Mining and tailings deposition can cause serious heavy metal(loids)pollution to the surrounding soil environment.Soil microorganisms adapt their metabolism to such conditions,driving alterations in soil function.This ...Mining and tailings deposition can cause serious heavy metal(loids)pollution to the surrounding soil environment.Soil microorganisms adapt their metabolism to such conditions,driving alterations in soil function.This study aims to elucidate the response patterns of nitrogen-cycling microorganisms under long-term heavy metal(loids)exposure.The results showed that the diversity and abundance of nitrogen-cyclingmicroorganisms showed negative feedback to heavy metal(loids)concentrations.Denitrifying microorganisms were shown to be the dominant microorganisms with over 60%of relative abundance and a complex community structure including 27 phyla.Further,the key bacterial species in the denitrification process were calculated using a random forest model,where the top three key species(Pseudomonas stutzei,Sphingobium japonicum and Leifsonia rubra)were found to play a prominent role in nitrite reduction.Functional gene analysis and qPCR revealed that nirK,which is involved in nitrite reduction,significantly accumulated in the most metal-rich soil with the increase of absolute abundance of 63.86%.The experimental results confirmed that the activity of nitrite reductase(Nir)encoded by nirK in the soil was increased at high concentrations of heavy metal(loids).Partial least squares-path model identified three potential modes of nitrite reduction processes being stimulated by heavy metal(loids),the most prominent of which contributed to enhanced nirK abundance and soil Nir activity through positive stimulation of key species.The results provide new insights and preliminary evidence on the stimulation of nitrite reduction processes by heavy metal(loids).展开更多
The authors regret<an error occurred regarding the spelling of the author’s name in the final published manuscript.The correct spelling is Jingtao Bi,but it was mistakenly published as Jingtai Bi.We hereby request...The authors regret<an error occurred regarding the spelling of the author’s name in the final published manuscript.The correct spelling is Jingtao Bi,but it was mistakenly published as Jingtai Bi.We hereby request to correct the name to Jingtao Bi as originally intended.>.The authors would like to apologize for any inconvenience caused.展开更多
The electrochemical conversion of toxic nitrite(NO_(2)-)is a promising approach for the simultaneous removal of nitrogen contaminants and synthesis of ammonia(NH_(3)).In this study,we present the Er-doping-induced ele...The electrochemical conversion of toxic nitrite(NO_(2)-)is a promising approach for the simultaneous removal of nitrogen contaminants and synthesis of ammonia(NH_(3)).In this study,we present the Er-doping-induced electronic modulation of CoP integrated with nitrogen-doped carbon(CN)nanosheets supported on a titanium mesh(Er-CoP@NC/TM)for the electrocatalytic NO_(2)-reduction reaction(eNO_(2)-RR)for NH_(3)synthesis.The catalyst demonstrates a high Faraday efficiency of 97.08±2.22%and a high yield of 2087.60±17.10μmol h^(-1)cm^(-2)for NH_(3)production.Characterization and theoretical calculations revealed that Er-doping facilitated the electronic modulation of CoP in Er-CoP@NC/TM,which regulated the adsorption behaviors of intermediates and was the rate-limiting step for the eNO_(2)-RR,thereby enhancing the electrocatalytic performance.Quenching experiments and electron paramagnetic resonance tests suggest that both direct electrocatalytic reduction by active hydrogen and electron transfer are critical for the eNO_(2)-RR for NH_(3)synthesis.Furthermore,Er-CoP@NC/TM exhibited high performance across a wide range of NO_(2)-concentrations(0.05-0.1 mol L^(-1))and pH values(4-13).In addition,the catalyst demonstrated strong resistance to anions and a long cycle life in simulated wastewater environments.This study offers a powerful approach for the remediation of NO_(2)-wastewater and recovery of valuable inorganic compounds.展开更多
