电催化CO_(2)还原反应(Electrocatalytic CO_(2)reduction reaction, CO_(2)RR)在解决全球变暖和能源危机方面有着巨大的应用潜力,但目前催化效率低、催化产物多样等问题限制了CO_(2)RR反应的商业化应用。采用一锅法、碳化法制备了一系...电催化CO_(2)还原反应(Electrocatalytic CO_(2)reduction reaction, CO_(2)RR)在解决全球变暖和能源危机方面有着巨大的应用潜力,但目前催化效率低、催化产物多样等问题限制了CO_(2)RR反应的商业化应用。采用一锅法、碳化法制备了一系列不同镍含量的镍单原子催化剂,利用XRD、XPS、ICP-OES、HRTEM、HAADF-STEM、XAS等方法对镍单原子催化剂的形貌结构、原子价态、金属含量等方面进行表征,并通过电催化还原产物的法拉第效率(Faraday efficiency, FE)和电流密度(Current density,J)来评价其电催化性能。此外,还研究了电解实验装置的改变对升电催化性能的提升。实验结果表明,随着Ni单原子催化剂的Ni金属负载量增加,产物CO的FECO和JCO均增加。催化剂中Zn1Ni2-CN表现出了优异的CO_(2)RR催化性能,在H型电解池中,在-0.7 V vs. RHE电位下FECO达到89%,在-0.9 V vs. RHE下JCO达到6.99 mA·cm^(-2)。在流动电解池中,大范围电位变化下(-0.4~-1.2 V vs. RHE)FECO均保持在99%以上,且在-1.2 V vs. RHE电位下产物电流密度JCO达到174.5 mA·cm^(-2)。展开更多
The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces c...The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces challenges due to limitations in electrocatalytic activity and durability,especially for nonnoble metal-based catalysts.Here,naturally abundant bismuth-based nanosheets that can effectively drive CO_(2)-to-formate electrocatalytic reduction are prepared using the plasma-activated Bi_(2)Se_(3) followed by a reduction process.Thus-obtained plasma-activated Bi nanosheets(P-BiNS)feature ultrathin structures and high surface areas.Such nanostructures ensure the P-BiNS with outstanding eCO_(2)RR catalytic performance,highlighted by the current density of over 80 mA cm^(-2) and a formate Faradic efficiency of>90%.Furthermore,P-BiNS catalysts demonstrate excellent durability and stability without deactivation following over 50h of operation.The selectivity for formate production is also studied by density functional theory(DFT)calculations,validating the importance and efficacy of the stabilization of intermediates(^(*)OCHO)on the P-BiNS surfaces.This study provides a facile plasma-assisted approach for developing high-performance and low-cost electrocatalysts.展开更多
Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in re...Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.展开更多
The electrochemical carbon dioxide reduction reaction(eCO_(2)RR),which converts CO_(2)into various hydrocarbons or alcohols,has been extensively researched because it promises a sustainable energy economy.However,only...The electrochemical carbon dioxide reduction reaction(eCO_(2)RR),which converts CO_(2)into various hydrocarbons or alcohols,has been extensively researched because it promises a sustainable energy economy.However,only copper(Cu)can currently achieve stable and efficient hydrocarbon conversion in the eCO_(2)RR.Therefore,understanding the catalytic mechanisms and summarizing the research progress on synthesis strategies of Cu catalysts are essential for the eCO_(2)RR.This paper reviews Cu catalysts with different surface states of Cu catalysts:oxide-derived Cu,Cu nanoparticles,Cu single atoms,and Cu nanoclusters.It then reviews the development and progress of different Cu-catalyst preparation methods in recent years,focusing on the activity and selectivity of materials.Besides revealing the tendencies of catalytic selection and deep reactive mechanisms of Cu catalysts with four different surface states,this review can guide the subsequent construction of catalysts and provides an understanding of catalytic mechanisms.展开更多
Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose...Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose a general descriptor,the CO_(2)activity,to reveal the electrolyte–electrode-reaction relationship by thermodynamic calculations and experimental studies.Experimental studies agree well with theoretical predictions that both cations(Li^(+),Ca^(2+),Sr^(2+)and Ba^(2+))and anions(BO_(2)^(-),Ti_(5)O_(14)^(8-),SiO_(3)^(2-))can modulate the CO_(2)activity to control both cathode and anode reactions in a typical molten carbonate electrolyzer in terms of tuning reaction products and overpotentials.In this regard,the reduction of CO_(3)^(2-)can be interpreted as the direct reduction of CO_(2)generated from the dissociated CO_(3)^(2-),and the CO_(2)activity can be used as a general descriptor to predict the electrode reaction in molten carbonate.Overall,the CO_(2)activity descriptor unlocks the electrolyte–electrode-reaction relationship,thereby providing fundamental insights into guiding molten carbonate CO_(2)electrolysis.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
Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of...Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of the microenvironment at the reaction interface on the electrocatalytic performance(activity,selectivity,and durability)remains unclear.Here,we provide a comprehensive understanding of the interfacial microenvironment of gas-involving electrocatalysis,including carbon dioxide reduction reaction and nitrogen reduction reaction,and classify the factors affecting the reaction thermodynamics and kinetics into gas diffusion,proton supply,and electron transfer.This categorization allows a systematic survey of the literature focusing on electrolyzer-level(optimization of the device,control of the experimental condition,and design of the working electrode),electrolytelevel(increase of gas solubility,regulation of proton supply,and substitution of anodic reaction),and electrocatalyst-level strategies(promotion of gas affinity,adjustment of hydrophobicity,and enhancement of conductivity),aiming to retrieve the correlations between the microenvironment and electrochemical performance.Finally,priorities for future studies are suggested to support the comprehensive improvement of next-generation gas-involving electrochemical reactions.展开更多
Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity ...Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity at high current density is important for formate production,but remains challenging.Herein,the BiIn hybrid electrocatalyst,deriving from the Bi2O3/In2O3heterojunction(MOD-Biln),shows excellent catalytic performance for CO_(2)RR.The Faradaic efficiency of formate(FEHCOO-) can be realized over 90% at a wide potential window from-0.4 to-1.4 V vs.RHE,while the partial current density of formate(jHCOO-) reaches about 136.7 mA cm^(-2)at-1.4 V in flow cell without IR-compensation.In additio n,the MOD-Biln exhibits superior stability with high selectivity of formate at 100 mA cm^(-2).Systematic characterizations prove the optimized catalytic sites and interface charge transfer of MOD-Biln,while theoretical calculation confirms that the hybrid structure with dual Bi/In metal sites contribute to the optimal free energy of*H and*OCHO intermediates on MOD-Biln surface,thus accelerating the formation and desorption step of*HCOOH to final formate production.Our work provides a facile and useful strategy to develop highly-active and stable electrocatalysts for CO_(2)RR.展开更多
Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor select...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor selectivity and low current density due to its sluggish kinetics and multitudinous reaction pathways.Single-atom catalysts(SACs)demonstrate outstanding activity,excellent selectivity,and remarkable atom utilization efficiency,which give impetus to the search for electrocatalytic processes aiming at high selectivity.There appears significant activity in the development of efficient SACs for CO_(2)RR,while the density of the atomic sites remains a considerable barrier to be overcome.To construct high-metal-loading SACs,aggregation must be prevented,and thus novel strategies are required.The key to creating high-density atomically dispersed sites is designing enough anchoring sites,normally defects,to stabilize the highly mobile separated metal atoms.In this review,we summarized the advances in developing high-loading SACs through defect engineering,with a focus on the synthesis strategies to achieve high atomic site loading.Finally,the future opportunities and challenges for CO_(2)RR in the area of high-loading single-atom electrocatalysts are also discussed.展开更多
Copper(Cu)-based materials are known as the most attractive catalysts for electrochemical carbon dioxide reduction reaction(CO_(2)RR),especially the Cu^(+) species(e.g.,Cu_(2)O),which show excellent capability for cat...Copper(Cu)-based materials are known as the most attractive catalysts for electrochemical carbon dioxide reduction reaction(CO_(2)RR),especially the Cu^(+) species(e.g.,Cu_(2)O),which show excellent capability for catalyzing CO_(2) to C_(2+) chemicals because of their unique electronic structure.However,the active Cu^(+) species are prone to be reduced to metallic Cu under an electroreduction environment,thus resulting in fast deactivation and poor selectivity.Here,we developed an advanced surface modification strategy to maintain the active Cu^(+) species via assembling a protective layer of metal-organic framework(copper benzenetricarboxylate,CuBTC) on the surface of Cu_(2)O octahedron(Cu_(2)O@CuBTC).It's encouraging to see that the Cu_(2)O@CuBTC heterostructure outperforms the bare Cu_(2)O octahedron in catalyzing CO_(2) to C_(2+) chemicals and dramatically enhances the ratio of C_(2)H_(4)/CH_(4) products.A systematic study reveals that the introduced CuBTC shell plays a critical role in maintaining the active Cu^(+) species in Cu_(2)O@CuBTC heterostructure under reductive conditions.This work offers a practical strategy for improving the catalytic performance of CO_(2)RR over copper oxides and also establishes a route to maintain the state of valence-sensitive catalysts.展开更多
文摘电催化CO_(2)还原反应(Electrocatalytic CO_(2)reduction reaction, CO_(2)RR)在解决全球变暖和能源危机方面有着巨大的应用潜力,但目前催化效率低、催化产物多样等问题限制了CO_(2)RR反应的商业化应用。采用一锅法、碳化法制备了一系列不同镍含量的镍单原子催化剂,利用XRD、XPS、ICP-OES、HRTEM、HAADF-STEM、XAS等方法对镍单原子催化剂的形貌结构、原子价态、金属含量等方面进行表征,并通过电催化还原产物的法拉第效率(Faraday efficiency, FE)和电流密度(Current density,J)来评价其电催化性能。此外,还研究了电解实验装置的改变对升电催化性能的提升。实验结果表明,随着Ni单原子催化剂的Ni金属负载量增加,产物CO的FECO和JCO均增加。催化剂中Zn1Ni2-CN表现出了优异的CO_(2)RR催化性能,在H型电解池中,在-0.7 V vs. RHE电位下FECO达到89%,在-0.9 V vs. RHE下JCO达到6.99 mA·cm^(-2)。在流动电解池中,大范围电位变化下(-0.4~-1.2 V vs. RHE)FECO均保持在99%以上,且在-1.2 V vs. RHE电位下产物电流密度JCO达到174.5 mA·cm^(-2)。
基金partial support from the Jiujiang Research Institute at Xiamen University.
