the Cu-P domain preferentially reduces NO_(3)^(−)to*NO_(2),which desorbs as stable NO_(2)^(−);(2)the Co/CoFe-P domain subsequently reactivates NO_(2)^(−),and converts it efficiently into NH3.Moreover,phosphorus doping enhances*H supply,while Fe alloying with Co promotes NO_(2)^(−)hydrogenation,ensuring an efficient and synchronized tandem pathway for NO_(3)^(−)RR.The proposed*NO_(2)desorption-reactivation mechanism deepens the understanding of NO_(3)^(−)RR tandem process,thereby paving the way for designing more efficient tandem electrocatalysts.展开更多
Electrochemical nitrate reduction reaction(NO_(3)RR)is a sustainable strategy to treat wastewater and produce ammonia.However,it is still a challenge to prepare electrocatalysts with high activity and selectivity.Here...Electrochemical nitrate reduction reaction(NO_(3)RR)is a sustainable strategy to treat wastewater and produce ammonia.However,it is still a challenge to prepare electrocatalysts with high activity and selectivity.Herein,the CuO_(x) nanowires supported Ru nanoclusters(Ru-CuO_(x))were fabricated via a three-step procedure for efficient nitrate conversion and highly selective ammonia generation.The prepared RuCuO_(x) shows a high ammonia yield rate of 2286.5μg h^(-1) cm^(-2) at-0.7 V vs.RHE and Faradaic efficiency(FE)of 80.1%at-0.4 V vs.RHE.Additionally,the nitrate conversion rate exceeds 90%at the potential range from-0.2 to-0.7 V vs.RHE,and the ammonia selectivity can reach 97.7%at-0.7 V vs.RHE in100 mg L^(-1) NaNO_(3) solution.The systematic characterizations clarify that the introduction of Ru not only regulates the electronic structure of CuO_(x) and accelerates the reconstruction of CuO_(x) to Cu but also promotes H2O dissociation to generate active hydrogen.Moreover.in-situ Raman spectroscopy reveals that the formed Ru-Cu is considered the actual active species during the NO_(3)RR.Density functional theory(DFT)calculations further prove that the obtained Ru-Cu facilitates the adsorption of nitrate and lowers the Gibbs free energy of the rate-determining step,thus improving the NO_(3)RR performance.展开更多
Hydrolysis of ammonia borane is deemed as a promising technique for robust hydrogen production,yet its deployment is still restricted due to the sluggish kinetics of the water dissociation step.An appropriate catalyst...Hydrolysis of ammonia borane is deemed as a promising technique for robust hydrogen production,yet its deployment is still restricted due to the sluggish kinetics of the water dissociation step.An appropriate catalyst that can effectively reduce the H_(2)O dissociation barrier is quite desirable for sustainable ammonia borane-to-hydrogen conversion.Herein,an amino pre-coordination confinement strategy is profiled to achieve sub-2 nm ordered PtCo intermetallics uniformly on N-doped hollow mesoporous carbon spheres(O-PtCo/NHMS)for ammonia borane catalytic hydrolysis.Such a confined approach showcases the capacity of preventing nanoparticles from agglomeration and growth for accurate size control and can be extended to other ordered intermetallic systems(e.g.PtFe and PtCu).As for the ammonia borane hydrolysis,the ordered PtCo intermetallics have delivered a five times higher turnover frequency activity of 1264.1 min^(-1) than that of the disordered PtCo catalyst,together with excellent catalytic durability.Mechanism studies indicate that the ordered PtCo structure promotes the balanced adsorption of H_(2)O and ammonia borane molecules at Co and Pt sites and reduces the energy barrier for the rate-determining H_(2)O dissociation step to boost the ammonia borane hydrolysis.This work provides valuable insights into the rational design of efficient ordered PtM intermetallic catalysts and expands their application in hydrogen production via ammonia borane hydrolysis.展开更多
We synthesized Ru_(1)Cu_(25)P_(7.5)/TiO_(2)catalyst using sodium borohydride(NaBH_(4))as reductant in a facile strategy.The highly dispersed RuCuP nanoclusters are anchored on the TiO_(2)surface with an average partic...We synthesized Ru_(1)Cu_(25)P_(7.5)/TiO_(2)catalyst using sodium borohydride(NaBH_(4))as reductant in a facile strategy.The highly dispersed RuCuP nanoclusters are anchored on the TiO_(2)surface with an average particle size of 2.62 nm.The catalyst shows excellent catalytic activity when applied to the hydrolysis of AB,which owns a high turnover frequency value of 531.56 mol_(H2)mol_(Ru)^(-1)min^(-1)and a low activation energy of 46.38 kJ·mol^(-1),it also exhibits good durability which maintains 61.13%initial activity after five cycles.The high catalytic performance of Ru_(1)Cu_(25)P_(7.5)/TiO_(2)may be attributed to the synergistic effects between Ru,Cu,and P elements,fine particle size,good dispersion,and the tight adhesion between nanoclusters and carrier.展开更多
Green ammonia,produced by harnessing renewable solar energy to split nitrogen,plays a pivotal role in both agricultural practices and forthcoming energy configurations,driving the sustainable development of human soci...Green ammonia,produced by harnessing renewable solar energy to split nitrogen,plays a pivotal role in both agricultural practices and forthcoming energy configurations,driving the sustainable development of human society with zero-carbon emissions.However,nitrogen photoreduction currently faces the challenges of poor activation ability and low yield,and it is still challenging to unravel the intertwined problems in this field and provide direction for its development due to the complex reaction mechanism and multidisciplinary aspects such as photochemistry,catalysis,interface science,and technology.This review focuses on capturing the latest advances in photocatalytic nitrogen-to-ammonia conversion,delving into fundamental principles regarding the process,efficient photocatalysts for practical ammonia synthesis,and well-designed catalytic environments.Besides,this article provides insightful guidelines for analyzing complicated reaction mechanisms and identifying key bottlenecks or specific rate-determining steps,such as reactant activation,interfacial reaction engineering,and hydrogen evolution side reactions.By integrating perspectives from atomic mechanisms,nanoscale photocatalysts,microscale interfacial engineering,and macroscale reaction system design,this review advances the development of nitrogen photoreduction from proof-of-concept discoveries to viable solar-to-chemical conversion technologies,while also providing a valuable entry point for researchers into this burgeoning field.展开更多
The traditional ammonia synthesis via the Haber–Bosch process requires large consumption of highpurity H_(2) and causes significant carbon emissions owing to the energy-intensive and complex hydrogen production steps...The traditional ammonia synthesis via the Haber–Bosch process requires large consumption of highpurity H_(2) and causes significant carbon emissions owing to the energy-intensive and complex hydrogen production steps conducted under harsh reaction conditions.Herein,we report a cyclic catalytic process for the production of NH_(3) by directly utilizing earth-abundant CH_(4) as a hydrogen source for N_(2) hydrogenation while simultaneously co-producing H_(2) over an alumina-supported iron catalyst(Fe/Al_(2)O_(3)).It achieves exceptional productivities of 2300μmol g^(-1)h^(-1)for NH_(3) and 400 mmol g^(-1)h^(-1)for H_(2) at700℃.By eliminating the coke that results from CH_(4) pyrolysis through a reaction with the greenhouse gas CO_(2) to produce valuable CO,we establish an atom-economic cyclic catalytic process while producing a CO stream intrinsically separated in the regeneration step.Mechanistic investigations indicate that the iron species in Fe/Al_(2) O_(3) serve as tri-functional active sites for CH_(4) pyrolysis,N_(2) hydrogenation,and coke elimination to produce CO,thus enabling an efficient and environmentally friendly cyclic catalytic process.展开更多
