Electrocatalytic nitrate reduction reaction(e-NO_(3)RR)offers a promising alternative method for nitrogen cycling and ammonia(NH3)production under ambient conditions.However,the method is still in the dilemma of lower...Electrocatalytic nitrate reduction reaction(e-NO_(3)RR)offers a promising alternative method for nitrogen cycling and ammonia(NH3)production under ambient conditions.However,the method is still in the dilemma of lowering the reaction overpotential and increasing the reaction activity.We successfully developed the composition-adjustable Co_(6)Mo_(6)C/Co/N-doped carbon(NC)catalysts by in situ carbonization of Co-based metal-organic framework(MOF)with the constrained phosphomolybdic acid.After adjusting the ratio of Co0 and Co_(6)Mo_(6)C,Co_(6)Mo_(6)C/Co/NC-3 could satisfy both NO_(3)−conversion at low potential and NH_(x)hydrogenation,and synthesize ammonia efficiently through the synergistic effect of Co0 and Co_(6)Mo_(6)C.It achieved an ammonia yield rate as 1233.2μg·h^(−1)·mgcat^(−1)and Faradaic efficiency of NH4+93.6%at−0.33 V vs.reversible hydrogen electrode(RHE).Importantly,density functional theory(DFT)calculations and experimental results have demonstrated for the first time the excellent adsorption of nitrite(NO_(2)^(−))by the Mo sites of Co_(6)Mo_(6)C during e-NO_(3)RR,avoiding the undesirable accumulation of NO_(2)^(−).展开更多
Electrochemical conversion of CO_(2)to CO is an economically feasible method for mitigating greenhouse gas emissions.Among various electrochemical approaches,solid oxide electrolysis cells(SOECs)show high potential fo...Electrochemical conversion of CO_(2)to CO is an economically feasible method for mitigating greenhouse gas emissions.Among various electrochemical approaches,solid oxide electrolysis cells(SOECs)show high potential for CO_(2)reduction reaction(CO_(2)-RR)due to their ability to operate at high temperatures,resulting in fast reaction kinetics and increased efficiency.Considering their main energy loss is still associated with the large overpotential at the fuel electrode,the development of the highly efficient and durable cathode for SOECs has been extensively searched after.Here,we propose an A-site doping strategy to enhance the properties of Sr_(2)Fe_(1.5)Mo_(0.5)O_(6−δ)(SFM),which improve its performance as a cathode in SOECs for CO_(2)-RR,demonstrating favorable activity and durability.The structural and physiochemical characterizations,together with DFT calculations,show that the partial replacement of Sr by Bi in the SFM double perovskite not only improves CO_(2) adsorption capability at the catalyst surface but also enhances oxygen ionic conduction inside the bulk oxide,resulting in enhanced CO_(2)electrocatalysis performance in SOECs.Specifically,a La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(0.2)O_(3−δ) (LSGM)electrolyte-supported single cell with the new Bi-doped SFM cathode demonstrates a large current density of 1620 mA cm^(−2) at a cell potential of 1.6 V at 850°C with good operational stability up to 200 h.Bi-doped SFM thus represents a highly promising cathode for ceramic CO_(2)electrolyzers and could accelerate our transition towards a carbon-neutral society.展开更多
In recent years, interest in hydrogen as a fuel has sharply increased in the field of alternative and green energy due to its high energy capability and zero-emission behaviour. As a result, research in the developmen...In recent years, interest in hydrogen as a fuel has sharply increased in the field of alternative and green energy due to its high energy capability and zero-emission behaviour. As a result, research in the development of new highly efficient methods for producing high-purity hydrogen is relevant. This paper presents, for the first time, the test results of an electrochemical cell with a proton-conducting La_(0.9)Sr_(0.1)ScO_(3-δ) electrolyte and symmetrical Sr_(1.95)Fe_(1.4)Ni_(0.1)Mo_(0.5)O_(6-δ)+ La_(0.9)Sr_(0.1)Sc_(0.9)Co_(0.1)O_(3-δ) electrodes as a hybrid setup for electricity generation in proton ceramic fuel cell mode, for hydrogen separation from H_(2)+ Ar mixture and the production of high-purity hydrogen from methane with simultaneous CO_(2) utilization.It was found that this electrochemical cell generates high flow rates of hydrogen during its separation through a proton-conducting membrane from H_(2)+ Ar mixture, about 500 cm^(3)h^(-1)cm^(-2)at a current density of 0.6 A cm^(-2)as well as about 370 cm^(3) h^(-1)cm^(-2)at a current density of 0.5 A cm^(-2) from CH_(4)+ CO_(2) mixture at 800 ℃ which shows that these cells are promising for hydrogen production.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22065030 and U22A20391)the Natural Science Foundation of Ningxia Province(No.2022AAC03109)X.M.L.expresses gratitude for the support received from the Ningxia Youth Talent Support Project of Science and Technology,as well as Professor Guidong Yang.
