As virulence-determining genes, RR1 and RR2 encode the small subunit and large subunit of viral ribonucleotide reductase(RR) in pseudorabies virus which have been extensively studied in mice. However,their role in pig...As virulence-determining genes, RR1 and RR2 encode the small subunit and large subunit of viral ribonucleotide reductase(RR) in pseudorabies virus which have been extensively studied in mice. However,their role in pigs has not been adequately investigated. In this study, we deleted RR1 and RR2 genes based on a TK/g E/g I triple gene-deleted pseudorabies virus and tested its efficacy in pigs as a vaccine candidate. The rescued virus showed similar growth properties and plaque size in vitro as its parent strain. In an animal study, the virus could elicit humoral immune responses shown by generation of g B-specific antibodies and virus neutralizing antibodies.However, vaccination could not provide protection against virulent pseudorabies virus challenge since vaccinated pigs showed clinical pseudorabies-specific syndromes. The deficiency in protection may due to the generation of late and low levels of gB antibodies and virus neutralizing antibodies.展开更多
Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent...Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent bonds and the limited modifiability of COFs with irreversible covalent bonds restricted the enhancement of the pCO_(2)RR performance.Herein,three phthalocyanine-based COFs with ether-linked,CoOP,CoPOP,and CoBOP,were successfully prepared via in situ polycondensation using modifiable bis-phthalonitrile.CoBOP achieved a record of syngas performance in pCO_(2)RR systems with photosensitizers and sacrificial agents(CO 83.7 mmol g^(-1)h^(-1)and H_254.7 mmol g^(-1)h^(-1)),surpassing most COF photocatalysts.Additionally,CoOP,CoPOP,and CoBOP exhibit stabilities in extreme environments owing to their irreversible covalent bonds.Experimental and density functional theory analyses confirm that the optimally matched the lowest unoccupied molecular orbital of the linking unit between the photosensitizer and active unit endowed Co BOP with the highest photoelectron transfer efficiency among the three catalysts,boosting its pCO_(2)RR activity.This work is highly instructive for designing COFs with structure-adjustable and irreversible covalent bonds.展开更多
Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon di...Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.展开更多
CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient...CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient three-phase reaction interface that significantly enhances current density.However,current hydrophobic modification methods face difficulties in achieving precise and substantial control over wettability,and the hydrophobic modifiers tend to significantly impair the conductivity of the electrode and ion transport capabilities.This study employs Nafion ionomers to hydrophobically modify the threedimensional catalyst layer,revealing the bifunctionality of Nafion.The fluorinated backbone of Nafion ensures the hydrophobicity of the entire catalyst layer,while its sulfonic acid groups promote ion transport,without significantly affecting the conductivity of the electrode.Furthermore,by employing modifiers with distinct wettability characteristics,a highly efficient and large-scale manipulation of the hydrophilic/hydrophobic properties of the catalyst layer was successfully realized.The electrode,constructed with silver nanopowder as a representative catalyst and modified with the hydrophobic ionomer Nafion,exhibits a substantial enhancement in both catalytic activity and durability.The optimized electrode exhibited exceptional electrocatalytic performance in both flow cell and membrane electrode assembly(MEA)configurations.Notably,in the MEA,the electrode achieved a remarkable CO Faradaic efficiency(FE)of 93.3%at a total current density of 200 mA cm^(-2),while maintaining stable operation for over 62 h.展开更多