Perovskite solar cells have achieved remarkable progress in photovoltaic efficiency.However,interfacial defects at the buried and upper interfaces of perovskite layer remain a critical challenge,leading to charge reco...Perovskite solar cells have achieved remarkable progress in photovoltaic efficiency.However,interfacial defects at the buried and upper interfaces of perovskite layer remain a critical challenge,leading to charge recombination,ion migration,and iodine oxidation.To address this,we propose a novel all-in-one modification strategy employing ammonia borane(BNH6)as a multifunctional complex.By incorporating BNH6 at both buried and upper interfaces simultaneously,we achieve dualinterfacial defect passivation and iodide oxidation suppression through three key mechanisms:(1)hydrolysis-induced interaction with SnO_(2),(2)coordination with Pb^(2+),and(3)inhibition of I−oxidation.This approach significantly enhances device performance,yielding a champion power conversion efficiency(PCE)of 26.43%(certified 25.98%).Furthermore,the unencapsulated device demonstrates prominent enhanced operation stability,maintaining 90%of its initial PCE after 500 h under continuous illumination.Notably,our strategy eliminates the need for separate interface treatments,streamlining fabrication and offering a scalable route toward high-performance perovskite photovoltaics.展开更多
Pre-chamber ignition technology can address the issue of uneven in-cylinder mixture combustion in large-bore marine engines.The impact of various pre-chamber structures on the formation of the mixture and jet flames w...Pre-chamber ignition technology can address the issue of uneven in-cylinder mixture combustion in large-bore marine engines.The impact of various pre-chamber structures on the formation of the mixture and jet flames within the pre-chamber is explored.This study performed numerical simulations on a large-bore marine ammonia/hydrogen pre-chamber engine prototype,considering pre-chamber volume,throat diameter,the distance between the hydrogen injector and the spark plug,and the hydrogen injector angle.Compared with the original engine,when the pre-chamber volume is 73.4 ml,the throat diameter is 14 mm,the distance ratio is 0.92,and the hydrogen injector angle is 80°.Moreover,the peak pressure in the pre-chamber increased by 23.1%,and that in the main chamber increased by 46.3%.The results indicate that the performance of the original engine is greatly enhanced by altering its fuel and pre-chamber structure.展开更多
Ammonia(NH3)has been widely recognized as a key precursor of atmospheric secondary aerosol formation.Vehicle emission is a major source of urban atmospheric NH3.With the tightening of emission standards and the growin...Ammonia(NH3)has been widely recognized as a key precursor of atmospheric secondary aerosol formation.Vehicle emission is a major source of urban atmospheric NH3.With the tightening of emission standards and the growing trend of vehicle fleet electrification,it is imperative to update the emission factors for NH3 from real-world on-road fleets.In this study,a tunnel measurement was conducted in the urban area of Tianjin,China.The fleet-average NH3 emission factor(EF)was 11.2 mg/(km·veh),significantly lower than those in previous studies,showing the benefit of emission standard updating.Through a multiple linear regression analysis,the EFs of light-duty gasoline vehicles,light-duty diesel vehicles,and heavy-duty diesel vehicles(HDDVs)were estimated to be 5.7±0.6 mg/(km·veh),40.8±5.1 mg/(km·veh),and 160.2±16.6 mg/(km·veh),respectively.Based on the results from this study,we found that HDDVs,which comprise<3%of the total vehicles may contribute approximately 22%of total NH3 emissions in Tianjin.Our results highlight NH3 emissions from HDDVs,a previously potentially overlooked source of NH3 emissions in urban areas.The actual on-road NH3 emissions from HDDVs may exceed current expectations,posing a growing concern for the future.展开更多
Accelerated industrialization combined with over-applied nitrogen fertilizers results in serious nitrate pollution insurface and ground water,disrupting the balance of the global nitrogen cycle.Electrochemical nitrate...Accelerated industrialization combined with over-applied nitrogen fertilizers results in serious nitrate pollution insurface and ground water,disrupting the balance of the global nitrogen cycle.Electrochemical nitrate reduction(eNO_(3)RR)emerges as an attractive strategy to simultaneously enable nitrate removal and decentralized ammo-nia fabrication,restoring the globally perturbed nitrogen cycle.However,complex deoxygenation-hydrogenationprocesses and sluggish proton-electron transfer kinetics significantly hinder practical application of eNO_(3)RR.In this study,we developed carbon-coated Cu-Ni bimetallic catalysts derived from metal-organic frameworks(MOFs)to facilitate eNO_(3)RR.The unique structural features of catalyst promote enhanced synergy between Cuand Ni,effectively addressing critical challenges in nitrate reduction.Comprehensive structural and electrochem-ical analysis demonstrate that electrochemical nitrate-to-nitrite conversion mainly takes place on active Cu sites,the introduction of Ni could efficiently accelerate the generation of aquatic active hydrogen,promoting the hy-drogenation of oxynitrides during eNO_(3)RR.In addition,Ni introduction could push up the d-band center of thecatalyst,thus enhancing the adsorption and activation of nitrate and the corresponding intermediates.Detailedreaction pathways for nitrate-to-ammonia conversion are illuminated by rotating disk electrode(RDE),in-situFourier-transform infrared spectroscopy,in-situ Raman spectrum and electrochemical impedance spectroscopy(EIS).Benefiting from the synergistic effect of Cu and Ni,optimum catalyst exhibited excellent nitrate reductionperformance.This work provides a new idea for elucidating the underlying eNO_(3)RR reaction mechanisms andcontributes a promising strategy for designing efficient bimetallic electrocatalysts.展开更多
Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances ar...Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances are far from practical needs due to the lack of efficient electrocatalysts.Engineering the lattice of metal-based nanomaterials via phase control has emerged as an effective strategy to modulate their intrinsic electrocatalytic properties.Herein,we realize boron(B)-insertion-induced phase regulation of rhodium(Rh)nanocrystals to obtain amorphous Rh_(4)B nanoparticles(NPs)and hexagonal close-packed(hcp)RhB NPs through a facile wet-chemical method.A high Faradaic efficiency(92.1±1.2%)and NH_(3) yield rate(629.5±11.0μmol h^(−1) cm^(−2))are achieved over hcp RhB NPs,far superior to those of most reported NORR nanocatalysts.In situ spectro-electrochemical analysis and density functional theory simulations reveal that the excellent electrocatalytic performances of hcp RhB NPs are attributed to the upshift of d-band center,enhanced NO adsorption/activation profile,and greatly reduced energy barrier of the rate-determining step.A demonstrative Zn-NO battery is assembled using hcp RhB NPs as the cathode and delivers a peak power density of 4.33 mW cm−2,realizing simultaneous NO removal,NH3 synthesis,and electricity output.展开更多
