Ammonium toxicity in plants remains poorly understood despite extensive research.While nitrate is known to benefit plant growth,the synergistic effects of nitrate in mitigating ammonium toxicity,even at low concentrat...Ammonium toxicity in plants remains poorly understood despite extensive research.While nitrate is known to benefit plant growth,the synergistic effects of nitrate in mitigating ammonium toxicity,even at low concentrations,are not fully elucidated.This review delves into the physiological and molecular nature of this phenomenon.To date,nitrate-dependent alleviation of ammonium toxicity is the result of cumulative consequences of the role of nitrate as a nutrient and signal in plant performance.The ability to counteract the ammonium-induced acidification through nitrate uptake and metabolism,the enhancement of potassium uptake as an essential nitrate counterion,and the nitratedependent signaling of key factors involved in ammonium assimilation,ROS scavenging,and growth hormone biosynthesis,are the most relevant hallmarks.In addition,evidence suggests that the availability of nitrate and ammonium has driven ecological selection in plants,determining current N preferences,and may have led to the selection of nitrate-dependent and ammonium-sensitive domesticated crops and the inefficient use of N fertilizers in agriculture.As ammonium toxicity limits N fertilization options and reduces agricultural yields,when it could be a more sustainable and cheaper alternative to nitrate,this review provides a better understanding of how plants use nitrate to counteract the problematic aspects of ammonium nutrition.展开更多
Nitrate pollution is a severe threat to the fragile ecosystems in karst regions.However,our knowledge of the sources and transformations of nitrate in karst cave groundwater is still limited.This study aimed to invest...Nitrate pollution is a severe threat to the fragile ecosystems in karst regions.However,our knowledge of the sources and transformations of nitrate in karst cave groundwater is still limited.This study aimed to investigate the temporal and spatial patterns of nitrate dynamics in the underground water of karst caves located on the south bank of the Qingjiang River in central China,through a comprehensive application of multiple approaches,such as hydrochemistry,nitrogen and oxygen isotope compositions of nitrate,and a Bayesian isotope mixing model(SIMMR).During the sampling period(from December 2018 to December 2019),the nitrate concentration did not show an apparent temporal variation;meanwhile,no water samples in this study had a nitrate concentration higher than the limit for drinking water,but the nitrate concentration in karst underground rivers is significantly higher than that in surface water.The results of the comprehensive analyses revealed that the predominant nitrate sources included nitrification in soil and chemical fertilizer,which had mean percentages of 43%and 32%,respectively.The source contribution varied in the outlet water among different caves.The soil-derived nitrate in the underground water from the Shizi Cave accounted for the highest proportion(49%),while chemical-fertilizer-derived nitrate in the underground water from the Mishui Cave accounted for the highest proportion(36%).The dualisotope signatures of nitrate supported a major influence on nitrogen dynamics in the cave underground from nitrification.These findings suggest that nitrate carried by underground rivers in karst caves should be alerted when making the nitrate balance in rivers flowing through karst areas.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
In comparison with their 2D and 3D counterparts,1D covalent organic frameworks(COFs)have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry bet...In comparison with their 2D and 3D counterparts,1D covalent organic frameworks(COFs)have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry between corresponding building blocks and linking units in addition to the unmanageable packing of 1D organic chains once formed.Herein,two novel imide-linked 1D COFs with phthalocyanine building blocks,namely NiPc-CZDM-COF and NiPc-CZDL-COF,were fabricated from the hydrothermal synthesis reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(II)(NiPc(COOH)_(8))with 9H-carbazole-3,6-diamine(CZDM)and 4,4′-(9H-carbazole-3,6-diyl)dianiline(CZDL),respectively.Two COFs have high crystallinity on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy.Due to their high ratio of exposed active centers on the edge sites of porous ribbons,both NiPc-CZDM-COF and NiPc-CZDL-COF electrodes display high utilization efficiency of NiPc electroactive sites of 8.0%and 7.5% according to the electrochemical measurement,resulting in their excellent capacity toward electrocatalytic nitrate reduction with the nitrate-to-NH3 Faradaic efficiency of nearly 100%.In particular,NiPc-CZDM-COF electrode exhibits superior electrocatalytic performance with high NH_(3) partial current density of−246 mA/cm^(2),ammonia yield rate of 19.5 mg cm^(−2) h^(−1),and turnover frequency of 5.8 s^(−1) at−1.2 V in an H-type cell associated with its higher conductivity.This work reveals the good potential of 1D porous crystalline materials in electrocatalysis.展开更多
