Nitrogen(N)is the most important nutrient for plants;however,microbe-mediated N transformation under different N forms is unclear.This experiment investigated the effects of four treatments fertilized with various N f...Nitrogen(N)is the most important nutrient for plants;however,microbe-mediated N transformation under different N forms is unclear.This experiment investigated the effects of four treatments fertilized with various N forms,no N(control,CK),100%ammonium N(AN),100%nitrate N(NN),and 50%ammonium N+50%nitrate N(ANNN),on soil chemical properties,rhizosphere bacterial network,and rice growth.The ANNN treatment enhanced soil pH by 6.9%,soil organic carbon by 12%,and microbial biomass N(MBN)by 60%compared to CK.The linear discriminant effect size(LEfSe)analysis indicated four highly abundant biomarkers of bacterial communities each in the CK,NN,and AN treatments,while the ANNN treatment showed six highly abundant biomarkers with maximum effect size and linear discriminant analysis(LDA)score>4.The 16S rRNA gene-predicted functions under PICRUST indicated glutathione metabolism and proteasome and Tax4Fun recorded amino acid metabolism in the ANNN treatment.The combination of ammonium and nitrate N(i.e.,the ANNN treatment)significantly increased the expression levels of the genes encoding N metabolism,including AMT1,NRT2.1,GS1,and GOGAT1,and induced 39%,27%,35%,and 38%increase in nitrate reductase,nitrite reductase,glutamine synthetase,and glutamate synthase,respectively,in comparison to CK.In addition,the ANNN treatment promoted rice leaf photosynthetic rate by 37%,transpiration rate by 41%,CO_(2) exchange rate by 11%,and stomatal conductance by 18%compared to CK,while increased N use efficiency(NUE)by 10%and 19%,respectively,compared to the AN and NN treatments.These findings suggest that the combination of ammonium and nitrate N can promote bacterial community abundance,composition,and functional pathways by improving soil properties and can increase NUE and rice growth.This study provides a theoretical basis for the rational application of N fertilizers and the implications of this approach for future sustainable crop production.展开更多
Nitrate synthesis is an important process for agriculture and industry,but suffers from energy-intensive steps including the synthesis and subsequent oxidation of ammonia.Herein,we present a selective N_(2)transformat...Nitrate synthesis is an important process for agriculture and industry,but suffers from energy-intensive steps including the synthesis and subsequent oxidation of ammonia.Herein,we present a selective N_(2)transformation to nitrate by guiding the charge neutralization of self-electrified water microdroplets in an artificial cloud generated with the portable ultrasonic atomizer.The electron and ion transfer in the charge neutralization of water microdroplets on metal micromesh enables an up to~40-fold increase in the reactivity of nitrate formation reaction driven by ultrasonic energy.A robust semi-continuous N_(2)oxidation by a Ni-mesh-screened cloud system was achieved,providing nitrate with~12 mM concentration every 20 h.These findings emphasize the potential of harnessing the microdroplet-mediated cloud electrochemistry of N_(2)in decentralizing the current mass production of fertilizer.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
Low-affinity nitrate transporter genes have been identified in subfamilies 4-8 of the rice nitrate transporter 1(NRT1)/peptide transporter family(NPF),but the OsNPF3 subfamily responsible for nitrate and phytohormone ...Low-affinity nitrate transporter genes have been identified in subfamilies 4-8 of the rice nitrate transporter 1(NRT1)/peptide transporter family(NPF),but the OsNPF3 subfamily responsible for nitrate and phytohormone transport and rice growth and development remains unknown.In this study,we described OsNPF3.1 as an essential nitrate and phytohormone transporter gene for rice tillering and nitrogen utilization efficiency(NUtE).OsNPF3.1 possesses four major haplotypes of its promoter sequence in 517 cultivars,and its expression is positively associated with tiller number.Its expression was higher in the basal part,culm,and leaf blade than in other parts of the plant,and was strongly induced by nitrate,abscisic acid(ABA)and gibberellin 3(GA_3)in the root and shoot of rice.Electrophysiological experiments demonstrated that OsNPF3.1 is a pH-dependent low-affinity nitrate transporter,with rice protoplast uptake assays showing it to be an ABA and GA_3 transporter.OsNPF3.1 overexpression significantly promoted ABA accumulation in the roots and GA accumulation in the basal part of the plant which inhibited axillary bud outgrowth and rice tillering,especially at high nitrate concentrations.The NUtE of OsNPF3.1-overexpressing plants was enhanced under low and medium nitrate concentrations,whereas the NUtE of OsNPF3.1 clustered regularly interspaced short palindromic repeats(CRISPR)plants was increased under high nitrate concentrations.The results indicate that OsNPF3.1 transports nitrate and phytohormones in different rice tissues under different nitrate concentrations.The altered OsNPF3.1 expression improves NUtE in the OsNPF3.1-overexpressing and CRISPR lines at low and high nitrate concentrations,respectively.展开更多
