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
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
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
Cu^(2+)in copper-based catalysts can facilitate the hydrogenation of the CH_(4)production pathway via the electrochemical carbon dioxide reduction reaction(ECRR).However,Cu^(2+)species in copper oxides are unstable an...Cu^(2+)in copper-based catalysts can facilitate the hydrogenation of the CH_(4)production pathway via the electrochemical carbon dioxide reduction reaction(ECRR).However,Cu^(2+)species in copper oxides are unstable and have been revealed to reduce to Cu^(0)under the applied cathodic potential.In this work,we reported an A-site modulation strategy to stabilize Cu^(2+)in perovskite for efficient ECRR to CH_(4).After the introduction of Ca^(2+)in La_(2)CuO_(4),the obtained LaCa_(0.4)CuO_(3-δ)is stable during ECRR.We achieved a59.6%±3.8%CH4faradaic efficiency at-1.30 V versus reversible hydrogen electrode in H-cell and a partial current density of 155.0 m A/cm^(2)in membrane electrode assembly.DFT calculations and in situ Raman spectroscopy show that Cu^(2+)facilitates the hydrogenation of*CH_(2)O to*CH_(3)O and the further production of CH_(4).This work introduces an efficient strategy to stabilize Cu^(2+)and provides an understanding of Cu^(2+)in promoting ECRR to CH_(4).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
Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low r...Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.展开更多
Single-and dual-atom catalysts(SACs and DACs)on single-layer graphene are widely investigated for a wide range of electrochemical reactions.However,the effect of van der Waals interactions on the activity of these cat...Single-and dual-atom catalysts(SACs and DACs)on single-layer graphene are widely investigated for a wide range of electrochemical reactions.However,the effect of van der Waals interactions on the activity of these catalysts has not been investigated through systematic high-throughput screening.Here we introduce the concept of van der Waals interactions through a double-layer DAC structure which has axial d orbital modification towards enhanced CO_(2) reduction reaction(CO_(2)RR),hydrogen evolution reaction(HER),oxygen reduction reaction(ORR),and oxygen evolution reaction(OER).We applied density functional theory(DFT)to screen 3d,4d,and 5d transition metals supported by double-layer nitrogen-doped graphene,denoted as M2N8.We sought catalysts with high thermodynamic and electrochemical stabilities along with low overpotentials for CO_(2)RR,ORR,OER,or HER.We find that HER can take place inside the van der Waals gap of V2N8 and Co2N8 leading to overpotentials of 0.10 and 0.16 V.Moreover,ORR and OER can take place on the surface of Fe2N8 and Ir2N8,respectively,leading to overpotentials of 0.39 and 0.37 V.DFT predicts a CO_(2)RR overpotential of 0.85 V towards CO on the surface of Co2N8 along with the HER overpotential of 0.16 V inside the van der Waals gap of Co2N8 towards the production of syngas(CO+H_(2)).This paper provides fundamental insights into the design of advanced multi-layer catalysts by applying the concept of van der Waals interactions for electrochemistry at room temperature.展开更多
Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations i...Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations in current analytical techniques.Herein,using precisely structured metal nanoclusters as models,we discovered that altering the electronegativity of substituents on donor thiolate ligands can modulate the bond dissociation energy of coordinated phosphine ligands on the clusters.This change leads to the selective dissociation of ligands during the catalytic process,thereby enabling control over catalytic selectivity with an abrupt increase in formate production from~0%to 23%.This work provides crucial insights into understanding ligand interactions on metal nanoparticle surfaces at the atomic level and lays the foundation for designing highly selective catalysts in the future.展开更多
