Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,...Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N coupling.However,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO_(2)reduction reaction(CO_(2)RR).To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu_(2)-based N-doped carbon(Cu_(2)N_(6)C_(10))catalyst for CO_(2)RR.These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction micro-environment.Due to the sluggishness of CO_(2),the formation of a solvation electric layer by anions(F^(-),Cl^(-),Br^(-),and I^(-))and cations(Na+,Mg^(2+),K+,and Ca^(2+))leads to electron transfer towards the Cu surface.This process significantly accelerates the reduction of CO_(2).These results reveal that*CO intermediates play a pivotal role in N-integrated CO_(2)RR.Remarkably,the Cu_(2)-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date.Our findings reveal that through the process of a condensation reaction between*CO and NH_(2)OH for urea synthesis,*NO_(3)-is reduced to*NH_(3),and*CO_(2)to*CCO at dual Cu atom sites.This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH_(3)and the ketene intermediate.Furthermore,we found that the I-and Mg^(2+)ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca^(2+)were present.Furthermore,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the dominant side reaction,shifting from hydrogen production in acidic conditions to water reduction in alkaline ones.This study introduces a novel approach using ion-H_(2)O cages to significantly enhance the efficiency of C–N coupling reactions.展开更多
Nitrogen,one of the most crucial nutrients present in grapes and musts,plays a key role in yeast activities during alcoholic fermentation.Such influences are imposed on yeast growth and fermentation performances inclu...Nitrogen,one of the most crucial nutrients present in grapes and musts,plays a key role in yeast activities during alcoholic fermentation.Such influences are imposed on yeast growth and fermentation performances including the formation of secondary metabolites.Saccharomyces cerevisiae,the main yeast responsible for fermentation,has been studied extensively regarding nitrogen impacts.On the other hand,a similar study for non-Saccharomyces yeasts,whose contributions to winemaking have gradually been acknowledged,remains to be fully explored,with a few studies being reported.This review starts by discussing nitrogen impacts on non-Saccharomyces yeast growth and fermentation kinetics in different case scenarios,then proceeds to summarize the nitrogen preferences of individual yeast strains with regulation mechanisms elucidated by recent studies.Detailed discussions on the influences on the production of volatile compounds and proposed pathways therein are made,followed by future work suggested as the final section.In summarizing the nitrogen impacts on non-Saccharomyces yeasts throughout alcoholic fermentation,this review will be helpful in obtaining a more comprehensive view on these non-conventional wine yeasts in terms of nutrient requirements and corresponding volatile production.Research gaps will therefore be elucidated for future research.展开更多
Background:Nitrogen(N)deposition affects forest stoichiometric flexibility through changing soil nutrient availability to influence plant uptake.However,the effect of N deposition on the flexibility of carbon(C),N,and...Background:Nitrogen(N)deposition affects forest stoichiometric flexibility through changing soil nutrient availability to influence plant uptake.However,the effect of N deposition on the flexibility of carbon(C),N,and phosphorus(P)in forest plant-soil-microbe systems remains unclear.Methods:We conducted a meta-analysis based on 751 pairs of observations to evaluate the responses of plant,soil and microbial biomass C,N and P nutrients and stoichiometry to N addition in different N intensity(050,50–100,>100 kg·ha^(-1)·year^(-1)of N),duration(0–5,>5 year),method(understory,canopy),and matter(ammonium N,nitrate N,organic N,mixed N).Results:N addition significantly increased plant N:P(leaf:14.98%,root:13.29%),plant C:P(leaf:6.8%,root:25.44%),soil N:P(13.94%),soil C:P(10.86%),microbial biomass N:P(23.58%),microbial biomass C:P(12.62%),but reduced plant C:N(leaf:6.49%,root:9.02%).Furthermore,plant C:N:P stoichiometry changed significantly under short-term N inputs,while soil and microorganisms changed drastically under high N addition.Canopy N addition primarily affected plant C:N:P stoichiometry through altering plant N content,while understory N inputs altered more by influencing soil C and P content.Organic N significantly influenced plant and soil C:N and C:P,while ammonia N changed plant N:P.Plant C:P and soil C:N were strongly correlated with mean annual precipitation(MAT),and the C:N:P stoichiometric flexibility in soil and plant under N addition connected with soil depth.Besides,N addition decoupled the correlations between soil microorganisms and the plant.Conclusions:N addition significantly increased the C:P and N:P in soil,plant,and microbial biomass,reducing plant C:N,and aggravated forest P limitations.Significantly,these impacts were contingent on climate types,soil layers,and N input forms.The findings enhance our comprehension of the plant-soil system nutrient cycling mechanisms in forest ecosystems and plant strategy responses to N deposition.展开更多
