Synergistic effect of nitrocellulose coating on structural and reactivity stabilization of ammonium nitrate oxidizer

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.

Oxygen‑Coordinated Single Mn Sites for Efficient Electrocatalytic Nitrate Reduction to Ammonia

Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection.Here,we report an efficient NitRR catalyst composed of single Mn sites with atomically dispersed oxygen(O)coordination on bacterial cellulose-converted graphitic carbon(Mn-O-C).Evidence of the atomically dispersed Mn-(O-C_(2))_(4)moieties embedding in the exposed basal plane of carbon surface is confirmed by X-ray absorption spectroscopy.As a result,the as-synthesized Mn-O-C catalyst exhibits superior NitRR activity with an NH_(3)yield rate(RNH_(3))of 1476.9±62.6μg h^(−1)cm^(−2)at−0.7 V(vs.reversible hydrogen electrode,RHE)and a faradaic efficiency(FE)of 89.0±3.8%at−0.5 V(vs.RHE)under ambient conditions.Further,when evaluated with a practical flow cell,Mn-O-C shows a high RNH_(3)of 3706.7±552.0μg h^(−1)cm^(−2)at a current density of 100 mA cm−2,2.5 times of that in the H cell.The in situ FT-IR and Raman spectroscopic studies combined with theoretical calculations indicate that the Mn-(O-C_(2))_(4)sites not only effectively inhibit the competitive hydrogen evolution reaction,but also greatly promote the adsorption and activation of nitrate(NO_(3)^(−)),thus boosting both the FE and selectivity of NH_(3)over Mn-(O-C_(2))_(4)sites.

Nitrate reduction capacity of the oral microbiota is impaired in periodontitis:potential implications for systemic nitric oxide availability

The reduction of nitrate to nitrite by the oral microbiota has been proposed to be important for oral health and results in nitric oxide formation that can improve cardiometabolic conditions. Studies of bacterial composition in subgingival plaque suggest that nitrate-reducing bacteria are associated with periodontal health, but the impact of periodontitis on nitrate-reducing capacity(NRC)and, therefore, nitric oxide availability has not been evaluated. The current study aimed to evaluate how periodontitis affects the NRC of the oral microbiota. First, 16S rRNA sequencing data from five different countries were analyzed, revealing that nitratereducing bacteria were significantly lower in subgingival plaque of periodontitis patients compared with healthy individuals(P < 0.05 in all five datasets with n = 20–82 samples per dataset). Secondly, subgingival plaque, saliva, and plasma samples were obtained from 42 periodontitis patients before and after periodontal treatment. The oral NRC was determined in vitro by incubating saliva with 8 mmol/L nitrate(a concentration found in saliva after nitrate-rich vegetable intake) and compared with the NRC of 15healthy individuals. Salivary NRC was found to be diminished in periodontal patients before treatment(P < 0.05) but recovered to healthy levels 90 days post-treatment. Additionally, the subgingival levels of nitrate-reducing bacteria increased after treatment and correlated negatively with periodontitis-associated bacteria(P < 0.01). No significant effect of periodontal treatment on the baseline saliva and plasma nitrate and nitrite levels was found, indicating that differences in the NRC may only be revealed after nitrate intake. Our results suggest that an impaired NRC in periodontitis could limit dietary nitrate-derived nitric oxide levels, and the effect on systemic health should be explored in future studies.

OsNPF3.1,a nitrate,abscisic acid and gibberellin transporter gene,is essential for rice tillering and nitrogen utilization efficiency

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.

Identifying the Hydrochemical Characteristics,Genetic Mechanisms and Potential Human Health Risks of Fluoride and Nitrate Enriched Groundwater in the Tongzhou District,Beijing,North China