The need for bi-functional catalysts that facilit-ate both the oxygen reduction(ORR)and carbon dioxide re-duction(CO_(2)RR)reactions arises from their potential to help solve the critical problems of carbon neutrality...The need for bi-functional catalysts that facilit-ate both the oxygen reduction(ORR)and carbon dioxide re-duction(CO_(2)RR)reactions arises from their potential to help solve the critical problems of carbon neutrality and renew-able energy conversion.However,there are few reports on the development of bi-functional catalysts for zinc-air bat-tery-driven CO_(2)RR devices.We introduce a novel approach for synthesizing Fe_(2)N/Fe_(3)C species embedded in nitrogen-doped carbon nanofibers by electrospinning a solution of Hemin and polyacrylonitrile in N,N-dimethylformamide.The material has an exceptional catalytic performance,with a half-wave potential of 0.91 V versus RHE for the ORR and values of over 90%for both the selectivity and Faradaic efficiency for the CO_(2)RR.The high catalytic performances are attrib-uted to the strong coupling between the Fe_(3)C/Fe_(2)N heterostructure and the Fe-N-C sites in the nitrogen-doped carbon nan-ofibers.Notably,both Fe_(3)C and Fe_(2)N play distinct roles in both the ORR and CO_(2)RR.This investigation indicates a way for designing advanced carbon-based bi-functional catalysts for use in this field.展开更多
The conventional steelmaking process emits 1.8 tons of CO_(2) to produce 1 ton of crude steel,making the steel industry the world's largest emitting manufacturing sector.Here,we propose and demonstrate a renewable...The conventional steelmaking process emits 1.8 tons of CO_(2) to produce 1 ton of crude steel,making the steel industry the world's largest emitting manufacturing sector.Here,we propose and demonstrate a renewable route based on electrified carbon cycling,which significantly reduces CO_(2) emission by 83%.The critical step of the route involves electrochemical CO_(2) reduction(CO_(2)RR)to produce CO-rich syngas,which reduces iron ore into metallic iron(Fe_(x)O_(y)-to-Fe),effectively closing the carbon cycling.A technoeconomic analysis(TEA)reveals that the energy efficiency of this novel process is dependent on the operating parameters of CO_(2)RR,with optimal efficiency occurring at the current density range of 150-200mAcm^(-2).As a proof-of-concept study,sulfur vacancy(V_(S))-engineered Ag_(3)CuS_(2) was developed as a high-performance CO_(2)RR electrocatalyst.This catalyst yields a CO-rich syngas at a high Faradaic efficiency(FE)close to 100%at a cell voltage of 2.5 V.The CO_(2)RR-produced syngas effectively reduced iron oxide into metallic iron.The implementation of electrified carbon cycling significantly increases the utilization of electricity in steel production,reaching 88.7%.This research describes a sustainable way to reshape the ironmaking process and ultimately neutralize the steel industry.展开更多
The electrochemical CO_(2) reduction reaction(eCO_(2)RR),producing gaseous C_(2+)products such as ethylene(C_(2)H_(4)),represents a sustainable strategy to mitigate the greenhouse effect.Inspired by the promotion effe...The electrochemical CO_(2) reduction reaction(eCO_(2)RR),producing gaseous C_(2+)products such as ethylene(C_(2)H_(4)),represents a sustainable strategy to mitigate the greenhouse effect.Inspired by the promotion effect of the cyano group(-C≡N) for C-C coupling in organic chemistry,several cyano-containing organocatalysts have been found to be capable of directly converting CO_(2) into C_(2)H_(4) with-C≡N as the active center during the eCO_(2)RR.The selectivity of C_(2)H_(4) for the representative catalyst,metal-free dicyandiamide(DCD),reached 27.6 % after partial hydrogenation in KHCO_(3) solution.In addition,its selectivity can be further improved to 57.7 % when coupled with oriented Cu crystals.The experimental and computational results collectively reveal that charge redistribution between Cu{100} and DCD promotes the partial hydrogenation of the cyano group and lays the foundation for the reduced energy barrier for the CO_(2) reduction on-C≡N.This study breaks the limitations of traditional metal/metal oxide-based catalysts by using cyano-containing organocatalysts for direct C_(2+) product generation,expanding the eCO_(2)RR catalyst library.In addition,this research elucidates the role of charge redistribution and cyano group hydrogenation in lowering reaction barriers,providing fundamental guidance for the design of new organocatalysts.展开更多