Eutrophication caused by inputs of excess nitrogen(N) has become a serious environmental problem in Hangzhou Bay(China),but the sources of this nitrogen are not well understood.In this study,the August 2019 distributi...Eutrophication caused by inputs of excess nitrogen(N) has become a serious environmental problem in Hangzhou Bay(China),but the sources of this nitrogen are not well understood.In this study,the August 2019 distributions of salinity,nutrients [nitrate(NO_(3)^(-)),nitrite,ammonium,and phosphate],and the stable isotopic composition of NO_(3)^(-)(δ^(15)N and δ^(18)O) were used to investigate sources of dissolved inorganic nitrogen(DIN) to Hangzhou B ay.Spatial distributions of nitrate,salinity,and nitrate δ^(18)O indicate that the Qiantang River,the Changjiang River,and nearshore coastal waters may all contribute nitrate to the bay.Based on the isotopic compositions of nitrate in these potential source waters and conservative mixing of nitrate in our study area,we suggest that the NO_(3)^(- )in Hangzhou B ay was likely derived mainly from soils,synthetic N fertilizer,and manure and sewage.End-member modeling indicates that in the upper half of the bay,the Qiantang River was a very important DIN source,possibly contributing more than 50% of DIN in the bay head area.In the lower half of the bay,DIN was sourced mainly from strongly intruding coastal water.DIN coming directly from the Changjiang River made a relatively small contribution to Hangzhou Bay DIN in August 2019.展开更多
Reasonable nitrogen(N) application is a promising strategy for reducing crop cadmium(Cd) toxicity. However, the specific form of N and the required amount that affect Cd tolerance and accumulation in rice remain uncle...Reasonable nitrogen(N) application is a promising strategy for reducing crop cadmium(Cd) toxicity. However, the specific form of N and the required amount that affect Cd tolerance and accumulation in rice remain unclear. This study explored the influence of different N-fertilizer forms(NH_(4)NO_(3), NH_4Cl, and KNO_(3)) and dosages on Cd tolerance and uptake in Cd-stressed N-sensitive and N-insensitive indica rice accessions. The results indicated that the Cd tolerance of N-sensitive indica accessions is more robust than that of N-insensitive ones. Furthermore, the shoot Cd content and Cd translocation rate in both N-sensitive and N-insensitive indica accessions decreased with an appropriate supply of NH_(4)NO_(3) and NH_4Cl, whereas they were comparable or slightly increased with increased KNO_(3). Unfortunately, we did not find significant and regular differences in Cd accumulation or translocation between N-sensitive and N-insensitive rice accessions. Consistent with the reduction of shoot Cd content, the addition of NH_(4)NO_(3) and NH_4Cl also inhibited the instantaneous root Cd^(2+) uptake. The expression changes of Cd transport-related genes under different N forms and dosages suggested that the decreased shoot Cd content, caused by the increased supply of NH_(4)NO_(3) and NH_4Cl, is likely achieved by reducing the transcription of OsNRAMP1 and OsIRT1. In summary, our findings reveal that an appropriate supply of NH_(4)NO_(3) and NH_4Cl could reduce Cd uptake and transport in rice seedlings, suggesting that rational N management could reduce the Cd risk in rice production.展开更多
The 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
Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by...Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by the lack of highly reactive and selective electrocatalysts .Herein, for the first time, nickel foam supported Co_(4) N was designed as a high-performance NITRR catalyst by an in-situ nonmetal leaching-induced strategy.At the optimal potential, the Co_(4) N/NF catalyst achieves ultra-high Faraday efficiency and NH_(3) selectivity of 95.4% and 99.4%, respectively.Ex situ X-ray absorption spectroscopy (XAS), together with other experiments powerfully reveal that the nitrogen vacancies produced by nitrogen leaching are stable and play a key role in boosting nitrate reduction to ammonia.Theoretical calculations confirm that Co_(4) N with abundant nitrogen vacancies can optimize the adsorption energies of NO_(3)^(-) and intermediates, lower the free energy (Δ G ) of the potential-determining step (*NH_(3) to NH_(3) ) and inhibit the formation of N-containing byproducts.In addition, we also conclude that the nitrogen vacancies can stabilize the adsorbed hydrogen, making H_(2) quite difficult to produce, and lowering ΔG from *NO to *NOH, which facilitates the selective reduction of nitrate.This study reveals significant insights about the in-situ nonmetal leaching to enhance the NITRR activity.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