Over recent decades,fuel cell technologies have emerged as viable solutions to address the energy and environmental challenges stemming from fossil fuel dependence.Especially,ammonia has gained increasing attention as...Over recent decades,fuel cell technologies have emerged as viable solutions to address the energy and environmental challenges stemming from fossil fuel dependence.Especially,ammonia has gained increasing attention as an attractive alternative to hydrogen,offering comparable energy density while maintaining carbon-free characteristics,along with superior storage and transport properties that give direct ammonia fuel cells(DAFCs)distinct safety advantages over hydrogen-based systems.Central to this technology is the anodic ammonia oxidation reaction(AOR),where platinum(Pt)remains the most efficient catalyst after years of intensive research.This review offers a comprehensive overview of Ptbased AOR electrocatalysts with potential for application in low-temperature DAFCs.Following an introductory section highlighting key historical developments and catalytic breakthroughs,a fundamental understanding of low-temperature DAFC operation and AOR mechanisms is systematically presented.Subsequently,it outlines the advancements in Pt-based catalysts from simple monometallic systems to sophisticated multimetallic alloys and composites,highlighting material innovations and performance enhancements.Afterward,key challenges and future research directions for advancing AOR electrocatalysts are identified,with the aim of providing valuable guidance for developing practical,highperformance,and low-temperature DAFC systems.展开更多
Since the proposal of achieving dual carbon goals,countries worldwide have been actively seeking next-generation energy technologies.Ammonia energy,particularly green ammonia,has recently become a focal point of globa...Since the proposal of achieving dual carbon goals,countries worldwide have been actively seeking next-generation energy technologies.Ammonia energy,particularly green ammonia,has recently become a focal point of global attention.The global green ammonia market is expected to grow from USD 17 million in 2021 to USD 5.415 billion by 2030,with a growth rate of 90.2%during this period.As a fossil energy company primarily focused on oil and natural gas,CNPC faces significant pressure to transition to low-carbon operations and achieve dual carbon goals.Keeping track of the current status and technological advancements in ammonia energy development can support CNPC in more effectively implementing its new energy strategy.展开更多
The oxophilicity of metal oxides is usually utilized to improve the ammonia oxidation reaction(AOR)activity of Pt-based catalysts.But the effect of strong interaction between Pt and metal oxides on AOR is not studied....The oxophilicity of metal oxides is usually utilized to improve the ammonia oxidation reaction(AOR)activity of Pt-based catalysts.But the effect of strong interaction between Pt and metal oxides on AOR is not studied.Herein,experimental and density functional theory calculation results indicate that a strong interaction is built between Pt and reducible CeOx by high-temperature reduction,which induces the electronic interaction due to the difference of work fu nction,then optimizing the competitive adsorption behavior of*OH and*NH_(3)based on hard-soft acid-base principle.Accordingly,the optimal sample achieves an AOR peak current density of 329 mA mg_(Pt)^(-1),which is 2.4 times that of Pt.Meanwhile,it also shows satisfied hydrogen evolution reaction activity with an overpotential of only 24.3 mV at-10 mA cm^(-2)due to the optimization of*H adsorption energy on Pt by CeO_(x).Therefore,this work proposes an AOR activity enhancement mechanism of metal oxides in terms of the strong interaction,and sheds light on developing effective bifunctional catalysts for ammonia electrolysis.展开更多
As an emergent energy carrier,ammonia benefits from a well-established industrial infrastructure for its transportation and production,positioning it as a promising candidate toward a carbon-free energy landscape.With...As an emergent energy carrier,ammonia benefits from a well-established industrial infrastructure for its transportation and production,positioning it as a promising candidate toward a carbon-free energy landscape.Within this context,the electrocatalytic ammonia oxidation reaction(AOR)is pivotal.Platinum(Pt),recognized as the most efficient AOR catalyst,has undergone extensive development over the years,yielding notable advancements across various domains,ranging from elucidating the reaction mechanism to exploring innovative materials.This review begins by elucidating the mechanism of ammonia oxidation,summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods.Subsequently,it outlines the research progress surrounding different Pt-based catalysts,followed by a discussion on standard protocols for electrochemical ammonia oxidation testing,which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts.Moreover,the review addresses current challenges in ammonia oxidation and outlines potential future directions,providing a comprehensive outlook on the field.展开更多
Ammonia is the cornerstone of modern agriculture,providing a critical nitrogen source for global food production and serving as a key raw material for numerous industrial chemicals.Electrocatalytic nitrate reduction,a...Ammonia is the cornerstone of modern agriculture,providing a critical nitrogen source for global food production and serving as a key raw material for numerous industrial chemicals.Electrocatalytic nitrate reduction,as an environmentally friendly method for synthesizing ammonia,not only mitigates the reliance on current ammonia synthesis processes fed by traditional fossil fuels but also effectively reduces nitrate pollution resulting from agricultural and industrial activities.This review explores the fundamental principles of electrocata lytic nitrate reduction,focusing on the key steps of electron transfer and ammonia formation.Additionally,it summarizes the critical factors influencing the performance and selectivity of the reaction,including the properties of the electrolyte,operating voltage,electrode materials,and design of the electrolytic cell.Further discussion of recent advances in electrocatalysts,including pure metal catalysts,metal oxide catalysts,non-metallic catalysts,and composite catalysts,highlights their significant roles in enhancing both the efficiency and selectivity of electrocata lytic nitrate to ammonia(NRA)reactions.Critical challenges for the industrial NRA trials and further outlooks are outlined to propel this strategy toward real-world applications.Overall,the review provides an in-depth overview and comprehensive understanding of electrocata lytic NRA technology,thereby promoting further advancements and innovations in this domain.展开更多
