Copper (Cu) is a special electrocatalyst for CO_(2) reduction reaction (CO_(2)RR) to multi-carbon products.Experimentally introducing grain boundaries (GBs) into Cu-based catalysts is an efficient strategy to improve ...Copper (Cu) is a special electrocatalyst for CO_(2) reduction reaction (CO_(2)RR) to multi-carbon products.Experimentally introducing grain boundaries (GBs) into Cu-based catalysts is an efficient strategy to improve the selectivity of C^(2+) products.However,it is still elusive for the C^(2+) product generation on Cu GBs due to the complex active sites.In this work,we found that the tandem catalysis pathway on adjacent active motifs of Cu GB is responsible for the enhanced activity for C^(2+)production by first principles calculations.By electronic structure analysis shows,the d-band center of GB site is close to the Fermi level than Cu(100) facet,the Cu atomic sites at grain boundary have shorter bond length and stronger bonding with*CO,which can enhance the adsorption of*CO at GB sites.Moreover,CO_(2)protonation is more favorable on the region Ⅲ motif (0.84 e V) than at Cu(100) site (1.35 e V).Meanwhile,the region Ⅱ motif also facilitate the C–C coupling (0.72 e V) compared to the Cu(100) motif (1.09 e V).Therefore,the region Ⅲ and Ⅱ motifs form a tandem catalysis pathway,which promotes the C^(2+)selectivity on Cu GBs.This work provides new insights into CO_(2)RR process.展开更多
Currently most of research efforts for selective electrocatalysis CO_(2) reduction to C2+products have relied on crystalline Cu-based catalysts;amorphous Cu with abundant low-coordinated atoms holds greater promise fo...Currently most of research efforts for selective electrocatalysis CO_(2) reduction to C2+products have relied on crystalline Cu-based catalysts;amorphous Cu with abundant low-coordinated atoms holds greater promise for this conversion yet remains relatively underexplored.Here we report an amorphous urchin-like Cu@nanosilica hybrid synthesized by electrostatic coupling Si polyanions with Cu salt in hydrothermal processes.The Cu@nanosilica electrocatalyst displays excellent CO_(2) electroreduction activity and selectivity with a Faradic efficiency of 70.5%for C2+product production,and higher stability compared to the crystalline Cu counterpart.The solar-driven CO_(2) electrolysis yields an energy efficiency of 20%for C2+product production.Mechanism study reveals that the urchin-like Cu@nanosilica catalyst with amorphous Cu/Cu^(+)dispersion enhances CO_(2) adsorption and activation to facilitate generation of CO_(2)^(-)*and possible CO^(*)intermediates,and suppresses hydrogen evolution concurrently.The combined effects of both aspects promote efficient C2+product production from CO_(2) electroreduction.展开更多
Electrochemical CO2 reduction is a promising strategy for the utilization of CO2 and intermittent excess electricity.Cu is the only single metal catalyst that can electrochemically convert CO2 into multicarbon product...Electrochemical CO2 reduction is a promising strategy for the utilization of CO2 and intermittent excess electricity.Cu is the only single metal catalyst that can electrochemically convert CO2 into multicarbon products.However,Cu exhibits an unfavorable activity and selectivity for the generation of C2 products because of the insufficient amount of CO*provided for the C‐C coupling.Based on the strong CO2 adsorption and ultrafast reaction kinetics of CO*formation on Pd,an intimate CuPd(100)interface was designed to lower the intermediate reaction barriers and improve the efficiency of C2 product formation.Density functional theory(DFT)calculations