Covalent organic frameworks(COFs)are newly developed crystalline substances that are garnering growing interest because of their ultrahigh porosity,crystalline nature,and easy-modified architecture,showing promise in ...Covalent organic frameworks(COFs)are newly developed crystalline substances that are garnering growing interest because of their ultrahigh porosity,crystalline nature,and easy-modified architecture,showing promise in the field of photocatalysis.However,it is difficult for pure COFs materials to achieve excellent photocatalytic hydrogen production due to their severe carrier recombination problems.To mitigate this crucial issue,establishing heterojunction is deemed an effective approach.Nonetheless,many of the metal-containing materials that have been used to construct heterojunctions with COFs own a number of drawbacks,including small specific surface area and rare active sites(for inorganic semiconductor materials),wider bandgaps and higher preparation costs(for MOFs).Therefore,it is necessary to choose metal-free materials that are easy to prepare.Red phosphorus(RP),as a semiconductor material without metal components,with suitable bandgap,moderate redox potential,relatively minimal toxicity,is affordable and readily available.Herein,a range of RP/TpPa-1-COF(RP/TP1C)composites have been successfully prepared through solvothermal method.The two-dimensional structure of the two materials causes strong interactions between the materials,and the construction of heterojunctions effectively inhibits the recombination of photogenic charge carriers.As a consequence,the 9%RP/TP1C composite,with the optimal photocatalytic ability,achieves a photocatalytic H2 evolution rate of 6.93 mmol g^(-1) h^(-1),demonstrating a 10.19-fold increase compared to that of bare RP and a 4.08-fold improvement over that of pure TP1C.This article offers a novel and innovative method for the advancement of efficient COF-based photocatalysts.展开更多
Red phosphorus has been well-recognized as promising anode materials for lithium-ion batteries(LIBs)and potassium-ion batteries(PIBs)due to its extremely high theoretical capacity and low cost.However,the huge volume ...Red phosphorus has been well-recognized as promising anode materials for lithium-ion batteries(LIBs)and potassium-ion batteries(PIBs)due to its extremely high theoretical capacity and low cost.However,the huge volume change and poor electric conductivity severely limit its further practical application.Herein,the nanoscale ultrafine red phosphorus has been successfully confined in a three-dimensional pitch-based porous carbon skeleton composed of well-interconnected carbon nanosheets through the vaporization-condensation method.Except for the traditional requirement of high electric conductivity and stable mechanical stability,the micropores and small mesopores in the porous carbon matrix centered at 1 to 3 nm and the abundant amount of oxygen-containing functional groups are also beneficial for the high loading and dispersion of red phosphorus.As anode for LIBs,the composite exhibits high reversible discharge capacities of 968 mAh g^(-1),excellent rate capabilities of 593 mAh g^(-1)at 2 A g^(-1),and long cycle performance of 557 mAh g^(-1)at 2 A g^(-1).More impressively,as the anode for PIBs,the composite presents a high reversible capacity of 661 mAh g^(-1)and a stable capacity of 312 mAh g^(-1)at 0.5 A g^(-1)for 500 cycles with a capacity retention up to 84.3%.This work not only sheds light on the structure design of carbon hosts with specific pore structure but also open an avenue for high value-added utilization of coal tar pitch.展开更多
Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dime...Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dimensional nitrogen‐doped porous carbon(1D/3D NPC)is prepared by carbonizing the composite of Zn‐MOF‐74 crystals in situ grown on a commercial melamine sponge(MS),for electrochemical CO_(2) reduction reaction(CO_(2)RR).The 1D/3D NPC exhibits a high CO/H_(2) ratio(5.06)and CO yield(31 mmol g^(−1)h^(−1))at−0.55 V,which are 13.7 times and 21.4 times those of 1D porous carbon(derived from Zn‐MOF‐74)and N‐doped carbon(carbonized by MS),respectively.This is attributed to the unique spatial environment of 1D/3D NPC,which increases the adsorption capacity of CO_(2) and promotes electron transfer from the 3D N‐doped carbon framework to 1D carbon,improving the reaction kinetics of CO_(2)RR.Experimental results and charge density difference plots indicate that the active site of CO_(2)RR is the positively charged carbon atom adjacent to graphitic N on 1D carbon and the active site of HER is the pyridinic N on 1D carbon.The presence of pyridinic N and pyrrolic N reduces the number of electron transfer,decreasing the reaction kinetics and the activity of CO_(2)RR.The CO/H_(2) ratio is related to the distribution of N species and the specific surface area,which are determined by the degree of spatial confinement effect.The CO/H_(2) ratios can be regulated by adjusting the carbonization temperature to adjust the degree of spatial confinement effect.Given the low cost of feedstock and easy strategy,1D/3D NPC catalysts have great potential for industrial application.展开更多