Exploring high-performance electrocatalysts for the nitrate reduction reaction(NO_(3)RR)is crucial for environmental nitrate removal and ammonia synthesis.Single-atom collaboration with cluster can provide sufficient ...Exploring high-performance electrocatalysts for the nitrate reduction reaction(NO_(3)RR)is crucial for environmental nitrate removal and ammonia synthesis.Single-atom collaboration with cluster can provide sufficient active sites for catalysts to promote NO_(3)RR,yet the unclear synergistic effect between the two hinders their rational design.Herein,a series of Ir_(3)clusters and metal single atoms co-embedded in graphitic carbon nitride(g-CN)catalysts(Ir_(3)M1)were constructed,and the synergistic effects of Ir_(3)clusters and M1 single atoms on the NO_(3)RR catalytic mechanism and activity were systematically explored using density functional theory(DFT)calculations combined with machine learning.Comprehensive evaluations of structural stability and catalytic activity demonstrate that the synergy between single atoms and clusters effectively balances the adsorption energies of key intermediates,yielding exceptional catalytic performance(the limiting potential of Ir_(3)Ti_(1)can reach−0.22 V).Machine learning models further clarify the synergistic mechanism,where the geometric configurations of clusters serve as critical features for modulating the catalytic activity of single-atom sites,whereas the electronic structures of single atoms directly govern the reactivity of cluster sites.This DFT-machine learning approach provides theoretical guidelines for catalyst design and a predictive framework for efficient NO_(3)RR electrocatalysts.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
To address the deficiencies in comprehensive surface contamination prevention strategies within China's nitrate-affected regions,this research innovatively proposes the DITAPH model-a systematic framework integrat...To address the deficiencies in comprehensive surface contamination prevention strategies within China's nitrate-affected regions,this research innovatively proposes the DITAPH model-a systematic framework integrating groundwater nitrate vulnerability assessment and Nitrate Vulnerable Zones(NVZs)delineation through optimization of hydrogeological parameters.Based on detailed hydrogeological and hydrochemical investigations,the DITAPH model was applied in the plain areas of Quanzhou to evaluate its applicability.The model selected hydrogeological parameters(depth of groundwater,lithology of the vadose zone,topographic slope,aquifer water yield property),one climatic parameter(precipitation),and two anthropogenic parameters(land use type and population density)as assessment indicators.The results of the groundwater nitrate vulnerability assessment showed that the low,relatively low,relatively high,and high groundwater nitrate vulnerability zones in the study area accounted for 5.96%,35.44%,53.74%and 4.86%of the total area,respectively.Groundwater nitrate vulnerability was most strongly influenced by human activities,followed by groundwater depth and topographic slope.The high vulnerability zone is mainly affected by domestic and industrial wastewater,whereas the relatively high groundwater nitrate vulnerability zone is primarily influenced by agricultural activities.Validation of the DITAPH model revealed a significant positive correlation between the DITAPH index(DI)and nitrate concentration(ρ(NO3−)).The results of the NVZs delineated by the DITAPH model are reliable and can serve as a tool for water resource management planning,guiding the development of targeted measures in the NVZs to prevent groundwater contamination.展开更多
Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt...Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.展开更多
Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and l...Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and long-range electric vehicles.However,technical barriers such as dendrite growth and poor Li plating/stripping reversibility severely hinder the practical application of LMBs.However,lithium nitrate(LiNO_(3))is found to be able to stabilize the Li/electrolyte interface and has been used to address the above challenges.To date,considerable research efforts have been devoted toward understanding the roles of LiNO_(3) in regulating the surface properties of Li anodes and toward the development of many effective strategies.These research efforts are partially mentioned in some articles on LMBs and yet have not been reviewed systematically.To fill this gap,we discuss the recent advances in fundamental and technological research on LiNO_(3) and its derivatives for improving the performances of LMBs,particularly for Li-sulfur(S),Li-oxygen(O),and Li-Li-containing transition-metal oxide(LTMO)batteries,as well as LiNO_(3)-containing recipes for precursors in battery materials and interphase fabrication.This review pays attention to the effects of LiNO_(3) in lithium-based batteries,aiming to provide scientific guidance for the optimization of electrode/electrolyte interfaces and enrich the design of advanced LMBs.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
Nitrate is the primary nitrogen source for plants and is a signaling molecule regulating various plant developmental processes. Despite its significance, limited information is available on nitrate signaling in Vitis ...Nitrate is the primary nitrogen source for plants and is a signaling molecule regulating various plant developmental processes. Despite its significance, limited information is available on nitrate signaling in Vitis vinifera. We identified nine Vv RWP-RK genes distributed across eight chromosomes using genome-wide identification and evolutionary analyses. Among these, Vv NLP1-4 and Vv RKD1-5 are associated with nitrate signaling and reproductive growth, respectively. To investigate their potential functions, structures, cis-acting promoter elements,functional structural domains, phylogenetic trees, spatiotemporal expression levels in different tissues at different developmental stages,potential protein-protein interaction networks, synteny(gene content), collinearity(gene order), and three-dimensional protein structure prediction were explored. We found that long-term nitrate application dramatically promoted grapevine plantlet development, including primary root length and leaf growth, and Vv NLP1.1, Vv NLP1.2, and Vv NLP2 were highly expressed in ‘Thompson Seedless' root tissues under nitrate-enriched conditions. To clarify the critical role of nitrate in grapevine growth, we observed that nuclear localization of Vv NLP1.1increased significantly following nitrate treatment. Vv NLP1.1 was found to bind to the promoter of the primary nitrate response gene Vv NRT1.1,driving its transcriptional activity. These findings indicate that Vv NLP1.1 is a core transcription factor of the nitrate signaling pathway in grapevine. Nitrate molecular docking analysis revealed that Vv NLP1.1 directly binds to nitrate ions, indicating its potential role as a nitrate sensor capable of directly perceiving nitrate concentration. We also discovered that short-term nitrate starvation impacts Vv NLP1.1 promoter activity, linked to the abscisic acid-binding element(ABRE) motif in its promoter region. Our results thus provide new insights into the molecular mechanisms underlying various physiological processes in grapevine, particularly the nitrate signaling pathway, and provide a theoretical basis for improving nitrogen use efficiency(NUE) in grapevine.展开更多