The electrochemical carbon dioxide reduction reaction(CO_(2)RR)can convert carbon dioxide into highvalue chemical substances and fuels by utilizing renewable electricity,which can not only complete the carbon cycle bu...The electrochemical carbon dioxide reduction reaction(CO_(2)RR)can convert carbon dioxide into highvalue chemical substances and fuels by utilizing renewable electricity,which can not only complete the carbon cycle but also effectively alleviate the problems of global warming and energy shortage.Nickelbased catalysts hold great promise and unbeatable merits for the electroreduction of carbon dioxide due to their excellent catalytic properties and activity.However,there were few review papers on the application of nickel-based catalysts in carbon dioxide electroreduction.This paper,therefore,presents the current status of research on nickel-based catalysts in carbon dioxide electroreduction categorized by different products.First,the advantages of CO_(2) electroreduction and nickel-based catalysts as well as the basic principles of CO_(2) electroreduction are presented;then the different types of nickel-based catalysts that can convert CO_(2) into different products are described in detail,including their syntheses,performances,and mechanisms.Finally,the common features of nickel-based catalysts towards different carbon dioxide electroreduction products,as well as the outlooks for the development of nickel-based catalysts will be summarized.It is highly expected that this review will help in the future research and development of nickel-based catalysts towards CO_(2) conversion.展开更多
Rare earth-based functional nanomaterials have wide applications in catalytic CO_(2)reduction reaction(CO_(2)RR)due to their impressive performance.In particular,the superior oxygen storage and release ability of Ce^(...Rare earth-based functional nanomaterials have wide applications in catalytic CO_(2)reduction reaction(CO_(2)RR)due to their impressive performance.In particular,the superior oxygen storage and release ability of Ce^(4+)/Ce^(3+)reversible pairs,the high coordination number and rich coordination geometry of lanthanide(La)metal ions and the unique stereoselectivity of samarium(Sm)reagents have aroused more and more interest among scientists.To enhance the catalytic activity of Ce,La,Sm(CLS)-based catalysts,recent developments of various modification strategies have been performed to promote the charge transfer and activation of CO_(2).This review constructively discussed the synthesis of modified CLS-based materials and the corresponding applications in thermal catalytic CO_(2)RR,photocatalytic CO_(2)RR,and electrocatalytic CO_(2)RR.Finally,the current difficulties of these materials and further research on the modification of rare earth-based catalysts,as well as the potential future development have been identified.展开更多
Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to ethylene(C_(2)H_(4))represents a promising approach to reducing CO_(2)emissions and producing high-value chemicals.The ethylene productivity is always limited by t...Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to ethylene(C_(2)H_(4))represents a promising approach to reducing CO_(2)emissions and producing high-value chemicals.The ethylene productivity is always limited by the slow reaction kinetics and the high-performance catalysts are significantly desired.Many efforts have been made to develop a catalyst to activate CO_(2)molecules.However,as another reactant,H2O activation does not receive the attention it deserves.In particular,slow H2O dissociation kinetics limit the rate of proton supply,severely impairing the production of C_(2)H_(4).Here,we designed a MgO-modified CuO catalyst(MgO/CuO),which can promote H2O dissociation and enhance CO_(2)adsorption at the same time to realize the efficient ethylene production.The optimal catalyst exhibits a Faraday efficiency for C_(2)H_(4)reached 54.4%at−1.4 V vs.RHE in an H-cell,which is 1.4 times that of pure CuO(37.9%),and it was further enhanced to a 56.7%in a flow cell,with a high current density of up to 535.9 mA cm−2 at−1.0 V vs.RHE.Experimental and theoretical calculations show that MgO/CuO plays a bifunctional role in the CO_(2)RR,which facilitates the adsorption and activation of CO_(2)by CuO and simultaneously accelerates H2O dissociation by MgO doping.The in situ XRD experiments demonstrate that the introduction of MgO protects CuO active phase to avoid overreduction and preserves the active centers for CO_(2)RR.In combination with in situ FTIR and DFT calculations,the protonation process from*CO to*COH and asymmetric C–C coupling step are promoted by the enhanced water activation and proton coupling on MgO/CuO.This work provides new insights into the CO_(2)and H_(2)O coactivation mechanism in CO_(2)RR and a potential universal strategy to design ethylene production electrocatalysts.展开更多