Fluoride and nitrate enriched groundwater are potential threats to the safety of the groundwater supply that may cause significant effects on human health and public safety,especially in aggregated population areas and economic hubs.This study focuses on the high F^(−)and NO_(3)^(−)concentration groundwater in Tongzhou District,Beijing,North China.A total of 36 groundwater samples were collected to analyze the hydrochemical characteristics,elucidate genetic mechanisms and evaluate the potential human health risks.The results of the analysis indicate:Firstly,most of the groundwater samples are characterized by Mg-HCO_(3) and Na-HCO_(3) with the pH ranging from 7.19 to 8.28 and TDS with a large variation across the range 471-2337 mg/L.The NO_(3)^(−)concentration in 38.89%groundwater samples and the F^(−)concentration in 66.67%groundwater samples exceed the permissible limited value.Secondly,F^(−)in groundwater originates predominantly from water-rock interactions and the fluorite dissolution,which is also regulated by cation exchange,competitive adsorption of HCO_(3)−and an alkaline environment.Thirdly,the effect of sewage disposal and agricultural activities have a significant effect on high NO3-concentration,while the high F^(−)concentration is less influenced by anthropogenic activity.The alkaline environment favors nitrification,thus being conducive to the production of NO_(3)^(−).Finally,the health risk assessment is evaluated for different population groups.The results indicate that high NO_(3)^(−)and F^(−)concentration in groundwater would have the largest threat to children’s health.The findings of this study could contribute to the provision of a scientific basis for groundwater supply policy formulation relating to public health in Tongzhou District.

Preliminary discussion on the ignition mechanism of exploding foil initiators igniting boron potassium nitrate

Exploding foil initiator(EFI)is a kind of advanced device for initiating explosives,but its function is unstable when it comes to directly igniting pyrotechnics.To solve the problem,this research aims to reveal the ignition mechanism of EFIs directly igniting pyrotechnics.An oscilloscope,a photon Doppler velocimetry,and a plasma spectrum measurement system were employed to obtain information of electric characteristics,impact pressure,and plasma temperature.The results of the electric characteristics and the impact pressure were inconsistent with ignition results.The only thing that the ignition success tests had in common was that their plasma all had a relatively long period of high-temperature duration(HTD).It eventually concludes that the ignition mechanism in this research is the microconvection heat transfer rather than the shock initiation,which differs from that of exploding foil initiators detonating explosives.Furthermore,the methods for evaluating the ignition success of semiconductor bridge initiators are not entirely applicable to the tests mentioned in this paper.The HTD is the critical parameter for judging the ignition success,and it is influenced by two factors:the late time discharge and the energy of the electric explosion.The longer time of the late time discharge and the more energy of the electric explosion,the easier it is to expand the HTD,which improves the probability of the ignition success.

Enhanced electrochemical nitrate removal from groundwater by simply calcined Ti nanopores with modified surface characters

A simple and convenient preparation method with high catalytic reduction activity is crucial for the remediation of nitrate contamination.In this study,the innovation for fabricating a nanoelectrode was developed by calcinating the anodized plate to alter the surface crystalline phase of the material.The prepared calcined Ti nanopores(TNPs)electrode could effectively remove up to 95.1%nitrate from simulated groundwater at 30 mA·cm^(-2)electrolysis for 90 min,while under the same conditions,the removal efficiency of nanoelectrode prepared by conventional methods was merely 52.5%.Scanning electron microscopy images indicated that the calcined TNP nanoelectrode was porous with different pore sizes.The higher nitrate removal efficiency of TNPs-500(95.1%)than TNPs-400(77.5%)and TNPs-550(93.4%)may resulted from the positive nonlinear response of the larger electrochemical active surface area,the improved electron transfer and suitable surface structure,and not the“anatase-torutile”of surface TiO_(2)nanotubes.After 90 min of electrolysis,using RuO_(2)as an anode and adding 0.3 g·L^(-1)NaCl solution,87.5%nitrate was removed,and the by-products(ammonia and nitrite)were negligible.Increased temperature and alkaline conditions can enhance the nitrate removal,while higher initial nitrate concentration only improved the nitrate removal slightly.Moreover,The TNPs-500 electrode also exhibited excellent nitrate removal performance in real groundwater with the efficiency at 82.9%and 92.1%after 90 and 120 min,which were 0.87(removal efficiency=95.1%),0.92(removal efficiency=100%)of the efficiency for simulated groundwater,indicating the widely applicable conditions of the TNPs-500 electrode.This approach of surface-bonded elements and structure modification through calcination significantly improves catalytic activity and will guide the simple designing of functional nanostructured electrodes with wide application conditions.