A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic effic...A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic efficiency and yield rate of 97.54%and 33.64 mg h^(-1)mg_(cat)^(-1),respectively.Electrons are more likely to be transferred from Cu to t-ZrO_(2)at the electron-rich interface due to the lower work function,which promotes the formation of highly active Cu species and facilitates NO_(3^(-))adsorption,ensuring selective conversion into NH_(3).展开更多
Zinc-nitrate battery could produce electrical power,remove pollutant nitrate and obtain value-added ammonia,where the cathodic reaction of converting nitrate to ammonia is sluggish and complex due to the involvement o...Zinc-nitrate battery could produce electrical power,remove pollutant nitrate and obtain value-added ammonia,where the cathodic reaction of converting nitrate to ammonia is sluggish and complex due to the involvement of multi-electron transfer.Thus,highly efficient catalysts for nitrate reduction reaction(NO_(3)RR)are greatly needed.In this work,we report a high entropy hydroxide(HE-OH)as an excellent NO3RR catalyst,which could achieve high NH_(3)Faradaic efficiencies(e.g.,nearly 100%at-0.3 V versus reversible hydrogen electrode)and high yield rates(e.g.,30.4 mg h^(-1)cm^(-2)at-0.4 V).Moreover,HE-OH could also deliver a current density of 10 mA/cm^(2) at an overpotential of 260 mV for oxygen evolution reaction.The assembled zinc-nitrate battery using HE-OH as the cathode demonstrates a high power density(e.g.,3.62 mW/cm^(2)),rechargeability and stability.展开更多
Revealing the dynamic reconfiguration of catalysts and the evolution of active species during catalysis,elucidating and regulating the reconfiguration mechanism are paramount to the development of highperformance elec...Revealing the dynamic reconfiguration of catalysts and the evolution of active species during catalysis,elucidating and regulating the reconfiguration mechanism are paramount to the development of highperformance electrochemical nitrate reduction(NO_(3)RR)to ammonia.In-situ characterizations can precisely track reaction process and unveil the origin of activity enhancement.Here,in-situ reconstruction of pre-catalyst Co_(3)O_(4)fabricates a stable heterojunction Co(OH)_(2)/Co_(3)O_(4)to boost NO_(3)RR to ammonia.Insitu generated heterojunction accelerates the transformation of^(*)NO_(3)to^(*)NO_(2),while Co(OH)_(2)promotes the dissociation of water to active*H species for the hydrogenation of^(*)N species,and thereby improving the deoxygenation and hydrogenation ability of NO_(3)RR to NH_(3)and achieving a high Faradaic efficiency(FE)about 96.2%and a high NH_(3)production rate of 218.5μmol h^(-1)mg_(cat)^(-1)at-0.3 V.Density functional theory(DFT)calculations verified that in-situ formed active species Co(OH)_(2)on Co_(3)O_(4)markedly decreased the energy barrier of^(*)NO_(3)→^(*)NO_(2)and accelerated the hydrogenation step of^(*)NH→^(*)NH_(2)→^(*)NH_(3).Co(OH)_(2)/Co_(3)O_(4)heterostructure-based Zn-NO_(3)^(-)cell achieves excellent energy supply(1.22 V),a high ammonia yield rate(48.9μmol h^(-1)cm^(-2)),and a high FE(91%).The establishment of the structure-activity relationship during NO_(3)RR provides guidance for designing advanced electrode materials,and the in-situ evolution of species on the electrode surface unveils the intrinsic nature of improved catalytic performance.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 present work aims to stabilize the room temperature allotropic transition of ammonium nitrate(AN)particles utilizing a microencapsulation technique,which involves solvent/non-solvent in which nitrocellulose(NC)has...The present work aims to stabilize the room temperature allotropic transition of ammonium nitrate(AN)particles utilizing a microencapsulation technique,which involves solvent/non-solvent in which nitrocellulose(NC)has been employed as a coating agent.The SEM micrographs revealed distinct features of both pure AN and NC,contrasting with the irregular granular surface topography of the coated AN particles,demonstrating the adherence of NC on the AN surface.Structural analysis via infrared spectroscopy(IR)demonstrated a successful association of AN and NC,with slight shifts observed in IR bands indicating interfacial interactions.Powder X-ray Diffraction(PXRD)analysis further elucidated the structural changes induced by the coating process,revealing that the NC coating altered the crystallization pattern of its pure form.Thermal analysis demonstrates distinct profiles for pure and coated AN,for which the coated sample exhibits a temperature increase and an enthalpy decrease of the room temperature allotropic transition by 6℃,and 36%,respectively.Furthermore,the presence of NC coating alters the intermolecular forces within the composite system,leading to a reduction in melting enthalpy of coated AN by~39%compared to pure AN.The thermal decomposition analysis shows a two-step thermolysis process for coated AN,with a significant increase in the released heat by about 78%accompanied by an increase in the activation barrier of NC and AN thermolysis,demonstrating a stabilized reactivity of the AN-NC particles.These findings highlight the synergistic effect of NC coating on AN particles,which contributed to a structural and reactive stabilization of both AN and NC,proving the potential application of NC-coated AN as a strategically advantageous oxidizer in composite solid propellant formulations.展开更多