The deployment of non-precious metal catalysts for the production of COx-free hydrogen via the ammonia decomposition reaction(ADR)presents a promising yet great challenge.In the present study,two crystal structures of...The deployment of non-precious metal catalysts for the production of COx-free hydrogen via the ammonia decomposition reaction(ADR)presents a promising yet great challenge.In the present study,two crystal structures of α-MoC and β-Mo_(2)C catalysts with different Mo/C ratios were synthesized,and their ammonia decomposition performance as well as structural evolution in ADR was investigated.The β-Mo_(2)C catalyst,characterized by a higher Mo/C ratio,demonstrated a remarkable turnover frequency of 1.3 s^(-1),which is over tenfold higher than that ofα-MoC(0.1 s^(-1)).An increase in the Mo/C ratio of molybdenum carbide revealed a direct correlation between the surface Mo/C ratio and the hydrogen yield.The transient response surface reaction indicated that the combination of N*and N*derived from NH_(3) dissociation represents the rate-determining step in the ADR,andβ-Mo2C exhibited exceptional proficiency in facilitating this pivotal step.Concurrently,the accumulation of N*species on the carbide surface could induce the phase transition of molybdenum carbide to nitride,which follows a topological transformation.It is discovered that such phase evolution was affected by the Mo-C surface and reaction temperature simultaneously.When the kinetics of combination of N*was accelerated by rising temperatures and its accumulation on the carbide surface was mitigated,β-Mo_(2)C maintained its carbide phase,preventing nitridation during the ADR at 810℃.Our results contribute to an in-depth understanding of the molybdenum carbides’catalytic properties in ADR and highlight the nature of the carbide-nitride phase transition in the reaction.展开更多
This study focuses on the spatiotemporal distribution,urban-rural variations,and driving factors of ammonia Vertical Column Densities(VCDs)in China’s Yangtze River Delta region(YRD)from 2008 to 2020.Utilizing data fr...This study focuses on the spatiotemporal distribution,urban-rural variations,and driving factors of ammonia Vertical Column Densities(VCDs)in China’s Yangtze River Delta region(YRD)from 2008 to 2020.Utilizing data from the Infrared Atmospheric Sounding Interfer-ometer(IASI),Generalized Additive Models(GAM),and the GEOS-Chem chemical transport model,we observed a significant increase of NH_(3)VCDs in the YRD between 2014 and 2020.The spatial distribution analysis revealed higher NH_(3)concentrations in the northern part of the YRD region,primarily due to lower precipitation,alkaline soil,and intensive agricul-tural activities.NH_(3)VCDs in the YRD region increased significantly(65.18%)from 2008 to 2020.The highest growth rate occurs in the summer,with an annual average growth rate of 7.2%during the period from 2014 to 2020.Agricultural emissions dominated NH_(3)VCDs during spring and summer,with high concentrations primarily located in the agricultural areas adjacent to densely populated urban zones.Regions within several large urban areas have been discovered to exhibit relatively stable variations in NH_(3)VCDs.The rise in NH_(3)VCDs within the YRD region was primarily driven by the reduction of acidic gases like SO_(2),as emphasized by GAM modeling and sensitivity tests using the GEOS-Chem model.The concentration changes of acidic gases contribute to over 80%of the interannual variations in NH_(3)VCDs.This emphasizes the crucial role of environmental policies targeting the reduction of these acidic gases.Effective emission control is urgent tomitigate environmental hazards and secondary particulate matter,especially in the northern YRD.展开更多
The removal of ammonia nitrogen(NH_(4)^(+)-N)and bacteria from aquaculture wastewater holds paramount ecological and production significance.In this study,Pt/RuO_(2)/g-C_(3)N_(4)photocatalysts were prepared by deposit...The removal of ammonia nitrogen(NH_(4)^(+)-N)and bacteria from aquaculture wastewater holds paramount ecological and production significance.In this study,Pt/RuO_(2)/g-C_(3)N_(4)photocatalysts were prepared by depositing Pt and RuO_(2)particles onto g-C_(3)N_(4).The physicochemical properties of photocatalysts were explored by X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM),X-ray diffraction(XRD),and UV–vis diffuse reflectance spectrometer(UV–vis DRS).The photocatalysts were then applied to the removal of both NH_(4)^(+)-N and bacteria from simulated mariculture wastewater.The results clarified that the removals of both NH_(4)^(+)-N and bacteria were in the sequence of g-C_(3)N_(4)<RuO_(2)/g-C_(3)N_(4)<Pt/g-C_(3)N_(4)<Pt/RuO_(2)/g-C_(3)N_(4).This magnificent photocatalytic ability of Pt/RuO_(2)/g-C_(3)N_(4)can be interpreted by the transfer of holes from g-C_(3)N_(4)to RuO_(2)to facilitate the in situ generation of HClO from Cl^(−)in wastewater,while Pt extracts photogenerated electrons for H_(2)formation to enhance the reaction.The removal of NH_(4)^(+)-N and disinfection effect were more pronounced in simulated seawater than in purewater.The removal efficiency ofNH_(4)^(+)-N increases with an increase in pH of wastewater,while the bactericidal effect was more significant under a lower pH in a pH range of 6–9.In actual seawater aquaculture wastewater,Pt/RuO_(2)/g-C_(3)N_(4)still exhibits effective removal efficiency of NH_(4)^(+)-N and bactericidal performance under sunlight.This study provides an alternative avenue for removement of NH_(4)^(+)-N and bacteria from saline waters under sunlight.展开更多
文摘The electrocatalytic reduction of nitric oxide for ammonia synthesis(NORR)is a key green energy conversion technology.Its efficiency relies on high-performance electrocatalysts to enhance both ammonia yield(Y_(NH3))and Faradaic efficiency(F_(NH3)).However,conventional experimental methods for screening high-activity NORR catalysts often entail high resource consumption and time costs.Machine learning combined with SHAP feature analysis was employed to establish a stacked ensemble model that integrates multiple algorithms,to allow for a systematic investigation of the key descriptors governing NORR performance based on an experimental dataset.Evaluation of eight model algorithms revealed that the Stacked-SVR model achieved an R^(2)of 0.9223 and an RMSE of 0.0608 for predicting on the test set,whereas the Stacked-RF model achieved an R^(2)of 0.9042 and an RMSE of 0.0900 for predicting.The stacked ensemble model integrates the strengths of individual algorithms and demonstrates strong NORR prediction performance while avoiding overfitting.SHAP feature analysis results revealed that the Cu content in the catalyst composition has the most significant impact on catalytic performance.Moreover,the combination of the wet chemical reduction synthesis,a carbon fiber(CF)conductive substrate,and HCl electrolyte is more favorable for enhancing catalytic activity.Additionally,moderately lowering the working potential,controlling the electrolyte volume at low to medium levels,reducing catalyst loading,and increasing electrolyte concentration were found to synergistically enhance both and.
