Electrochemical CO_(2) reduction reaction(CO_(2) RR)exhibits remarkable potential in producing valuable chemicals with renewable energy.Operating CO_(2) RR in acidic media is beneficial to solve the issue of low carbo...Electrochemical CO_(2) reduction reaction(CO_(2) RR)exhibits remarkable potential in producing valuable chemicals with renewable energy.Operating CO_(2) RR in acidic media is beneficial to solve the issue of low carbon utilization brought by(bi)carbonate formation at the cathode.Suppressing the competing hydrogen evolution reaction and achieving stable CO_(2) RR performance remains challenging.Herein,we constructed a 3-dimensional Cu(3D-Cu)gas diffusion electrode(GDE)to achieve efficient C_(2)H_(4) production with a partial current density(j C_(2)H_(4))of over 470 mA cm^(2) and a Faradaic efficiency(FE C_(2)H_(4)) of 40%.With pause electrolysis,the decay rate of the j C_(2)H_(4) is only half that of the traditional constant electrolysis.The GDE after constant electrolysis was found to suffer from severe salt formation,leading to the decreased activity and poor stability.展开更多
The development of highly selective,cost-effective,and energy-efficient electrocatalysts is critical for carbon dioxide reduction reaction(CO_(2)RR)to produce high-value products.Herein,we propose a facile strategy to...The development of highly selective,cost-effective,and energy-efficient electrocatalysts is critical for carbon dioxide reduction reaction(CO_(2)RR)to produce high-value products.Herein,we propose a facile strategy to obtain F,N co-doped carbon-coated iron carbide(Fe3C)nanoparticles by using biomolecule guanine and hexadecafluorophthalocyanine iron as raw materials.Remarkably,this method involves only one-step pyrolysis and does not require any guiding agent or sacrificial template.Benefiting from the advantageous surface microenvironment adjustments achieved through graphitic N(GN)and F co-doping,Fe3C@NF-G-1000 demonstrates exceptional efficacy in the electroreduction of CO_(2)to carbon monoxide(CO)with an impressive Faradic efficiency(FEco)up to 98%at the potential of−0.55 V(vs.reversible hydrogen electrode(RHE)).Furthermore,it delivers a remarkable current density of up to−43 mA·cm^(−2)and exhibits virtually no current attenuation over a span of 20 h within the flow cell.Insights from density functional theory(DFT)calculations reveal that the composite structure of GN and F co-doped graphitic layer and Fe3C exhibits different electron density distributions from that of iron carbide nanoparticles.This is attributed to the synergistic effect of the composite structure leading to the enrichment of electrons in the graphite layer on the surface,which contributes to the stability of the key reaction intermediate*COOH,thus,resulting in an enhanced catalytic activity and efficiency.Overall,this work introduces a new and promising approach to the design of green and low-cost carbon-coated metal materials for CO_(2)reduction reactions.展开更多
Electrochemical CO_(2)conversion into value-added chemicals is a promising technology to solve the greenhouse effect and recycle chemical energy.However,the electrochemical CO_(2)reduction reaction(e-CO_(2)RR)is serio...Electrochemical CO_(2)conversion into value-added chemicals is a promising technology to solve the greenhouse effect and recycle chemical energy.However,the electrochemical CO_(2)reduction reaction(e-CO_(2)RR)is seriously compromised by weak CO_(2)adsorption and a rough CO_(2)activation process based on the chemical inertness of the CO_(2)molecule and the formed fragile metal–C/O bond.In this paper,we designed and fabricated Au particles embedded in ZrO_(2).The configuration of Au particles being of positive charge and ZrO_(2)with negative charge is induced and generated by metal–support interactions(MSIs).As a result,Au/ZrO_(2)@C presents a big difference in the CO_(2)conversion compared with the known work,affording a formate yield of 112.5μmol·cm^(−2)·h^(−1)at−1.1 V vs.reversible hydrogen electrode(RHE),and a max formate Faradaic efficiency of up to 94.1%at−0.9 V vs.RHE.This superior performance was attributed to the activated Au–ZrO_(2)interface to form the Au^(δ+)species.Both insitu Fourier transform infrared(FTIR)spectroscopy and theoretical calculations show that the MSIs configuration can be inclined to the*OCO intermediate generation on Au^(δ+)species activating CO_(2)molecules and then accelerate the formation of the*OCHO intermediate in e-CO_(2)RR,thereby favoring the CO_(2)conversion to formate.展开更多