Background:Hypertrophy of the ligamentumflavum(HLF)is a common contributor to spinal stenosis which results in significant neurological impairments.Circular RNA(circRNA)circ_0003609 has been linked to HLF;however,the ex...Background:Hypertrophy of the ligamentumflavum(HLF)is a common contributor to spinal stenosis which results in significant neurological impairments.Circular RNA(circRNA)circ_0003609 has been linked to HLF;however,the exact mechanism by which it causes this disease is unclear.Methods:Circ_0003609 expressions were regulated in HLF cells by overexpression vectors and RNA interference.Cell proliferation andfibrosis-related gene expression were checked by the Cell Counting Kit-8(CCK-8)assay and western blotting.CircBank’s prediction of the association between miR-155 and circ_0003609 was supported by a dual-luciferase reporter experiment.The function of the miR-155/sirtuin 1(SIRT1)axis in controlling HLFfibrosis was further examined.Results:Overexpression of circ_0003609 suppressed HLF cell propagation andfibrosis compared to its silencing.It was found that circ_0003609 served as the sponge for miR-155 and that the circ_0003609/miR-155 axis controlled thefibrosis of HLF cells.It was found that circ_0003609 acted as a sponge for miR-155,regulating thefibrosis of HLF cells.Further,miR-155 targets SIRT1,and the miR-155/SIRT1 axis promotes HLF cellfibrosis.Conclusion:Circ_0003609 ameliorates hypertrophied ligamentumflavum(LF)by modulating the miR-155/SIRT1 axis,indicating a potential treatment approach for HLF.展开更多
Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineere...Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance.Among various types of promising nanomaterials,metal–organic frameworks(MOFs)are competitive candidates for developing efficient electrocatalytic NH_(3) synthesis from simple nitrogen-containing molecules or ions,such as N_(2) and NO_(3)^(−).In this review,recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH_(3) are collected,categorized,and discussed,including their application in the N_(2) reduction reaction(NRR)and the NO_(3)^(−)reduction reaction(NO3RR).Firstly,the fundamental principles are illustrated,such as plausible mechanisms of NH_(3) generation from N_(2) and NO_(3)^(−),the apparatus of corresponding electrocatalysis,parameters for evaluation of reaction efficiency,and detection methods of yielding NH_(3).Then,the electrocatalysts for NRR processes are discussed in detail,including pristine MOFs,MOF-hybrids,MOF-derived N-doped porous carbons,single atomic catalysts from pyrolysis of MOFs,and other MOF-related materials.Subsequently,MOF-related NO3RR processes are also listed and discussed.Finally,the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH_(3) synthesis are presented,such as the evolution of investigation methods with artificial intelligence,innovation in synthetic methods of MOF-related catalysts,advancement of characterization techniques,and extended electrocatalytic reactions.展开更多
Electrocatalytic nitrogen reduction reaction is a carbon-free and energy-saving strategy for efficient synthesis of ammonia under ambient conditions.Here,we report the synthesis of nanosized Bi2O3 particles grown on f...Electrocatalytic nitrogen reduction reaction is a carbon-free and energy-saving strategy for efficient synthesis of ammonia under ambient conditions.Here,we report the synthesis of nanosized Bi2O3 particles grown on functionalized exfoliated graphene(Bi2O3/FEG)via a facile electrochemical deposition method.The obtained free-standing Bi2O3/FEG achieves a high Faradaic efficiency of 11.2%and a large NH3 yield of 4.21±0.14μgNH3 h^-1 cm^-2 at-0.5 V versus reversible hydrogen electrode in 0.1 M Na2SO4,better than that in the strong acidic and basic media.Benefiting from its strong interaction of Bi 6p band with the N2p orbitals,binder-free characteristic,and facile electron transfer,Bi2O3/FEG achieves superior catalytic performance and excellent long-term stability as compared with most of the previous reported catalysts.This study is significant to design low-cost,high-efficient Bi-based electrocatalysts for electrochemical ammonia synthesis.展开更多