Carbon(C),nitrogen(N),and phosphorus(P)are of fundamental importance for growth and nutrient dynamics within plant organs and deserve more attention at regional to global scales.However,our knowledge of how these nutr...Carbon(C),nitrogen(N),and phosphorus(P)are of fundamental importance for growth and nutrient dynamics within plant organs and deserve more attention at regional to global scales.However,our knowledge of how these nutrients vary with tree size,organ age,or root order at the individual level remains limited.We determined C,N,and P contents and their stoichiometric ratios(i.e.,nutrient traits)in needles,branches,and fine roots at different organ ages(0-3-year-old needles and branches)and root orders(1st-4th order roots)from 64 Pinus koraiensis of varying size(Diameter at breast height ranged from 0.3 to 100 cm)in northeast China.Soil factors were also measured.The results show that nutrient traits were regulated by tree size,organ age,or root order rather than soil factors.At a whole-plant level,nutrient traits decreased in needles and fine roots but increased in branches with tree size.At the organ level,age or root order had a negative effect on C,N,and P and a positive effect on stoichiometric ratios.Our results demonstrate that nutrient variations are closely related to organ-specific functions and ecophysiological processes at an individual level.It is suggested that the nutrient acquisition strategy by younger trees and organ fractions with higher nutrient content is for survival.Conversely,nutrient storage strategy in older trees and organ fractions are mainly for steady growth.Our results clarified the nutrient utilization strategies during tree and organ ontogeny and suggest that tree size and organ age or root order should be simultaneously considered to understand the complexities of nutrient variations.展开更多
Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-...Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-products.However,the chemical inertness of nitrogen and poor activated capacity on catalyst surface usually produce low ammonia yield and faradic efficiency.Herein,the microfluidic technology is proposed to efficiently fabricate enriched iridium nanodots/carbon architecture.Owing to in-situ co-precipitation reaction and microfluidic manipulation,the iridium nanodots/carbon nanomaterials possess small average size,uniform dispersion,high conductivity and abundant active sites,producing good proton activation and rapid electrons transmission and moderate adsorption/desorption capacity.As a result,the as-prepared iridium nanodots/carbon nanomaterials realize large ammonia yield of 28.73 μg h^(-1) cm^(-2) and faradic efficiency of 9.14%in KOH solution.Moreover,the high ammonia yield of 11.21 μg h^(-1) cm^(-2) and faradic efficiency of 24.30%are also achieved in H_(2)SO_(4) solution.The microfluidic method provides a reference for large-scale fabrication of nano-sized catalyst materials,which may accelerate the progress of electrocatalytic NRR in industrialization field.展开更多
The most important process before leaf senescence is nutrient resorption,which reduces nutrient loss and maximizes plant fitness during the subsequent growth period.However,plants must retain certain levels of nitroge...The most important process before leaf senescence is nutrient resorption,which reduces nutrient loss and maximizes plant fitness during the subsequent growth period.However,plants must retain certain levels of nitrogen(N)in their leaves to maintain carbon assimilation during hardening.The objective of this study was to investigate the tradeoffs in N investment between leaf N resorption and N for photosynthesis in seedlings with increased soil fertility during the hardening period.A field experiment was conducted to determine if and how soil fertility treatments(17,34,or 68 mg N seedling−1)affected N resorption and allocation to the photosynthetic apparatus in Quercus mongolica leaves during the hardening period.Seedlings were sampled at T1(after terminal bud formation),T2(between terminal bud formation and end of the growing period),and T3(at the end of the growing period).Results showed that photosynthetic N content continued to rise in T2,while N resorption started from non-photosynthetic N.Leaf N allocation to the photosynthetic apparatus increased as soil fertility increased,delaying N resorption.Additionally,soil fertility significantly affected N partitioning among different photosynthetic components,maintaining or increasing photosynthetic traits during senescence.This study demonstrates a tradeoff in N investment between resorption and photosynthesis to maintain photosynthetic assimilation capacity during the hardening period,and that soil fertility impacts this balance.Q.mongolica leaves primarily resorbed N from the non-photosynthetic apparatus and invested it in the photosynthetic apparatus,whereas different photosynthetic N component allocations effectively improved this pattern.展开更多