Copper(Cu)is widely used in the electrochemical carbon dioxide reduction reaction(ECO_(2)RR)for efficient methane(CH_(4))product.However,the morphology and valence of Cu-based catalysts are usually unstable under reac...Copper(Cu)is widely used in the electrochemical carbon dioxide reduction reaction(ECO_(2)RR)for efficient methane(CH_(4))product.However,the morphology and valence of Cu-based catalysts are usually unstable under reaction conditions.In this work,we prepared Ce-doped MOF-199 precursor(Ce/HKUST-1)and further obtained nanoparticle electrocatalyst Ce/CuO_(x)-NPs by cyclic voltammetry(CV)pretreatment.The Faradic efficiency of methane(FE_(CH_(4)))maintains above 62%within a broad potential window of 350 mV and the maximum FE_(CH_(4))reaches 67.4%with a partial current density of 293 mA/cm^(2)at-1.6 V vs.a reversible hydrogen electrode.Catalyst characterization and theoretical calculations revealed that the unique electronic structure and large ionic radius of Cerium(Ce)not only promoted the generation of key intermediate*CO but also lowered energy barrier of the*CO to*CHO step.This study provides a novel and efficient catalyst for methane production in ECO_(2)RR and offers profound insights into constructing high performance Cu-based catalysts.展开更多
基金supported by grant from Major Science and Technology Program in Henan Province (131100110200)Innovation Scientists and Technicians Troop Construction Projects of Henan Province (142101510001)+1 种基金Talents Plan for Scientific and Technological Innovation in Henan Province (144200510002)Science and Technology Innovation team in Henan Province (C20130005)
文摘As virulence-determining genes, RR1 and RR2 encode the small subunit and large subunit of viral ribonucleotide reductase(RR) in pseudorabies virus which have been extensively studied in mice. However,their role in pigs has not been adequately investigated. In this study, we deleted RR1 and RR2 genes based on a TK/g E/g I triple gene-deleted pseudorabies virus and tested its efficacy in pigs as a vaccine candidate. The rescued virus showed similar growth properties and plaque size in vitro as its parent strain. In an animal study, the virus could elicit humoral immune responses shown by generation of g B-specific antibodies and virus neutralizing antibodies.However, vaccination could not provide protection against virulent pseudorabies virus challenge since vaccinated pigs showed clinical pseudorabies-specific syndromes. The deficiency in protection may due to the generation of late and low levels of gB antibodies and virus neutralizing antibodies.
基金financially supported by the Innovation Capability Support Program of Shaanxi—Science and Technology Innovation Team Project(No.2025RS-CXTD-024)the Fundamental Research Foundation of SHCCIG New Materials Technology Research Institute Co.,Ltd(No.D5204230171)+3 种基金the Fundamental Research Funds for the Central Universities(G2025KY05240)the Natural Science Basic Research Program of Shaanxi(Program No.2024JC-YBQN-0073)the Fundamental Research Funds for the Central Universities(No.D5000250204)Young Talent Fund of Association for Science and Technology in Shaanxi(No.20230101)。
文摘Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent bonds and the limited modifiability of COFs with irreversible covalent bonds restricted the enhancement of the pCO_(2)RR performance.Herein,three phthalocyanine-based COFs with ether-linked,CoOP,CoPOP,and CoBOP,were successfully prepared via in situ polycondensation using modifiable bis-phthalonitrile.CoBOP achieved a record of syngas performance in pCO_(2)RR systems with photosensitizers and sacrificial agents(CO 83.7 mmol g^(-1)h^(-1)and H_254.7 mmol g^(-1)h^(-1)),surpassing most COF photocatalysts.Additionally,CoOP,CoPOP,and CoBOP exhibit stabilities in extreme environments owing to their irreversible covalent bonds.Experimental and density functional theory analyses confirm that the optimally matched the lowest unoccupied molecular orbital of the linking unit between the photosensitizer and active unit endowed Co BOP with the highest photoelectron transfer efficiency among the three catalysts,boosting its pCO_(2)RR activity.This work is highly instructive for designing COFs with structure-adjustable and irreversible covalent bonds.