showed that the CuPd(100)interface enhanced the CO2 adsorption and decreased the CO2*hydrogenation energy barrier,which was beneficial for the C‐C coupling.The potential‐determining step(PDS)barrier of CO2 to C2 products on the CuPd(100)interface was 0.61 eV,which was lower than that on Cu(100)(0.72 eV).Encouraged by the DFT calculation results,the CuPd(100)interface catalyst was prepared by a facile chemical solution method and characterized by transmission electron microscopy.CO2 temperature‐programmed desorption and gas sensor experiments further confirmed the enhancement of the CO2 adsorption and CO2*hydrogenation ability of the CuPd(100)interface catalyst.Specifically,the obtained CuPd(100)interface catalyst exhibited a C2 Faradaic efficiency of 50.3%±1.2%at‒1.4 VRHE in 0.1 M KHCO3,which was 2.1 times higher than that of the Cu catalyst(23.6%±1.5%).This study provides the basis for the rational design of Cu‐based electrocatalysts for the generation of multicarbon products by fine‐tuning the intermediate reaction barriers.展开更多
Cu-based materials are ideal catalysts for CO_(2) electrocatalytic reduction reaction(CO_(2)RR) into multicarbon products.However,such reactions require stringent conditions on local environments of catalyst surfaces,...Cu-based materials are ideal catalysts for CO_(2) electrocatalytic reduction reaction(CO_(2)RR) into multicarbon products.However,such reactions require stringent conditions on local environments of catalyst surfaces,which currently are the global pressing challenges.Here,a stabilized activation of Cu^(0)/Cu^(+)-onAg interface by N_(2) cold plasma treatment was developed for improving Faradaic efficiency(FE) of CO_(2)RR into C2 products.The resultant Ag@Cu-CuN_x exhibits a C2 FE of 72% with a partial current density of-14.9 mA cm^(-2) at-1.0 V vs.RHE(reversible hydrogen electrode).Combining density functional theory(DFT) and experimental investigations,we unveiled that Cu^(0)/Cu^(+) species can be co ntrollably tu ned by the incorporation of nitrogen to form CuN_x on Ag surface,i.e.,Ag@Cu-CuN_x.This strategy enhances ^(*)CO intermediates generation and accelerates C-C coupling both thermodynamically and kinetically.The intermediates O^(*)C^(*)CO,^(*)COOH,and ^(*)CO were detected by in-situ attenuated total internal reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS).The uncovered CO_(2)RR-into-C2 products were carried out along CO_(2)→^(*)COOH→^(*)CO→O^(*)C^(*)CO→^(*)C_(2)H_(3)O→^(*)C_(2)H_(4)O→ C_(2)H_(5)OH(or ^(*)C_(2)H_(3)O→^(*)O+C_(2)H_(4)) paths over Ag@Cu-CuN_x electrocatalyst.This work provides a new approach to design Cu-based electrocatalysts with high-efficiency,mild condition,and stable CO_(2)RR to C2 products.展开更多
以2-氯喹啉和苯硼酸为原料,在四(三苯基膦)钯作催化剂下反应得到主配体2-苯基喹啉(pq),之后pq与水合三氯化铱在乙二醇单乙醚溶剂中反应得到铱的氯桥二聚体(pq)_2Ir(μ-Cl_2)Ir(pq)_2,然后在碱性条件下和乙酰丙酮反应合成出高效磷光红光...以2-氯喹啉和苯硼酸为原料,在四(三苯基膦)钯作催化剂下反应得到主配体2-苯基喹啉(pq),之后pq与水合三氯化铱在乙二醇单乙醚溶剂中反应得到铱的氯桥二聚体(pq)_2Ir(μ-Cl_2)Ir(pq)_2,然后在碱性条件下和乙酰丙酮反应合成出高效磷光红光材料二(2-苯基喹啉-C2,N')(乙酰丙酮)合铱(Ⅲ)Ir(pq)_2(acac)。通过元素分析、红外光谱、核磁共振谱(~1 H NMR、^(13)C NMR)、质谱和单晶X射线衍射等表征手段确定了分子结构,利用紫外-可见吸收光谱和光致发光光谱对其光物理性能进行了测试。结果表明,Ir(pq)_2(acac)为电中性八面体配合物,Ir—O键的平均长度为0.21741(18)nm,而Ir—C键的平均长度0.1983(3)nm,Ir—N键的平均长度为0.2079(2)nm,在600nm处出现了较强的红光发射,其合成产率>95%,该方法适于Ir(pq)_2(acac)的小批量制备。展开更多