Cropland nitrate leaching is the major nitrogen(N) loss pathway, and it contributes significantly to water pollution. However, cropland nitrate leaching estimates show great uncertainty due to variations in input data...Cropland nitrate leaching is the major nitrogen(N) loss pathway, and it contributes significantly to water pollution. However, cropland nitrate leaching estimates show great uncertainty due to variations in input datasets and estimation methods. Here, we presented a re-evaluation of Chinese cropland nitrate leaching, and identified and quantified the sources of uncertainty by integrating three cropland area datasets, three N input datasets, and three estimation methods. The results revealed that nitrate leaching from Chinese cropland averaged 6.7±0.6 Tg N yr^(-1)in 2010, ranging from 2.9 to 15.8 Tg N yr^(-1)across 27 different estimates. The primary contributor to the uncertainty was the estimation method, accounting for 45.1%, followed by the interaction of N input dataset and estimation method at 24.4%. The results of this study emphasize the need for adopting a robust estimation method and improving the compatibility between the estimation method and N input dataset to effectively reduce uncertainty. This analysis provides valuable insights for accurately estimating cropland nitrate leaching and contributes to ongoing efforts that address water pollution concerns.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
Bacillus velezensis M3-1 strain isolated from the sediment of Myriophyllum aquatium con-structedwetlandswas found to efficiently convert NO_(3)^(-)-N to NO_(2)^(−)-N,and the requirements for carbon source additionwere...Bacillus velezensis M3-1 strain isolated from the sediment of Myriophyllum aquatium con-structedwetlandswas found to efficiently convert NO_(3)^(-)-N to NO_(2)^(−)-N,and the requirements for carbon source additionwere not very rigorous.Thiswork demonstrates,for the first time,the feasibility of using the synergy of anammox and Bacillus velezensis M3-1 microorganisms for nitrogen removal.In this study,the possibility of M3-1 that converted NO_(3)^(−)-N produced by anammox to NO_(2)^(−)-N was verified in an anaerobic reactor.The NO_(3)^(−)-N reduction ability of M3-1 and denitrifying bacteria in coupling system was investigated under different C/N conditions,and it was found that M3-1 used carbon sources preferentially over denitrifying bacteria.By adjusting the ratio of NH4+-N to NO_(2)^(−)-N,it was found that the NO_(2)^(−)-N con-verted from NO_(3)^(−)-N by M3-1 participated in the original anammox.The nitrogen removal efficacy(NRE)of the coupled system was increased by 12.1%,compared to the control group anammox system at C/N=2:1.Functional gene indicated that itmight be a nitrate reducing bacterium.This study shows that the nitrate reduction rate achieved by the Bacillus velezensis M3-1 can be high enough for removing nitrate produced by anammox process,which would enable improve nitrogen removal from wastewater.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
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
Nitrate pollution poses a significant environmental challenge,and photocatalytic nitrate reduction has garnered considerable attention due to its efficiency and environmental advantages.Among these,the development of ...Nitrate pollution poses a significant environmental challenge,and photocatalytic nitrate reduction has garnered considerable attention due to its efficiency and environmental advantages.Among these,the development of Schottky junctions shows considerable potential for practical applications.However,the impact of metal nanoparticle size within Schottky junctions on photocatalytic nitrate reduction remains largely unexplored.In this study,we propose a novel method to modulate metal nanoparticle size within Schottky junctions by controlling light intensity during the photodeposition process.Smaller Au nanoparticles were found to enhance electron accumulation at active sites by promoting charge transfer from COF to Au,thereby improving internal electron transport.Additionally,the Schottky barrier effectively suppressed reverse electron transfer while enhancing NO_(3)^(–)adsorption and activation.The Au_(2-)COF exhibited remarkable nitrate reduction performance,achieving an ammonia yield of 382.48μmol g^(–1)h^(–1),5.7 times higher than that of pure COF.This work provides novel theoretical and practical insights into using controlled light intensity to regulate metal nanoparticle size within Schottky junctions,thereby enhancing photocatalytic nitrate reduction.展开更多