基金financially supported by the National Natural Science Foundation of China(52271200)Guangdong Basic and Applied Basic Research Foundation(2024A1515010393)USTB MatCom of Beijing Advanced Innovation Center for Materials Genome Engineering。
文摘Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.
基金National Key R&D Program of China(2023YFA1507902,2021YFA1500804)the National Natural Science Foundation of China(22121004,22038009,22250008)+2 种基金the Haihe Laboratory of Sustainable Chemical Transformations(CYZC202107)the Program of Introducing Talents of Discipline to Universities,China(No.BP0618007)the Xplorer Prize,China,for their financial support。
文摘CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient three-phase reaction interface that significantly enhances current density.However,current hydrophobic modification methods face difficulties in achieving precise and substantial control over wettability,and the hydrophobic modifiers tend to significantly impair the conductivity of the electrode and ion transport capabilities.This study employs Nafion ionomers to hydrophobically modify the threedimensional catalyst layer,revealing the bifunctionality of Nafion.The fluorinated backbone of Nafion ensures the hydrophobicity of the entire catalyst layer,while its sulfonic acid groups promote ion transport,without significantly affecting the conductivity of the electrode.Furthermore,by employing modifiers with distinct wettability characteristics,a highly efficient and large-scale manipulation of the hydrophilic/hydrophobic properties of the catalyst layer was successfully realized.The electrode,constructed with silver nanopowder as a representative catalyst and modified with the hydrophobic ionomer Nafion,exhibits a substantial enhancement in both catalytic activity and durability.The optimized electrode exhibited exceptional electrocatalytic performance in both flow cell and membrane electrode assembly(MEA)configurations.Notably,in the MEA,the electrode achieved a remarkable CO Faradaic efficiency(FE)of 93.3%at a total current density of 200 mA cm^(-2),while maintaining stable operation for over 62 h.
文摘The need for bi-functional catalysts that facilit-ate both the oxygen reduction(ORR)and carbon dioxide re-duction(CO_(2)RR)reactions arises from their potential to help solve the critical problems of carbon neutrality and renew-able energy conversion.However,there are few reports on the development of bi-functional catalysts for zinc-air bat-tery-driven CO_(2)RR devices.We introduce a novel approach for synthesizing Fe_(2)N/Fe_(3)C species embedded in nitrogen-doped carbon nanofibers by electrospinning a solution of Hemin and polyacrylonitrile in N,N-dimethylformamide.The material has an exceptional catalytic performance,with a half-wave potential of 0.91 V versus RHE for the ORR and values of over 90%for both the selectivity and Faradaic efficiency for the CO_(2)RR.The high catalytic performances are attrib-uted to the strong coupling between the Fe_(3)C/Fe_(2)N heterostructure and the Fe-N-C sites in the nitrogen-doped carbon nan-ofibers.Notably,both Fe_(3)C and Fe_(2)N play distinct roles in both the ORR and CO_(2)RR.This investigation indicates a way for designing advanced carbon-based bi-functional catalysts for use in this field.
基金funded by the National Natural Science Foundation of China(U23A20545,52331001)China BaoWu Low Carbon Metallurgy Innovation Foundation-BWLCF202113the Fundamental Research Funds for the Central Universities(N2202012).