Electrocatalytic nitrate reduction reaction (NO_(3)-RR) to ammonia under ambient conditions is expected to be a green process for ammonia synthesis and alleviate water pollution issues.We report a CuO nanoparticles in...Electrocatalytic nitrate reduction reaction (NO_(3)-RR) to ammonia under ambient conditions is expected to be a green process for ammonia synthesis and alleviate water pollution issues.We report a CuO nanoparticles incorporated on nitrogen-doped porous carbon (CuO@NC) catalyst for NO_(3)-RR.Part of Cu(Ⅱ) is reduced to Cu(Ⅰ) during the NO_(3)-RR process to construct Cu(Ⅰ)-Cu(Ⅱ) pairs,confirmed by in situ X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.Density functional theory (DFT) calculations indicated that the formation of Cu(Ⅰ) could provide a reaction path with smaller energy barrier for NO_(3)-RR,while Cu(Ⅱ) effectively suppressed the competition of hydrogen evolution reaction (HER).As a result,CuO@NC catalyst achieved a Faradaic efficiency of 84.2% at -0.49 V versus reversible hydrogen electrode (RHE),and a NH_(3)yield rate of 17.2 mg h^(-1)mg^(-1)cat.at -0.79 V vs.RHE,higher than the HaberBosch process (<3.4 g h^(-1)g^(-1)cat.).This work may open a new avenue for effective NO_(3)-RR by modulating oxidation states.展开更多
Nitrate(NO_(3)^(-))accumulation and transport processes in the thick vadose zone affect the evolution of the groundwater NO_(3)^(-)content in intensive agricultural regions.Agricultural land-use change(ALUC),typically...Nitrate(NO_(3)^(-))accumulation and transport processes in the thick vadose zone affect the evolution of the groundwater NO_(3)^(-)content in intensive agricultural regions.Agricultural land-use change(ALUC),typically accompanied by substantial alterations in nitrogen fertilizer application and irrigation practices,is an important influencing factor.This study evaluated the changes in NO_(3)^(-)accumulation and transport in the deep vadose zone(DVZ,below the root zone),and the groundwater NO_(3)^(-)content associated with ALUC from grain to vegetable fields in the North China Plain(NCP).The ALUC from grain to vegetable resulted in nitrate–nitrogen(NO_(3)^(-)-N)accumulation in DVZ increased by 235.5 kg ha^(-1)m^(-1)(163.2%)in the piedmont plain and 224.9 kg ha^(-1)m^(-1)(102.7%)in the central plain,respectively.This change accelerated downward transport velocity in the DVZ(from 0.81±0.47 to 0.89±0.55 m yr^(-1)in the piedmont plain,and from 0.24±0.12 to 0.92±0.12 m yr^(-1)in the central plain)and increased NO_(3)^(-)leaching fluxes.High transport velocity and leaching fluxes resulted in chemical N-fertilizer entering the aquifer in several areas in the piedmont plain.The impact of the agricultural activity intensity changes,accompanied by the ALUC,on groundwater quantity and quality should be considered in similar regions.展开更多
Asian cultivated rice is one of the most important cereal crops globally,feeding approximately 50%of the world's population.Increasing rice nitrogen use efficiency(NUE)is crucial for achieving high yields with low...Asian cultivated rice is one of the most important cereal crops globally,feeding approximately 50%of the world's population.Increasing rice nitrogen use efficiency(NUE)is crucial for achieving high yields with low nitrogen inputs(Xu et al.,2012;Hu et al.,2023).However,modern cultivars are typically bred for high yields through excessive nitrogen fertilizer use,leading to the loss of beneficial alleles associated with high NUE during the breeding process(Wang and Peng,2017;Hu et al.,2023).Genetic improvement for high NUE should be a key strategy in breeding“Green Super Rice”(GSR)(Yu et al.,2021)and water-saving and drought-resistance rice(WDR)(Luo,2010;Xia et al.,2022)for sustainable agriculture.Asian cultivated rice is highly diverse and harbors vital genetic variants essential for adaptation to different environments(Wing et al.,2018).展开更多
基金funding from Deutsche Forschungsgemeinschaft (DFG)supported by an MCIN Ry C Programme MCIN/ AEI/10.13039/501100011033+2 种基金by the ‘European Union Next Generation EU/PRTR’ under grant no. RYC2021-032345-Isupported by the AEI (grant no. PID2019-107463RJ-I00/ AEI/10.13039/501100011033)the Regional Research and Development Programme of the Government of Navarre (call 2019, project Nitro Healthy, PC068)
文摘Ammonium toxicity in plants remains poorly understood despite extensive research.While nitrate is known to benefit plant growth,the synergistic effects of nitrate in mitigating ammonium toxicity,even at low concentrations,are not fully elucidated.This review delves into the physiological and molecular nature of this phenomenon.To date,nitrate-dependent alleviation of ammonium toxicity is the result of cumulative consequences of the role of nitrate as a nutrient and signal in plant performance.The ability to counteract the ammonium-induced acidification through nitrate uptake and metabolism,the enhancement of potassium uptake as an essential nitrate counterion,and the nitratedependent signaling of key factors involved in ammonium assimilation,ROS scavenging,and growth hormone biosynthesis,are the most relevant hallmarks.In addition,evidence suggests that the availability of nitrate and ammonium has driven ecological selection in plants,determining current N preferences,and may have led to the selection of nitrate-dependent and ammonium-sensitive domesticated crops and the inefficient use of N fertilizers in agriculture.As ammonium toxicity limits N fertilization options and reduces agricultural yields,when it could be a more sustainable and cheaper alternative to nitrate,this review provides a better understanding of how plants use nitrate to counteract the problematic aspects of ammonium nutrition.