Strategies of selective electroreduction of aqueous nitrate to N_(2) in chloride-free system:A critical review

Electroreduction of nitrate has been gaining wide attention in recent years owing to it's beneficial for converting nitrate into benign N_(2) from the perspective of electrocatalytic denitrification or into value-added ammonia from the perspective of electrocatalytic NH_(3) synthesis.By reason of the undesired formation of ammonia is dominant during electroreduction of nitrate-containing wastewater,chloride has been widely used to improve N_(2) selectivity.Nevertheless,selective electroreduction of nitrate to N2 gas in chloride-containing system poses several drawbacks.In this review,we focus on the key strategies for efficiently enhancing N_(2) selectivity of electroreduction of nitrate in chloride-free system,including optimal selection of elements,combining an active metal catalyst with another metal,manipulating the crystalline morphology and facet orientation,constructing core–shell structure catalysts,etc.Before summarizing the strategies,four possible reaction pathways of electro-reduction of nitrate to N_(2) are discussed.Overall,this review attempts to provide practical strategies for enhancing N2 selectivity without the aid of electrochlorination and highlight directions for future research for designing appropriate electrocatalyst for final electrocatalytic denitrifi-cation.

Solution-flame hybrid synthesis of defect-enriched mesoporous CuO_(x) nanowires for enhanced electrochemical nitrate-to-ammonia production

Electrochemical nitrate reduction(ENR)is an economical and eco-friendly method for converting industrial wastewater into valuable ammonia under atmospheric conditions.The main challenge lies in designing and developing highly durable ENR electrocatalysts.This study introduces defect-rich mesoporous CuO_(x) nanowires electrocatalyst synthesized using a novel solution-flame(sol-flame)hybrid method to control mesoporosity and introduce surface defects,thereby enhancing the electrochemical nitrate-toammonia production performance.We found surface defects(oxygen vacancies and Cu^(+))and unique mesoporous nanowire structure composed of tightly interconnected nanoparticles.The sol-flamesynthesized CuO_(x) nanowires(sf-CuO NWs)achieved superior ammonia yield rate(0.51 mmol h^(-1)cm^(-2)),faradaic efficiency(97.3%),and selectivity(86.2%)in 1 M KOH electrolyte(2000 ppm nitrate).This performance surpasses that of non-porous and less-defective CuO NWs and is attributed to the increased surface area and rapid electron transport facilitated by the distinctive morphology and generated defects.Theoretical calculation further suggests oxygen vacancies enhance NO_(3)^(-)adsorption on the sf-CuO NWs’surface and mitigate the competing hydrogen evolution reaction.This study outlines a strategic design and simple synthesis approach for nanowire electrocatalysts that boost the efficiency of electrochemical nitrate-to-ammonia conversion.

Progress in electrocatalytic nitrate reduction for green energy:Catalyst engineering,mechanisms,and techno-economic feasibility

Ammonia(NH_(3))is an irreplaceable chemical that has been widely demanded to keep the sustainable development of modern society.However,its industrial production consumes a huge amount of energy and releases extraordinary greenhouse gases(GHGs),leading to various environmental issues.Achieving the green production of ammonia is a great challenge,which has been extensively pursued in the last decade.In this review,the most promising strategy,electrochemical nitrate reduction reaction(e-NO_(3)RR),is comprehensively investigated to give a complete understanding of its development and mechanism and provide guidance for future directions.However,owing to the complex reactions and limited selectivity,a comprehensive understanding of the mechanisms is crucial to further development and commercialization.Moreover,NO_(3)^(-)RR is a promising strategy for simultaneous water treatment and NH_(3)production.A detailed overview of the recent progress in NO_(3)^(-)RR for NH_(3)production with nontransition and transition metal based electrocatalysts is summarized.In addition,critical advanced techniques,future challenges,and prospects are discussed to guide future research on transition metal-based catalysts for commercial NH_(3)synthesis by NO_(3)^(-)reduction.

Appropriate Supply of Ammonium Nitrogen and Ammonium Nitrate Reduces Cadmium Content in Rice Seedlings by Inhibiting Cadmium Uptake and Transport

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.