Utilizing plasmonic effects to assist electrochemical reactions exhibits a huge potential in tuning the reaction activities and product selectivity,which is most appealing especially in chemical reactions with multipl...Utilizing plasmonic effects to assist electrochemical reactions exhibits a huge potential in tuning the reaction activities and product selectivity,which is most appealing especially in chemical reactions with multiple products,such as CO_(2)reduction reaction(CO_(2)RR).However,a comprehensive review of the development and the underlying mechanisms in plasmon-assisted electrocatalytic CO_(2)RR remains few and far between.Herein,the fundamentals of localized surface plasmonic resonance(LSPR)excitation and the properties of typical plasmonic metals(including Au,Ag,and Cu)are retrospected.Subsequently,the potential mechanisms of plasmonic effects(such as hot carrier effects and photothermal effects)on the reaction performance in the field of plasmon-assisted electrocatalytic CO_(2)RR are summarized,which provides directions for the future development of this field.It is concluded that plasmonic catalysts exhibit potential capabilities in enhancing CO_(2)RR while more in situ techniques are essential to further clarify the inner mechanisms.展开更多
Electrochemical conversion of CO2 into fuels is a promising means to solve greenhouse effect and recycle chemical energy. However, the CO2 reduction reaction(CO2 RR) is limited by the high overpotential, slow kinetics...Electrochemical conversion of CO2 into fuels is a promising means to solve greenhouse effect and recycle chemical energy. However, the CO2 reduction reaction(CO2 RR) is limited by the high overpotential, slow kinetics and the accompanied side reaction of hydrogen evolution reaction. Au nanocatalysts exhibit high activity and selectivity toward the reduction of CO2 into CO. Here, we explore the Faradaic efficiency(FE)of CO2 RR catalyzed by 50 nm gold colloid and trisoctahedron. It is found that the maximum FE for CO formation on Au trisoctahedron reaches 88.80% at -0.6 V, which is 1.5 times as high as that on Au colloids(59.04% at -0.7 V). The particle-size effect of Au trisoctahedron has also been investigated, showing that the FE for CO decreases almost linearly to 62.13% when the particle diameter increases to 100 nm. The Xray diffraction characterizations together with the computational hydrogen electrode(CHE) analyses reveal that the(2 2 1) facets on Au trisoctahedron are more feasible than the(1 1 1) facets on Au colloids in stabilizing the critical intermediate COOH*, which are responsible for the higher FE and lower overpotential observed on Au trisoctahedron.展开更多
Electrocatalytic CO_(2) reduction is great promising in alleviating the excessive CO_(2) emission and the conversion to valuable productions.Herein we report the in-situ controlled growth of Bismuth nanoflower/graphdi...Electrocatalytic CO_(2) reduction is great promising in alleviating the excessive CO_(2) emission and the conversion to valuable productions.Herein we report the in-situ controlled growth of Bismuth nanoflower/graphdiyne heterostructures(Bi/GDY)for efficient CO_(2) conversion toward formate.Based on GDY,the obtained electrocatalyst exhibits a partial current density of 19.2 mA/cm^(2) and high reaction selectivity towards formate with a high Faradic efficiency of 91.7%at−1.03 V vs.RHE,and an energy efficiency of 58.8%.The high formate yield rates could be maintained at around 300µ.mol/(cm^(2)·h)over a wide potential range.Detailed characterizations show that the unique interface structures between GDY and Bi can enhance the charge transfer ability,increase the number of active sites,and improve the long-term stability,and finally reach high-performance electrocatalytic conversion of CO_(2) to formate.展开更多
Electrocatalysis has become an attractive strategy for the artificial reduction of CO_(2) to high-value chemicals.However,the design and development of highly selective and stable non-noble metal electrocatalysts that...Electrocatalysis has become an attractive strategy for the artificial reduction of CO_(2) to high-value chemicals.However,the design and development of highly selective and stable non-noble metal electrocatalysts that convert CO_(2) to CO are still a challenge.As a new type of two-dimensional carbon material,graphdiyne(GDY),is rarely used to explore the application in carbon dioxide reduction reaction(CO_(2)RR).Therefore,we tried to use GDY as a substrate to stabilize the copper-nickel alloy nanoparticles(NPs)to synthesize Cu/Ni@GDY.Cu/Ni@GDY requires an overpotential(−0.61 V)to 10 mA/cm^(2) for the formation of CO,and it shows better activity than Au and Ag,achieving a higher Faraday efficiency of about 95.2%and high stability of about 26 h at an overpotential(−0.70 V).The electronic interaction between GDY substrate and Cu/Ni alloy NPs and the large specific surface area of GDY is responsible for the high performance.展开更多
基金the financial support from the Research Grants Council of the Hong Kong Special Administrative Region(project no.24304920).
