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 NH3 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
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
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
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
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
Nitrate contamination of groundwater is a worldwide problem, particularly in agricultural countries. Exposure to high levels of nitrates in groundwater can have adverse effects on the health of residents who use groun...Nitrate contamination of groundwater is a worldwide problem, particularly in agricultural countries. Exposure to high levels of nitrates in groundwater can have adverse effects on the health of residents who use groundwater for drinking. This study aims to assess the health risk associated with the ingestion of nitrates in well water in the town of M’bahiakro. Health risk maps were created on the basis of hazard quotients (HQ) using the US Environmental Protection Agency (USEPA) health risk assessment model. The results indicate that residents of the Koko, Dougouba and Baoulekro neighbourhoods, whatever their age, are potentially exposed to the toxic effects of NO3−during their daily intake of nitrate-contaminated well water, with reference to hazard quotients (HQ) greater than 1. Nitrate concentrations in the groundwater should therefore be controlled in order to prevent their harmful effects on the health of the population and guarantee its use in rice-growing activities in M’Bahiakro.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
The electrochemical conversion of nitrate,a widespread water pollutant,into valuable ammonia represents a green and decentralized approach to ammonia synthesis.However,the sluggish multielectronproton coupling path an...The electrochemical conversion of nitrate,a widespread water pollutant,into valuable ammonia represents a green and decentralized approach to ammonia synthesis.However,the sluggish multielectronproton coupling path and the low reactive species(nitrate and proton)concentration at the catalyst interface inhibit the efficiency of ammonia production from nitrate reduction reaction(NitRR).Herein,we introduce a novel iron-based tandem catalyst encapsulated by reduced graphene oxide(denoted as Fe-rGO),with a superior ammonia production rate of 47.815 mg h^(-1)mg_(ca)^(t-1)and a high Faraday efficiency(FE)of 96.51%at an applied potential of-0.5 V.It also delivers a robust stability with FE above90%under a current density of 250 mA cm^(-2)for 50 h.In situ X-ray absorption spectroscopy reveals that the FeO_(x)is dynamically translated to Fe~0 site concurrently with the enhancement of the NH_(3)production rate,suggesting the Fe^(0) site as hydrogenation active center.The asymmetric distribution of surface charges of rGO not only enriches nitrate ions at the catalytic interface and promotes the hydrogenation process in NitRR,but also protects the iron species and ensures their stability during electrolysis.The Zn-NO_(3)^(-)battery demonstrates an impressive FE of 88.6%,highlighting its exceptional potential for practical applications.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
Due to the discharge of industrialwastewater,urban domestic sewage,and intensive marine aquaculture tailwater,nitrate(NO_(3)^(−))pollution has emerged as a significant issue in offshore waters.Nitrate pollution affect...Due to the discharge of industrialwastewater,urban domestic sewage,and intensive marine aquaculture tailwater,nitrate(NO_(3)^(−))pollution has emerged as a significant issue in offshore waters.Nitrate pollution affects aquatic life and may interact with other pollutants,leading to comprehensive toxicity.Cadmium(Cd^(2+))is the most widespread metal contaminant,adversely affecting aquatic life in the coastal waters of China.Despite this,few studies have focused on the synergistic toxicity of NO_(3)^(−)and Cd^(2+)in marine organisms.This study conducted a 30-day exposure experiment on marine Japanese flounder(Paralichthys olivaceus)to explore the synergistic toxicity of NO_(3)^(−)and Cd^(2+).Our results demonstrated that the exposure to Cd^(2+)alone induced slight histopathological changes in the liver.However,malformations such as hepatic vacuolar degeneration and sinusoid dilatationwere exacerbated under co-exposure.Moreover,co-exposure induced the downregulation of antioxidants and the upregulation of the product malonaldehyde(MDA)from lipid peroxidation,indicating potent oxidative stress in the liver.The increased mRNA expression of IL-8,TNF-α,and IL-1β,along with the decreased expression level of TGF-β,indicated a synergistic inflammatory response in the organisms.Furthermore,the co-exposure led to an abnormal expression of P53,caspase-3,caspase-9,Bcl-2,and Bax,and disturbed the apoptosis in the liver through TUNEL staining analysis.Overall,our results imply that co-exposure synergistically affects inflammation,redox status,and apoptosis in flounders.Therefore,the findings from this study provide valuable perspectives on the ecological risk assessment of marine teleosts co-exposure to NO_(3)^(−)and Cd^(2+).展开更多