Ammonia(NH_(3))is a fundamental chemical in agriculture and an ideal hydrogen carrier.Consequently,NH_(3)synthesis strategies with high efficiency,energy conservation,environmental friendliness,and sustainability are ...Ammonia(NH_(3))is a fundamental chemical in agriculture and an ideal hydrogen carrier.Consequently,NH_(3)synthesis strategies with high efficiency,energy conservation,environmental friendliness,and sustainability are desired eminently.The nitrite(NO_(2)^(-))reduction reaction(NO_(2-)RR)to NH_(3)offers a feasibly low-energy consumption and continuable approach to replace industrial NH_(3)synthesis.Herein,polyethyleneimine(PEI)modified Au core Rh shell nanodendrites(Au@Rh-NDs)nanohybrid(Au@Rh-NDs/PEI)with branched structure is synthesized,which achieves the high NH_(3)yield(1.68 mg h^(-1)mg_(cat)^(-1))and Faradaic efficiency(FE)of 95.86%for NO_(2)^(-)-RR at-0.39 V potential in neutral electrolyte.Particularly,the introduction of PEI significantly enhances the electroactivity of Au@Rh-NDs at low concentration of 1 mM NaNO_(2),which originates from the enrichment function of PEI for NO_(2)^(-)-ion.In addition,the Au basement permits the sustainable solar power to expedite the NO_(2)^(-)-RR at Au@Rh-NDs/PEI owing to the localized surface plasmon resonance(LSPR)of the Au core substrate.This work may provide an admissible tactic to build excellent catalysts on account of organic molecule-mediated interfacial engineering in a variety of fields of catalysis and electrocatalysis.展开更多
Electrochemical nitrite(NO_(2)^(−))reduction offers a sustainable route for ammonia(NH_(3))synthesis while simultaneously removing contaminants in wastewater.However,its efficiency is often limited by low catalytic ef...Electrochemical nitrite(NO_(2)^(−))reduction offers a sustainable route for ammonia(NH_(3))synthesis while simultaneously removing contaminants in wastewater.However,its efficiency is often limited by low catalytic efficiency and the competitive hydrogen evolution reaction at low NO_(2)^(−)concentrations.Herein,we report an intermittent pulsed electrolysis(IPE)strategy using copper oxide(Cu_(x)O)nanowires,which significantly enhances the NH3 yield rate and Faradaic efficiency(FE)at lower reactant concentrations.In situ experiments and theoretical calculations reveal that alternating between open-circuit and cathodic potentials modulates the copper oxidation states,stabilizing the catalytically active cuprous oxide(Cu_(2)O).Consequently,the IPE approach provides an outstanding NH3 yield rate of 115.10 mg·h^(−1)·cm^(−2)and FE of 91.14%in the presence of 25 mM NO_(2)^(−),markedly outperforming conventional constant potential electrolysis.展开更多
Electrocatalytic reduction of nitrate pollutants to produce ammonia offers an effective approach to realizing the artificial nitrogen cycle and replacing the energyintensive Haber-Bosch process.Nitrite is an important...Electrocatalytic reduction of nitrate pollutants to produce ammonia offers an effective approach to realizing the artificial nitrogen cycle and replacing the energyintensive Haber-Bosch process.Nitrite is an important intermediate product in the reduction of nitrate to ammonia.Therefore,the mechanism of converting nitrite into ammonia warrants further investigation.Molecular cobalt catalysts are regarded as promising for nitrite reduction reactions(NO_(2)^(−)RR).However,designing and controlling the coordination environment of molecular catalysts is crucial for studying the mechanism of NO_(2)^(−)RR and catalyst design.Herein,we develop a molecular platform of cobalt porphyrin with three coordination microenvironments(Co-N_(3)X_(1),X=N,O,S).Electrochemical experiments demonstrate that cobalt porphyrin with O coordination(CoOTPP)exhibits the lowest onset potential and the highest activity for NO_(2)^(−)RR in ammonia production.Under neutral,nonbuffered conditions over a wide potential range(−1.0 to−1.5 V versus AgCl/Ag),the Faradaic efficiency of nearly 90%for ammonia was achieved and reached 94.5%at−1.4 V versus AgCl/Ag,with an ammonia yield of 6,498μgh^(−1)and a turnover number of 22,869 at−1.5V versus AgCl/Ag.In situ characterization and density functional theory calculations reveal that modulating the coordination environment alters the electron transfer mode of the cobalt active center and the charge redistribution caused by the break of the ligand field.Therefore,this results in enhanced electrochemical activity for NO_(2)^(−)RR in ammonia production.This study provides valuable guidance for designing adjustments to the coordination environment of molecular catalysts to enhance catalytic activity.展开更多