基金supported by the National Natural Science Foundation of China(Nos.42372355,42530706)。
文摘Nitrate pollution is a severe threat to the fragile ecosystems in karst regions.However,our knowledge of the sources and transformations of nitrate in karst cave groundwater is still limited.This study aimed to investigate the temporal and spatial patterns of nitrate dynamics in the underground water of karst caves located on the south bank of the Qingjiang River in central China,through a comprehensive application of multiple approaches,such as hydrochemistry,nitrogen and oxygen isotope compositions of nitrate,and a Bayesian isotope mixing model(SIMMR).During the sampling period(from December 2018 to December 2019),the nitrate concentration did not show an apparent temporal variation;meanwhile,no water samples in this study had a nitrate concentration higher than the limit for drinking water,but the nitrate concentration in karst underground rivers is significantly higher than that in surface water.The results of the comprehensive analyses revealed that the predominant nitrate sources included nitrification in soil and chemical fertilizer,which had mean percentages of 43%and 32%,respectively.The source contribution varied in the outlet water among different caves.The soil-derived nitrate in the underground water from the Shizi Cave accounted for the highest proportion(49%),while chemical-fertilizer-derived nitrate in the underground water from the Mishui Cave accounted for the highest proportion(36%).The dualisotope signatures of nitrate supported a major influence on nitrogen dynamics in the cave underground from nitrification.These findings suggest that nitrate carried by underground rivers in karst caves should be alerted when making the nitrate balance in rivers flowing through karst areas.
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supported by the Natural Science Foundation(NSF)of China(Nos.22205015,22175020,and 22235001)the National Postdoctoral Program for Innovative Talents(No.BX20220032)+2 种基金the China Postdoctoral Science Foundation Funded Project(No.2022BG013)the Fundamental Research Funds for the Central Universities(Nos.00007709,00007770,and FRFBR-23-02B)University of Science and Technology Beijing is gratefully acknowledged.
文摘In comparison with their 2D and 3D counterparts,1D covalent organic frameworks(COFs)have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry between corresponding building blocks and linking units in addition to the unmanageable packing of 1D organic chains once formed.Herein,two novel imide-linked 1D COFs with phthalocyanine building blocks,namely NiPc-CZDM-COF and NiPc-CZDL-COF,were fabricated from the hydrothermal synthesis reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(II)(NiPc(COOH)_(8))with 9H-carbazole-3,6-diamine(CZDM)and 4,4′-(9H-carbazole-3,6-diyl)dianiline(CZDL),respectively.Two COFs have high crystallinity on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy.Due to their high ratio of exposed active centers on the edge sites of porous ribbons,both NiPc-CZDM-COF and NiPc-CZDL-COF electrodes display high utilization efficiency of NiPc electroactive sites of 8.0%and 7.5% according to the electrochemical measurement,resulting in their excellent capacity toward electrocatalytic nitrate reduction with the nitrate-to-NH3 Faradaic efficiency of nearly 100%.In particular,NiPc-CZDM-COF electrode exhibits superior electrocatalytic performance with high NH_(3) partial current density of−246 mA/cm^(2),ammonia yield rate of 19.5 mg cm^(−2) h^(−1),and turnover frequency of 5.8 s^(−1) at−1.2 V in an H-type cell associated with its higher conductivity.This work reveals the good potential of 1D porous crystalline materials in electrocatalysis.
基金the financial support from the Shandong Province colleges and universities youth innovation technology plan innovation team project(2022KJ285)the Natural Science Foundation of Shandong Province(ZR2022QE076)+1 种基金the National Natural Science Foundation of China(52202092)the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China(2023KJ104).
文摘Exploring high-performance electrocatalysts for the nitrate reduction reaction(NO_(3)RR)is crucial for environmental nitrate removal and ammonia synthesis.Single-atom collaboration with cluster can provide sufficient active sites for catalysts to promote NO_(3)RR,yet the unclear synergistic effect between the two hinders their rational design.Herein,a series of Ir_(3)clusters and metal single atoms co-embedded in graphitic carbon nitride(g-CN)catalysts(Ir_(3)M1)were constructed,and the synergistic effects of Ir_(3)clusters and M1 single atoms on the NO_(3)RR catalytic mechanism and activity were systematically explored using density functional theory(DFT)calculations combined with machine learning.Comprehensive evaluations of structural stability and catalytic activity demonstrate that the synergy between single atoms and clusters effectively balances the adsorption energies of key intermediates,yielding exceptional catalytic performance(the limiting potential of Ir_(3)Ti_(1)can reach−0.22 V).Machine learning models further clarify the synergistic mechanism,where the geometric configurations of clusters serve as critical features for modulating the catalytic activity of single-atom sites,whereas the electronic structures of single atoms directly govern the reactivity of cluster sites.This DFT-machine learning approach provides theoretical guidelines for catalyst design and a predictive framework for efficient NO_(3)RR electrocatalysts.
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supported by the National Key Research and Development Program of China(No.2022YFF1301301)the Natural Science Foundation of Xiamen Municipality(No.3502Z202472047)the Geological Survey Program of China Geological Survey(DD20190303).