In this work,an effective catalyst of Cu/MnOOH has been successfully constructed for electrochemical nitrate reduction reaction(e NO_(3)RR)for synthesis of ammonia(NH_(3))under ambient conditions.The substrate of MnOO...In this work,an effective catalyst of Cu/MnOOH has been successfully constructed for electrochemical nitrate reduction reaction(e NO_(3)RR)for synthesis of ammonia(NH_(3))under ambient conditions.The substrate of MnOOH plays an important role on the size and electronic structure of Cu nanoparticles,where Cu has the ultrafine size of 2.2 nm and positive shift of its valence states,which in turn causes the increased number of Cu active sites and enhanced intrinsic activity of every active site.As a result,this catalyst realizes an excellent catalytic performance on eNO_(3)RR with the maximal NH_(3)Faraday efficiency(FE)(96.8%)and the highest yield rate(55.51 mg h^(-1)cm^(-2))at a large NH_(3)partial current density of700 m A/cm^(2),which could help to promote the industrialization of NH_(3)production under ambient conditions.展开更多
Nitrate(NO3-)is a widespread pollutant in high-salt wastewater and causes serious harm to human health.Although electrochemical removal of nitrate has been demonstrated to be a promising treatment method,the developme...Nitrate(NO3-)is a widespread pollutant in high-salt wastewater and causes serious harm to human health.Although electrochemical removal of nitrate has been demonstrated to be a promising treatment method,the development of low-cost electro-catalysts is still challenging.In this work,a phosphate modified iron(P-Fe)cathode was prepared for electrochemical removal of nitrate in high-salt wastewater.The phosphate modification greatly improved the activity of iron,and the removal rate of nitrate on P-Fe was three times higher than that on Fe electrode.Further experiments and density functional theory(DFT)calculations demonstrated that the modification of phosphoric acid improved the stability and the activity of the zero-valent iron electrode effectively for NO_(3)^(-) removal.The nitrate was firstly electrochemically reduced to ammonium,and then reacted with the anodic generated hypochlorite to N_(2).In this study,a strategy was developed to improve the activity and stability of metal electrode for NO_(3)^(-)removal,which opened up a new field for the efficient reduction of NO3-removal by metal electrode materials.展开更多
Electrochemical reduction of nitrate(NO_(3^(-)))serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia(NH_(3))synthesis process.The Cu electrocatalyst is widely recognized for its stron...Electrochemical reduction of nitrate(NO_(3^(-)))serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia(NH_(3))synthesis process.The Cu electrocatalyst is widely recognized for its strong adsorption capacity towards nitrate,but its limited H adsorption and slow hydrogenation of oxynitride intermediates hinder the efficiency of converting NO_(3^(-))into NH_(3).Herein,a series of nanocomposite catalysts composed of CuO nanostructure with low NiO content that grow in-situ on carbon paper(Cu O/Ni O_(x)-CP)were synthesized via hydrothermal method and calcination for enhanced nitrate electroreduction utilizing the strong nitrate adsorption capacity of copper and excellent water dissociation ability of NiO to supply hydrogen free radicals(·H).In-situ Raman spectroscopy reveals dynamic reconstruction of Cu/NiO_(x)during the electrochemical nitrate reduction process from Cu O/NiO_(x).Due to the synergistic effect of Cu and NiO,a high Faradaic efficiency(FE,~97.9%)and yield rate(YR,391.5μmol h^(-1)cm^(-2))of ammonia are achieved on CuO/NiO_(2.3%)-CP.Electron paramagnetic resonance(EPR)proves that the presence of Ni O enhances the generation of·H,which can be rapidly consumed during nitrate reduction process.Density functional theory(DFT)calculations indicate that the activation energy of Ni O(0.57 eV)is much lower than Cu(0.84 e V)for water splitting to generate·H,thus facilitating*NO hydrogenations.This drives us to create more effective catalysts for nitrate reduction under neutral conditions by promoting H2O dissociation.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
基金financially supported by the National Natural Science Foundation of China(No.32172109)the Natural Science Foundation of Guangdong Province,China(No.2021A1515010566).
