To reduce the greenhouse effect caused by the surgery of nitrogen-oxides concentration in the atmosphere and develop a future energy carrier of renewables,it is very critical to develop more efficient,controllable,and...To reduce the greenhouse effect caused by the surgery of nitrogen-oxides concentration in the atmosphere and develop a future energy carrier of renewables,it is very critical to develop more efficient,controllable,and highly sensitive catalytic materials.In our work,we proposed that nitric oxide(NO),as a supplement to N_(2) for the synthesis of ammonia,which is equipped with a lower barrier.And the study highlighted the potential of CeO_(2)(111)nanosheets with La doping and oxygen vacancy(OV)as a high-performance,controllable material for NO capture at the site of Vo site,and separation the process of hydrogenation.We also reported that the E_(ads) of-1.12 eV with horizontal adsorption and the Bader charge of N increasing of 0.53|e|and O increasing of 0.17|e|at the most active site of reduction-OV predicted.It is worth noting thatΔG of NORR(NO reduction reaction)shows good performance(thermodynamically spontaneous reaction)to synthesize ammonia and water at room temperature in the theoretical calculation.展开更多
Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption...Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption and waste gas emissions.To address this,electrocatalytic nitric oxide reduction reaction(NORR)has emerged as a promising strategy to bridge NH3consumption to NH3production,harnessing renewable electricity for a sustainable future.Copper(Cu)stands out as a prominent electrocatalyst for NO reduction,given its exceptional NH3yield and selectivity.However,a crucial aspect that remains insufficiently explored is the effects of morphology and valence states of Cu on the NORR performance.In this investigation,we synthesized CuO nanowires(CuO-NF)and Cu nanocubes(Cu-NF)as cathodes through an in situ growth method.Remarkably,CuO-NF exhibited an impressive NH3yield of 0.50±0.02 mg cm^(-2)h^(-1)at-0.6 V vs.reversible hydrogen electrode(RHE)with faradaic efficiency of29,68%±1,35%,surpassing that of Cu-NF(0.17±0.01 mg cm^(-2)h^(-1),16.18%±1.40%).Throughout the electroreduction process,secondary cubes were generated on the CuO-NF surface,preserving their nanosheet cluster morphology,sustained by an abundant supply of subsurface oxygen(s-O)even after an extended duration of 10 h,until s-O depletion ensued.Conversely,Cu-NF exhibited inadequate s-O content,leading to rapid crystal collapse within the same timeframe.The distinctive current-potential relationship,akin to a volcano-type curve,was attributed to distinct NO hydrogenation mechanisms.Further Tafel analysis revealed the exchange current density(i0)and standard heterogeneous rate constant(k0)for CuO-NF,yielding 3.44×10^(-6)A cm^(-2)and 3.77×10^(-6)cm^(-2)s^(-1)when NORR was driven by overpotentials.These findings revealed the potential of CuO-NF for NO reduction and provided insights into the intricate interplay between crystal morphology,valence states,and electrochemical performance.展开更多