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...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.展开更多
The properties of the carbon nanotube powder microelectrodes (denoted CNTPME) are remarkably altered by anodic pretreatment and preadsorption of mediators. It seems that anodic pretreatment leads the long and tangled...The properties of the carbon nanotube powder microelectrodes (denoted CNTPME) are remarkably altered by anodic pretreatment and preadsorption of mediators. It seems that anodic pretreatment leads the long and tangled carbon nanotubes to be partially cut shorter, resulting in more openings as shown by TEM. Besides, the anodic pretreatment may adjust the hydrophobicity of nanotubes to match with that of Os(bpy)32+. As a result, the real surface area and the ability of adsorbing mediator Os(bpy)32+ of the nanotubes are markedly increased so as to effectively catalyze NO2- reduction in acidic solution.展开更多
Electrochemical nitrite reduction reaction(NO_(2)^(-)RR) is a potential sustainable route for regulating the nitrogen cycle and ambient ammonia(NH_(3)) synthesis.However,it remains a challenge to precisely regulate th...Electrochemical nitrite reduction reaction(NO_(2)^(-)RR) is a potential sustainable route for regulating the nitrogen cycle and ambient ammonia(NH_(3)) synthesis.However,it remains a challenge to precisely regulate the reaction pathways and inhibit competing reactions(e.g.hydrogenolysis) for efficient and selective NH_(3) production in an aqueous solution environment.Here,we utilize the Schottky barrier-induced surface electric field to construct high-density electron-deficient Pd nanoparticles by modulating the N content in the carbon carrier to promote the enrichment and immobilization of NO_(2)^(-)on the electrode surface,which ensures the ultimate selectivity for NH_(3).With these properties,Pd@N_(0.14)C with the highest N content achieved excellent catalytic performance for the reduction of NO_(2)^(-)to NH_(3) with the 100% Faraday efficiency at-0.5 and-0.6 V vs,reversible hydrogen electrode(RHE) for NH_(3) production,which was significantly better than Pd/C and Pd@N_(x)C samples with lower N content.This study opens new avenues for rational construction of efficient electrocatalysts for nitrite removal and NH_(3) electrosynthesis.展开更多
The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development ...The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development of efficient bifunctional electrocatalysts.Herein,we put forward a high-efficiency coelectrolysis system by coupling the nitrite reduction reaction(NO_(2)RR)and the glycerol oxidation reaction(GOR)over a novel heterogeneous β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl catalyst.Theβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl shows excellent bifunctional performance with high Faradaic efficiencies of formate(90.1%)and NH_(3)(91.9%)at cell voltage of 1.5 V,high yield rate of formate(89.6 mg h^(-1)cm^(-2))and NH_(3)(36.07 mg h^(-1)cm^(-2))at cell voltage of 1.9 V,and superior stability in an anion exchange membrane co-electrolyzer.The in-situ Raman result confirms the unique Co/Cu-based bimetallic synergistic sites of β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl towards superior GOR performance,while the operando Fourier transform infrared spectroscopy demonstrates the improved protonation kinetics of key intermediates and optimized water dissociation ability ofβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl for high NO_(2)RR activity.Our work illuminates alternative avenues to exploit the innovative and energy-saving technology for the co-production of high-added chemicals.展开更多