Electrocatalytic reduction of carbon dioxide is one of the most effective strategies to achieve carbon neutrality and energy sustainability.Although high-value multi-carbon products have been widely studied,limited el...Electrocatalytic reduction of carbon dioxide is one of the most effective strategies to achieve carbon neutrality and energy sustainability.Although high-value multi-carbon products have been widely studied,limited electrocatalysts have been reported for the selective conversion of ethane.More importantly,the factors tuning the selectivity between ethane and ethylene have not been clarified.Here,Zn@Cu nanowire arrays(Zn@Cu-NWAs) catalyst is proposed to stimulate the maintenance of efficient CO_(2)-to-C_(2)H_(6) conversion at high current densities.Meanwhile,in order to investigate the factors affecting the interconversion between ethane and ethylene,the counterpart catalyst that facilitates C–C coupling to ethylene was also synthesized.Time-of-flight secondary-ion mass spectroscopy(TOF-SIMS),in-situ Raman spectroscopy,and simulation results show that Zn@Cu-NWAs can provide a localized proton corridor environment for the formation of ethane,accelerating the further proton-coupled CO_(2) reduction reaction(CO_(2)RR)kinetics.Hence,this catalyst delivered an ethane Faraday efficiency of over 65% at-1.14 V vs.RHE with a total current density of 142.3 mA/cm^(2).This work provides a new perspective on regulating the local microenvironment to modify the selectivity of multi-carbon products.展开更多
For any C2-cofinite vertex product and the P（z）-tensor product finite length are proved to exist, which operator superalgebra V, the tensor of any two admissible V-modules of are shown to be isomorphic, and their co...For any C2-cofinite vertex product and the P（z）-tensor product finite length are proved to exist, which operator superalgebra V, the tensor of any two admissible V-modules of are shown to be isomorphic, and their constructions are given explicitly in this paper.展开更多
Electroreduction of carbon dioxide(CO_(2)ER)into value-added chemical compounds has presented as a promising route for renewable carbon cycle,which alleviates global warming concern.Compared with traditional C1 produc...Electroreduction of carbon dioxide(CO_(2)ER)into value-added chemical compounds has presented as a promising route for renewable carbon cycle,which alleviates global warming concern.Compared with traditional C1 products,high-value multicarbon products converted from atmospheric CO_(2) via CO_(2)ER have attracted dramatic interest due to their significant economic efficiency,however desired catalytic selectivity of multicarbon products is difficult to achieve because of the high thermodynamic barriers and complex reaction pathways.To replace currently used precious-metal based catalysts,developing highly efficient and precious-metal-free CO_(2)ER catalysts based on earth abundant elements is the top priority to meet the requirements of industrialization.Although certain progress has been made,there are still few systematic reports on the non-precious metal heterogeneous(NPMH)CO_(2)ER electrocatalysts for efficient conversion of CO_(2) to multicarbon products.Herein,we summarize the latest research advances in recent developments of NPMH electrocatalysts,including nanostructured Cu,Cu-based bimetallic catalysts,Cu-based complexes,and carbon-based Cu-free catalysts for electroreduction of CO_(2) into high-value multicarbon products.The corresponding CO_(2)ER performances are discussed in the order of the types of multicarbon products,specifically for ethanol(C2H5OH),ethylene(C2H4),ethane(C2H6),acetic acid(CH3COOH),propanol(C3H7OH),and other O^(2+)products with a special attention paid to understand the structure-activity relationship.Moreover,key strategies and characterization techniques for catalytic mechanism insights,and unsolved issues and future trends for enhancing the CO_(2)ER performance of NPMH electrocatalysts are highlighted,which provides a constructive guidance on the development of CO_(2)ER electrocatalysts with high activity and selectivity for multicarbon products.展开更多