The catalytic activity and selectivity of CO_(2)reduction reaction(CO_(2)RR)towards C1 and C2 products are fundamentally restricted by the inherent linear scaling relationship among the adsorption-free energies of int...The catalytic activity and selectivity of CO_(2)reduction reaction(CO_(2)RR)towards C1 and C2 products are fundamentally restricted by the inherent linear scaling relationship among the adsorption-free energies of intermediates.To face this challenge,we have proposed a novel multifunctional M1M2@BN electrocatalysts to break the linear scaling relationships in CO_(2)RR and efficiently obtain C1 and C2 products.Our results reveal that the optimal limiting potential is increased from−0.58 V for M@BN to−0.39 V for M1M2@BN,which achieves ultrahigh activity of CO_(2)RR.Further mechanism analysis illuminates that M1M2@BN can selectivity modulate the adsorption strength of OCHO*and OCH_(2)O*/OCHOH*,breaking the linear scaling relationship of adsorption-free energies of key intermediates to achieve the enhanced catalytic activity.Notably,the sufficient active sites on M_(1)M_(2)@BN electrocatalysts can promote the sluggish C–C coupling by capturing two CO intermediates simultaneously,further generating high-value multi-carbon(CH_(2)CH_(2)OH)products.Meanwhile,the thermodynamic stability of M1M2@BN has been demonstrated by ab initio molecular dynamics(AIMD)simulations,which shows the feasibility of commercial application in CO_(2)RR.Our findings provide a novel strategy to modulate the binding strength of intermediates and develop the design of efficient multi-active-site CO_(2)RR electrocatalysts.展开更多
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 from the National Natural Science Foundation of China(Nos.22308246,22478278)Central Government Guides the Special Fund Projects of Local Scientific and Technological Development(No.YDZJSX20231A015)the Fundamental Research Program of Shanxi Province(No.202203021212266)。
文摘Cu^(2+)in copper-based catalysts can facilitate the hydrogenation of the CH_(4)production pathway via the electrochemical carbon dioxide reduction reaction(ECRR).However,Cu^(2+)species in copper oxides are unstable and have been revealed to reduce to Cu^(0)under the applied cathodic potential.In this work,we reported an A-site modulation strategy to stabilize Cu^(2+)in perovskite for efficient ECRR to CH_(4).After the introduction of Ca^(2+)in La_(2)CuO_(4),the obtained LaCa_(0.4)CuO_(3-δ)is stable during ECRR.We achieved a59.6%±3.8%CH4faradaic efficiency at-1.30 V versus reversible hydrogen electrode in H-cell and a partial current density of 155.0 m A/cm^(2)in membrane electrode assembly.DFT calculations and in situ Raman spectroscopy show that Cu^(2+)facilitates the hydrogenation of*CH_(2)O to*CH_(3)O and the further production of CH_(4).This work introduces an efficient strategy to stabilize Cu^(2+)and provides an understanding of Cu^(2+)in promoting ECRR to CH_(4).
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.
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.
基金William A.Goddard III thanks the US National Science Foundation(No.CBET-2311117)for supportGuanHua Chen acknowledges financial support from the General Research Fund(Grant No.17309620)Research Grants Council(RGC:T23-713/22-R).
文摘Single-and dual-atom catalysts(SACs and DACs)on single-layer graphene are widely investigated for a wide range of electrochemical reactions.However,the effect of van der Waals interactions on the activity of these catalysts has not been investigated through systematic high-throughput screening.Here we introduce the concept of van der Waals interactions through a double-layer DAC structure which has axial d orbital modification towards enhanced CO_(2) reduction reaction(CO_(2)RR),hydrogen evolution reaction(HER),oxygen reduction reaction(ORR),and oxygen evolution reaction(OER).We applied density functional theory(DFT)to screen 3d,4d,and 5d transition metals supported by double-layer nitrogen-doped graphene,denoted as M2N8.We sought catalysts with high thermodynamic and electrochemical stabilities along with low overpotentials for CO_(2)RR,ORR,OER,or HER.We find that HER can take place inside the van der Waals gap of V2N8 and Co2N8 leading to overpotentials of 0.10 and 0.16 V.Moreover,ORR and OER can take place on the surface of Fe2N8 and Ir2N8,respectively,leading to overpotentials of 0.39 and 0.37 V.DFT predicts a CO_(2)RR overpotential of 0.85 V towards CO on the surface of Co2N8 along with the HER overpotential of 0.16 V inside the van der Waals gap of Co2N8 towards the production of syngas(CO+H_(2)).This paper provides fundamental insights into the design of advanced multi-layer catalysts by applying the concept of van der Waals interactions for electrochemistry at room temperature.