Comprehensive understanding of the thriving electrocatalytic nitrate/nitrite reduction to ammonia under ambient conditions

Ammonia(NH_(3))is a multifunctional compound that is an important feedstock for the agricultural and pharmaceutical industries and attractive energy storage medium.At present,NH_(3)synthesis is highly dependent on the conventional Haber–Bosch process that operates under harsh conditions,which consumes large quantities of fossil fuels and releases a large amount of carbon dioxide.As an alternative,electrosynthesis is a prospective method for producing NH_(3)under normal temperature and pressure conditions.Although electrocatalytic nitrogen reduction to ammonia has attracted considerable attentions,the low solubility of N_(2)and high N≡N cracking energy render the achievements of high NH_(3) yield rate and Faradaic efficiency difficult.Nitrate and nitrite(NO_(x)^(-))are common N-containing pollutants.Due to their high solubilities and low dissociation energy of N=O,NO_(x)^(-)−are ideal raw materials for NH_(3) production.Therefore,electrocatalytic NO_(x)^(-)−reduction to NH_(3)(eNO_(x)RR)is a prospective strategy to simultaneously realise environmental protection and NH_(3) synthesis.This review offers a comprehensive understanding of the thriving eNO_(x)RR under ambient conditions.At first,the popular theory and mechanism of eNO_(x)RR and a summary of the measurement system and evaluation criteria are introduced.Thereafter,various strategies for developing NO_(x)−reduction catalysts are systematically presented and discussed.Finally,the challenges and possible prospects of electrocatalytic NO_(x)^(-1) reduction are outlined to facilitate energy-saving and environmentally friendly large-scale synthesis of NH_(3) in the future.

Cocrystallisation of high-energy oxidant ammonium dinitramide with triaminoguanidine nitrate for reduced hygroscopicity

In this work,we utilize a cocrystallization technique to solve the problem of high hygroscopicity of the high-energy oxidant ammonium dinitramide(ADN).For this purpose,a non-hygroscopic oxidant,triaminoguanidine nitrate(TAGN),is selected as the cocrystallization ligand.The ADN/TAGN system is simulated by using Material Studio 5.5 software,and the DFT of ADN and TAGN molecules are calculated by Gaussian09 software.The most stable molar ratio of the ADN/TAGN cocrystallization is determined to be 1:1,and the hydrogen bonding between the H atom of ADN and the O atom in the TAGN is the driving force for the formation of cocrystals in this system.Moreover,the electrostatic potential interaction pairing energy difference(ΔEpair)<0 kJ·mol^(-1)(-12.71 kJ·mol^(-1))for nADN:nTAGN=1:1 again indicates cocrystallization at this molar ratio.The crystal structure and crystal morphology is predicted.And the hygroscopicity of ADN/TAGN cocrystal at 20℃and 40%relative humidity is calculated to be only 0.45%.The mechanism of hygroscopicity is investigated by examining the roughness of each crystal surface.Overall,the more hygroscopic it is in terms of surface roughness,with the roughest crystal surface(012)having a hygroscopicity of 1.78,which corresponds to a saturated hygroscopicity of 0.61%.The results show that the(001)crystal surface has the smallest band gap(1.06 eV)and the largest sensitivity.Finally,the oxygen equilibrium value for the ADN/TAGN system is calculated to be-8.2%.

Preparation of high purity ruthenium nitrosyl nitrate from spent Ru-Zn/ZrO_(2)catalyst

Preparation of high purity ruthenium nitrosyl nitrate using spent Ru-Zn/ZrO_(2)catalyst was studied,including melting and leaching to obtain potassium ruthenate solution,reduction,dissolving,concentrating and drying to obtain ruthenium trichloride,nitrosation and hydrolysis to obtain ruthenium nitrosyl hydroxide,removing of K^(+)and Cl^(-),and neutralization with nitric acid.The effects of temperature,concentration,time and pH on the yield and purity of intermediates and final product were studied,and the optimum process conditions were obtained.The yield of ruthenium nitrosyl nitrate is 92%,the content of ruthenium in high purity product is 32.16%,and the content of Cl^(-)and K^(+)are much less than 0.005%.The reaction kinetics of ruthenium nitrosyl chloride to ruthenium nitrosyl hydroxide was studied.The reaction orders of Ru(NO)Cl_(3)at 40,55 and 70℃are 0.39,0.37 and 0.39,respectively,while those of KOH are 0.16,0.15 and 0.17,respectively.The activation energy is-2.33 k J/mol.

Electrocatalysts with atomic-level site for nitrate reduction to ammonia

Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.