文摘Nitrogen(N)is the most important nutrient for plants;however,microbe-mediated N transformation under different N forms is unclear.This experiment investigated the effects of four treatments fertilized with various N forms,no N(control,CK),100%ammonium N(AN),100%nitrate N(NN),and 50%ammonium N+50%nitrate N(ANNN),on soil chemical properties,rhizosphere bacterial network,and rice growth.The ANNN treatment enhanced soil pH by 6.9%,soil organic carbon by 12%,and microbial biomass N(MBN)by 60%compared to CK.The linear discriminant effect size(LEfSe)analysis indicated four highly abundant biomarkers of bacterial communities each in the CK,NN,and AN treatments,while the ANNN treatment showed six highly abundant biomarkers with maximum effect size and linear discriminant analysis(LDA)score>4.The 16S rRNA gene-predicted functions under PICRUST indicated glutathione metabolism and proteasome and Tax4Fun recorded amino acid metabolism in the ANNN treatment.The combination of ammonium and nitrate N(i.e.,the ANNN treatment)significantly increased the expression levels of the genes encoding N metabolism,including AMT1,NRT2.1,GS1,and GOGAT1,and induced 39%,27%,35%,and 38%increase in nitrate reductase,nitrite reductase,glutamine synthetase,and glutamate synthase,respectively,in comparison to CK.In addition,the ANNN treatment promoted rice leaf photosynthetic rate by 37%,transpiration rate by 41%,CO_(2) exchange rate by 11%,and stomatal conductance by 18%compared to CK,while increased N use efficiency(NUE)by 10%and 19%,respectively,compared to the AN and NN treatments.These findings suggest that the combination of ammonium and nitrate N can promote bacterial community abundance,composition,and functional pathways by improving soil properties and can increase NUE and rice growth.This study provides a theoretical basis for the rational application of N fertilizers and the implications of this approach for future sustainable crop production.
基金supported by the National Key R&D Program of China(2022YFA1504603)the National Natural Science Foundation of China(22025206,22172163)+1 种基金the Dalian Innovation Support Plan for High Level Talents(2022RG13)the Fundamental Research Funds for the Central Universities(20720220008)。
文摘Nitrate synthesis is an important process for agriculture and industry,but suffers from energy-intensive steps including the synthesis and subsequent oxidation of ammonia.Herein,we present a selective N_(2)transformation to nitrate by guiding the charge neutralization of self-electrified water microdroplets in an artificial cloud generated with the portable ultrasonic atomizer.The electron and ion transfer in the charge neutralization of water microdroplets on metal micromesh enables an up to~40-fold increase in the reactivity of nitrate formation reaction driven by ultrasonic energy.A robust semi-continuous N_(2)oxidation by a Ni-mesh-screened cloud system was achieved,providing nitrate with~12 mM concentration every 20 h.These findings emphasize the potential of harnessing the microdroplet-mediated cloud electrochemistry of N_(2)in decentralizing the current mass production of fertilizer.
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 the Guizhou Provincial Excellent Young Talents Project of Science and Technology,China(YQK(2023)002)the Guizhou Provincial Science and Technology Projects,China((2022)Key 008)+2 种基金the Guizhou Provincial Science and Technology Support Plan,China((2022)Key 026)the Key Laboratory of Molecular Breeding for Grain and Oil Crops in Guizhou Province,China((2023)008)the Key Laboratory of Functional Agriculture of Guizhou Provincial Higher Education Institutions,China((2023)007)。
文摘Low-affinity nitrate transporter genes have been identified in subfamilies 4-8 of the rice nitrate transporter 1(NRT1)/peptide transporter family(NPF),but the OsNPF3 subfamily responsible for nitrate and phytohormone transport and rice growth and development remains unknown.In this study,we described OsNPF3.1 as an essential nitrate and phytohormone transporter gene for rice tillering and nitrogen utilization efficiency(NUtE).OsNPF3.1 possesses four major haplotypes of its promoter sequence in 517 cultivars,and its expression is positively associated with tiller number.Its expression was higher in the basal part,culm,and leaf blade than in other parts of the plant,and was strongly induced by nitrate,abscisic acid(ABA)and gibberellin 3(GA_3)in the root and shoot of rice.Electrophysiological experiments demonstrated that OsNPF3.1 is a pH-dependent low-affinity nitrate transporter,with rice protoplast uptake assays showing it to be an ABA and GA_3 transporter.OsNPF3.1 overexpression significantly promoted ABA accumulation in the roots and GA accumulation in the basal part of the plant which inhibited axillary bud outgrowth and rice tillering,especially at high nitrate concentrations.The NUtE of OsNPF3.1-overexpressing plants was enhanced under low and medium nitrate concentrations,whereas the NUtE of OsNPF3.1 clustered regularly interspaced short palindromic repeats(CRISPR)plants was increased under high nitrate concentrations.The results indicate that OsNPF3.1 transports nitrate and phytohormones in different rice tissues under different nitrate concentrations.The altered OsNPF3.1 expression improves NUtE in the OsNPF3.1-overexpressing and CRISPR lines at low and high nitrate concentrations,respectively.