In the viewpoint of ammonia economy,electrochemical N2 reduction reaction(NRR)under mild condition is a very promising approach for sustainable development.By virtue of robust activity and low cost,transition-metalbas...In the viewpoint of ammonia economy,electrochemical N2 reduction reaction(NRR)under mild condition is a very promising approach for sustainable development.By virtue of robust activity and low cost,transition-metalbased materials become one kind of the most attractive electrocatalysts in realizing ammonia synthesis to the industrial level.However,the investigation related to NRR electrocatalysts still mainly rely on costly substance or fabrication process,which greatly restrict their large-scale applications.In this work,a simple fabricated FeS2 electrode is adopted as NRR catalysts.The abundant surface defects due to the existence of Cr element,as well as the synergistic effect between FeS2 crystal planes provided excellent electrocatalytic performance with a high NH3 yield rate(11.5μg h^-1mg^-1 Fe)and Faradaic efficiency(14.6%)at-0.2 V vs.reversible hydrogen electrode(RHE)toward NRR under ambient conditions.The superior catalytic performance of such non-precious metal catalysts would strongly promote the application of NRR process industrially.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52071171,52202248,22101105)Liaoning Province Centrally Guided Local Science and Technology Development Fund Program(2024JH6/100700010,2024JH6/100700011)+8 种基金Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(2024-35)Open Research Fund of Guangdong Advanced Carbon Materials Co.,Ltd.(Kargen-2024B1001),and Key Research Project of Department of Education of Liaoning Province(LJKZZ20220015)T.M.acknowledged the Australian Research Council(ARC)through Future Fellowship(FT210100298)Discovery Project(DP220100603)Linkage Project(LP210200504,LP220100088,LP230200897)Industrial Transformation Research Hub(IH240100009)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077)the Australian Renewable Energy Agency(ARENA)as part of ARENA's Transformative Research Accelerating Commercialisation Program(TM021)European Commission's Australia-Spain Network for Innovation and Research Excellence(AuSpire)。
文摘Covalent organic frameworks(COFs)are newly developed crystalline substances that are garnering growing interest because of their ultrahigh porosity,crystalline nature,and easy-modified architecture,showing promise in the field of photocatalysis.However,it is difficult for pure COFs materials to achieve excellent photocatalytic hydrogen production due to their severe carrier recombination problems.To mitigate this crucial issue,establishing heterojunction is deemed an effective approach.Nonetheless,many of the metal-containing materials that have been used to construct heterojunctions with COFs own a number of drawbacks,including small specific surface area and rare active sites(for inorganic semiconductor materials),wider bandgaps and higher preparation costs(for MOFs).Therefore,it is necessary to choose metal-free materials that are easy to prepare.Red phosphorus(RP),as a semiconductor material without metal components,with suitable bandgap,moderate redox potential,relatively minimal toxicity,is affordable and readily available.Herein,a range of RP/TpPa-1-COF(RP/TP1C)composites have been successfully prepared through solvothermal method.The two-dimensional structure of the two materials causes strong interactions between the materials,and the construction of heterojunctions effectively inhibits the recombination of photogenic charge carriers.As a consequence,the 9%RP/TP1C composite,with the optimal photocatalytic ability,achieves a photocatalytic H2 evolution rate of 6.93 mmol g^(-1) h^(-1),demonstrating a 10.19-fold increase compared to that of bare RP and a 4.08-fold improvement over that of pure TP1C.This article offers a novel and innovative method for the advancement of efficient COF-based photocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.52071171,52202248,22208138)Natural Science Foundation of Liaoning Province(2020-MS-137,2023-MS-140)+7 种基金Doctoral Start-up Foundation of Liaoning Province,China(2020-BS-081)Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)Linkage Project(LP210100467,LP210200504,LP210200345,LP220100088)Industrial Transformation Training center(IC180100005)schemesCSIRO Energy center and Kick-Start Project,and the Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077)Young Scientific Project of the Department of Education of Liaoning Province(LJKQZ20222263,LQN202008)Anhui Province Key Laboratory of Coal Clean Conversion and High Valued Utilization,Anhui University of Technology(CHV22-05).