文摘To address the deficiencies in comprehensive surface contamination prevention strategies within China's nitrate-affected regions,this research innovatively proposes the DITAPH model-a systematic framework integrating groundwater nitrate vulnerability assessment and Nitrate Vulnerable Zones(NVZs)delineation through optimization of hydrogeological parameters.Based on detailed hydrogeological and hydrochemical investigations,the DITAPH model was applied in the plain areas of Quanzhou to evaluate its applicability.The model selected hydrogeological parameters(depth of groundwater,lithology of the vadose zone,topographic slope,aquifer water yield property),one climatic parameter(precipitation),and two anthropogenic parameters(land use type and population density)as assessment indicators.The results of the groundwater nitrate vulnerability assessment showed that the low,relatively low,relatively high,and high groundwater nitrate vulnerability zones in the study area accounted for 5.96%,35.44%,53.74%and 4.86%of the total area,respectively.Groundwater nitrate vulnerability was most strongly influenced by human activities,followed by groundwater depth and topographic slope.The high vulnerability zone is mainly affected by domestic and industrial wastewater,whereas the relatively high groundwater nitrate vulnerability zone is primarily influenced by agricultural activities.Validation of the DITAPH model revealed a significant positive correlation between the DITAPH index(DI)and nitrate concentration(ρ(NO3−)).The results of the NVZs delineated by the DITAPH model are reliable and can serve as a tool for water resource management planning,guiding the development of targeted measures in the NVZs to prevent groundwater contamination.
基金supported by the National Natural Science Foundation of China(Grant Nos.:21825201,52401244 and 52201227)Henan Province Key Research and Development and Promotion Program(Scientific and Technological Breakthrough Project:232102240088 and 252102230078)+3 种基金the Key Research&Development and Promotion of Special Project(Scientific Problem Tackling)of Henan Province(252102230078)Doctoral Research Startup Fund Project of Henan Open University(BSJH-2025-04)Zhejiang Provincial Natural Science Foundation of China(LQ24B020005,LQ23B030001)China Postdoctoral Science Foundation(2024M762442).
文摘Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.
基金supported by the Yunnan Fundamental Research Projects(Grant Nos.202401AU070163 and 202501AT070298)the Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(Grant No.2023-XMDJ-00617107)+5 种基金the University Service Key Industry Project of Yunnan Province(Grant No.FWCY-ZD2024005)the Expert Workstation Support Project of Yunnan Province(Grant No.202405AF140069)the Scientific Research Foundation of Kunming University of Science and Technology(Grant No.20220122)the Analysis and Test Foundation of Kunming University of Science and Technology(Grant No.2023T20220122)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(Grant No.2025QN02057)the Ordos City Strategic Pioneering Science and Technology Special Program for New Energy(Grant No.DC2400003365).
文摘Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and long-range electric vehicles.However,technical barriers such as dendrite growth and poor Li plating/stripping reversibility severely hinder the practical application of LMBs.However,lithium nitrate(LiNO_(3))is found to be able to stabilize the Li/electrolyte interface and has been used to address the above challenges.To date,considerable research efforts have been devoted toward understanding the roles of LiNO_(3) in regulating the surface properties of Li anodes and toward the development of many effective strategies.These research efforts are partially mentioned in some articles on LMBs and yet have not been reviewed systematically.To fill this gap,we discuss the recent advances in fundamental and technological research on LiNO_(3) and its derivatives for improving the performances of LMBs,particularly for Li-sulfur(S),Li-oxygen(O),and Li-Li-containing transition-metal oxide(LTMO)batteries,as well as LiNO_(3)-containing recipes for precursors in battery materials and interphase fabrication.This review pays attention to the effects of LiNO_(3) in lithium-based batteries,aiming to provide scientific guidance for the optimization of electrode/electrolyte interfaces and enrich the design of advanced LMBs.
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supported by the National Natural Science Foundation of China(Grant Nos.32260727,32472670,and 32371924)the Natural Science Foundation of Ningxia(Grant Nos.2024AAC02039 and 2022AAC02024)+2 种基金the Key Research and Development Program of Xinjiang Uygur Autonomous Region(Grant No.2022B02034-3)the Key Research and Development Program of Ningxia Hui Autonomous Region(Grant No.2024BBF01003)the Science and Technology Plan Project of Xi'an City(Grant No.23NYGG0028).