文摘The conventional steelmaking process emits 1.8 tons of CO_(2) to produce 1 ton of crude steel,making the steel industry the world's largest emitting manufacturing sector.Here,we propose and demonstrate a renewable route based on electrified carbon cycling,which significantly reduces CO_(2) emission by 83%.The critical step of the route involves electrochemical CO_(2) reduction(CO_(2)RR)to produce CO-rich syngas,which reduces iron ore into metallic iron(Fe_(x)O_(y)-to-Fe),effectively closing the carbon cycling.A technoeconomic analysis(TEA)reveals that the energy efficiency of this novel process is dependent on the operating parameters of CO_(2)RR,with optimal efficiency occurring at the current density range of 150-200mAcm^(-2).As a proof-of-concept study,sulfur vacancy(V_(S))-engineered Ag_(3)CuS_(2) was developed as a high-performance CO_(2)RR electrocatalyst.This catalyst yields a CO-rich syngas at a high Faradaic efficiency(FE)close to 100%at a cell voltage of 2.5 V.The CO_(2)RR-produced syngas effectively reduced iron oxide into metallic iron.The implementation of electrified carbon cycling significantly increases the utilization of electricity in steel production,reaching 88.7%.This research describes a sustainable way to reshape the ironmaking process and ultimately neutralize the steel industry.
基金financial support provided by the National Natural Science Foundation of China (52472304)。
文摘The electrochemical CO_(2) reduction reaction(eCO_(2)RR),producing gaseous C_(2+)products such as ethylene(C_(2)H_(4)),represents a sustainable strategy to mitigate the greenhouse effect.Inspired by the promotion effect of the cyano group(-C≡N) for C-C coupling in organic chemistry,several cyano-containing organocatalysts have been found to be capable of directly converting CO_(2) into C_(2)H_(4) with-C≡N as the active center during the eCO_(2)RR.The selectivity of C_(2)H_(4) for the representative catalyst,metal-free dicyandiamide(DCD),reached 27.6 % after partial hydrogenation in KHCO_(3) solution.In addition,its selectivity can be further improved to 57.7 % when coupled with oriented Cu crystals.The experimental and computational results collectively reveal that charge redistribution between Cu{100} and DCD promotes the partial hydrogenation of the cyano group and lays the foundation for the reduced energy barrier for the CO_(2) reduction on-C≡N.This study breaks the limitations of traditional metal/metal oxide-based catalysts by using cyano-containing organocatalysts for direct C_(2+) product generation,expanding the eCO_(2)RR catalyst library.In addition,this research elucidates the role of charge redistribution and cyano group hydrogenation in lowering reaction barriers,providing fundamental guidance for the design of new organocatalysts.
基金the funding support from the National Natural Science Foundation of China(No.22308066)the Science and Technology Major Program of Guangxi(No.Guike AA23062018)+2 种基金the Guangxi Science and Technology Base and Talent Special Project(Nos.2021AC19353,2022AC20018,AD23026311)the Natural Science Foundation of Guangxi Province(No.2024GXNSFAA010271)the Innovation Project of Guangxi Graduate Education(No.YCBZ2022012)。
文摘Copper(Cu)is widely used in the electrochemical carbon dioxide reduction reaction(ECO_(2)RR)for efficient methane(CH_(4))product.However,the morphology and valence of Cu-based catalysts are usually unstable under reaction conditions.In this work,we prepared Ce-doped MOF-199 precursor(Ce/HKUST-1)and further obtained nanoparticle electrocatalyst Ce/CuO_(x)-NPs by cyclic voltammetry(CV)pretreatment.The Faradic efficiency of methane(FE_(CH_(4)))maintains above 62%within a broad potential window of 350 mV and the maximum FE_(CH_(4))reaches 67.4%with a partial current density of 293 mA/cm^(2)at-1.6 V vs.a reversible hydrogen electrode.Catalyst characterization and theoretical calculations revealed that the unique electronic structure and large ionic radius of Cerium(Ce)not only promoted the generation of key intermediate*CO but also lowered energy barrier of the*CO to*CHO step.This study provides a novel and efficient catalyst for methane production in ECO_(2)RR and offers profound insights into constructing high performance Cu-based catalysts.