Electroreduction of greenhouse gas CO_(2) into value-added fuels and chemicals provides a promising pathway to address the issues of energy crisis and environmental change.However,the regulations of the selectivity to...Electroreduction of greenhouse gas CO_(2) into value-added fuels and chemicals provides a promising pathway to address the issues of energy crisis and environmental change.However,the regulations of the selectivity towards C2 product and the competing hydrogen evolution reaction(HER)are major challenges for CO_(2) reduction reaction(CO_(2)RR).Here,we develop an interface-enhanced strategy by depositing a thin layer of nitrogen-doped graphene(N-G)on a Cu foam surface(Cu-N-G)to selectively promote the ethanol pathway in CO_(2)RR.Compared to the undetectable ethanol selectivity of pure Cu and Cu@graphene(Cu-G),Cu-N-G has boosted the ethanol selectivity to 33.1%in total Faradic efficiency(FE)at−0.8 V vs.reversible hydrogen electrode(RHE).The experimental and density functional theory(DFT)results verify that the interconnected graphene coating can not only serve as the fast charge transport channel but also provide confined nanospace for mass transfer.The N doping can not only trigger the intrinsic interaction between N in N-G and CO_(2) molecule for enriching the local concentration of reactants but also promote the average valence state of Cu for C–C coupling pathways.The confinement effect at the interface of Cu-N-G can not only provide high adsorbed hydrogen(Had)coverage but also stabilize the key*HCCHOH intermediate towards ethanol pathway.The provided interface-enhanced strategy herein is expected to inspire the design of Cubased CO_(2)RR electrocatalysts towards multi-carbon products.展开更多
基金the National Natural Science Foundation of China(21872174,22002189,U1932148)the International Science and Technology Cooperation Program(2017YFE0127800,2018YFE0203402)+5 种基金the Hunan Provincial Science and Technology Program(2017XK2026)the Hunan Province Key Field R&D Program(2020WK2002)the Hunan Provincial Natural Science Foundation of China(2020JJ2041,2020JJ5691)the Shenzhen Science and Technology Innovation Project(JCYJ20180307151313532)the Fundamental Research Funds for the Central Universities of Central South University。
文摘Copper (Cu) is a special electrocatalyst for CO_(2) reduction reaction (CO_(2)RR) to multi-carbon products.Experimentally introducing grain boundaries (GBs) into Cu-based catalysts is an efficient strategy to improve the selectivity of C^(2+) products.However,it is still elusive for the C^(2+) product generation on Cu GBs due to the complex active sites.In this work,we found that the tandem catalysis pathway on adjacent active motifs of Cu GB is responsible for the enhanced activity for C^(2+)production by first principles calculations.By electronic structure analysis shows,the d-band center of GB site is close to the Fermi level than Cu(100) facet,the Cu atomic sites at grain boundary have shorter bond length and stronger bonding with*CO,which can enhance the adsorption of*CO at GB sites.Moreover,CO_(2)protonation is more favorable on the region Ⅲ motif (0.84 e V) than at Cu(100) site (1.35 e V).Meanwhile,the region Ⅱ motif also facilitate the C–C coupling (0.72 e V) compared to the Cu(100) motif (1.09 e V).Therefore,the region Ⅲ and Ⅱ motifs form a tandem catalysis pathway,which promotes the C^(2+)selectivity on Cu GBs.This work provides new insights into CO_(2)RR process.