基金The Zhejiang Provincial Natural Science Foundation of China under contract No.LZ22D060002the Key R&D Program of Zhejiang under contract No.2022C03044the National Key Research and Development Program of China under contract No.2021YFC3101702。
文摘Eutrophication caused by inputs of excess nitrogen(N) has become a serious environmental problem in Hangzhou Bay(China),but the sources of this nitrogen are not well understood.In this study,the August 2019 distributions of salinity,nutrients [nitrate(NO_(3)^(-)),nitrite,ammonium,and phosphate],and the stable isotopic composition of NO_(3)^(-)(δ^(15)N and δ^(18)O) were used to investigate sources of dissolved inorganic nitrogen(DIN) to Hangzhou B ay.Spatial distributions of nitrate,salinity,and nitrate δ^(18)O indicate that the Qiantang River,the Changjiang River,and nearshore coastal waters may all contribute nitrate to the bay.Based on the isotopic compositions of nitrate in these potential source waters and conservative mixing of nitrate in our study area,we suggest that the NO_(3)^(- )in Hangzhou B ay was likely derived mainly from soils,synthetic N fertilizer,and manure and sewage.End-member modeling indicates that in the upper half of the bay,the Qiantang River was a very important DIN source,possibly contributing more than 50% of DIN in the bay head area.In the lower half of the bay,DIN was sourced mainly from strongly intruding coastal water.DIN coming directly from the Changjiang River made a relatively small contribution to Hangzhou Bay DIN in August 2019.
基金supported by the National Natural Science Foundation of China (Grant No.31971872)the Open Research Fund of State Key Laboratory of Hybrid Rice, China (Grant No.2022KF02)+3 种基金the National Natural Science Foundation of China (Grant Nos.32101755 and 32188102)the Zhejiang Provincial Natural Science Foundation, China (Grant No.LY22C130005)the Key Research and Development Program of Zhejiang Province, China (Grant No.2021C02056)the ‘Pioneer’ and ‘Leading Goose’ R&D Program of Zhejiang, China (Grant No.2023C02014)。
文摘Reasonable nitrogen(N) application is a promising strategy for reducing crop cadmium(Cd) toxicity. However, the specific form of N and the required amount that affect Cd tolerance and accumulation in rice remain unclear. This study explored the influence of different N-fertilizer forms(NH_(4)NO_(3), NH_4Cl, and KNO_(3)) and dosages on Cd tolerance and uptake in Cd-stressed N-sensitive and N-insensitive indica rice accessions. The results indicated that the Cd tolerance of N-sensitive indica accessions is more robust than that of N-insensitive ones. Furthermore, the shoot Cd content and Cd translocation rate in both N-sensitive and N-insensitive indica accessions decreased with an appropriate supply of NH_(4)NO_(3) and NH_4Cl, whereas they were comparable or slightly increased with increased KNO_(3). Unfortunately, we did not find significant and regular differences in Cd accumulation or translocation between N-sensitive and N-insensitive rice accessions. Consistent with the reduction of shoot Cd content, the addition of NH_(4)NO_(3) and NH_4Cl also inhibited the instantaneous root Cd^(2+) uptake. The expression changes of Cd transport-related genes under different N forms and dosages suggested that the decreased shoot Cd content, caused by the increased supply of NH_(4)NO_(3) and NH_4Cl, is likely achieved by reducing the transcription of OsNRAMP1 and OsIRT1. In summary, our findings reveal that an appropriate supply of NH_(4)NO_(3) and NH_4Cl could reduce Cd uptake and transport in rice seedlings, suggesting that rational N management could reduce the Cd risk in rice production.
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financial supports from National Natural Science Foundation of China(Nos.91741105,22006120)Program for Innovation Team Building at Institutions of Higher Education in Chongqing(No.CXTDX201601011)Chongqing Municipal Natural Science Foundation(No.cstc2018jcyjAX0625).