Electrochemical is considered an attractive approach to recycling the pollution NO(NORR)and producing the valuable NH_(3),which could simultaneously solve the two challenging problems,i.e.,NO removal and NH_(3)synthes...Electrochemical is considered an attractive approach to recycling the pollution NO(NORR)and producing the valuable NH_(3),which could simultaneously solve the two challenging problems,i.e.,NO removal and NH_(3)synthesis.Current research efforts focus less on NORR due to the lack of effective catalysts.Herein,based on DFT calculation,we try to explore effective pyrrole-type TM-N_(4)(TM=V,Cr,Mn,Fe,Co,Ni,Cu,Ru,Rh,Ta)catalysts for achieving the direct NORR.Among the investigated systems,Fe-N_(4)exhibits excellent catalytic activity and high NH_(3)selectivity.Moreover,the free energy of adsorption of N*has been proposed as a descriptor to predict and screen the effective TM-N_(4)catalyst for NORR and the crystal orbital halmilton populations(COHP)is used to describe the intrinsic relationship between metal atoms and the adsorption free energy of N^(*)intermediate.This work has provided a theoretical picture of TM-N4catalyzing NO to NH_(3),which will establish guidelines for the rational design of NORR catalysts and other electrochemical reactions.展开更多
死亡是每个生命无法逃离的最终结局,学会面对死亡就是学会更好地生活。本文通过对西方文学精品《小妇人》(Little Women)与《纳尔齐斯与歌尔德蒙》(Narzib und Goldmund)中瘟疫叙事的分析,启发读者在感受瘟疫肆虐的人间惨状时,也要积极...死亡是每个生命无法逃离的最终结局,学会面对死亡就是学会更好地生活。本文通过对西方文学精品《小妇人》(Little Women)与《纳尔齐斯与歌尔德蒙》(Narzib und Goldmund)中瘟疫叙事的分析,启发读者在感受瘟疫肆虐的人间惨状时,也要积极探讨死亡的意义及面对死亡应有的态度。展开更多
一氧化氮电还原反应将工业废气转化为有价值的氨,表现出极具潜力的应用前景.在本工作中,我们合成了具有高比表面积和丰富缺陷的氧化铜纳米片催化剂,在流动池中氨法拉第效率达到92.1%,在-0.2 V vs.RHE时,一氧化氮电还原电流密度和氨的生...一氧化氮电还原反应将工业废气转化为有价值的氨,表现出极具潜力的应用前景.在本工作中,我们合成了具有高比表面积和丰富缺陷的氧化铜纳米片催化剂,在流动池中氨法拉第效率达到92.1%,在-0.2 V vs.RHE时,一氧化氮电还原电流密度和氨的生产速率分别达到1.1 A cm^(-2)和7356μmol cm^(-2)h^(-1).在电流密度超过400 m A cm-2时,氨法拉第效率在50小时保持在80%以上.准原位X射线光电子能谱和原位X射线吸收光谱结果表明氧化铜纳米片在一氧化氮电还原过程中被电化学还原成单质铜.与铜纳米颗粒相比,氧化铜纳米片展现出较高的电化学表面积和一氧化氮电还原的内在活性.展开更多
基金funded by the Natural Science Foundation of China(No.21603109)the Henan Joint Fund of the National Natural Science Foundation of China(No.U1404216)+1 种基金the Scientific Research Program Funded by Shaanxi Provincial Education Department(No.20JK0676)the Special Fund of Tianshui Normal University,China(No.CXJ2020-08)。
文摘To reduce the greenhouse effect caused by the surgery of nitrogen-oxides concentration in the atmosphere and develop a future energy carrier of renewables,it is very critical to develop more efficient,controllable,and highly sensitive catalytic materials.In our work,we proposed that nitric oxide(NO),as a supplement to N_(2) for the synthesis of ammonia,which is equipped with a lower barrier.And the study highlighted the potential of CeO_(2)(111)nanosheets with La doping and oxygen vacancy(OV)as a high-performance,controllable material for NO capture at the site of Vo site,and separation the process of hydrogenation.We also reported that the E_(ads) of-1.12 eV with horizontal adsorption and the Bader charge of N increasing of 0.53|e|and O increasing of 0.17|e|at the most active site of reduction-OV predicted.It is worth noting thatΔG of NORR(NO reduction reaction)shows good performance(thermodynamically spontaneous reaction)to synthesize ammonia and water at room temperature in the theoretical calculation.