基金supported financially by the Key Project of the National Ministry of Science and Technology (No.2022YFC3705005)the Open Foundation of Key Laboratory of Industrial Ecology and Environmental Engineering,MOE (KLIEEE-22-05)
文摘The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexity of NO_(3)^(−)RR,yet challenges remain in optimizing performance and elucidating tandem mechanisms.Herein,we report a Cu@Co/CoFe-P tandem electrocatalyst featuring a phosphorus-doped heterostructure with dual active sites(Cu-P and Co/CoFe-P).This catalyst achieves an exceptional NH_(3)yield of 175.40 mg h^(−1)cm^(−2)and a record-high current density exceeding 2 A cm^(−2),with the electro-synthesized NH3 directly converted into NH4Cl.In situ spectroscopic analysis and density functional theory(DFT)calculations reveal a novel desorption-reactivation tandem mechanism:(1)the Cu-P domain preferentially reduces NO_(3)^(−)to*NO_(2),which desorbs as stable NO_(2)^(−);(2)the Co/CoFe-P domain subsequently reactivates NO_(2)^(−),and converts it efficiently into NH3.Moreover,phosphorus doping enhances*H supply,while Fe alloying with Co promotes NO_(2)^(−)hydrogenation,ensuring an efficient and synchronized tandem pathway for NO_(3)^(−)RR.The proposed*NO_(2)desorption-reactivation mechanism deepens the understanding of NO_(3)^(−)RR tandem process,thereby paving the way for designing more efficient tandem electrocatalysts.
基金the Natural Science Foundation of China(Grant No.NSFC-22072062,22202098)the Science and Technology Project of China Northern Rare Earth(BFXT-2023-D-0048 and BFXT-2022-D-0078)。
文摘Electrochemical nitrate reduction reaction(NO_(3)RR)is a sustainable strategy to treat wastewater and produce ammonia.However,it is still a challenge to prepare electrocatalysts with high activity and selectivity.Herein,the CuO_(x) nanowires supported Ru nanoclusters(Ru-CuO_(x))were fabricated via a three-step procedure for efficient nitrate conversion and highly selective ammonia generation.The prepared RuCuO_(x) shows a high ammonia yield rate of 2286.5μg h^(-1) cm^(-2) at-0.7 V vs.RHE and Faradaic efficiency(FE)of 80.1%at-0.4 V vs.RHE.Additionally,the nitrate conversion rate exceeds 90%at the potential range from-0.2 to-0.7 V vs.RHE,and the ammonia selectivity can reach 97.7%at-0.7 V vs.RHE in100 mg L^(-1) NaNO_(3) solution.The systematic characterizations clarify that the introduction of Ru not only regulates the electronic structure of CuO_(x) and accelerates the reconstruction of CuO_(x) to Cu but also promotes H2O dissociation to generate active hydrogen.Moreover.in-situ Raman spectroscopy reveals that the formed Ru-Cu is considered the actual active species during the NO_(3)RR.Density functional theory(DFT)calculations further prove that the obtained Ru-Cu facilitates the adsorption of nitrate and lowers the Gibbs free energy of the rate-determining step,thus improving the NO_(3)RR performance.
基金National Natural Science Foundation of China(Grants Nos.92266107,92366207,52401245,and 52371236)the China Manned Space Station program(JZ-20190104)+3 种基金Technology Innovation Leading Program of Shaanxi Province(2024QCY-KXJ-011)Science Fund for Distinguished Young Scholars of Shaanxi Province(No.2025JC-JCQN-001)Major Scientific and Technological Innovation Special Plan of Xianyang Science and Technology Plan Project(No.L2024-ZDKJ-ZDCGZH-0026)the Fundamental Research Funds for the Central Universities.
文摘Hydrolysis of ammonia borane is deemed as a promising technique for robust hydrogen production,yet its deployment is still restricted due to the sluggish kinetics of the water dissociation step.An appropriate catalyst that can effectively reduce the H_(2)O dissociation barrier is quite desirable for sustainable ammonia borane-to-hydrogen conversion.Herein,an amino pre-coordination confinement strategy is profiled to achieve sub-2 nm ordered PtCo intermetallics uniformly on N-doped hollow mesoporous carbon spheres(O-PtCo/NHMS)for ammonia borane catalytic hydrolysis.Such a confined approach showcases the capacity of preventing nanoparticles from agglomeration and growth for accurate size control and can be extended to other ordered intermetallic systems(e.g.PtFe and PtCu).As for the ammonia borane hydrolysis,the ordered PtCo intermetallics have delivered a five times higher turnover frequency activity of 1264.1 min^(-1) than that of the disordered PtCo catalyst,together with excellent catalytic durability.Mechanism studies indicate that the ordered PtCo structure promotes the balanced adsorption of H_(2)O and ammonia borane molecules at Co and Pt sites and reduces the energy barrier for the rate-determining H_(2)O dissociation step to boost the ammonia borane hydrolysis.This work provides valuable insights into the rational design of efficient ordered PtM intermetallic catalysts and expands their application in hydrogen production via ammonia borane hydrolysis.
基金Funded by the National Natural Science Foundation of China(No.21805217)the Fundamental Research Funds for the Central Universities(WUT:2019IVB014 and 2021IVA014)。
文摘We synthesized Ru_(1)Cu_(25)P_(7.5)/TiO_(2)catalyst using sodium borohydride(NaBH_(4))as reductant in a facile strategy.The highly dispersed RuCuP nanoclusters are anchored on the TiO_(2)surface with an average particle size of 2.62 nm.The catalyst shows excellent catalytic activity when applied to the hydrolysis of AB,which owns a high turnover frequency value of 531.56 mol_(H2)mol_(Ru)^(-1)min^(-1)and a low activation energy of 46.38 kJ·mol^(-1),it also exhibits good durability which maintains 61.13%initial activity after five cycles.The high catalytic performance of Ru_(1)Cu_(25)P_(7.5)/TiO_(2)may be attributed to the synergistic effects between Ru,Cu,and P elements,fine particle size,good dispersion,and the tight adhesion between nanoclusters and carrier.
基金financially supported by the National Energy Green Hydrogen Refining Research&Development Center,National Natural Science Foundation of China(No.22476222)Natural Science Funds of Guangdong for Distinguished Young Scholar(No.2022B1515020098).
文摘Green ammonia,produced by harnessing renewable solar energy to split nitrogen,plays a pivotal role in both agricultural practices and forthcoming energy configurations,driving the sustainable development of human society with zero-carbon emissions.However,nitrogen photoreduction currently faces the challenges of poor activation ability and low yield,and it is still challenging to unravel the intertwined problems in this field and provide direction for its development due to the complex reaction mechanism and multidisciplinary aspects such as photochemistry,catalysis,interface science,and technology.This review focuses on capturing the latest advances in photocatalytic nitrogen-to-ammonia conversion,delving into fundamental principles regarding the process,efficient photocatalysts for practical ammonia synthesis,and well-designed catalytic environments.Besides,this article provides insightful guidelines for analyzing complicated reaction mechanisms and identifying key bottlenecks or specific rate-determining steps,such as reactant activation,interfacial reaction engineering,and hydrogen evolution side reactions.By integrating perspectives from atomic mechanisms,nanoscale photocatalysts,microscale interfacial engineering,and macroscale reaction system design,this review advances the development of nitrogen photoreduction from proof-of-concept discoveries to viable solar-to-chemical conversion technologies,while also providing a valuable entry point for researchers into this burgeoning field.