文摘Electrochemical CO_(2) reduction reaction(CO_(2) RR)exhibits remarkable potential in producing valuable chemicals with renewable energy.Operating CO_(2) RR in acidic media is beneficial to solve the issue of low carbon utilization brought by(bi)carbonate formation at the cathode.Suppressing the competing hydrogen evolution reaction and achieving stable CO_(2) RR performance remains challenging.Herein,we constructed a 3-dimensional Cu(3D-Cu)gas diffusion electrode(GDE)to achieve efficient C_(2)H_(4) production with a partial current density(j C_(2)H_(4))of over 470 mA cm^(2) and a Faradaic efficiency(FE C_(2)H_(4)) of 40%.With pause electrolysis,the decay rate of the j C_(2)H_(4) is only half that of the traditional constant electrolysis.The GDE after constant electrolysis was found to suffer from severe salt formation,leading to the decreased activity and poor stability.
基金the financial support from the National Natural Science Foundation of China(Nos.22072018 and 22372039)the Natural Science Foundation of Fujian Province of China(No.2021J06010).
文摘The development of highly selective,cost-effective,and energy-efficient electrocatalysts is critical for carbon dioxide reduction reaction(CO_(2)RR)to produce high-value products.Herein,we propose a facile strategy to obtain F,N co-doped carbon-coated iron carbide(Fe3C)nanoparticles by using biomolecule guanine and hexadecafluorophthalocyanine iron as raw materials.Remarkably,this method involves only one-step pyrolysis and does not require any guiding agent or sacrificial template.Benefiting from the advantageous surface microenvironment adjustments achieved through graphitic N(GN)and F co-doping,Fe3C@NF-G-1000 demonstrates exceptional efficacy in the electroreduction of CO_(2)to carbon monoxide(CO)with an impressive Faradic efficiency(FEco)up to 98%at the potential of−0.55 V(vs.reversible hydrogen electrode(RHE)).Furthermore,it delivers a remarkable current density of up to−43 mA·cm^(−2)and exhibits virtually no current attenuation over a span of 20 h within the flow cell.Insights from density functional theory(DFT)calculations reveal that the composite structure of GN and F co-doped graphitic layer and Fe3C exhibits different electron density distributions from that of iron carbide nanoparticles.This is attributed to the synergistic effect of the composite structure leading to the enrichment of electrons in the graphite layer on the surface,which contributes to the stability of the key reaction intermediate*COOH,thus,resulting in an enhanced catalytic activity and efficiency.Overall,this work introduces a new and promising approach to the design of green and low-cost carbon-coated metal materials for CO_(2)reduction reactions.
基金supported by the National Key Research and Development Program of China(No.2021YFB3500100)the National Natural Science Foundation of China(No.21805122)Industrial Support Plan Project of Colleges and Universities in Gansu Province(No.2021CYZC19).
文摘Electrochemical CO_(2)conversion into value-added chemicals is a promising technology to solve the greenhouse effect and recycle chemical energy.However,the electrochemical CO_(2)reduction reaction(e-CO_(2)RR)is seriously compromised by weak CO_(2)adsorption and a rough CO_(2)activation process based on the chemical inertness of the CO_(2)molecule and the formed fragile metal–C/O bond.In this paper,we designed and fabricated Au particles embedded in ZrO_(2).The configuration of Au particles being of positive charge and ZrO_(2)with negative charge is induced and generated by metal–support interactions(MSIs).As a result,Au/ZrO_(2)@C presents a big difference in the CO_(2)conversion compared with the known work,affording a formate yield of 112.5μmol·cm^(−2)·h^(−1)at−1.1 V vs.reversible hydrogen electrode(RHE),and a max formate Faradaic efficiency of up to 94.1%at−0.9 V vs.RHE.This superior performance was attributed to the activated Au–ZrO_(2)interface to form the Au^(δ+)species.Both insitu Fourier transform infrared(FTIR)spectroscopy and theoretical calculations show that the MSIs configuration can be inclined to the*OCO intermediate generation on Au^(δ+)species activating CO_(2)molecules and then accelerate the formation of the*OCHO intermediate in e-CO_(2)RR,thereby favoring the CO_(2)conversion to formate.
基金supported by the National Key R&D Program of China(Grant No.2022YFA1505000)the National Natural Science Foundation of China(Grant No.22072158)the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB36000000).