文摘The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces challenges due to limitations in electrocatalytic activity and durability,especially for nonnoble metal-based catalysts.Here,naturally abundant bismuth-based nanosheets that can effectively drive CO_(2)-to-formate electrocatalytic reduction are prepared using the plasma-activated Bi_(2)Se_(3) followed by a reduction process.Thus-obtained plasma-activated Bi nanosheets(P-BiNS)feature ultrathin structures and high surface areas.Such nanostructures ensure the P-BiNS with outstanding eCO_(2)RR catalytic performance,highlighted by the current density of over 80 mA cm^(-2) and a formate Faradic efficiency of>90%.Furthermore,P-BiNS catalysts demonstrate excellent durability and stability without deactivation following over 50h of operation.The selectivity for formate production is also studied by density functional theory(DFT)calculations,validating the importance and efficacy of the stabilization of intermediates(^(*)OCHO)on the P-BiNS surfaces.This study provides a facile plasma-assisted approach for developing high-performance and low-cost electrocatalysts.
基金supported by the Fundamental Research Funds for the Central Universities (FRF-EYIT-23-07)。
文摘Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.
基金supported by the Tianjin Science and Technology support key projects (20JCYBJC01420)。
文摘The electrochemical carbon dioxide reduction reaction(eCO_(2)RR),which converts CO_(2)into various hydrocarbons or alcohols,has been extensively researched because it promises a sustainable energy economy.However,only copper(Cu)can currently achieve stable and efficient hydrocarbon conversion in the eCO_(2)RR.Therefore,understanding the catalytic mechanisms and summarizing the research progress on synthesis strategies of Cu catalysts are essential for the eCO_(2)RR.This paper reviews Cu catalysts with different surface states of Cu catalysts:oxide-derived Cu,Cu nanoparticles,Cu single atoms,and Cu nanoclusters.It then reviews the development and progress of different Cu-catalyst preparation methods in recent years,focusing on the activity and selectivity of materials.Besides revealing the tendencies of catalytic selection and deep reactive mechanisms of Cu catalysts with four different surface states,this review can guide the subsequent construction of catalysts and provides an understanding of catalytic mechanisms.
基金funded by National Natural Science Foun-dation of China(No.52031008,21673162).
文摘Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose a general descriptor,the CO_(2)activity,to reveal the electrolyte–electrode-reaction relationship by thermodynamic calculations and experimental studies.Experimental studies agree well with theoretical predictions that both cations(Li^(+),Ca^(2+),Sr^(2+)and Ba^(2+))and anions(BO_(2)^(-),Ti_(5)O_(14)^(8-),SiO_(3)^(2-))can modulate the CO_(2)activity to control both cathode and anode reactions in a typical molten carbonate electrolyzer in terms of tuning reaction products and overpotentials.In this regard,the reduction of CO_(3)^(2-)can be interpreted as the direct reduction of CO_(2)generated from the dissociated CO_(3)^(2-),and the CO_(2)activity can be used as a general descriptor to predict the electrode reaction in molten carbonate.Overall,the CO_(2)activity descriptor unlocks the electrolyte–electrode-reaction relationship,thereby providing fundamental insights into guiding molten carbonate CO_(2)electrolysis.