基金supported by the Fundamental Research Funds for the Central Universities(FRF-EYIT-23-07)。
文摘Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption and waste gas emissions.To address this,electrocatalytic nitric oxide reduction reaction(NORR)has emerged as a promising strategy to bridge NH3consumption to NH3production,harnessing renewable electricity for a sustainable future.Copper(Cu)stands out as a prominent electrocatalyst for NO reduction,given its exceptional NH3yield and selectivity.However,a crucial aspect that remains insufficiently explored is the effects of morphology and valence states of Cu on the NORR performance.In this investigation,we synthesized CuO nanowires(CuO-NF)and Cu nanocubes(Cu-NF)as cathodes through an in situ growth method.Remarkably,CuO-NF exhibited an impressive NH3yield of 0.50±0.02 mg cm^(-2)h^(-1)at-0.6 V vs.reversible hydrogen electrode(RHE)with faradaic efficiency of29,68%±1,35%,surpassing that of Cu-NF(0.17±0.01 mg cm^(-2)h^(-1),16.18%±1.40%).Throughout the electroreduction process,secondary cubes were generated on the CuO-NF surface,preserving their nanosheet cluster morphology,sustained by an abundant supply of subsurface oxygen(s-O)even after an extended duration of 10 h,until s-O depletion ensued.Conversely,Cu-NF exhibited inadequate s-O content,leading to rapid crystal collapse within the same timeframe.The distinctive current-potential relationship,akin to a volcano-type curve,was attributed to distinct NO hydrogenation mechanisms.Further Tafel analysis revealed the exchange current density(i0)and standard heterogeneous rate constant(k0)for CuO-NF,yielding 3.44×10^(-6)A cm^(-2)and 3.77×10^(-6)cm^(-2)s^(-1)when NORR was driven by overpotentials.These findings revealed the potential of CuO-NF for NO reduction and provided insights into the intricate interplay between crystal morphology,valence states,and electrochemical performance.
基金financially supported by the National Natural Science Foundation of China(Nos.21725103,52072362)National Key R&D Program of China(No.2021YFB4000401)Youth Innovation Promotion Association CAS(No.E1202002)。
文摘Electrochemical is considered an attractive approach to recycling the pollution NO(NORR)and producing the valuable NH_(3),which could simultaneously solve the two challenging problems,i.e.,NO removal and NH_(3)synthesis.Current research efforts focus less on NORR due to the lack of effective catalysts.Herein,based on DFT calculation,we try to explore effective pyrrole-type TM-N_(4)(TM=V,Cr,Mn,Fe,Co,Ni,Cu,Ru,Rh,Ta)catalysts for achieving the direct NORR.Among the investigated systems,Fe-N_(4)exhibits excellent catalytic activity and high NH_(3)selectivity.Moreover,the free energy of adsorption of N*has been proposed as a descriptor to predict and screen the effective TM-N_(4)catalyst for NORR and the crystal orbital halmilton populations(COHP)is used to describe the intrinsic relationship between metal atoms and the adsorption free energy of N^(*)intermediate.This work has provided a theoretical picture of TM-N4catalyzing NO to NH_(3),which will establish guidelines for the rational design of NORR catalysts and other electrochemical reactions.
基金supported by the National Key R&D Program of China (2023YFA1508002)the National Natural Science Foundation of China (22125205 and 92015302)+2 种基金the Fundamental Research Funds for the Central Universities (20720220008)Dalian National Laboratory for Clean Energy (DNL201923)the Photon Science Center for Carbon Neutrality。
文摘一氧化氮电还原反应将工业废气转化为有价值的氨,表现出极具潜力的应用前景.在本工作中,我们合成了具有高比表面积和丰富缺陷的氧化铜纳米片催化剂,在流动池中氨法拉第效率达到92.1%,在-0.2 V vs.RHE时,一氧化氮电还原电流密度和氨的生产速率分别达到1.1 A cm^(-2)和7356μmol cm^(-2)h^(-1).在电流密度超过400 m A cm-2时,氨法拉第效率在50小时保持在80%以上.准原位X射线光电子能谱和原位X射线吸收光谱结果表明氧化铜纳米片在一氧化氮电还原过程中被电化学还原成单质铜.与铜纳米颗粒相比,氧化铜纳米片展现出较高的电化学表面积和一氧化氮电还原的内在活性.