文摘Red phosphorus has been well-recognized as promising anode materials for lithium-ion batteries(LIBs)and potassium-ion batteries(PIBs)due to its extremely high theoretical capacity and low cost.However,the huge volume change and poor electric conductivity severely limit its further practical application.Herein,the nanoscale ultrafine red phosphorus has been successfully confined in a three-dimensional pitch-based porous carbon skeleton composed of well-interconnected carbon nanosheets through the vaporization-condensation method.Except for the traditional requirement of high electric conductivity and stable mechanical stability,the micropores and small mesopores in the porous carbon matrix centered at 1 to 3 nm and the abundant amount of oxygen-containing functional groups are also beneficial for the high loading and dispersion of red phosphorus.As anode for LIBs,the composite exhibits high reversible discharge capacities of 968 mAh g^(-1),excellent rate capabilities of 593 mAh g^(-1)at 2 A g^(-1),and long cycle performance of 557 mAh g^(-1)at 2 A g^(-1).More impressively,as the anode for PIBs,the composite presents a high reversible capacity of 661 mAh g^(-1)and a stable capacity of 312 mAh g^(-1)at 0.5 A g^(-1)for 500 cycles with a capacity retention up to 84.3%.This work not only sheds light on the structure design of carbon hosts with specific pore structure but also open an avenue for high value-added utilization of coal tar pitch.
基金National Natural Science Foundation of China,Grant/Award Numbers:51873085,52071171,52202248The Australian Government through the Cooperative Research Centres Projects,Grant/Award Number:CRCPⅩⅢ000077+10 种基金Linkage Project,Grant/Award Numbers:LP210100467,LP210200345,LP210200504,LP220100088Natural Science Foundation of Liaoning Province‐Outstanding Youth Foundation,Grant/Award Number:2022‐YQ‐14Discovery Project,Grant/Award Number:DP220100603China Scholarship Council(CSC Scholarship),Grant/Award Number:202006800009Liaoning Revitalization Talents Program,Grant/Award Number:XLYC2007056Australian Research Council(ARC)through Future Fellowship,Grant/Award Numbers:FT210100298,FT210100806Shenyang Science and Technology Project,Grant/Award Number:21‐108‐9‐04Industrial Transformation Training Centre schemes,Grant/Award Number:IC180100005Natural Science Foundation of Liaoning Province,Grant/Award Number:2020‐MS‐137Key Research Project of Department of Education of Liaoning Province,Grant/Award Number:LJKZZ20220015Liaoning BaiQianWan Talents Program,Grant/Award Number:LNBQW2018B0048。
文摘Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dimensional nitrogen‐doped porous carbon(1D/3D NPC)is prepared by carbonizing the composite of Zn‐MOF‐74 crystals in situ grown on a commercial melamine sponge(MS),for electrochemical CO_(2) reduction reaction(CO_(2)RR).The 1D/3D NPC exhibits a high CO/H_(2) ratio(5.06)and CO yield(31 mmol g^(−1)h^(−1))at−0.55 V,which are 13.7 times and 21.4 times those of 1D porous carbon(derived from Zn‐MOF‐74)and N‐doped carbon(carbonized by MS),respectively.This is attributed to the unique spatial environment of 1D/3D NPC,which increases the adsorption capacity of CO_(2) and promotes electron transfer from the 3D N‐doped carbon framework to 1D carbon,improving the reaction kinetics