Ambient electrochemical nitrite(NO_(2)^(-))reduction is viewed as an effective and sustainable approach for simul-taneously removing NO_(2)^(-)and producing ammonia(NH_(3)).However,the complex multi-electron transfer ...Ambient electrochemical nitrite(NO_(2)^(-))reduction is viewed as an effective and sustainable approach for simul-taneously removing NO_(2)^(-)and producing ammonia(NH_(3)).However,the complex multi-electron transfer steps involved in the NO_(2)^(-)reduction reaction(NO_(2)^(-)RR)lead to sluggish kinetics and low product selectivity toward NH_(3),underscoring the need for NH_(3)synthesis electrocatalysts with high activity and durability.Herein,we report amorphous indium-tin oxide sputtered on a TiO_(2)nanobelt array on a Ti plate(ITO@TiO_(2)/TP)as a 3D NH_(3)-producing catalyst for the NO_(2)^(-).In 0.5 M LiClO_(4)with 0.1 M NO_(2)^(-),it shows greatly boosted NO_(2)^(-)RR activity toward NH_(3)production,with excellent selectivity,achieving a large NH_(3)yield of 411.3μmol h^(-1)cm^(-2)and a high Faradaic efficiency of 82.6%.It also shows high durability for continuous electrolysis.A Zn-NO_(2)^(-)battery with ITO@TiO_(2)/TP cathode offers an NH_(3)yield of 23.1μmol h^(-1)cm^(-2)and a peak power density of 1.22 m.展开更多
Highly efficient and green ammonia production is an important demand for modern agriculture.In this study,a two-step ammonia production method is developed using a gliding arc discharge in combination with Cu/Cu_(2)O ...Highly efficient and green ammonia production is an important demand for modern agriculture.In this study,a two-step ammonia production method is developed using a gliding arc discharge in combination with Cu/Cu_(2)O electrocatalysis.In this method,NO_(x)is provided by the gliding arc discharge and then electrolyzed by Cu/Cu_(2)O after alkaline absorption.The electrical characteristics,the optical characteristics and the NO_(x)production are investigated in discharges at different input voltage and the gas flow.The dependence of ammonia production through Cu/Cu_(2)O electrocatalysis on pH value and reduction potential are determined by colorimetric method.In our study,two discharge modes are observed.At high input voltage and low gas flow,the discharge is operated with a stable plasma channel which is called the steady arc gliding discharge mode(A-G mode).As lowering input voltage and raising gas flow,the plasma channel is destroyed and high frequency breakdown occurs instead,which is known as the breakdown gliding discharge mode(B-G mode).The optimal NO_(x)production of 7.34 mmol h^(-1)is obtained in the transition stage of the two discharge modes.The ammonia yield reaches0.402 mmol h^(-1)cm^(-2)at pH value of 12.7 and reduction potential of-1.0 V versus reversible hydrogen electrode(RHE).展开更多
The reduction of nitrite at Au or carbon electrode in-H_2SO_4 was found to follow achemical-electrochemical (CE) mechanism with a very thin (4×10(-8)cm) preceding reaction zone.It was proposed and experimentally ...The reduction of nitrite at Au or carbon electrode in-H_2SO_4 was found to follow achemical-electrochemical (CE) mechanism with a very thin (4×10(-8)cm) preceding reaction zone.It was proposed and experimentally verified that for such kind of electrode processes the totalreaction the could be effectively enhanced by using electrodes with increased true surface area.such as porous electrodes. As a combination of porous electrode and microelectrode, the powdermicroclectrode shows excellent performance for nitrite detection.展开更多
It was newly found that the electrodes modified by applying ethanol solutions of Nationcontaining os(bpy)32+ onto the substrate electrode (the one-step method) show two pairs of stableredox peaks of Os(bpy)32+/3+ on c...It was newly found that the electrodes modified by applying ethanol solutions of Nationcontaining os(bpy)32+ onto the substrate electrode (the one-step method) show two pairs of stableredox peaks of Os(bpy)32+/3+ on cyclic voltammogram near 0.54V and 0.25V, respectively. Thesemoditied electrodes can effectively mediate and catalyze the first and second steps of nitritereduction in acidic media in the potential region 0-0.9V when the loading in the coating (X=F(Os2+) / F(SO3-)) and pH in solution are below 0. 17 and 4, respectively. When X is between 0.33and 0. 17. only the current peak near 0.54V appears regardless of solution pH and only the first stepof NO2 reduction is catalyzed. Thus the modified electrode provides a very useful flexibility thatone can control the reaction pathway and catalytic activity of nitrite reduction by simply changingthe concentration of the mediator in the coating.展开更多
基金supported by the National Natural Science Foundation of China(No.41977029).