文摘Nitrate is the primary nitrogen source for plants and is a signaling molecule regulating various plant developmental processes. Despite its significance, limited information is available on nitrate signaling in Vitis vinifera. We identified nine Vv RWP-RK genes distributed across eight chromosomes using genome-wide identification and evolutionary analyses. Among these, Vv NLP1-4 and Vv RKD1-5 are associated with nitrate signaling and reproductive growth, respectively. To investigate their potential functions, structures, cis-acting promoter elements,functional structural domains, phylogenetic trees, spatiotemporal expression levels in different tissues at different developmental stages,potential protein-protein interaction networks, synteny(gene content), collinearity(gene order), and three-dimensional protein structure prediction were explored. We found that long-term nitrate application dramatically promoted grapevine plantlet development, including primary root length and leaf growth, and Vv NLP1.1, Vv NLP1.2, and Vv NLP2 were highly expressed in ‘Thompson Seedless' root tissues under nitrate-enriched conditions. To clarify the critical role of nitrate in grapevine growth, we observed that nuclear localization of Vv NLP1.1increased significantly following nitrate treatment. Vv NLP1.1 was found to bind to the promoter of the primary nitrate response gene Vv NRT1.1,driving its transcriptional activity. These findings indicate that Vv NLP1.1 is a core transcription factor of the nitrate signaling pathway in grapevine. Nitrate molecular docking analysis revealed that Vv NLP1.1 directly binds to nitrate ions, indicating its potential role as a nitrate sensor capable of directly perceiving nitrate concentration. We also discovered that short-term nitrate starvation impacts Vv NLP1.1 promoter activity, linked to the abscisic acid-binding element(ABRE) motif in its promoter region. Our results thus provide new insights into the molecular mechanisms underlying various physiological processes in grapevine, particularly the nitrate signaling pathway, and provide a theoretical basis for improving nitrogen use efficiency(NUE) in grapevine.
基金supported by the Natural Scientific Foundation of China(Nos.22127803,22174110,22203050)Natural Scientific Foundation of Shandong(No.ZR2022QB002)China Postdoctoral Science Foundation(No.2020T130331)。
文摘A novel Cu-t-ZrO_(2)catalyst with enhanced electronic metal-support interaction(EMSI)is designed for efficient electrocatalytic conversion of nitrate(NO_(3^(-)))to ammonia(NH_(3)),achieving a remarkable Faradaic efficiency and yield rate of 97.54%and 33.64 mg h^(-1)mg_(cat)^(-1),respectively.Electrons are more likely to be transferred from Cu to t-ZrO_(2)at the electron-rich interface due to the lower work function,which promotes the formation of highly active Cu species and facilitates NO_(3^(-))adsorption,ensuring selective conversion into NH_(3).
基金financially supported by the National Natural Science Foundation of China(Nos.22209040 and 22202063)。
文摘Zinc-nitrate battery could produce electrical power,remove pollutant nitrate and obtain value-added ammonia,where the cathodic reaction of converting nitrate to ammonia is sluggish and complex due to the involvement of multi-electron transfer.Thus,highly efficient catalysts for nitrate reduction reaction(NO_(3)RR)are greatly needed.In this work,we report a high entropy hydroxide(HE-OH)as an excellent NO3RR catalyst,which could achieve high NH_(3)Faradaic efficiencies(e.g.,nearly 100%at-0.3 V versus reversible hydrogen electrode)and high yield rates(e.g.,30.4 mg h^(-1)cm^(-2)at-0.4 V).Moreover,HE-OH could also deliver a current density of 10 mA/cm^(2) at an overpotential of 260 mV for oxygen evolution reaction.The assembled zinc-nitrate battery using HE-OH as the cathode demonstrates a high power density(e.g.,3.62 mW/cm^(2)),rechargeability and stability.
基金supported by National Natural Science Foundation of China(22162025)the Youth Innovation Team of Shaanxi Universities+2 种基金the Open and Innovation Fund of Hubei Three Gorges Laboratory(SK232001)the Regional Innovation Capability Leading Program of Shaanxi(2022QFY07-03,2022QFY07-06)the Shaanxi Province Training Program of Innovation and Entrepreneurship for Undergraduates(S202210719108)。
文摘Revealing the dynamic reconfiguration of catalysts and the evolution of active species during catalysis,elucidating and regulating the reconfiguration mechanism are paramount to the development of highperformance electrochemical nitrate reduction(NO_(3)RR)to ammonia.In-situ characterizations can precisely track reaction process and unveil the origin of activity enhancement.Here,in-situ reconstruction of pre-catalyst Co_(3)O_(4)fabricates a stable heterojunction Co(OH)_(2)/Co_(3)O_(4)to boost NO_(3)RR to ammonia.Insitu generated heterojunction accelerates the transformation of^(*)NO_(3)to^(*)NO_(2),while Co(OH)_(2)promotes the dissociation of water to active*H species for the hydrogenation of^(*)N species,and thereby improving the deoxygenation and hydrogenation ability of NO_(3)RR to NH_(3)and achieving a high Faradaic efficiency(FE)about 96.2%and a high NH_(3)production rate of 218.5μmol h^(-1)mg_(cat)^(-1)at-0.3 V.Density functional theory(DFT)calculations verified that in-situ formed active species Co(OH)_(2)on Co_(3)O_(4)markedly decreased the energy barrier of^(*)NO_(3)→^(*)NO_(2)and accelerated the hydrogenation step of^(*)NH→^(*)NH_(2)→^(*)NH_(3).Co(OH)_(2)/Co_(3)O_(4)heterostructure-based Zn-NO_(3)^(-)cell achieves excellent energy supply(1.22 V),a high ammonia yield rate(48.9μmol h^(-1)cm^(-2)),and a high FE(91%).The establishment of the structure-activity relationship during NO_(3)RR provides guidance for designing advanced electrode materials,and the in-situ evolution of species on the electrode surface unveils the intrinsic nature of improved catalytic performance.