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National Natural Science Foundationof China,Grant/Award Numbers:U21A20332,52103226,52071226Outstanding Youth Foundation of Jiangsu Province,Grant/Award Number:BK20220061+2 种基金Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20201171Key Research and Development Plan of Jiangsu Province,Grant/Award Number:BE2020003-3Fellowship of China Postdoctoral Science Foundation,Grant/Award Number:2021M702382。
文摘Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of the microenvironment at the reaction interface on the electrocatalytic performance(activity,selectivity,and durability)remains unclear.Here,we provide a comprehensive understanding of the interfacial microenvironment of gas-involving electrocatalysis,including carbon dioxide reduction reaction and nitrogen reduction reaction,and classify the factors affecting the reaction thermodynamics and kinetics into gas diffusion,proton supply,and electron transfer.This categorization allows a systematic survey of the literature focusing on electrolyzer-level(optimization of the device,control of the experimental condition,and design of the working electrode),electrolytelevel(increase of gas solubility,regulation of proton supply,and substitution of anodic reaction),and electrocatalyst-level strategies(promotion of gas affinity,adjustment of hydrophobicity,and enhancement of conductivity),aiming to retrieve the correlations between the microenvironment and electrochemical performance.Finally,priorities for future studies are suggested to support the comprehensive improvement of next-generation gas-involving electrochemical reactions.
基金financially supported by the National Natural Science Foundation of China (Grant Nos. 22205205)the Zhejiang Provincial Natural Science Foundation of China (Grant Nos.LQ22B030008)the Science Foundation of Zhejiang Sci-Tech University (ZSTU)(Grant Nos. 21062337-Y and 22062312-Y)。
文摘Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity at high current density is important for formate production,but remains challenging.Herein,the BiIn hybrid electrocatalyst,deriving from the Bi2O3/In2O3heterojunction(MOD-Biln),shows excellent catalytic performance for CO_(2)RR.The Faradaic efficiency of formate(FEHCOO-) can be realized over 90% at a wide potential window from-0.4 to-1.4 V vs.RHE,while the partial current density of formate(jHCOO-) reaches about 136.7 mA cm^(-2)at-1.4 V in flow cell without IR-compensation.In additio n,the MOD-Biln exhibits superior stability with high selectivity of formate at 100 mA cm^(-2).Systematic characterizations prove the optimized catalytic sites and interface charge transfer of MOD-Biln,while theoretical calculation confirms that the hybrid structure with dual Bi/In metal sites contribute to the optimal free energy of*H and*OCHO intermediates on MOD-Biln surface,thus accelerating the formation and desorption step of*HCOOH to final formate production.Our work provides a facile and useful strategy to develop highly-active and stable electrocatalysts for CO_(2)RR.
基金This project was supported by the National Natural Science Foundation of China(U19A2017,22272206,51976143)Natural Science Foundation of Hunan Province(S2021JJMSXM3153).
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor selectivity and low current density due to its sluggish kinetics and multitudinous reaction pathways.Single-atom catalysts(SACs)demonstrate outstanding activity,excellent selectivity,and remarkable atom utilization efficiency,which give impetus to the search for electrocatalytic processes aiming at high selectivity.There appears significant activity in the development of efficient SACs for CO_(2)RR,while the density of the atomic sites remains a considerable barrier to be overcome.To construct high-metal-loading SACs,aggregation must be prevented,and thus novel strategies are required.The key to creating high-density atomically dispersed sites is designing enough anchoring sites,normally defects,to stabilize the highly mobile separated metal atoms.In this review,we summarized the advances in developing high-loading SACs through defect engineering,with a focus on the synthesis strategies to achieve high atomic site loading.Finally,the future opportunities and challenges for CO_(2)RR in the area of high-loading single-atom electrocatalysts are also discussed.
基金the Fundamental Research Funds for Central Universities (BLX202151)the National Natural Science Foundation of China (22208021, 52225003, 22109004)。
文摘Copper(Cu)-based materials are known as the most attractive catalysts for electrochemical carbon dioxide reduction reaction(CO_(2)RR),especially the Cu^(+) species(e.g.,Cu_(2)O),which show excellent capability for catalyzing CO_(2) to C_(2+) chemicals because of their unique electronic structure.However,the active Cu^(+) species are prone to be reduced to metallic Cu under an electroreduction environment,thus resulting in fast deactivation and poor selectivity.Here,we developed an advanced surface modification strategy to maintain the active Cu^(+) species via assembling a protective layer of metal-organic framework(copper benzenetricarboxylate,CuBTC) on the surface of Cu_(2)O octahedron(Cu_(2)O@CuBTC).It's encouraging to see that the Cu_(2)O@CuBTC heterostructure outperforms the bare Cu_(2)O octahedron in catalyzing CO_(2) to C_(2+) chemicals and dramatically enhances the ratio of C_(2)H_(4)/CH_(4) products.A systematic study reveals that the introduced CuBTC shell plays a critical role in maintaining the active Cu^(+) species in Cu_(2)O@CuBTC heterostructure under reductive conditions.This work offers a practical strategy for improving the catalytic performance of CO_(2)RR over copper oxides and also establishes a route to maintain the state of valence-sensitive catalysts.