基金financial support from the National Key R&D Program of China(2022YFA1504500 and 2023YFA1506300)the National Natural Science Foundation of China(22588201,22225204,and 22472169)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0600100)Liaoning Binhai Laboratory(LBLG-2024-03)。
文摘The traditional ammonia synthesis via the Haber–Bosch process requires large consumption of highpurity H_(2) and causes significant carbon emissions owing to the energy-intensive and complex hydrogen production steps conducted under harsh reaction conditions.Herein,we report a cyclic catalytic process for the production of NH_(3) by directly utilizing earth-abundant CH_(4) as a hydrogen source for N_(2) hydrogenation while simultaneously co-producing H_(2) over an alumina-supported iron catalyst(Fe/Al_(2)O_(3)).It achieves exceptional productivities of 2300μmol g^(-1)h^(-1)for NH_(3) and 400 mmol g^(-1)h^(-1)for H_(2) at700℃.By eliminating the coke that results from CH_(4) pyrolysis through a reaction with the greenhouse gas CO_(2) to produce valuable CO,we establish an atom-economic cyclic catalytic process while producing a CO stream intrinsically separated in the regeneration step.Mechanistic investigations indicate that the iron species in Fe/Al_(2) O_(3) serve as tri-functional active sites for CH_(4) pyrolysis,N_(2) hydrogenation,and coke elimination to produce CO,thus enabling an efficient and environmentally friendly cyclic catalytic process.
基金supported by grants from the National Natural Science Foundation of China(Grant Nos.22334007).
文摘Perovskite solar cells have achieved remarkable progress in photovoltaic efficiency.However,interfacial defects at the buried and upper interfaces of perovskite layer remain a critical challenge,leading to charge recombination,ion migration,and iodine oxidation.To address this,we propose a novel all-in-one modification strategy employing ammonia borane(BNH6)as a multifunctional complex.By incorporating BNH6 at both buried and upper interfaces simultaneously,we achieve dualinterfacial defect passivation and iodide oxidation suppression through three key mechanisms:(1)hydrolysis-induced interaction with SnO_(2),(2)coordination with Pb^(2+),and(3)inhibition of I−oxidation.This approach significantly enhances device performance,yielding a champion power conversion efficiency(PCE)of 26.43%(certified 25.98%).Furthermore,the unencapsulated device demonstrates prominent enhanced operation stability,maintaining 90%of its initial PCE after 500 h under continuous illumination.Notably,our strategy eliminates the need for separate interface treatments,streamlining fabrication and offering a scalable route toward high-performance perovskite photovoltaics.
基金Supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions under Grant No.014000319/2018-00391.
文摘Pre-chamber ignition technology can address the issue of uneven in-cylinder mixture combustion in large-bore marine engines.The impact of various pre-chamber structures on the formation of the mixture and jet flames within the pre-chamber is explored.This study performed numerical simulations on a large-bore marine ammonia/hydrogen pre-chamber engine prototype,considering pre-chamber volume,throat diameter,the distance between the hydrogen injector and the spark plug,and the hydrogen injector angle.Compared with the original engine,when the pre-chamber volume is 73.4 ml,the throat diameter is 14 mm,the distance ratio is 0.92,and the hydrogen injector angle is 80°.Moreover,the peak pressure in the pre-chamber increased by 23.1%,and that in the main chamber increased by 46.3%.The results indicate that the performance of the original engine is greatly enhanced by altering its fuel and pre-chamber structure.
基金supported by the National key research and development program of China(No.2022YFE0135000)the National Natural Science Foundation of China(No.42175123)the Natural Science Foundation of Tianjin(No.23JCJQJC00170).
文摘Ammonia(NH3)has been widely recognized as a key precursor of atmospheric secondary aerosol formation.Vehicle emission is a major source of urban atmospheric NH3.With the tightening of emission standards and the growing trend of vehicle fleet electrification,it is imperative to update the emission factors for NH3 from real-world on-road fleets.In this study,a tunnel measurement was conducted in the urban area of Tianjin,China.The fleet-average NH3 emission factor(EF)was 11.2 mg/(km·veh),significantly lower than those in previous studies,showing the benefit of emission standard updating.Through a multiple linear regression analysis,the EFs of light-duty gasoline vehicles,light-duty diesel vehicles,and heavy-duty diesel vehicles(HDDVs)were estimated to be 5.7±0.6 mg/(km·veh),40.8±5.1 mg/(km·veh),and 160.2±16.6 mg/(km·veh),respectively.Based on the results from this study,we found that HDDVs,which comprise<3%of the total vehicles may contribute approximately 22%of total NH3 emissions in Tianjin.Our results highlight NH3 emissions from HDDVs,a previously potentially overlooked source of NH3 emissions in urban areas.The actual on-road NH3 emissions from HDDVs may exceed current expectations,posing a growing concern for the future.
基金supported by the Natural Science Foundation of China(No.52101279)the Key Scientific Research Foundation of Education department of Hunan Province(No.24A0003)the Scientific Research Project of Education Department of Hunan Province(No.21B000)and the Fundamental Research Funds for the Central Universities of Central South University.
文摘Accelerated industrialization combined with over-applied nitrogen fertilizers results in serious nitrate pollution insurface and ground water,disrupting the balance of the global nitrogen cycle.Electrochemical nitrate reduction(eNO_(3)RR)emerges as an attractive strategy to simultaneously enable nitrate removal and decentralized ammo-nia fabrication,restoring the globally perturbed nitrogen cycle.However,complex deoxygenation-hydrogenationprocesses and sluggish proton-electron transfer kinetics significantly hinder practical application of eNO_(3)RR.In this study,we developed carbon-coated Cu-Ni bimetallic catalysts derived from metal-organic frameworks(MOFs)to facilitate eNO_(3)RR.The unique structural features of catalyst promote enhanced synergy between Cuand Ni,effectively addressing critical challenges in nitrate reduction.Comprehensive structural and electrochem-ical analysis demonstrate that electrochemical nitrate-to-nitrite conversion mainly takes place on active Cu sites,the introduction of Ni could efficiently accelerate the generation of aquatic active hydrogen,promoting the hy-drogenation of oxynitrides during eNO_(3)RR.In addition,Ni introduction could push up the d-band center of thecatalyst,thus enhancing the adsorption and activation of nitrate and the corresponding intermediates.Detailedreaction pathways for nitrate-to-ammonia conversion are illuminated by rotating disk electrode(RDE),in-situFourier-transform infrared spectroscopy,in-situ Raman spectrum and electrochemical impedance spectroscopy(EIS).Benefiting from the synergistic effect of Cu and Ni,optimum catalyst exhibited excellent nitrate reductionperformance.This work provides a new idea for elucidating the underlying eNO_(3)RR reaction mechanisms andcontributes a promising strategy for designing efficient bimetallic electrocatalysts.