The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing mul...The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing multiple intermediates and pathways.Herein,we utilized defective BC_(3)monolayer-supported SACs as a prototype to investigate the cooperative effects of SACs and their support on the catalytic performance of the nitrogen reduction reaction(NRR)for ammonia(NH_(3))production.The results showed that these SACs can be firmly stabilized on these defective BC_(3)supports with high stability against aggregation.Furthermore,co-activation of the inert N_(2)reactant was observed in certain embedded SACs and their neighboring B atoms on certain BC3 sheets due to the noticeable charge transfer and significant N–N bond elongation.Our high-throughput screening revealed that the Mo/DV_(CC)and W/DV_(CC)exhibit superior NRR catalytic performance,characterized by a low limiting potential of−0.33 and−0.43 V,respectively,which can be further increased under acid conditions based on the constant potential method.Moreover,varying NRR catalytic activities can be attributed to the differences in the valence state of active sites.Remarkably,further microkinetic modeling analysis displayed that the turnover frequency of N_(2)–to–NH_(3)conversion on Mo/DV_(CC)is as large as 1.20×10^(−3)s^(−1)site^(−1) at 700 K and 100 bar,thus guaranteeing its ultra-fast reaction rate.Our results not only suggest promising advanced electrocatalysts for NRR but also offer an effective avenue to regulate the electrocatalytic performance via the co-catalytic metal–support interactions.展开更多
Sustainable nitrogen fixation driven by renewable energy sources under mild conditions has been widely sought to replace the industrial Haber-Bosch process.The fixation of nitrogen in the form of NO_(x)^(-)and NH_4^(+...Sustainable nitrogen fixation driven by renewable energy sources under mild conditions has been widely sought to replace the industrial Haber-Bosch process.The fixation of nitrogen in the form of NO_(x)^(-)and NH_4^(+)into aqueous solutions using electricity-driven gas-liquid discharge plasma is considered a promising prescription.In this paper,a scalable bubble discharge excited by nanosecond pulse power is employed for nitrogen fixation in the liquid phase.The nitrogen fixation performance and the mechanisms are analyzed by varying the power supply parameters,working gas flow rate and composition.The results show that an increase in voltage and frequency can result in an enhanced NO_(3)^(-)yield.Increases in the gas flow rate can result in inadequate activation of the working gas,which together with more inefficient mass transfer efficiencies can reduce the yield.The addition of O_(2) effectively elevates NO_(3)^(-)production while simultaneously inhibiting NH_4^(+) production.The addition of H_(2)O vapor increases the production of OH and H,thereby promoting the generation of reactive nitrogen and enhancing the yield of nitrogen fixation.However,the excessive addition of O_(2) and H_(2)O vapor results in negative effect on the yield of nitrogen fixation,due to the significant weakening of the discharge intensity.The optimal nitrogen fixation yield was up to 16.5 μmol/min,while the optimal energy consumption was approximately 21.3 MJ/mol in this study.Finally,the mechanism related to nitrogen fixation is discussed through the optical emission spectral(OES) information in conjunction with the simulation of energy loss paths in the plasma by BOLSIG+.The work advances knowledge of the effect of parameter variations on nitrogen fixation by gas-liquid discharge for higher yield and energy production.展开更多
基金National Natural Science Foundation of China(U22B20149,22308376)Outstanding Young Scholars Foundation of China University of Petroleum(Beijing)(2462023BJRC015)Foundation of United Institute for Carbon Neutrality(CNIF20230209)。