文摘Mining and tailings deposition can cause serious heavy metal(loids)pollution to the surrounding soil environment.Soil microorganisms adapt their metabolism to such conditions,driving alterations in soil function.This study aims to elucidate the response patterns of nitrogen-cycling microorganisms under long-term heavy metal(loids)exposure.The results showed that the diversity and abundance of nitrogen-cyclingmicroorganisms showed negative feedback to heavy metal(loids)concentrations.Denitrifying microorganisms were shown to be the dominant microorganisms with over 60%of relative abundance and a complex community structure including 27 phyla.Further,the key bacterial species in the denitrification process were calculated using a random forest model,where the top three key species(Pseudomonas stutzei,Sphingobium japonicum and Leifsonia rubra)were found to play a prominent role in nitrite reduction.Functional gene analysis and qPCR revealed that nirK,which is involved in nitrite reduction,significantly accumulated in the most metal-rich soil with the increase of absolute abundance of 63.86%.The experimental results confirmed that the activity of nitrite reductase(Nir)encoded by nirK in the soil was increased at high concentrations of heavy metal(loids).Partial least squares-path model identified three potential modes of nitrite reduction processes being stimulated by heavy metal(loids),the most prominent of which contributed to enhanced nirK abundance and soil Nir activity through positive stimulation of key species.The results provide new insights and preliminary evidence on the stimulation of nitrite reduction processes by heavy metal(loids).
文摘The authors regret<an error occurred regarding the spelling of the author’s name in the final published manuscript.The correct spelling is Jingtao Bi,but it was mistakenly published as Jingtai Bi.We hereby request to correct the name to Jingtao Bi as originally intended.>.The authors would like to apologize for any inconvenience caused.
文摘The electrochemical conversion of toxic nitrite(NO_(2)-)is a promising approach for the simultaneous removal of nitrogen contaminants and synthesis of ammonia(NH_(3)).In this study,we present the Er-doping-induced electronic modulation of CoP integrated with nitrogen-doped carbon(CN)nanosheets supported on a titanium mesh(Er-CoP@NC/TM)for the electrocatalytic NO_(2)-reduction reaction(eNO_(2)-RR)for NH_(3)synthesis.The catalyst demonstrates a high Faraday efficiency of 97.08±2.22%and a high yield of 2087.60±17.10μmol h^(-1)cm^(-2)for NH_(3)production.Characterization and theoretical calculations revealed that Er-doping facilitated the electronic modulation of CoP in Er-CoP@NC/TM,which regulated the adsorption behaviors of intermediates and was the rate-limiting step for the eNO_(2)-RR,thereby enhancing the electrocatalytic performance.Quenching experiments and electron paramagnetic resonance tests suggest that both direct electrocatalytic reduction by active hydrogen and electron transfer are critical for the eNO_(2)-RR for NH_(3)synthesis.Furthermore,Er-CoP@NC/TM exhibited high performance across a wide range of NO_(2)-concentrations(0.05-0.1 mol L^(-1))and pH values(4-13).In addition,the catalyst demonstrated strong resistance to anions and a long cycle life in simulated wastewater environments.This study offers a powerful approach for the remediation of NO_(2)-wastewater and recovery of valuable inorganic compounds.