文摘Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by the lack of highly reactive and selective electrocatalysts .Herein, for the first time, nickel foam supported Co_(4) N was designed as a high-performance NITRR catalyst by an in-situ nonmetal leaching-induced strategy.At the optimal potential, the Co_(4) N/NF catalyst achieves ultra-high Faraday efficiency and NH_(3) selectivity of 95.4% and 99.4%, respectively.Ex situ X-ray absorption spectroscopy (XAS), together with other experiments powerfully reveal that the nitrogen vacancies produced by nitrogen leaching are stable and play a key role in boosting nitrate reduction to ammonia.Theoretical calculations confirm that Co_(4) N with abundant nitrogen vacancies can optimize the adsorption energies of NO_(3)^(-) and intermediates, lower the free energy (Δ G ) of the potential-determining step (*NH_(3) to NH_(3) ) and inhibit the formation of N-containing byproducts.In addition, we also conclude that the nitrogen vacancies can stabilize the adsorbed hydrogen, making H_(2) quite difficult to produce, and lowering ΔG from *NO to *NOH, which facilitates the selective reduction of nitrate.This study reveals significant insights about the in-situ nonmetal leaching to enhance the NITRR activity.
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supported by the National Key Research and Development Program of China (2023YFD1902703)the National Natural Science Foundation of China (Key Program) (U23A20158)。
文摘Cropland nitrate leaching is the major nitrogen(N) loss pathway, and it contributes significantly to water pollution. However, cropland nitrate leaching estimates show great uncertainty due to variations in input datasets and estimation methods. Here, we presented a re-evaluation of Chinese cropland nitrate leaching, and identified and quantified the sources of uncertainty by integrating three cropland area datasets, three N input datasets, and three estimation methods. The results revealed that nitrate leaching from Chinese cropland averaged 6.7±0.6 Tg N yr^(-1)in 2010, ranging from 2.9 to 15.8 Tg N yr^(-1)across 27 different estimates. The primary contributor to the uncertainty was the estimation method, accounting for 45.1%, followed by the interaction of N input dataset and estimation method at 24.4%. The results of this study emphasize the need for adopting a robust estimation method and improving the compatibility between the estimation method and N input dataset to effectively reduce uncertainty. This analysis provides valuable insights for accurately estimating cropland nitrate leaching and contributes to ongoing efforts that address water pollution concerns.
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).
基金supported by the National Natural Sci-ence Foundation of China(Nos.42177099,91951108,and 21976197)the Knowledge Innovation Program of Shenzhen(No.JSGG20191129112812329),and the CAS International Part-nership Program(No.121311KYSB20200017)the special fund of State Key Joint Laboratory of Environment Simula-tion and Pollution Control(No.21Z02ESPCR).
文摘Bacillus velezensis M3-1 strain isolated from the sediment of Myriophyllum aquatium con-structedwetlandswas found to efficiently convert NO_(3)^(-)-N to NO_(2)^(−)-N,and the requirements for carbon source additionwere not very rigorous.Thiswork demonstrates,for the first time,the feasibility of using the synergy of anammox and Bacillus velezensis M3-1 microorganisms for nitrogen removal.In this study,the possibility of M3-1 that converted NO_(3)^(−)-N produced by anammox to NO_(2)^(−)-N was verified in an anaerobic reactor.The NO_(3)^(−)-N reduction ability of M3-1 and denitrifying bacteria in coupling system was investigated under different C/N conditions,and it was found that M3-1 used carbon sources preferentially over denitrifying bacteria.By adjusting the ratio of NH4+-N to NO_(2)^(−)-N,it was found that the NO_(2)^(−)-N con-verted from NO_(3)^(−)-N by M3-1 participated in the original anammox.The nitrogen removal efficacy(NRE)of the coupled system was increased by 12.1%,compared to the control group anammox system at C/N=2:1.Functional gene indicated that itmight be a nitrate reducing bacterium.This study shows that the nitrate reduction rate achieved by the Bacillus velezensis M3-1 can be high enough for removing nitrate produced by anammox process,which would enable improve nitrogen removal from wastewater.
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.