基金financially supported by the National Natural Science Foundation of China(Nos.22301155,22171156,21803001)Taishan Scholar Foundation of Shandong Province(China)+2 种基金the Natural Science Foundation of Shandong Province(No.ZR2023QB122)Shandong Province Excellent Youth Innovation TeamStartup Funds from Qingdao University of Science and Technology
文摘Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations in current analytical techniques.Herein,using precisely structured metal nanoclusters as models,we discovered that altering the electronegativity of substituents on donor thiolate ligands can modulate the bond dissociation energy of coordinated phosphine ligands on the clusters.This change leads to the selective dissociation of ligands during the catalytic process,thereby enabling control over catalytic selectivity with an abrupt increase in formate production from~0%to 23%.This work provides crucial insights into understanding ligand interactions on metal nanoparticle surfaces at the atomic level and lays the foundation for designing highly selective catalysts in the future.
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR)can convert carbon dioxide into highvalue chemical substances and fuels by utilizing renewable electricity,which can not only complete the carbon cycle but also effectively alleviate the problems of global warming and energy shortage.Nickelbased catalysts hold great promise and unbeatable merits for the electroreduction of carbon dioxide due to their excellent catalytic properties and activity.However,there were few review papers on the application of nickel-based catalysts in carbon dioxide electroreduction.This paper,therefore,presents the current status of research on nickel-based catalysts in carbon dioxide electroreduction categorized by different products.First,the advantages of CO_(2) electroreduction and nickel-based catalysts as well as the basic principles of CO_(2) electroreduction are presented;then the different types of nickel-based catalysts that can convert CO_(2) into different products are described in detail,including their syntheses,performances,and mechanisms.Finally,the common features of nickel-based catalysts towards different carbon dioxide electroreduction products,as well as the outlooks for the development of nickel-based catalysts will be summarized.It is highly expected that this review will help in the future research and development of nickel-based catalysts towards CO_(2) conversion.
基金financial supports from the National Key Research and Development Program of China(Nos.2022YFB3504100 and 2021YFB3500600)National Natural Science Foundation of Jiangsu Province(No.BK20240567)+6 种基金Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.22KJB610012)Key R&D Program of Jiangsu Province(No.BE2022142)Jiangsu International Cooperation Project(No.BZ2021018)Nanjing Science and Technology Top Experts Gathering Plan,Cooperation Foundation for the Chunhui Plan Program of Ministry of Education of China(No.202200554)Open Project Program of Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science(No.M2024-7),MOEOpen Project Program of Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation(No.PSMER2023008)the Open Foundation of State Environmental Protection Key Laboratory of Soil Environmental Management and Pollution Control(No.SEMPC2023004)
文摘Rare earth-based functional nanomaterials have wide applications in catalytic CO_(2)reduction reaction(CO_(2)RR)due to their impressive performance.In particular,the superior oxygen storage and release ability of Ce^(4+)/Ce^(3+)reversible pairs,the high coordination number and rich coordination geometry of lanthanide(La)metal ions and the unique stereoselectivity of samarium(Sm)reagents have aroused more and more interest among scientists.To enhance the catalytic activity of Ce,La,Sm(CLS)-based catalysts,recent developments of various modification strategies have been performed to promote the charge transfer and activation of CO_(2).This review constructively discussed the synthesis of modified CLS-based materials and the corresponding applications in thermal catalytic CO_(2)RR,photocatalytic CO_(2)RR,and electrocatalytic CO_(2)RR.Finally,the current difficulties of these materials and further research on the modification of rare earth-based catalysts,as well as the potential future development have been identified.