基金supported by the National Natural Science Foundation of China(22273056)the National Training Program of Innovation and Entrepreneurship for Undergraduates(202410718010)+2 种基金the Natural Science Basic Research Project of Shaanxi Province(2024JC-YBQN-0092)the Scientific research project of Shaanxi Institute of Basic Sciences(23JHQ003)the Scientific Research Program Funded by Education Department of Shaanxi Provincial Government(23JK0694)。
文摘Ammonia(NH_(3))is a fundamental chemical in agriculture and an ideal hydrogen carrier.Consequently,NH_(3)synthesis strategies with high efficiency,energy conservation,environmental friendliness,and sustainability are desired eminently.The nitrite(NO_(2)^(-))reduction reaction(NO_(2-)RR)to NH_(3)offers a feasibly low-energy consumption and continuable approach to replace industrial NH_(3)synthesis.Herein,polyethyleneimine(PEI)modified Au core Rh shell nanodendrites(Au@Rh-NDs)nanohybrid(Au@Rh-NDs/PEI)with branched structure is synthesized,which achieves the high NH_(3)yield(1.68 mg h^(-1)mg_(cat)^(-1))and Faradaic efficiency(FE)of 95.86%for NO_(2)^(-)-RR at-0.39 V potential in neutral electrolyte.Particularly,the introduction of PEI significantly enhances the electroactivity of Au@Rh-NDs at low concentration of 1 mM NaNO_(2),which originates from the enrichment function of PEI for NO_(2)^(-)-ion.In addition,the Au basement permits the sustainable solar power to expedite the NO_(2)^(-)-RR at Au@Rh-NDs/PEI owing to the localized surface plasmon resonance(LSPR)of the Au core substrate.This work may provide an admissible tactic to build excellent catalysts on account of organic molecule-mediated interfacial engineering in a variety of fields of catalysis and electrocatalysis.
基金supported in part by the National Key R&D Program of China(No.2024YFA1509400)the National Natural Science Foundation of China(No.52302094)Natural Science Foundation of Jiangxi,China(No.20232ACB203002).
文摘Electrochemical nitrite(NO_(2)^(−))reduction offers a sustainable route for ammonia(NH_(3))synthesis while simultaneously removing contaminants in wastewater.However,its efficiency is often limited by low catalytic efficiency and the competitive hydrogen evolution reaction at low NO_(2)^(−)concentrations.Herein,we report an intermittent pulsed electrolysis(IPE)strategy using copper oxide(Cu_(x)O)nanowires,which significantly enhances the NH3 yield rate and Faradaic efficiency(FE)at lower reactant concentrations.In situ experiments and theoretical calculations reveal that alternating between open-circuit and cathodic potentials modulates the copper oxidation states,stabilizing the catalytically active cuprous oxide(Cu_(2)O).Consequently,the IPE approach provides an outstanding NH3 yield rate of 115.10 mg·h^(−1)·cm^(−2)and FE of 91.14%in the presence of 25 mM NO_(2)^(−),markedly outperforming conventional constant potential electrolysis.
基金National Key Research and Development Program of China,Grant/Award Number:2022YFC2105800National Natural Science Foundation of China,Grant/Award Numbers:21901084,21905106,22279041+2 种基金Higher Education Discipline Innovation Project,Grant/Award Number:B17020Specific Research Fund of the Innovation Platform for Academicians of Hainan Province,China,Grant/Award Number:YSPTZX202321Natural Science Foundation of Jilin Province,Grant/Award Number:SKL202302017.
文摘Electrocatalytic reduction of nitrate pollutants to produce ammonia offers an effective approach to realizing the artificial nitrogen cycle and replacing the energyintensive Haber-Bosch process.Nitrite is an important intermediate product in the reduction of nitrate to ammonia.Therefore,the mechanism of converting nitrite into ammonia warrants further investigation.Molecular cobalt catalysts are regarded as promising for nitrite reduction reactions(NO_(2)^(−)RR).However,designing and controlling the coordination environment of molecular catalysts is crucial for studying the mechanism of NO_(2)^(−)RR and catalyst design.Herein,we develop a molecular platform of cobalt porphyrin with three coordination microenvironments(Co-N_(3)X_(1),X=N,O,S).Electrochemical experiments demonstrate that cobalt porphyrin with O coordination(CoOTPP)exhibits the lowest onset potential and the highest activity for NO_(2)^(−)RR in ammonia production.Under neutral,nonbuffered conditions over a wide potential range(−1.0 to−1.5 V versus AgCl/Ag),the Faradaic efficiency of nearly 90%for ammonia was achieved and reached 94.5%at−1.4 V versus AgCl/Ag,with an ammonia yield of 6,498μgh^(−1)and a turnover number of 22,869 at−1.5V versus AgCl/Ag.In situ characterization and density functional theory calculations reveal that modulating the coordination environment alters the electron transfer mode of the cobalt active center and the charge redistribution caused by the break of the ligand field.Therefore,this results in enhanced electrochemical activity for NO_(2)^(−)RR in ammonia production.This study provides valuable guidance for designing adjustments to the coordination environment of molecular catalysts to enhance catalytic activity.