文摘Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N coupling.However,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO_(2)reduction reaction(CO_(2)RR).To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu_(2)-based N-doped carbon(Cu_(2)N_(6)C_(10))catalyst for CO_(2)RR.These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction micro-environment.Due to the sluggishness of CO_(2),the formation of a solvation electric layer by anions(F^(-),Cl^(-),Br^(-),and I^(-))and cations(Na+,Mg^(2+),K+,and Ca^(2+))leads to electron transfer towards the Cu surface.This process significantly accelerates the reduction of CO_(2).These results reveal that*CO intermediates play a pivotal role in N-integrated CO_(2)RR.Remarkably,the Cu_(2)-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date.Our findings reveal that through the process of a condensation reaction between*CO and NH_(2)OH for urea synthesis,*NO_(3)-is reduced to*NH_(3),and*CO_(2)to*CCO at dual Cu atom sites.This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH_(3)and the ketene intermediate.Furthermore,we found that the I-and Mg^(2+)ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca^(2+)were present.Furthermore,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the dominant side reaction,shifting from hydrogen production in acidic conditions to water reduction in alkaline ones.This study introduces a novel approach using ion-H_(2)O cages to significantly enhance the efficiency of C–N coupling reactions.
基金supported by grants from the National Natural Science Foundation of China(32172340)。
文摘Nitrogen,one of the most crucial nutrients present in grapes and musts,plays a key role in yeast activities during alcoholic fermentation.Such influences are imposed on yeast growth and fermentation performances including the formation of secondary metabolites.Saccharomyces cerevisiae,the main yeast responsible for fermentation,has been studied extensively regarding nitrogen impacts.On the other hand,a similar study for non-Saccharomyces yeasts,whose contributions to winemaking have gradually been acknowledged,remains to be fully explored,with a few studies being reported.This review starts by discussing nitrogen impacts on non-Saccharomyces yeast growth and fermentation kinetics in different case scenarios,then proceeds to summarize the nitrogen preferences of individual yeast strains with regulation mechanisms elucidated by recent studies.Detailed discussions on the influences on the production of volatile compounds and proposed pathways therein are made,followed by future work suggested as the final section.In summarizing the nitrogen impacts on non-Saccharomyces yeasts throughout alcoholic fermentation,this review will be helpful in obtaining a more comprehensive view on these non-conventional wine yeasts in terms of nutrient requirements and corresponding volatile production.Research gaps will therefore be elucidated for future research.
基金supported by the National Natural Science Foundation of China(Nos.31800369,32271686,U1904204)the State Scholarship Fund of Chinathe Innovation Scientists and Technicians Troop Construction Projects of Henan Province(No.182101510005)。
文摘Background:Nitrogen(N)deposition affects forest stoichiometric flexibility through changing soil nutrient availability to influence plant uptake.However,the effect of N deposition on the flexibility of carbon(C),N,and phosphorus(P)in forest plant-soil-microbe systems remains unclear.Methods:We conducted a meta-analysis based on 751 pairs of observations to evaluate the responses of plant,soil and microbial biomass C,N and P nutrients and stoichiometry to N addition in different N intensity(050,50–100,>100 kg·ha^(-1)·year^(-1)of N),duration(0–5,>5 year),method(understory,canopy),and matter(ammonium N,nitrate N,organic N,mixed N).Results:N addition significantly increased plant N:P(leaf:14.98%,root:13.29%),plant C:P(leaf:6.8%,root:25.44%),soil N:P(13.94%),soil C:P(10.86%),microbial biomass N:P(23.58%),microbial biomass C:P(12.62%),but reduced plant C:N(leaf:6.49%,root:9.02%).Furthermore,plant C:N:P stoichiometry changed significantly under short-term N inputs,while soil and microorganisms changed drastically under high N addition.Canopy N addition primarily affected plant C:N:P stoichiometry through altering plant N content,while understory N inputs altered more by influencing soil C and P content.Organic N significantly influenced plant and soil C:N and C:P,while ammonia N changed plant N:P.Plant C:P and soil C:N were strongly correlated with mean annual precipitation(MAT),and the C:N:P stoichiometric flexibility in soil and plant under N addition connected with soil depth.Besides,N addition decoupled the correlations between soil microorganisms and the plant.Conclusions:N addition significantly increased the C:P and N:P in soil,plant,and microbial biomass,reducing plant C:N,and aggravated forest P limitations.Significantly,these impacts were contingent on climate types,soil layers,and N input forms.The findings enhance our comprehension of the plant-soil system nutrient cycling mechanisms in forest ecosystems and plant strategy responses to N deposition.