Electrocatalytic reduction of nitrate to ammonia offers an environmentally friendly and sustainable approach for ammonia production,but it involves a multi-step reaction process with complex intermediates,and still fa...Electrocatalytic reduction of nitrate to ammonia offers an environmentally friendly and sustainable approach for ammonia production,but it involves a multi-step reaction process with complex intermediates,and still faces the challenge of high activity and high selectivity.Herein,a high-entropy nanoalloy was synthesized via high-temperature annealing of metal salt with dopamine as a carbon source for electrocatalytic reduction of nitrate to ammonia.The FeCoNiCuRu_(1.5)/C catalyst displays a conversion rate of 90.2%and an ammonia selectivity of 92.2% at-0.74 V(vs.RHE),significantly surpassing the performance of lowentropy alloys such as FeCo/C by 1.5–2 times.Moreover,FeCoNiCuRu_(1.5)/C maintains a consistent nitrate conversion rate of about 90.0% after 120 h of continuous operation(10 cycles),indicating high stability.The superior performance of FeCoNiCuRu_(1.5)/C can be attributed to the synergetic relay catalysis among Fe,Co,Ni,Cu,and Ru sites.This synergy enhances nitrate adsorption due to the optimized electronic structure of multiple active sites,which facilitates the nitrate reduction to intermediates.Subsequently,the effective active hydrogen produced at the Ru site,in conjunction with adjustments at other metal sites,promotes the selective transformation of the intermediates into ammonia.This work not only highlights the efficacy of synergetic relay electrocatalysis but also opens new avenues for developing highly efficient multi-site catalysts.展开更多
Electrochemical nitrate reduction reaction(NO_(3)^(-)RR)has emerged as a promising alternative for both wastewater treatment and producing NH_(3) sustainably.The construction of a composite with optimized regulation o...Electrochemical nitrate reduction reaction(NO_(3)^(-)RR)has emerged as a promising alternative for both wastewater treatment and producing NH_(3) sustainably.The construction of a composite with optimized regulation of electron states is a viable strategy for tuning the adsorption of reaction intermediates and promoting the subsequent hydrogenation of^(*)NO_(x) intermediates.Here,Pd nanoparticles were supported on N-doped carbon(NC)embedded with a single Fe atom(Pd@Fe-NC)to boost the NO_(3)^(-)conversion to NO_(2)^(-)and further promote NH_(3) generation.The catalyst shows a NH_3 production rate of 876.3 mmol h^(-1)g_(cat)^(-1)with a corresponding Faradaic efficiency of 92.5%at-0.7 V(versus RHE)under ambient conditions.In situ spectroscopy and theoretical calculations reveal that by embedding Fe atoms in the NC substrate,the electron transfer from Pd to the carbon substrate at the Pd/NC interface was enhanced,resulting in more pronounced electron-deficient Pd sites compared with those in Pd@NC.As a result,the electron-deficient Pd facilitates the adsorption of NO_(3)^(-).The adjacent atomic Fe sites efficiently promote water dissociation,providing abundant^(*)H for the hydrogenation of^(*)NO_(2) at Pd sites.The synergistic effects between Pd and single Fe atom sites simultaneously decrease the energy barrier for NO_(3)^(-)adsorption and hydrogenation,thereby promoting the conversion of NO_(3)^(-)to NH_(3).展开更多
Red mud(RM)is a solid waste generated in the aluminum industry after the extraction of alumina oxide;its multiple elements and higher pH value likely pose a severe threat to the environment after treatment.However,RM&...Red mud(RM)is a solid waste generated in the aluminum industry after the extraction of alumina oxide;its multiple elements and higher pH value likely pose a severe threat to the environment after treatment.However,RM's higher concentrations of metal components,particularly Fe_(2)O_(3)and rare earth elements(REEs),render RM promising for catalytic application.Hence,this work showed an efficient high-speed RM to catalyze electrocatalytic nitrate-to-ammonia reduction reaction(NARR).RM calcined at 500℃(RM-500)exhibited excellent catalytic performance.Faradaic efficiency of ammonia(FENH_(3))in an electrolyte solution containing 1 mol·L^(-1)NO_(3)-achieved a maximum value of 92.3%at-0.8 V(vs.RHE).Additionally,24-h cycle testing and post-reaction PXRD and SEM indicated that the RM-500 electrocatalyst is stable during NARR.The RM-500 demonstrated a high FE of NH_(3)-to-NO_(3)-of 89.7%at 1.85 V(vs.RHE),showing great potential in the ammonia fuel cells technology and achieving the nitrogen cycle.展开更多
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 NH3 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 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 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.