Physiological and molecular mechanisms of cytokinin involvement in nitrate-mediated adventitious root formation in apples

Potassium nitrate(KNO_(3))promotes adventitious root(AR)formation in apple stem cuttings.However,evidence for the possible involvement of cytokinin(CK)in KNO_(3)-mediated AR formation in apples is still lacking.In this study,we cultured GL-3 apple microshoots in different treatment combinations.While the T1(KNO_(3)9.4 mmol L^(-1)+6-benzyl adenine(6-BA)2.22μmol L^(-1))and T3(6-BA 2.22μmol L^(-1))treatments completely inhibited AR formation,the control,T2(KNO_(3)9.4 mmol L^(-1)),and T4(KNO_(3)9.4 mmol L^(-1)+lovastatin(Lov)1.24μmol L^(-1))treatments developed ARs.However,T4-treated microshoots developed fewer and shorter ARs,indicating that optimum CK synthesis is needed for normal AR growth.This also suggests that these fewer and shorter ARs developed because of the presence of KNO_(3) in the same medium.The anatomy of the stem basal part indicated that the inhibition of CK biosynthesis delayed AR primordia formation.The endogenous levels of indole-3-acetic acid(IAA)and zeatin riboside(ZR)were higher in T2-treated microshoots,while the abscisic acid(ABA),gibberellic acid 3(GA_(3)),and brassinosteroid(BR)levels were higher in T4-treated microshoots.The expression levels of MdNRT1.1and MdNRT2.1 were higher in T2-treated microshoots at 3 and 8 days,while MdRR2 and MdCKX5 were higher at 8 and 16 days,respectively.Furthermore,higher IAA levels increased MdWOX11 expression,which in turn increased MdLBD16 and MdLBD29 expression in response to T2.The combined expression of these genes stimulated adventitious rooting by upregulating cell cycle-related genes(MdCYCD1;1 and MdCYCD3;1)in response to T2 treatment.This study shows that specific genes and hormonal pathways contribute to KNO_(3)-CK-mediated adventitious rooting in apples.

Potential-dependent insights into the origin of high ammonia yield rate on copper surface via nitrate reduction:A computational and experimental study

Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.

Tracing nitrate sources in one of the world's largest eutrophicated bays(Hangzhou Bay):insights from nitrogen and oxygen isotopes

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.

Recent advances in electrocatalytic conversion of nitrates into high-value products

The electrocatalytic nitrate reduction reaction (NO_(3)RR) powered by renewable energy offers a promising approach for simultaneously reutilization of nitrate and synthesizing high-value products.Nevertheless,theoretical understanding of reaction mechanism was relative illusive,which is indispensable to rationally design of efficient catalysts.Besides,tuning the reaction microenvironment along with the scale-up device development is essential to promote the industrial deployment of electrocatalytic nitrate conversion,while relative research was overlooked.In this regard,recent advances in ammonia synthesis are firstly summarized,including the identification of active sites,exploration of the underlying reaction mechanisms,electrolyzer design and technical-economic analysis.Furthermore,electrocatalytic C–N coupling based on NO_(3)RR to produce higher-value products such as urea and amino acids are also reviewed,to extend the application potential and economic feasibility.Finally,we highlight the existing challenges and the demand of future research for NO_(3)RR.This review anticipates to provide insights into synthesis of high-value products via NO_(3)RR,bridging the gap from laboratory research to industrial fabrication.

Cu-based heterojunction catalysts for electrocatalytic nitrate reduction to ammonia

Copper-based catalysts have garnered wide attention in the field of electrocatalytic nitrate reduction for ammonia production due to their low hydrogen precipitation activity and high ammonia selectivity.However,they still face challenges pertaining of poor stability and low activity,which hinder their further application.Herein,we present a Cu_(2)O/Cu heterojunction catalyst supported on nitrogen-doped porous carbon for nitrate reduction.High resolution transmission electron microscopy(HRTEM)and X-ray Diffraction(XRD)results confirm the presence of Cu_(2)O/Cu heterojunctions,which serve as an active phase in catalysis.The nitrogen-doped porous carbon as a carrier not only enhances the catalyst’s stability,but also facilitates the exposure and dispersion of active sites.At-1.29 V(vs.RHE),the maximum production rate of ammonia reaches 8.8 mg/(mg·h)with a Faradaic efficiency of 92.8%.This study also elucidates the effect of Cu_(2)O-to-Cu ratio in the heterojunction on catalytic performance,thereby providing valuable insights for designing efficient nitrate reduction catalysts for ammonia production.