基金funding support from General Research Fund[Project No.14300525]from the Research Grants Council(RGC)of Hong Kong SAR,Chinafunding support from Natural Science Foundation of China(NSFC)Young Scientists Fund(Project No.22305203)+2 种基金NSFC Projects Nos.22309123,22422303,22303011,22033002,92261112 and U21A20328support from the Hong Kong Branch of National Precious Metals Material Engineering Research Center(NPMM)at City University of Hong Kongsupport from Young Collaborative Research Grant[Project No.C1003-23Y]support from RGC of Hong Kong SAR,China.
文摘Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances are far from practical needs due to the lack of efficient electrocatalysts.Engineering the lattice of metal-based nanomaterials via phase control has emerged as an effective strategy to modulate their intrinsic electrocatalytic properties.Herein,we realize boron(B)-insertion-induced phase regulation of rhodium(Rh)nanocrystals to obtain amorphous Rh_(4)B nanoparticles(NPs)and hexagonal close-packed(hcp)RhB NPs through a facile wet-chemical method.A high Faradaic efficiency(92.1±1.2%)and NH_(3) yield rate(629.5±11.0μmol h^(−1) cm^(−2))are achieved over hcp RhB NPs,far superior to those of most reported NORR nanocatalysts.In situ spectro-electrochemical analysis and density functional theory simulations reveal that the excellent electrocatalytic performances of hcp RhB NPs are attributed to the upshift of d-band center,enhanced NO adsorption/activation profile,and greatly reduced energy barrier of the rate-determining step.A demonstrative Zn-NO battery is assembled using hcp RhB NPs as the cathode and delivers a peak power density of 4.33 mW cm−2,realizing simultaneous NO removal,NH3 synthesis,and electricity output.
基金supported by the National Natural Science Foundation of China(No.52401284)the Natural Science Foundation of Jiangsu Province(No.BK20240957)+1 种基金the Key Research and Development Program of Nantong(No.GZ2024005)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX25_3677)。
文摘Over recent decades,fuel cell technologies have emerged as viable solutions to address the energy and environmental challenges stemming from fossil fuel dependence.Especially,ammonia has gained increasing attention as an attractive alternative to hydrogen,offering comparable energy density while maintaining carbon-free characteristics,along with superior storage and transport properties that give direct ammonia fuel cells(DAFCs)distinct safety advantages over hydrogen-based systems.Central to this technology is the anodic ammonia oxidation reaction(AOR),where platinum(Pt)remains the most efficient catalyst after years of intensive research.This review offers a comprehensive overview of Ptbased AOR electrocatalysts with potential for application in low-temperature DAFCs.Following an introductory section highlighting key historical developments and catalytic breakthroughs,a fundamental understanding of low-temperature DAFC operation and AOR mechanisms is systematically presented.Subsequently,it outlines the advancements in Pt-based catalysts from simple monometallic systems to sophisticated multimetallic alloys and composites,highlighting material innovations and performance enhancements.Afterward,key challenges and future research directions for advancing AOR electrocatalysts are identified,with the aim of providing valuable guidance for developing practical,highperformance,and low-temperature DAFC systems.
基金Integrating method of absorption and reaeration for CO_(2) capture(2023ZZ0101).
文摘Since the proposal of achieving dual carbon goals,countries worldwide have been actively seeking next-generation energy technologies.Ammonia energy,particularly green ammonia,has recently become a focal point of global attention.The global green ammonia market is expected to grow from USD 17 million in 2021 to USD 5.415 billion by 2030,with a growth rate of 90.2%during this period.As a fossil energy company primarily focused on oil and natural gas,CNPC faces significant pressure to transition to low-carbon operations and achieve dual carbon goals.Keeping track of the current status and technological advancements in ammonia energy development can support CNPC in more effectively implementing its new energy strategy.
基金supported by the National Natural Science Foundation of China(22162004,22479031)the Guangxi Science and Technology Program(2023AB38061)+1 种基金the Innovation Project of Guangxi Graduate Education(YCBZ2024053)the Highperformance Computing Platform of Guangxi University。
文摘The oxophilicity of metal oxides is usually utilized to improve the ammonia oxidation reaction(AOR)activity of Pt-based catalysts.But the effect of strong interaction between Pt and metal oxides on AOR is not studied.Herein,experimental and density functional theory calculation results indicate that a strong interaction is built between Pt and reducible CeOx by high-temperature reduction,which induces the electronic interaction due to the difference of work fu nction,then optimizing the competitive adsorption behavior of*OH and*NH_(3)based on hard-soft acid-base principle.Accordingly,the optimal sample achieves an AOR peak current density of 329 mA mg_(Pt)^(-1),which is 2.4 times that of Pt.Meanwhile,it also shows satisfied hydrogen evolution reaction activity with an overpotential of only 24.3 mV at-10 mA cm^(-2)due to the optimization of*H adsorption energy on Pt by CeO_(x).Therefore,this work proposes an AOR activity enhancement mechanism of metal oxides in terms of the strong interaction,and sheds light on developing effective bifunctional catalysts for ammonia electrolysis.
基金the National Key Research and Development Program of China(No.2022YFB4102000)the National Natural Science Foundation of China(Nos.22102018 and 52171201)+5 种基金the Huzhou Science and Technology Bureau(No.2022GZ45)the China Postdoctoral Science Foundation-Funded Project(No.2022M710601)the Huzhou Science and Technology Bureau(No.2023GZ02)the Natural Science Foundation of Sichuan Province(No.24NSFSC5779)the National Natural Science Foundation of China(Nos.22322201 and 22278067)the Natural Science Foundation of Sichuan Province(No.2023NSFSC0094)。
文摘As an emergent energy carrier,ammonia benefits from a well-established industrial infrastructure for its transportation and production,positioning it as a promising candidate toward a carbon-free energy landscape.Within this context,the electrocatalytic ammonia oxidation reaction(AOR)is pivotal.Platinum(Pt),recognized as the most efficient AOR catalyst,has undergone extensive development over the years,yielding notable advancements across various domains,ranging from elucidating the reaction mechanism to exploring innovative materials.This review begins by elucidating the mechanism of ammonia oxidation,summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods.Subsequently,it outlines the research progress surrounding different Pt-based catalysts,followed by a discussion on standard protocols for electrochemical ammonia oxidation testing,which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts.Moreover,the review addresses current challenges in ammonia oxidation and outlines potential future directions,providing a comprehensive outlook on the field.