文摘Nitrate contamination of groundwater is a worldwide problem, particularly in agricultural countries. Exposure to high levels of nitrates in groundwater can have adverse effects on the health of residents who use groundwater for drinking. This study aims to assess the health risk associated with the ingestion of nitrates in well water in the town of M’bahiakro. Health risk maps were created on the basis of hazard quotients (HQ) using the US Environmental Protection Agency (USEPA) health risk assessment model. The results indicate that residents of the Koko, Dougouba and Baoulekro neighbourhoods, whatever their age, are potentially exposed to the toxic effects of NO3−during their daily intake of nitrate-contaminated well water, with reference to hazard quotients (HQ) greater than 1. Nitrate concentrations in the groundwater should therefore be controlled in order to prevent their harmful effects on the health of the population and guarantee its use in rice-growing activities in M’Bahiakro.
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 the National Natural Science Foundation of China(12205300(H.S.),12405377(M.H.L))the Postdoctoral Science Foundation of China(2024M763694(M.H.L))+3 种基金the Natural Science Foundation of Hunan Province(2024JJ4027(H.S.))the Postdoctoral Fellowship Program of CPSF under Grant Number GZB20240859(M.H.L)financial support from the Hunan Normal University Program(grant05311204666)financial support from the 2024 Large Instrument Testing Open Fund of Hunan Normal University(24CSY033,24CSY086)。
文摘The electrochemical conversion of nitrate,a widespread water pollutant,into valuable ammonia represents a green and decentralized approach to ammonia synthesis.However,the sluggish multielectronproton coupling path and the low reactive species(nitrate and proton)concentration at the catalyst interface inhibit the efficiency of ammonia production from nitrate reduction reaction(NitRR).Herein,we introduce a novel iron-based tandem catalyst encapsulated by reduced graphene oxide(denoted as Fe-rGO),with a superior ammonia production rate of 47.815 mg h^(-1)mg_(ca)^(t-1)and a high Faraday efficiency(FE)of 96.51%at an applied potential of-0.5 V.It also delivers a robust stability with FE above90%under a current density of 250 mA cm^(-2)for 50 h.In situ X-ray absorption spectroscopy reveals that the FeO_(x)is dynamically translated to Fe~0 site concurrently with the enhancement of the NH_(3)production rate,suggesting the Fe^(0) site as hydrogenation active center.The asymmetric distribution of surface charges of rGO not only enriches nitrate ions at the catalytic interface and promotes the hydrogenation process in NitRR,but also protects the iron species and ensures their stability during electrolysis.The Zn-NO_(3)^(-)battery demonstrates an impressive FE of 88.6%,highlighting its exceptional potential for practical applications.
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supported by the National Natural Science Foundation of China(No.32202963)the Natural Science Foundation of Jiangsu Province(No.BK20220681)+3 种基金the Doctoral Program of Entrepreneurship and Innovation in Jiangsu Province(No.JSSCBS20221625)the Scientific Research Foundation Program of Jiangsu Ocean University(No.KQ22009)the Undergraduate Innovation&Entrepreneurship Training Program of Jiangsu Province,China(No.SY202411641631001)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX2023-112).
文摘Due to the discharge of industrialwastewater,urban domestic sewage,and intensive marine aquaculture tailwater,nitrate(NO_(3)^(−))pollution has emerged as a significant issue in offshore waters.Nitrate pollution affects aquatic life and may interact with other pollutants,leading to comprehensive toxicity.Cadmium(Cd^(2+))is the most widespread metal contaminant,adversely affecting aquatic life in the coastal waters of China.Despite this,few studies have focused on the synergistic toxicity of NO_(3)^(−)and Cd^(2+)in marine organisms.This study conducted a 30-day exposure experiment on marine Japanese flounder(Paralichthys olivaceus)to explore the synergistic toxicity of NO_(3)^(−)and Cd^(2+).Our results demonstrated that the exposure to Cd^(2+)alone induced slight histopathological changes in the liver.However,malformations such as hepatic vacuolar degeneration and sinusoid dilatationwere exacerbated under co-exposure.Moreover,co-exposure induced the downregulation of antioxidants and the upregulation of the product malonaldehyde(MDA)from lipid peroxidation,indicating potent oxidative stress in the liver.The increased mRNA expression of IL-8,TNF-α,and IL-1β,along with the decreased expression level of TGF-β,indicated a synergistic inflammatory response in the organisms.Furthermore,the co-exposure led to an abnormal expression of P53,caspase-3,caspase-9,Bcl-2,and Bax,and disturbed the apoptosis in the liver through TUNEL staining analysis.Overall,our results imply that co-exposure synergistically affects inflammation,redox status,and apoptosis in flounders.Therefore,the findings from this study provide valuable perspectives on the ecological risk assessment of marine teleosts co-exposure to NO_(3)^(−)and Cd^(2+).