文摘Nitrate pollution poses a significant environmental challenge,and photocatalytic nitrate reduction has garnered considerable attention due to its efficiency and environmental advantages.Among these,the development of Schottky junctions shows considerable potential for practical applications.However,the impact of metal nanoparticle size within Schottky junctions on photocatalytic nitrate reduction remains largely unexplored.In this study,we propose a novel method to modulate metal nanoparticle size within Schottky junctions by controlling light intensity during the photodeposition process.Smaller Au nanoparticles were found to enhance electron accumulation at active sites by promoting charge transfer from COF to Au,thereby improving internal electron transport.Additionally,the Schottky barrier effectively suppressed reverse electron transfer while enhancing NO_(3)^(–)adsorption and activation.The Au_(2-)COF exhibited remarkable nitrate reduction performance,achieving an ammonia yield of 382.48μmol g^(–1)h^(–1),5.7 times higher than that of pure COF.This work provides novel theoretical and practical insights into using controlled light intensity to regulate metal nanoparticle size within Schottky junctions,thereby enhancing photocatalytic nitrate reduction.
基金supported in part by National Natural Science Foundation of China(No.51925102)National Key R&D Program of China(No.2022YFA1504101)。
文摘In this work,an effective catalyst of Cu/MnOOH has been successfully constructed for electrochemical nitrate reduction reaction(e NO_(3)RR)for synthesis of ammonia(NH_(3))under ambient conditions.The substrate of MnOOH plays an important role on the size and electronic structure of Cu nanoparticles,where Cu has the ultrafine size of 2.2 nm and positive shift of its valence states,which in turn causes the increased number of Cu active sites and enhanced intrinsic activity of every active site.As a result,this catalyst realizes an excellent catalytic performance on eNO_(3)RR with the maximal NH_(3)Faraday efficiency(FE)(96.8%)and the highest yield rate(55.51 mg h^(-1)cm^(-2))at a large NH_(3)partial current density of700 m A/cm^(2),which could help to promote the industrialization of NH_(3)production under ambient conditions.
基金supported by the National Natural Science Foundation of China (No.22176068)the Research and Innovation Initiatives of WHPU (No.2022J03),the Hubei Provincial Natural Science Foundation (No.2023AFB938)the Scientific research project of Education Department of Hubei Province (No.D20221610).
文摘Nitrate(NO3-)is a widespread pollutant in high-salt wastewater and causes serious harm to human health.Although electrochemical removal of nitrate has been demonstrated to be a promising treatment method,the development of low-cost electro-catalysts is still challenging.In this work,a phosphate modified iron(P-Fe)cathode was prepared for electrochemical removal of nitrate in high-salt wastewater.The phosphate modification greatly improved the activity of iron,and the removal rate of nitrate on P-Fe was three times higher than that on Fe electrode.Further experiments and density functional theory(DFT)calculations demonstrated that the modification of phosphoric acid improved the stability and the activity of the zero-valent iron electrode effectively for NO_(3)^(-) removal.The nitrate was firstly electrochemically reduced to ammonium,and then reacted with the anodic generated hypochlorite to N_(2).In this study,a strategy was developed to improve the activity and stability of metal electrode for NO_(3)^(-)removal,which opened up a new field for the efficient reduction of NO3-removal by metal electrode materials.
基金supported by the National Natural Science Foundation of China(No.U22A20253)。
文摘Electrochemical reduction of nitrate(NO_(3^(-)))serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia(NH_(3))synthesis process.The Cu electrocatalyst is widely recognized for its strong adsorption capacity towards nitrate,but its limited H adsorption and slow hydrogenation of oxynitride intermediates hinder the efficiency of converting NO_(3^(-))into NH_(3).Herein,a series of nanocomposite catalysts composed of CuO nanostructure with low NiO content that grow in-situ on carbon paper(Cu O/Ni O_(x)-CP)were synthesized via hydrothermal method and calcination for enhanced nitrate electroreduction utilizing the strong nitrate adsorption capacity of copper and excellent water dissociation ability of NiO to supply hydrogen free radicals(·H).In-situ Raman spectroscopy reveals dynamic reconstruction of Cu/NiO_(x)during the electrochemical nitrate reduction process from Cu O/NiO_(x).Due to the synergistic effect of Cu and NiO,a high Faradaic efficiency(FE,~97.9%)and yield rate(YR,391.5μmol h^(-1)cm^(-2))of ammonia are achieved on CuO/NiO_(2.3%)-CP.Electron paramagnetic resonance(EPR)proves that the presence of Ni O enhances the generation of·H,which can be rapidly consumed during nitrate reduction process.Density functional theory(DFT)calculations indicate that the activation energy of Ni O(0.57 eV)is much lower than Cu(0.84 e V)for water splitting to generate·H,thus facilitating*NO hydrogenations.This drives us to create more effective catalysts for nitrate reduction under neutral conditions by promoting H2O dissociation.
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.