基金supported by the National Key Research and Development Program of China(2023YFE0120900)the National Natural Science Foundation of China(52377160)+2 种基金the National Natural Science Foundation of China National Young Talents Project(GYKP010)Shaanxi Provincial Natural Science Program(2023-JCYB-425)Xi’an Jiaotong University Young Top Talents Program。
文摘Ammonia is the cornerstone of modern agriculture,providing a critical nitrogen source for global food production and serving as a key raw material for numerous industrial chemicals.Electrocatalytic nitrate reduction,as an environmentally friendly method for synthesizing ammonia,not only mitigates the reliance on current ammonia synthesis processes fed by traditional fossil fuels but also effectively reduces nitrate pollution resulting from agricultural and industrial activities.This review explores the fundamental principles of electrocata lytic nitrate reduction,focusing on the key steps of electron transfer and ammonia formation.Additionally,it summarizes the critical factors influencing the performance and selectivity of the reaction,including the properties of the electrolyte,operating voltage,electrode materials,and design of the electrolytic cell.Further discussion of recent advances in electrocatalysts,including pure metal catalysts,metal oxide catalysts,non-metallic catalysts,and composite catalysts,highlights their significant roles in enhancing both the efficiency and selectivity of electrocata lytic nitrate to ammonia(NRA)reactions.Critical challenges for the industrial NRA trials and further outlooks are outlined to propel this strategy toward real-world applications.Overall,the review provides an in-depth overview and comprehensive understanding of electrocata lytic NRA technology,thereby promoting further advancements and innovations in this domain.
文摘The deployment of non-precious metal catalysts for the production of COx-free hydrogen via the ammonia decomposition reaction(ADR)presents a promising yet great challenge.In the present study,two crystal structures of α-MoC and β-Mo_(2)C catalysts with different Mo/C ratios were synthesized,and their ammonia decomposition performance as well as structural evolution in ADR was investigated.The β-Mo_(2)C catalyst,characterized by a higher Mo/C ratio,demonstrated a remarkable turnover frequency of 1.3 s^(-1),which is over tenfold higher than that ofα-MoC(0.1 s^(-1)).An increase in the Mo/C ratio of molybdenum carbide revealed a direct correlation between the surface Mo/C ratio and the hydrogen yield.The transient response surface reaction indicated that the combination of N*and N*derived from NH_(3) dissociation represents the rate-determining step in the ADR,andβ-Mo2C exhibited exceptional proficiency in facilitating this pivotal step.Concurrently,the accumulation of N*species on the carbide surface could induce the phase transition of molybdenum carbide to nitride,which follows a topological transformation.It is discovered that such phase evolution was affected by the Mo-C surface and reaction temperature simultaneously.When the kinetics of combination of N*was accelerated by rising temperatures and its accumulation on the carbide surface was mitigated,β-Mo_(2)C maintained its carbide phase,preventing nitridation during the ADR at 810℃.Our results contribute to an in-depth understanding of the molybdenum carbides’catalytic properties in ADR and highlight the nature of the carbide-nitride phase transition in the reaction.
基金supported by the Joint Funds of the National Natural Science Foundation of China(No.U21A2027)the New Cornerstone Science Foundation through the XPLORER PRIZE(2023-1033).
文摘This study focuses on the spatiotemporal distribution,urban-rural variations,and driving factors of ammonia Vertical Column Densities(VCDs)in China’s Yangtze River Delta region(YRD)from 2008 to 2020.Utilizing data from the Infrared Atmospheric Sounding Interfer-ometer(IASI),Generalized Additive Models(GAM),and the GEOS-Chem chemical transport model,we observed a significant increase of NH_(3)VCDs in the YRD between 2014 and 2020.The spatial distribution analysis revealed higher NH_(3)concentrations in the northern part of the YRD region,primarily due to lower precipitation,alkaline soil,and intensive agricul-tural activities.NH_(3)VCDs in the YRD region increased significantly(65.18%)from 2008 to 2020.The highest growth rate occurs in the summer,with an annual average growth rate of 7.2%during the period from 2014 to 2020.Agricultural emissions dominated NH_(3)VCDs during spring and summer,with high concentrations primarily located in the agricultural areas adjacent to densely populated urban zones.Regions within several large urban areas have been discovered to exhibit relatively stable variations in NH_(3)VCDs.The rise in NH_(3)VCDs within the YRD region was primarily driven by the reduction of acidic gases like SO_(2),as emphasized by GAM modeling and sensitivity tests using the GEOS-Chem model.The concentration changes of acidic gases contribute to over 80%of the interannual variations in NH_(3)VCDs.This emphasizes the crucial role of environmental policies targeting the reduction of these acidic gases.Effective emission control is urgent tomitigate environmental hazards and secondary particulate matter,especially in the northern YRD.
基金supported by the Science and Technology Planning Project of Fujian Province(No.2023Y4015)the Marine and Fishery Development Special Fund of Xiamen(No.23YYST064QCB36)the Natural Science Foundation of Fujian Province(No.2021J011210).
文摘The removal of ammonia nitrogen(NH_(4)^(+)-N)and bacteria from aquaculture wastewater holds paramount ecological and production significance.In this study,Pt/RuO_(2)/g-C_(3)N_(4)photocatalysts were prepared by depositing Pt and RuO_(2)particles onto g-C_(3)N_(4).The physicochemical properties of photocatalysts were explored by X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM),X-ray diffraction(XRD),and UV–vis diffuse reflectance spectrometer(UV–vis DRS).The photocatalysts were then applied to the removal of both NH_(4)^(+)-N and bacteria from simulated mariculture wastewater.The results clarified that the removals of both NH_(4)^(+)-N and bacteria were in the sequence of g-C_(3)N_(4)<RuO_(2)/g-C_(3)N_(4)<Pt/g-C_(3)N_(4)<Pt/RuO_(2)/g-C_(3)N_(4).This magnificent photocatalytic ability of Pt/RuO_(2)/g-C_(3)N_(4)can be interpreted by the transfer of holes from g-C_(3)N_(4)to RuO_(2)to facilitate the in situ generation of HClO from Cl^(−)in wastewater,while Pt extracts photogenerated electrons for H_(2)formation to enhance the reaction.The removal of NH_(4)^(+)-N and disinfection effect were more pronounced in simulated seawater than in purewater.The removal efficiency ofNH_(4)^(+)-N increases with an increase in pH of wastewater,while the bactericidal effect was more significant under a lower pH in a pH range of 6–9.In actual seawater aquaculture wastewater,Pt/RuO_(2)/g-C_(3)N_(4)still exhibits effective removal efficiency of NH_(4)^(+)-N and bactericidal performance under sunlight.This study provides an alternative avenue for removement of NH_(4)^(+)-N and bacteria from saline waters under sunlight.