基金supported by the National Natural Science Foundation of China(No.21872147 and 21805277)the Natural Science Foundation of Fujian Province(No.2018J05030 and 2019J05152)+2 种基金the Key Research Program of Frontier Sciences,CAS(No.ZDBSLY-SLH028)the DNL Cooperation Fund,CAS(DNL201924)the Strategic Priority Research Program,CAS(No.XDB20000000)。
文摘Currently most of research efforts for selective electrocatalysis CO_(2) reduction to C2+products have relied on crystalline Cu-based catalysts;amorphous Cu with abundant low-coordinated atoms holds greater promise for this conversion yet remains relatively underexplored.Here we report an amorphous urchin-like Cu@nanosilica hybrid synthesized by electrostatic coupling Si polyanions with Cu salt in hydrothermal processes.The Cu@nanosilica electrocatalyst displays excellent CO_(2) electroreduction activity and selectivity with a Faradic efficiency of 70.5%for C2+product production,and higher stability compared to the crystalline Cu counterpart.The solar-driven CO_(2) electrolysis yields an energy efficiency of 20%for C2+product production.Mechanism study reveals that the urchin-like Cu@nanosilica catalyst with amorphous Cu/Cu^(+)dispersion enhances CO_(2) adsorption and activation to facilitate generation of CO_(2)^(-)*and possible CO^(*)intermediates,and suppresses hydrogen evolution concurrently.The combined effects of both aspects promote efficient C2+product production from CO_(2) electroreduction.
文摘Electrochemical CO2 reduction is a promising strategy for the utilization of CO2 and intermittent excess electricity.Cu is the only single metal catalyst that can electrochemically convert CO2 into multicarbon products.However,Cu exhibits an unfavorable activity and selectivity for the generation of C2 products because of the insufficient amount of CO*provided for the C‐C coupling.Based on the strong CO2 adsorption and ultrafast reaction kinetics of CO*formation on Pd,an intimate CuPd(100)interface was designed to lower the intermediate reaction barriers and improve the efficiency of C2 product formation.Density functional theory(DFT)calculations showed that the CuPd(100)interface enhanced the CO2 adsorption and decreased the CO2*hydrogenation energy barrier,which was beneficial for the C‐C coupling.The potential‐determining step(PDS)barrier of CO2 to C2 products on the CuPd(100)interface was 0.61 eV,which was lower than that on Cu(100)(0.72 eV).Encouraged by the DFT calculation results,the CuPd(100)interface catalyst was prepared by a facile chemical solution method and characterized by transmission electron microscopy.CO2 temperature‐programmed desorption and gas sensor experiments further confirmed the enhancement of the CO2 adsorption and CO2*hydrogenation ability of the CuPd(100)interface catalyst.Specifically,the obtained CuPd(100)interface catalyst exhibited a C2 Faradaic efficiency of 50.3%±1.2%at‒1.4 VRHE in 0.1 M KHCO3,which was 2.1 times higher than that of the Cu catalyst(23.6%±1.5%).This study provides the basis for the rational design of Cu‐based electrocatalysts for the generation of multicarbon products by fine‐tuning the intermediate reaction barriers.
基金the National Natural Science Foundation of China (21902017)the Foundation of technological innovation and application development of Chongqing (cstc2021jscxmsxm X0308, CSTB2022BSXM-JCX0132)+1 种基金the Youth project of science and technology research program of Chongqing Education Commission of China (KJQN20211107)the Scientific Research Foundation of Chongqing University of Technology (2020ZDZ022, 2021PYZ13)。
文摘Cu-based materials are ideal catalysts for CO_(2) electrocatalytic reduction reaction(CO_(2)RR) into multicarbon products.However,such reactions require stringent conditions on local environments of catalyst surfaces,which currently are the global pressing challenges.Here,a stabilized activation of Cu^(0)/Cu^(+)-onAg interface by N_(2) cold plasma treatment was developed for improving Faradaic efficiency(FE) of CO_(2)RR into C2 products.The resultant Ag@Cu-CuN_x exhibits a C2 FE of 72% with a partial current density of-14.9 mA cm^(-2) at-1.0 V vs.RHE(reversible hydrogen electrode).Combining density functional theory(DFT) and experimental investigations,we unveiled that Cu^(0)/Cu^(+) species can be co ntrollably tu ned by the incorporation of nitrogen to form CuN_x on Ag surface,i.e.,Ag@Cu-CuN_x.This strategy enhances ^(*)CO intermediates generation and accelerates C-C coupling both thermodynamically and kinetically.The intermediates O^(*)C^(*)CO,^(*)COOH,and ^(*)CO were detected by in-situ attenuated total internal reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS).The uncovered CO_(2)RR-into-C2 products were carried out along CO_(2)→^(*)COOH→^(*)CO→O^(*)C^(*)CO→^(*)C_(2)H_(3)O→^(*)C_(2)H_(4)O→ C_(2)H_(5)OH(or ^(*)C_(2)H_(3)O→^(*)O+C_(2)H_(4)) paths over Ag@Cu-CuN_x electrocatalyst.This work provides a new approach to design Cu-based electrocatalysts with high-efficiency,mild condition,and stable CO_(2)RR to C2 products.