基金supported by the National Natural Science Foundation of China[Nos.U21A20332,52103226,52202275,52203314,and 12204253]the Distinguished Young Scholars Fund of Jiangsu Province[No.BK20220061]the Fellowship of China Postdoctoral Science Foundation[No.2021M702382]。
文摘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.
基金The authors are grateful to the National Natural Science Foundation of China for financial support for this work.
文摘The properties of the carbon nanotube powder microelectrodes (denoted CNTPME) are remarkably altered by anodic pretreatment and preadsorption of mediators. It seems that anodic pretreatment leads the long and tangled carbon nanotubes to be partially cut shorter, resulting in more openings as shown by TEM. Besides, the anodic pretreatment may adjust the hydrophobicity of nanotubes to match with that of Os(bpy)32+. As a result, the real surface area and the ability of adsorbing mediator Os(bpy)32+ of the nanotubes are markedly increased so as to effectively catalyze NO2- reduction in acidic solution.
文摘Electrochemical nitrite reduction reaction(NO_(2)^(-)RR) is a potential sustainable route for regulating the nitrogen cycle and ambient ammonia(NH_(3)) synthesis.However,it remains a challenge to precisely regulate the reaction pathways and inhibit competing reactions(e.g.hydrogenolysis) for efficient and selective NH_(3) production in an aqueous solution environment.Here,we utilize the Schottky barrier-induced surface electric field to construct high-density electron-deficient Pd nanoparticles by modulating the N content in the carbon carrier to promote the enrichment and immobilization of NO_(2)^(-)on the electrode surface,which ensures the ultimate selectivity for NH_(3).With these properties,Pd@N_(0.14)C with the highest N content achieved excellent catalytic performance for the reduction of NO_(2)^(-)to NH_(3) with the 100% Faraday efficiency at-0.5 and-0.6 V vs,reversible hydrogen electrode(RHE) for NH_(3) production,which was significantly better than Pd/C and Pd@N_(x)C samples with lower N content.This study opens new avenues for rational construction of efficient electrocatalysts for nitrite removal and NH_(3) electrosynthesis.
基金financially supported by the National Natural Science Foundation of China(22205205)the Science Foundation of Zhejiang Sci-Tech University(ZSTU)under Grant No.21062337-Y。
文摘The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development of efficient bifunctional electrocatalysts.Herein,we put forward a high-efficiency coelectrolysis system by coupling the nitrite reduction reaction(NO_(2)RR)and the glycerol oxidation reaction(GOR)over a novel heterogeneous β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl catalyst.Theβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl shows excellent bifunctional performance with high Faradaic efficiencies of formate(90.1%)and NH_(3)(91.9%)at cell voltage of 1.5 V,high yield rate of formate(89.6 mg h^(-1)cm^(-2))and NH_(3)(36.07 mg h^(-1)cm^(-2))at cell voltage of 1.9 V,and superior stability in an anion exchange membrane co-electrolyzer.The in-situ Raman result confirms the unique Co/Cu-based bimetallic synergistic sites of β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl towards superior GOR performance,while the operando Fourier transform infrared spectroscopy demonstrates the improved protonation kinetics of key intermediates and optimized water dissociation ability ofβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl for high NO_(2)RR activity.Our work illuminates alternative avenues to exploit the innovative and energy-saving technology for the co-production of high-added chemicals.