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 present work aims to stabilize the room temperature allotropic transition of ammonium nitrate(AN)particles utilizing a microencapsulation technique,which involves solvent/non-solvent in which nitrocellulose(NC)has been employed as a coating agent.The SEM micrographs revealed distinct features of both pure AN and NC,contrasting with the irregular granular surface topography of the coated AN particles,demonstrating the adherence of NC on the AN surface.Structural analysis via infrared spectroscopy(IR)demonstrated a successful association of AN and NC,with slight shifts observed in IR bands indicating interfacial interactions.Powder X-ray Diffraction(PXRD)analysis further elucidated the structural changes induced by the coating process,revealing that the NC coating altered the crystallization pattern of its pure form.Thermal analysis demonstrates distinct profiles for pure and coated AN,for which the coated sample exhibits a temperature increase and an enthalpy decrease of the room temperature allotropic transition by 6℃,and 36%,respectively.Furthermore,the presence of NC coating alters the intermolecular forces within the composite system,leading to a reduction in melting enthalpy of coated AN by~39%compared to pure AN.The thermal decomposition analysis shows a two-step thermolysis process for coated AN,with a significant increase in the released heat by about 78%accompanied by an increase in the activation barrier of NC and AN thermolysis,demonstrating a stabilized reactivity of the AN-NC particles.These findings highlight the synergistic effect of NC coating on AN particles,which contributed to a structural and reactive stabilization of both AN and NC,proving the potential application of NC-coated AN as a strategically advantageous oxidizer in composite solid propellant formulations.
基金National Natural Science Foundation of China (52371228, 52402045)fund of Key Laboratory of Advanced Materials of Ministry of Education(Advmat-2414)。
文摘Electrocatalytic nitrate reduction reaction (NO_(3)-RR) to ammonia under ambient conditions is expected to be a green process for ammonia synthesis and alleviate water pollution issues.We report a CuO nanoparticles incorporated on nitrogen-doped porous carbon (CuO@NC) catalyst for NO_(3)-RR.Part of Cu(Ⅱ) is reduced to Cu(Ⅰ) during the NO_(3)-RR process to construct Cu(Ⅰ)-Cu(Ⅱ) pairs,confirmed by in situ X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.Density functional theory (DFT) calculations indicated that the formation of Cu(Ⅰ) could provide a reaction path with smaller energy barrier for NO_(3)-RR,while Cu(Ⅱ) effectively suppressed the competition of hydrogen evolution reaction (HER).As a result,CuO@NC catalyst achieved a Faradaic efficiency of 84.2% at -0.49 V versus reversible hydrogen electrode (RHE),and a NH_(3)yield rate of 17.2 mg h^(-1)mg^(-1)cat.at -0.79 V vs.RHE,higher than the HaberBosch process (<3.4 g h^(-1)g^(-1)cat.).This work may open a new avenue for effective NO_(3)-RR by modulating oxidation states.
基金National Natural Science Foundation of China,No.41930865Project for Innovative Capacity Improvement in Hebei Province,No.225A4201D。
文摘Nitrate(NO_(3)^(-))accumulation and transport processes in the thick vadose zone affect the evolution of the groundwater NO_(3)^(-)content in intensive agricultural regions.Agricultural land-use change(ALUC),typically accompanied by substantial alterations in nitrogen fertilizer application and irrigation practices,is an important influencing factor.This study evaluated the changes in NO_(3)^(-)accumulation and transport in the deep vadose zone(DVZ,below the root zone),and the groundwater NO_(3)^(-)content associated with ALUC from grain to vegetable fields in the North China Plain(NCP).The ALUC from grain to vegetable resulted in nitrate–nitrogen(NO_(3)^(-)-N)accumulation in DVZ increased by 235.5 kg ha^(-1)m^(-1)(163.2%)in the piedmont plain and 224.9 kg ha^(-1)m^(-1)(102.7%)in the central plain,respectively.This change accelerated downward transport velocity in the DVZ(from 0.81±0.47 to 0.89±0.55 m yr^(-1)in the piedmont plain,and from 0.24±0.12 to 0.92±0.12 m yr^(-1)in the central plain)and increased NO_(3)^(-)leaching fluxes.High transport velocity and leaching fluxes resulted in chemical N-fertilizer entering the aquifer in several areas in the piedmont plain.The impact of the agricultural activity intensity changes,accompanied by the ALUC,on groundwater quantity and quality should be considered in similar regions.
基金supported by Joint Funds of National Natural Science Foundation of China(U24A20399)Natural Science Foundation of Shanghai(23JC1403500,22ZR1455300)+2 种基金Specific university discipline construction project(2023B10564002,2023B10564004)Shanghai Agricultural Science and Technology Innovation Program(2024-02-08-00-12-F00028)Earmarked Fund for China Agriculture Research System(CARS-01).
文摘Asian cultivated rice is one of the most important cereal crops globally,feeding approximately 50%of the world's population.Increasing rice nitrogen use efficiency(NUE)is crucial for achieving high yields with low nitrogen inputs(Xu et al.,2012;Hu et al.,2023).However,modern cultivars are typically bred for high yields through excessive nitrogen fertilizer use,leading to the loss of beneficial alleles associated with high NUE during the breeding process(Wang and Peng,2017;Hu et al.,2023).Genetic improvement for high NUE should be a key strategy in breeding“Green Super Rice”(GSR)(Yu et al.,2021)and water-saving and drought-resistance rice(WDR)(Luo,2010;Xia et al.,2022)for sustainable agriculture.Asian cultivated rice is highly diverse and harbors vital genetic variants essential for adaptation to different environments(Wing et al.,2018).