基金supported by the National Natural Science Foundation of China(Grant No.U21B2099,U22A20425,and 22208377)Natural Science Foundation of Shandong Province(ZR2021QE062)Fundamental Research Funds for the Central Universities,Ocean University of China(grant number 202364004)。
文摘Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to ethylene(C_(2)H_(4))represents a promising approach to reducing CO_(2)emissions and producing high-value chemicals.The ethylene productivity is always limited by the slow reaction kinetics and the high-performance catalysts are significantly desired.Many efforts have been made to develop a catalyst to activate CO_(2)molecules.However,as another reactant,H2O activation does not receive the attention it deserves.In particular,slow H2O dissociation kinetics limit the rate of proton supply,severely impairing the production of C_(2)H_(4).Here,we designed a MgO-modified CuO catalyst(MgO/CuO),which can promote H2O dissociation and enhance CO_(2)adsorption at the same time to realize the efficient ethylene production.The optimal catalyst exhibits a Faraday efficiency for C_(2)H_(4)reached 54.4%at−1.4 V vs.RHE in an H-cell,which is 1.4 times that of pure CuO(37.9%),and it was further enhanced to a 56.7%in a flow cell,with a high current density of up to 535.9 mA cm−2 at−1.0 V vs.RHE.Experimental and theoretical calculations show that MgO/CuO plays a bifunctional role in the CO_(2)RR,which facilitates the adsorption and activation of CO_(2)by CuO and simultaneously accelerates H2O dissociation by MgO doping.The in situ XRD experiments demonstrate that the introduction of MgO protects CuO active phase to avoid overreduction and preserves the active centers for CO_(2)RR.In combination with in situ FTIR and DFT calculations,the protonation process from*CO to*COH and asymmetric C–C coupling step are promoted by the enhanced water activation and proton coupling on MgO/CuO.This work provides new insights into the CO_(2)and H_(2)O coactivation mechanism in CO_(2)RR and a potential universal strategy to design ethylene production electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(Nos.52403306 and 51902084)the Natural Science Foundation of Hebei Province(Nos.B2024202047 and B2020202089)+1 种基金the Hebei Province Higher Education Science and Technology Research Foundation(No.QN2019030)the Program for Changjiang Scholars and Innovative Research Team in University(No.PCSIRT:IRT17R33).
文摘The catalytic activity and selectivity of CO_(2)reduction reaction(CO_(2)RR)towards C1 and C2 products are fundamentally restricted by the inherent linear scaling relationship among the adsorption-free energies of intermediates.To face this challenge,we have proposed a novel multifunctional M1M2@BN electrocatalysts to break the linear scaling relationships in CO_(2)RR and efficiently obtain C1 and C2 products.Our results reveal that the optimal limiting potential is increased from−0.58 V for M@BN to−0.39 V for M1M2@BN,which achieves ultrahigh activity of CO_(2)RR.Further mechanism analysis illuminates that M1M2@BN can selectivity modulate the adsorption strength of OCHO*and OCH_(2)O*/OCHOH*,breaking the linear scaling relationship of adsorption-free energies of key intermediates to achieve the enhanced catalytic activity.Notably,the sufficient active sites on M_(1)M_(2)@BN electrocatalysts can promote the sluggish C–C coupling by capturing two CO intermediates simultaneously,further generating high-value multi-carbon(CH_(2)CH_(2)OH)products.Meanwhile,the thermodynamic stability of M1M2@BN has been demonstrated by ab initio molecular dynamics(AIMD)simulations,which shows the feasibility of commercial application in CO_(2)RR.Our findings provide a novel strategy to modulate the binding strength of intermediates and develop the design of efficient multi-active-site CO_(2)RR electrocatalysts.