文摘Electrocatalytic nitrate reduction reaction(e-NO_(3)RR)offers a promising alternative method for nitrogen cycling and ammonia(NH3)production under ambient conditions.However,the method is still in the dilemma of lowering the reaction overpotential and increasing the reaction activity.We successfully developed the composition-adjustable Co_(6)Mo_(6)C/Co/N-doped carbon(NC)catalysts by in situ carbonization of Co-based metal-organic framework(MOF)with the constrained phosphomolybdic acid.After adjusting the ratio of Co0 and Co_(6)Mo_(6)C,Co_(6)Mo_(6)C/Co/NC-3 could satisfy both NO_(3)−conversion at low potential and NH_(x)hydrogenation,and synthesize ammonia efficiently through the synergistic effect of Co0 and Co_(6)Mo_(6)C.It achieved an ammonia yield rate as 1233.2μg·h^(−1)·mgcat^(−1)and Faradaic efficiency of NH4+93.6%at−0.33 V vs.reversible hydrogen electrode(RHE).Importantly,density functional theory(DFT)calculations and experimental results have demonstrated for the first time the excellent adsorption of nitrite(NO_(2)^(−))by the Mo sites of Co_(6)Mo_(6)C during e-NO_(3)RR,avoiding the undesirable accumulation of NO_(2)^(−).
基金financially supported by the State Key Laboratory of Clean Energy Utilization(Open Fund Project No.ZJUCEU2021001)Natural Science Foundation of Jiangsu Province(No.BK20221312).
文摘Electrochemical conversion of CO_(2)to CO is an economically feasible method for mitigating greenhouse gas emissions.Among various electrochemical approaches,solid oxide electrolysis cells(SOECs)show high potential for CO_(2)reduction reaction(CO_(2)-RR)due to their ability to operate at high temperatures,resulting in fast reaction kinetics and increased efficiency.Considering their main energy loss is still associated with the large overpotential at the fuel electrode,the development of the highly efficient and durable cathode for SOECs has been extensively searched after.Here,we propose an A-site doping strategy to enhance the properties of Sr_(2)Fe_(1.5)Mo_(0.5)O_(6−δ)(SFM),which improve its performance as a cathode in SOECs for CO_(2)-RR,demonstrating favorable activity and durability.The structural and physiochemical characterizations,together with DFT calculations,show that the partial replacement of Sr by Bi in the SFM double perovskite not only improves CO_(2) adsorption capability at the catalyst surface but also enhances oxygen ionic conduction inside the bulk oxide,resulting in enhanced CO_(2)electrocatalysis performance in SOECs.Specifically,a La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(0.2)O_(3−δ) (LSGM)electrolyte-supported single cell with the new Bi-doped SFM cathode demonstrates a large current density of 1620 mA cm^(−2) at a cell potential of 1.6 V at 850°C with good operational stability up to 200 h.Bi-doped SFM thus represents a highly promising cathode for ceramic CO_(2)electrolyzers and could accelerate our transition towards a carbon-neutral society.
文摘In recent years, interest in hydrogen as a fuel has sharply increased in the field of alternative and green energy due to its high energy capability and zero-emission behaviour. As a result, research in the development of new highly efficient methods for producing high-purity hydrogen is relevant. This paper presents, for the first time, the test results of an electrochemical cell with a proton-conducting La_(0.9)Sr_(0.1)ScO_(3-δ) electrolyte and symmetrical Sr_(1.95)Fe_(1.4)Ni_(0.1)Mo_(0.5)O_(6-δ)+ La_(0.9)Sr_(0.1)Sc_(0.9)Co_(0.1)O_(3-δ) electrodes as a hybrid setup for electricity generation in proton ceramic fuel cell mode, for hydrogen separation from H_(2)+ Ar mixture and the production of high-purity hydrogen from methane with simultaneous CO_(2) utilization.It was found that this electrochemical cell generates high flow rates of hydrogen during its separation through a proton-conducting membrane from H_(2)+ Ar mixture, about 500 cm^(3)h^(-1)cm^(-2)at a current density of 0.6 A cm^(-2)as well as about 370 cm^(3) h^(-1)cm^(-2)at a current density of 0.5 A cm^(-2) from CH_(4)+ CO_(2) mixture at 800 ℃ which shows that these cells are promising for hydrogen production.