文摘Utilizing plasmonic effects to assist electrochemical reactions exhibits a huge potential in tuning the reaction activities and product selectivity,which is most appealing especially in chemical reactions with multiple products,such as CO_(2)reduction reaction(CO_(2)RR).However,a comprehensive review of the development and the underlying mechanisms in plasmon-assisted electrocatalytic CO_(2)RR remains few and far between.Herein,the fundamentals of localized surface plasmonic resonance(LSPR)excitation and the properties of typical plasmonic metals(including Au,Ag,and Cu)are retrospected.Subsequently,the potential mechanisms of plasmonic effects(such as hot carrier effects and photothermal effects)on the reaction performance in the field of plasmon-assisted electrocatalytic CO_(2)RR are summarized,which provides directions for the future development of this field.It is concluded that plasmonic catalysts exhibit potential capabilities in enhancing CO_(2)RR while more in situ techniques are essential to further clarify the inner mechanisms.
基金This work was supported by the National Key Research and Development Program of China(2017YFA0206500)the National Natural Science Foundation of China(21635004 and 21675079)Part of the numerical calculations were carried out in the High Performance Computing Center(HPCC)of Nanjing University.
文摘Electrochemical conversion of CO2 into fuels is a promising means to solve greenhouse effect and recycle chemical energy. However, the CO2 reduction reaction(CO2 RR) is limited by the high overpotential, slow kinetics and the accompanied side reaction of hydrogen evolution reaction. Au nanocatalysts exhibit high activity and selectivity toward the reduction of CO2 into CO. Here, we explore the Faradaic efficiency(FE)of CO2 RR catalyzed by 50 nm gold colloid and trisoctahedron. It is found that the maximum FE for CO formation on Au trisoctahedron reaches 88.80% at -0.6 V, which is 1.5 times as high as that on Au colloids(59.04% at -0.7 V). The particle-size effect of Au trisoctahedron has also been investigated, showing that the FE for CO decreases almost linearly to 62.13% when the particle diameter increases to 100 nm. The Xray diffraction characterizations together with the computational hydrogen electrode(CHE) analyses reveal that the(2 2 1) facets on Au trisoctahedron are more feasible than the(1 1 1) facets on Au colloids in stabilizing the critical intermediate COOH*, which are responsible for the higher FE and lower overpotential observed on Au trisoctahedron.
基金supported by the National Natural Science Foundation of China (Nos.21790050,21790051,22021002)the National Key Research and Development Project of China (No.2018YFA0703501)the Key Program of the Chinese Academy of Sciences (No.XDPB13).
文摘Electrocatalytic CO_(2) reduction is great promising in alleviating the excessive CO_(2) emission and the conversion to valuable productions.Herein we report the in-situ controlled growth of Bismuth nanoflower/graphdiyne heterostructures(Bi/GDY)for efficient CO_(2) conversion toward formate.Based on GDY,the obtained electrocatalyst exhibits a partial current density of 19.2 mA/cm^(2) and high reaction selectivity towards formate with a high Faradic efficiency of 91.7%at−1.03 V vs.RHE,and an energy efficiency of 58.8%.The high formate yield rates could be maintained at around 300µ.mol/(cm^(2)·h)over a wide potential range.Detailed characterizations show that the unique interface structures between GDY and Bi can enhance the charge transfer ability,increase the number of active sites,and improve the long-term stability,and finally reach high-performance electrocatalytic conversion of CO_(2) to formate.
基金This work was supported by the National Natural Science Foundation of China(Nos.21771114,91956130)the Distinguished Young Scholars of Tianjin,China(No.19JCJQJC62000).
文摘Electrocatalysis has become an attractive strategy for the artificial reduction of CO_(2) to high-value chemicals.However,the design and development of highly selective and stable non-noble metal electrocatalysts that convert CO_(2) to CO are still a challenge.As a new type of two-dimensional carbon material,graphdiyne(GDY),is rarely used to explore the application in carbon dioxide reduction reaction(CO_(2)RR).Therefore,we tried to use GDY as a substrate to stabilize the copper-nickel alloy nanoparticles(NPs)to synthesize Cu/Ni@GDY.Cu/Ni@GDY requires an overpotential(−0.61 V)to 10 mA/cm^(2) for the formation of CO,and it shows better activity than Au and Ag,achieving a higher Faraday efficiency of about 95.2%and high stability of about 26 h at an overpotential(−0.70 V).The electronic interaction between GDY substrate and Cu/Ni alloy NPs and the large specific surface area of GDY is responsible for the high performance.