of CO_(2)RR.Experimental results and charge density difference plots indicate that the active site of CO_(2)RR is the positively charged carbon atom adjacent to graphitic N on 1D carbon and the active site of HER is the pyridinic N on 1D carbon.The presence of pyridinic N and pyrrolic N reduces the number of electron transfer,decreasing the reaction kinetics and the activity of CO_(2)RR.The CO/H_(2) ratio is related to the distribution of N species and the specific surface area,which are determined by the degree of spatial confinement effect.The CO/H_(2) ratios can be regulated by adjusting the carbonization temperature to adjust the degree of spatial confinement effect.Given the low cost of feedstock and easy strategy,1D/3D NPC catalysts have great potential for industrial application.
基金This research was supported by the Shanghai Natural Science Fund(No.21ZR1447500)Shanghai Jiao Tong University School of Medicine Affiliated Renji Hospital Baoshan Branch Medical Key Specialty Construction Project(No.rbzdzk-2023-001).
文摘Background:Hypertrophy of the ligamentumflavum(HLF)is a common contributor to spinal stenosis which results in significant neurological impairments.Circular RNA(circRNA)circ_0003609 has been linked to HLF;however,the exact mechanism by which it causes this disease is unclear.Methods:Circ_0003609 expressions were regulated in HLF cells by overexpression vectors and RNA interference.Cell proliferation andfibrosis-related gene expression were checked by the Cell Counting Kit-8(CCK-8)assay and western blotting.CircBank’s prediction of the association between miR-155 and circ_0003609 was supported by a dual-luciferase reporter experiment.The function of the miR-155/sirtuin 1(SIRT1)axis in controlling HLFfibrosis was further examined.Results:Overexpression of circ_0003609 suppressed HLF cell propagation andfibrosis compared to its silencing.It was found that circ_0003609 served as the sponge for miR-155 and that the circ_0003609/miR-155 axis controlled thefibrosis of HLF cells.It was found that circ_0003609 acted as a sponge for miR-155,regulating thefibrosis of HLF cells.Further,miR-155 targets SIRT1,and the miR-155/SIRT1 axis promotes HLF cellfibrosis.Conclusion:Circ_0003609 ameliorates hypertrophied ligamentumflavum(LF)by modulating the miR-155/SIRT1 axis,indicating a potential treatment approach for HLF.
基金support from the Natural Science Foundation of Liaoning Province(general program)(2020-MS-137)T.J.White would like to thank the MOE2019-T2-2-032 grant and Monetary Academic Resources for Research Grant 001561-00001 in Nanyang Technological University,Singapore+9 种基金T.Ma would like to thank the National Natural Science Foundation of China(Nos.52071171,52202248)Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Shenyang Science and Technology Project(21-108-9-04)Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)Linkage Project(LP210100467,LP210200504,LP210200345,LP220100088)Industrial Transformation Training Centre(IC180100005)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077)F.Wei would like to thank the A^(*)STAR career development fund C210112054Singapore structural metal alloy program grant No.A18b1B0061.A.K.Cheetham would like to thank the Ras al Khaimah Centre for Advanced Materials.