文摘以2-氯喹啉和苯硼酸为原料,在四(三苯基膦)钯作催化剂下反应得到主配体2-苯基喹啉(pq),之后pq与水合三氯化铱在乙二醇单乙醚溶剂中反应得到铱的氯桥二聚体(pq)_2Ir(μ-Cl_2)Ir(pq)_2,然后在碱性条件下和乙酰丙酮反应合成出高效磷光红光材料二(2-苯基喹啉-C2,N')(乙酰丙酮)合铱(Ⅲ)Ir(pq)_2(acac)。通过元素分析、红外光谱、核磁共振谱(~1 H NMR、^(13)C NMR)、质谱和单晶X射线衍射等表征手段确定了分子结构,利用紫外-可见吸收光谱和光致发光光谱对其光物理性能进行了测试。结果表明,Ir(pq)_2(acac)为电中性八面体配合物,Ir—O键的平均长度为0.21741(18)nm,而Ir—C键的平均长度0.1983(3)nm,Ir—N键的平均长度为0.2079(2)nm,在600nm处出现了较强的红光发射,其合成产率>95%,该方法适于Ir(pq)_2(acac)的小批量制备。
基金financially supported by the Outstanding Youth Project of Guangdong Natural Science Foundation (2021B1515020051)the financial support from the Basic and Applied Basic Research Foundation of Guangdong Province (2021B1515120024, 2022A1515011804)。
文摘Electrocatalytic reduction of carbon dioxide is one of the most effective strategies to achieve carbon neutrality and energy sustainability.Although high-value multi-carbon products have been widely studied,limited electrocatalysts have been reported for the selective conversion of ethane.More importantly,the factors tuning the selectivity between ethane and ethylene have not been clarified.Here,Zn@Cu nanowire arrays(Zn@Cu-NWAs) catalyst is proposed to stimulate the maintenance of efficient CO_(2)-to-C_(2)H_(6) conversion at high current densities.Meanwhile,in order to investigate the factors affecting the interconversion between ethane and ethylene,the counterpart catalyst that facilitates C–C coupling to ethylene was also synthesized.Time-of-flight secondary-ion mass spectroscopy(TOF-SIMS),in-situ Raman spectroscopy,and simulation results show that Zn@Cu-NWAs can provide a localized proton corridor environment for the formation of ethane,accelerating the further proton-coupled CO_(2) reduction reaction(CO_(2)RR)kinetics.Hence,this catalyst delivered an ethane Faraday efficiency of over 65% at-1.14 V vs.RHE with a total current density of 142.3 mA/cm^(2).This work provides a new perspective on regulating the local microenvironment to modify the selectivity of multi-carbon products.
基金Acknowledgements This work was supported by the China Postdoctoral Science Foundation （Grant No. 2013M540709）.
文摘For any C2-cofinite vertex product and the P（z）-tensor product finite length are proved to exist, which operator superalgebra V, the tensor of any two admissible V-modules of are shown to be isomorphic, and their constructions are given explicitly in this paper.