基金This work was supported by the National Natural Science Foundation of China(No.22072015).
文摘Ambient electrochemical nitrite(NO_(2)^(-))reduction is viewed as an effective and sustainable approach for simul-taneously removing NO_(2)^(-)and producing ammonia(NH_(3)).However,the complex multi-electron transfer steps involved in the NO_(2)^(-)reduction reaction(NO_(2)^(-)RR)lead to sluggish kinetics and low product selectivity toward NH_(3),underscoring the need for NH_(3)synthesis electrocatalysts with high activity and durability.Herein,we report amorphous indium-tin oxide sputtered on a TiO_(2)nanobelt array on a Ti plate(ITO@TiO_(2)/TP)as a 3D NH_(3)-producing catalyst for the NO_(2)^(-).In 0.5 M LiClO_(4)with 0.1 M NO_(2)^(-),it shows greatly boosted NO_(2)^(-)RR activity toward NH_(3)production,with excellent selectivity,achieving a large NH_(3)yield of 411.3μmol h^(-1)cm^(-2)and a high Faradaic efficiency of 82.6%.It also shows high durability for continuous electrolysis.A Zn-NO_(2)^(-)battery with ITO@TiO_(2)/TP cathode offers an NH_(3)yield of 23.1μmol h^(-1)cm^(-2)and a peak power density of 1.22 m.
文摘Highly efficient and green ammonia production is an important demand for modern agriculture.In this study,a two-step ammonia production method is developed using a gliding arc discharge in combination with Cu/Cu_(2)O electrocatalysis.In this method,NO_(x)is provided by the gliding arc discharge and then electrolyzed by Cu/Cu_(2)O after alkaline absorption.The electrical characteristics,the optical characteristics and the NO_(x)production are investigated in discharges at different input voltage and the gas flow.The dependence of ammonia production through Cu/Cu_(2)O electrocatalysis on pH value and reduction potential are determined by colorimetric method.In our study,two discharge modes are observed.At high input voltage and low gas flow,the discharge is operated with a stable plasma channel which is called the steady arc gliding discharge mode(A-G mode).As lowering input voltage and raising gas flow,the plasma channel is destroyed and high frequency breakdown occurs instead,which is known as the breakdown gliding discharge mode(B-G mode).The optimal NO_(x)production of 7.34 mmol h^(-1)is obtained in the transition stage of the two discharge modes.The ammonia yield reaches0.402 mmol h^(-1)cm^(-2)at pH value of 12.7 and reduction potential of-1.0 V versus reversible hydrogen electrode(RHE).
文摘The reduction of nitrite at Au or carbon electrode in-H_2SO_4 was found to follow achemical-electrochemical (CE) mechanism with a very thin (4×10(-8)cm) preceding reaction zone.It was proposed and experimentally verified that for such kind of electrode processes the totalreaction the could be effectively enhanced by using electrodes with increased true surface area.such as porous electrodes. As a combination of porous electrode and microelectrode, the powdermicroclectrode shows excellent performance for nitrite detection.
文摘It was newly found that the electrodes modified by applying ethanol solutions of Nationcontaining os(bpy)32+ onto the substrate electrode (the one-step method) show two pairs of stableredox peaks of Os(bpy)32+/3+ on cyclic voltammogram near 0.54V and 0.25V, respectively. Thesemoditied electrodes can effectively mediate and catalyze the first and second steps of nitritereduction in acidic media in the potential region 0-0.9V when the loading in the coating (X=F(Os2+) / F(SO3-)) and pH in solution are below 0. 17 and 4, respectively. When X is between 0.33and 0. 17. only the current peak near 0.54V appears regardless of solution pH and only the first stepof NO2 reduction is catalyzed. Thus the modified electrode provides a very useful flexibility thatone can control the reaction pathway and catalytic activity of nitrite reduction by simply changingthe concentration of the mediator in the coating.