文摘Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance.Among various types of promising nanomaterials,metal–organic frameworks(MOFs)are competitive candidates for developing efficient electrocatalytic NH_(3) synthesis from simple nitrogen-containing molecules or ions,such as N_(2) and NO_(3)^(−).In this review,recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH_(3) are collected,categorized,and discussed,including their application in the N_(2) reduction reaction(NRR)and the NO_(3)^(−)reduction reaction(NO3RR).Firstly,the fundamental principles are illustrated,such as plausible mechanisms of NH_(3) generation from N_(2) and NO_(3)^(−),the apparatus of corresponding electrocatalysis,parameters for evaluation of reaction efficiency,and detection methods of yielding NH_(3).Then,the electrocatalysts for NRR processes are discussed in detail,including pristine MOFs,MOF-hybrids,MOF-derived N-doped porous carbons,single atomic catalysts from pyrolysis of MOFs,and other MOF-related materials.Subsequently,MOF-related NO3RR processes are also listed and discussed.Finally,the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH_(3) synthesis are presented,such as the evolution of investigation methods with artificial intelligence,innovation in synthetic methods of MOF-related catalysts,advancement of characterization techniques,and extended electrocatalytic reactions.
基金financially supported by Liaoning Revitalization Talents Program—Pan Deng Scholars(XLYC1802005)Liaoning BaiQianWan Talents Program+4 种基金the National Science Fund of Liaoning Province for Excellent Young ScholarsScience and Technology Innovative Talents Support Program of Shenyang(RC180166)Australian Research Council(ARC)through Discovery Early Career Researcher Award(DE150101306)and Linkage Project(LP160100927)Faculty of Science Strategic Investment Funding of University of NewcastleCSIRO Newcastl Energy Centre。
文摘Electrocatalytic nitrogen reduction reaction is a carbon-free and energy-saving strategy for efficient synthesis of ammonia under ambient conditions.Here,we report the synthesis of nanosized Bi2O3 particles grown on functionalized exfoliated graphene(Bi2O3/FEG)via a facile electrochemical deposition method.The obtained free-standing Bi2O3/FEG achieves a high Faradaic efficiency of 11.2%and a large NH3 yield of 4.21±0.14μgNH3 h^-1 cm^-2 at-0.5 V versus reversible hydrogen electrode in 0.1 M Na2SO4,better than that in the strong acidic and basic media.Benefiting from its strong interaction of Bi 6p band with the N2p orbitals,binder-free characteristic,and facile electron transfer,Bi2O3/FEG achieves superior catalytic performance and excellent long-term stability as compared with most of the previous reported catalysts.This study is significant to design low-cost,high-efficient Bi-based electrocatalysts for electrochemical ammonia synthesis.
基金Liaoning Revitalization Talents Program-Pan Deng Scholars(XLYC1802005)Liaoning Bai-QianWan Talents Program,the National Science Fund of Liaoning Province for Excellent Young Scholars,Science and Technology Innovative Talents Support Program of Shenyang(RC180166)+2 种基金Australian Research Council(ARC)through Discovery Early Career Researcher Award(DE150101306)Linkage Project(LP160100927)Faculty of Science Strategic Investment Funding 2019 of University of Newcastle,and CSIRO Energy,Australia.
文摘In the viewpoint of ammonia economy,electrochemical N2 reduction reaction(NRR)under mild condition is a very promising approach for sustainable development.By virtue of robust activity and low cost,transition-metalbased materials become one kind of the most attractive electrocatalysts in realizing ammonia synthesis to the industrial level.However,the investigation related to NRR electrocatalysts still mainly rely on costly substance or fabrication process,which greatly restrict their large-scale applications.In this work,a simple fabricated FeS2 electrode is adopted as NRR catalysts.The abundant surface defects due to the existence of Cr element,as well as the synergistic effect between FeS2 crystal planes provided excellent electrocatalytic performance with a high NH3 yield rate(11.5μg h^-1mg^-1 Fe)and Faradaic efficiency(14.6%)at-0.2 V vs.reversible hydrogen electrode(RHE)toward NRR under ambient conditions.The superior catalytic performance of such non-precious metal catalysts would strongly promote the application of NRR process industrially.