基金supported by the National Key R&D Program of China (2022YFD2201100)Natural Science Foundation of Heilongjiang Province of China (TD2023C006)the Fundamental Research Funds for the Central Universities (2572022DS13).
文摘Carbon(C),nitrogen(N),and phosphorus(P)are of fundamental importance for growth and nutrient dynamics within plant organs and deserve more attention at regional to global scales.However,our knowledge of how these nutrients vary with tree size,organ age,or root order at the individual level remains limited.We determined C,N,and P contents and their stoichiometric ratios(i.e.,nutrient traits)in needles,branches,and fine roots at different organ ages(0-3-year-old needles and branches)and root orders(1st-4th order roots)from 64 Pinus koraiensis of varying size(Diameter at breast height ranged from 0.3 to 100 cm)in northeast China.Soil factors were also measured.The results show that nutrient traits were regulated by tree size,organ age,or root order rather than soil factors.At a whole-plant level,nutrient traits decreased in needles and fine roots but increased in branches with tree size.At the organ level,age or root order had a negative effect on C,N,and P and a positive effect on stoichiometric ratios.Our results demonstrate that nutrient variations are closely related to organ-specific functions and ecophysiological processes at an individual level.It is suggested that the nutrient acquisition strategy by younger trees and organ fractions with higher nutrient content is for survival.Conversely,nutrient storage strategy in older trees and organ fractions are mainly for steady growth.Our results clarified the nutrient utilization strategies during tree and organ ontogeny and suggest that tree size and organ age or root order should be simultaneously considered to understand the complexities of nutrient variations.
基金supported by the National Natural Science Foundation of China(22025801)and(22208190)National Postdoctoral Program for Innovative Talents(BX2021146)Shuimu Tsinghua Scholar Program(2021SM055).
文摘Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-products.However,the chemical inertness of nitrogen and poor activated capacity on catalyst surface usually produce low ammonia yield and faradic efficiency.Herein,the microfluidic technology is proposed to efficiently fabricate enriched iridium nanodots/carbon architecture.Owing to in-situ co-precipitation reaction and microfluidic manipulation,the iridium nanodots/carbon nanomaterials possess small average size,uniform dispersion,high conductivity and abundant active sites,producing good proton activation and rapid electrons transmission and moderate adsorption/desorption capacity.As a result,the as-prepared iridium nanodots/carbon nanomaterials realize large ammonia yield of 28.73 μg h^(-1) cm^(-2) and faradic efficiency of 9.14%in KOH solution.Moreover,the high ammonia yield of 11.21 μg h^(-1) cm^(-2) and faradic efficiency of 24.30%are also achieved in H_(2)SO_(4) solution.The microfluidic method provides a reference for large-scale fabrication of nano-sized catalyst materials,which may accelerate the progress of electrocatalytic NRR in industrialization field.
基金supported by the National Natural Science Foundation of China(No.32171764,No.32101503)the 5·5 Engineering Research&Innovation Team Project at the Beijing Forestry University(BLRC2023B08).