基金financially supported by the Shanghai Science and Technology Plan Project(No.23ZR1467000)Basic Research Project of Tongji University(No.22120240354)+2 种基金State Key Laboratory of Treatments and Recycling for Organic Effluents by Adsorption in Petroleum,Chemical Industry(No.SDHY2206)National Natural Science Foundation of China(No.21976134)the Fundamental Research Funds for the Central Universities。
文摘Electrocatalytic reduction of nitrate to ammonia offers an environmentally friendly and sustainable approach for ammonia production,but it involves a multi-step reaction process with complex intermediates,and still faces the challenge of high activity and high selectivity.Herein,a high-entropy nanoalloy was synthesized via high-temperature annealing of metal salt with dopamine as a carbon source for electrocatalytic reduction of nitrate to ammonia.The FeCoNiCuRu_(1.5)/C catalyst displays a conversion rate of 90.2%and an ammonia selectivity of 92.2% at-0.74 V(vs.RHE),significantly surpassing the performance of lowentropy alloys such as FeCo/C by 1.5–2 times.Moreover,FeCoNiCuRu_(1.5)/C maintains a consistent nitrate conversion rate of about 90.0% after 120 h of continuous operation(10 cycles),indicating high stability.The superior performance of FeCoNiCuRu_(1.5)/C can be attributed to the synergetic relay catalysis among Fe,Co,Ni,Cu,and Ru sites.This synergy enhances nitrate adsorption due to the optimized electronic structure of multiple active sites,which facilitates the nitrate reduction to intermediates.Subsequently,the effective active hydrogen produced at the Ru site,in conjunction with adjustments at other metal sites,promotes the selective transformation of the intermediates into ammonia.This work not only highlights the efficacy of synergetic relay electrocatalysis but also opens new avenues for developing highly efficient multi-site catalysts.
基金supported by the National Natural Science Foundation of China(No.22278108 and 22008048)the Natural Science Foundation of Tianjin(22JCYBJC00250 and 23JCQNJC00360)+1 种基金the Natural Science Foundation for Outstanding Youth Scholars of Hebei Province(No.B2024202008)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF2314)。
文摘Electrochemical nitrate reduction reaction(NO_(3)^(-)RR)has emerged as a promising alternative for both wastewater treatment and producing NH_(3) sustainably.The construction of a composite with optimized regulation of electron states is a viable strategy for tuning the adsorption of reaction intermediates and promoting the subsequent hydrogenation of^(*)NO_(x) intermediates.Here,Pd nanoparticles were supported on N-doped carbon(NC)embedded with a single Fe atom(Pd@Fe-NC)to boost the NO_(3)^(-)conversion to NO_(2)^(-)and further promote NH_(3) generation.The catalyst shows a NH_3 production rate of 876.3 mmol h^(-1)g_(cat)^(-1)with a corresponding Faradaic efficiency of 92.5%at-0.7 V(versus RHE)under ambient conditions.In situ spectroscopy and theoretical calculations reveal that by embedding Fe atoms in the NC substrate,the electron transfer from Pd to the carbon substrate at the Pd/NC interface was enhanced,resulting in more pronounced electron-deficient Pd sites compared with those in Pd@NC.As a result,the electron-deficient Pd facilitates the adsorption of NO_(3)^(-).The adjacent atomic Fe sites efficiently promote water dissociation,providing abundant^(*)H for the hydrogenation of^(*)NO_(2) at Pd sites.The synergistic effects between Pd and single Fe atom sites simultaneously decrease the energy barrier for NO_(3)^(-)adsorption and hydrogenation,thereby promoting the conversion of NO_(3)^(-)to NH_(3).
基金supported by grants from the National Natural Science Foundation of China (22178339)2023 Innovation-driven Development Special Foundation of Guangxi(AA23023021)the Hundred Talents Program (A) of the Chinese Academy of Sciences
文摘Red mud(RM)is a solid waste generated in the aluminum industry after the extraction of alumina oxide;its multiple elements and higher pH value likely pose a severe threat to the environment after treatment.However,RM's higher concentrations of metal components,particularly Fe_(2)O_(3)and rare earth elements(REEs),render RM promising for catalytic application.Hence,this work showed an efficient high-speed RM to catalyze electrocatalytic nitrate-to-ammonia reduction reaction(NARR).RM calcined at 500℃(RM-500)exhibited excellent catalytic performance.Faradaic efficiency of ammonia(FENH_(3))in an electrolyte solution containing 1 mol·L^(-1)NO_(3)-achieved a maximum value of 92.3%at-0.8 V(vs.RHE).Additionally,24-h cycle testing and post-reaction PXRD and SEM indicated that the RM-500 electrocatalyst is stable during NARR.The RM-500 demonstrated a high FE of NH_(3)-to-NO_(3)-of 89.7%at 1.85 V(vs.RHE),showing great potential in the ammonia fuel cells technology and achieving the nitrogen cycle.