基金financially support from by the National Natural Science Foundation of China(Nos.21922811,21878270,and 21961160742)the Zhejiang Provincial Natural Science Foundation of China(No.LR19B060002)+2 种基金the Fundamental Research Funds for the Central Universities(No.2020XZZX002-09)Zhejiang Key Laboratory of Marine Materials and Protective Technologies(No.2020K10)Key Laboratory of Marine Materials and Related Technologies,CAS,the Startup Foundation for Hundred-Talent Program of Zhejiang University,and the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2019R01006)to Y.H.
文摘Electroreduction of carbon dioxide(CO_(2)ER)into value-added chemical compounds has presented as a promising route for renewable carbon cycle,which alleviates global warming concern.Compared with traditional C1 products,high-value multicarbon products converted from atmospheric CO_(2) via CO_(2)ER have attracted dramatic interest due to their significant economic efficiency,however desired catalytic selectivity of multicarbon products is difficult to achieve because of the high thermodynamic barriers and complex reaction pathways.To replace currently used precious-metal based catalysts,developing highly efficient and precious-metal-free CO_(2)ER catalysts based on earth abundant elements is the top priority to meet the requirements of industrialization.Although certain progress has been made,there are still few systematic reports on the non-precious metal heterogeneous(NPMH)CO_(2)ER electrocatalysts for efficient conversion of CO_(2) to multicarbon products.Herein,we summarize the latest research advances in recent developments of NPMH electrocatalysts,including nanostructured Cu,Cu-based bimetallic catalysts,Cu-based complexes,and carbon-based Cu-free catalysts for electroreduction of CO_(2) into high-value multicarbon products.The corresponding CO_(2)ER performances are discussed in the order of the types of multicarbon products,specifically for ethanol(C2H5OH),ethylene(C2H4),ethane(C2H6),acetic acid(CH3COOH),propanol(C3H7OH),and other O^(2+)products with a special attention paid to understand the structure-activity relationship.Moreover,key strategies and characterization techniques for catalytic mechanism insights,and unsolved issues and future trends for enhancing the CO_(2)ER performance of NPMH electrocatalysts are highlighted,which provides a constructive guidance on the development of CO_(2)ER electrocatalysts with high activity and selectivity for multicarbon products.
基金supported by the National Natural Science Foundation of China(Nos.21907043 and 21801153)Shandong Provincial Natural Science Foundation(No.ZR2019BB025).
文摘Electroreduction of greenhouse gas CO_(2) into value-added fuels and chemicals provides a promising pathway to address the issues of energy crisis and environmental change.However,the regulations of the selectivity towards C2 product and the competing hydrogen evolution reaction(HER)are major challenges for CO_(2) reduction reaction(CO_(2)RR).Here,we develop an interface-enhanced strategy by depositing a thin layer of nitrogen-doped graphene(N-G)on a Cu foam surface(Cu-N-G)to selectively promote the ethanol pathway in CO_(2)RR.Compared to the undetectable ethanol selectivity of pure Cu and Cu@graphene(Cu-G),Cu-N-G has boosted the ethanol selectivity to 33.1%in total Faradic efficiency(FE)at−0.8 V vs.reversible hydrogen electrode(RHE).The experimental and density functional theory(DFT)results verify that the interconnected graphene coating can not only serve as the fast charge transport channel but also provide confined nanospace for mass transfer.The N doping can not only trigger the intrinsic interaction between N in N-G and CO_(2) molecule for enriching the local concentration of reactants but also promote the average valence state of Cu for C–C coupling pathways.The confinement effect at the interface of Cu-N-G can not only provide high adsorbed hydrogen(Had)coverage but also stabilize the key*HCCHOH intermediate towards ethanol pathway.The provided interface-enhanced strategy herein is expected to inspire the design of Cubased CO_(2)RR electrocatalysts towards multi-carbon products.