文摘The most important process before leaf senescence is nutrient resorption,which reduces nutrient loss and maximizes plant fitness during the subsequent growth period.However,plants must retain certain levels of nitrogen(N)in their leaves to maintain carbon assimilation during hardening.The objective of this study was to investigate the tradeoffs in N investment between leaf N resorption and N for photosynthesis in seedlings with increased soil fertility during the hardening period.A field experiment was conducted to determine if and how soil fertility treatments(17,34,or 68 mg N seedling−1)affected N resorption and allocation to the photosynthetic apparatus in Quercus mongolica leaves during the hardening period.Seedlings were sampled at T1(after terminal bud formation),T2(between terminal bud formation and end of the growing period),and T3(at the end of the growing period).Results showed that photosynthetic N content continued to rise in T2,while N resorption started from non-photosynthetic N.Leaf N allocation to the photosynthetic apparatus increased as soil fertility increased,delaying N resorption.Additionally,soil fertility significantly affected N partitioning among different photosynthetic components,maintaining or increasing photosynthetic traits during senescence.This study demonstrates a tradeoff in N investment between resorption and photosynthesis to maintain photosynthetic assimilation capacity during the hardening period,and that soil fertility impacts this balance.Q.mongolica leaves primarily resorbed N from the non-photosynthetic apparatus and invested it in the photosynthetic apparatus,whereas different photosynthetic N component allocations effectively improved this pattern.
基金financially supported in China by the Natural Science Funds for Distinguished Young Scholar of Heilongjiang Province (No. JC2018004)
文摘The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing multiple intermediates and pathways.Herein,we utilized defective BC_(3)monolayer-supported SACs as a prototype to investigate the cooperative effects of SACs and their support on the catalytic performance of the nitrogen reduction reaction(NRR)for ammonia(NH_(3))production.The results showed that these SACs can be firmly stabilized on these defective BC_(3)supports with high stability against aggregation.Furthermore,co-activation of the inert N_(2)reactant was observed in certain embedded SACs and their neighboring B atoms on certain BC3 sheets due to the noticeable charge transfer and significant N–N bond elongation.Our high-throughput screening revealed that the Mo/DV_(CC)and W/DV_(CC)exhibit superior NRR catalytic performance,characterized by a low limiting potential of−0.33 and−0.43 V,respectively,which can be further increased under acid conditions based on the constant potential method.Moreover,varying NRR catalytic activities can be attributed to the differences in the valence state of active sites.Remarkably,further microkinetic modeling analysis displayed that the turnover frequency of N_(2)–to–NH_(3)conversion on Mo/DV_(CC)is as large as 1.20×10^(−3)s^(−1)site^(−1) at 700 K and 100 bar,thus guaranteeing its ultra-fast reaction rate.Our results not only suggest promising advanced electrocatalysts for NRR but also offer an effective avenue to regulate the electrocatalytic performance via the co-catalytic metal–support interactions.
基金National Natural Science Foundation of China (Grant Nos. 52277151 and 51907088)。
文摘Sustainable nitrogen fixation driven by renewable energy sources under mild conditions has been widely sought to replace the industrial Haber-Bosch process.The fixation of nitrogen in the form of NO_(x)^(-)and NH_4^(+)into aqueous solutions using electricity-driven gas-liquid discharge plasma is considered a promising prescription.In this paper,a scalable bubble discharge excited by nanosecond pulse power is employed for nitrogen fixation in the liquid phase.The nitrogen fixation performance and the mechanisms are analyzed by varying the power supply parameters,working gas flow rate and composition.The results show that an increase in voltage and frequency can result in an enhanced NO_(3)^(-)yield.Increases in the gas flow rate can result in inadequate activation of the working gas,which together with more inefficient mass transfer efficiencies can reduce the yield.The addition of O_(2) effectively elevates NO_(3)^(-)production while simultaneously inhibiting NH_4^(+) production.The addition of H_(2)O vapor increases the production of OH and H,thereby promoting the generation of reactive nitrogen and enhancing the yield of nitrogen fixation.However,the excessive addition of O_(2) and H_(2)O vapor results in negative effect on the yield of nitrogen fixation,due to the significant weakening of the discharge intensity.The optimal nitrogen fixation yield was up to 16.5 μmol/min,while the optimal energy consumption was approximately 21.3 MJ/mol in this study.Finally,the mechanism related to nitrogen fixation is discussed through the optical emission spectral(OES) information in conjunction with the simulation of energy loss paths in the plasma by BOLSIG+.The work advances knowledge of the effect of parameter variations on nitrogen fixation by gas-liquid discharge for higher yield and energy production.
