Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)acc...Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.展开更多
The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous me...The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.展开更多
The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-b...The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-based electrocatalyst was developed for use in gas-diffusion electrodes(GDE),and the effect of nitrogen(N)doping on the ECR activity of ZnO electrocatalysts was investigated.Initially,a ZnO nanosheet was prepared via the hydrothermal method,and nitridation was performed at different times to control the N-doping content.With an increase in the N-doping content,the morphological properties of the nanosheet changed significantly,namely,the 2D nanosheets transformed into irregularly shaped nanoparticles.Furthermore,the ECR performance of Zn O electrocatalysts with different N-doping content was assessed in 1.0 M KHCO_(3) electrolyte using a gas-diffusion electrode-based ECR cell.While the ECR activity increased after a small amount of N doping,it decreased for higher N doping content.Among them,the N:ZnO-1 h electrocatalysts showed the best CO selectivity,with a faradaic efficiency(FE_(CO))of 92.7%at-0.73 V vs.reversible hydrogen electrode(RHE),which was greater than that of an undoped Zn O electrocatalyst(FE_(CO)of 63.4%at-0.78 V_(RHE)).Also,the N:ZnO-1 h electrocatalyst exhibited outstanding durability for 16 h,with a partial current density of-92.1 mA cm^(-2).This improvement of N:ZnO-1 h electrocatalyst can be explained by density functional theory calculations,demonstrating that this improvement of N:ZnO-1 h electrocatalyst comes from(ⅰ)the optimized active sites lowering the free energy barrier for the rate-determining step(RDS),and(ⅱ)the modification of electronic structure enhancing the electron transfer rate by N doping.展开更多
Surface charge localization and inferior charge transfer efficiency seriously restrict the supply of reactive hydrogen and the reaction dynamics of CO_(2) photoreduction performance of photocatalysts.Herein,chemically...Surface charge localization and inferior charge transfer efficiency seriously restrict the supply of reactive hydrogen and the reaction dynamics of CO_(2) photoreduction performance of photocatalysts.Herein,chemically bonded BiVO_(4)/Bi_(19)Cl_(3)S_(27)(BVO/BCS)S-scheme heterojunction with a strong internal electric field is designed.Experimental and density function theory calculation results confirm that the elaborated heterojunction accelerates the vectorial migration of photogenerated charges from BiVO_(4) to Bi_(19)Cl_(3)S_(27) via the interfacial chemical bonding interactions(i.e.,Bi-O and Bi-S bonds)between Bi atoms of BVO and S atoms of BCS or Bi atoms of BCS and O atoms of BVO under light irradiation,breaking the interfacial barrier and surface charge localization of Bi_(19)Cl_(3)S_(27),and further decreasing the energy of reactive hydrogen generation,CO_(2) absorption and activation.The separation efficiency of photogenerated carriers is much more efficient than that counterpart individual in BVO/BCS S-scheme heterojunction system.As a result,BVO/BCS heterojunction exhibits a significantly improved continuous photocatalytic performance for CO_(2) reduction and the 24 h CO yield reaches 678.27μmol⋅g^(-1).This work provides an atomic-level insight into charge transfer kinetics and CO_(2) reduction mechanism in S-scheme heterojunction.展开更多
By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2...By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2) into CO.Generally,NiFe_(2_)O_(4) oxygen carriers have demonstrated remarkable efficiency in chemical looping CO_(2) conversion.Nevertheless,the intricate process of atomic migration and evolution within the internal structure of bimetallic oxygen carriers during continuous high‐temperature redox cycling remains unclear.Consequently,the lack of a fundamental understanding of the complex ionic migration and oxygen transfer associated with energy conversion processes hampers the design of high‐performance oxygen carriers.Thus,in this study,we employed in situ characterization techniques and theoretical calculations to investigate the ion migration behavior and structural evolution in the bulk of NiFe_(2_)O_(4) oxygen carriers during H_(2) reduction and CO_(2)/lab air oxidation cycles.We discovered that during the H_(2) reduction step,lattice oxygen rapidly migrates to vacancy layers to replenish consumed active oxygen species,while Ni leaches from the material and migrates to the surface.During the CO_(2) splitting step,Ni migrates toward the core of the bimetallic oxygen carrier,forming Fe–Ni alloys.During the air oxidation step,Fe–Ni migrates outward,creating a hollow structure owing to the Kirkendall effect triggered by the swift transfer of lattice oxygen.The metal atom migration paths depend on the oxygen transfer rates.These discoveries highlight the significance of regulating the release–recovery rate of lattice oxygen to uphold the structures and reactivity of oxygen carriers.This work offers a comprehensive understanding of the oxidation/reduction‐driven atomic interdiffusion behavior of bimetallic oxygen carriers.展开更多
Chemical looping combustion has the potential to be an efficient and low-cost technology capable of contributing to the reduction of the atmospheric concentration of CO_(2) in order to reach the 1.5/2°C goal and ...Chemical looping combustion has the potential to be an efficient and low-cost technology capable of contributing to the reduction of the atmospheric concentration of CO_(2) in order to reach the 1.5/2°C goal and mitigate climate change.In this process,a metal oxide is used as oxygen carrier in a dual fluidized bed to generate clean CO_(2) via combustion of biomass.Most commonly,natural ores or synthetic materials are used as oxygen carrier whereas both must meet special requirements for the conversion of solid fuels.Synthetic oxygen carriers are characterized by higher reactivity at the expense of higher costs versus the lower-cost natural ores.To determine the viability of both possibilities,a techno-economic comparison of a synthetic material based on manganese,iron,and copper to the natural ore ilmenite was conducted.The synthetic oxygen carrier was characterized and tested in a pilot plant,where high combustion efficiencies up to 98.4%and carbon capture rates up to 98.5%were reached.The techno-economic assessment resulted in CO_(2) capture costs of 75 and 40€/tCO_(2) for the synthetic and natural ore route respectively,whereas a sensitivity analysis showed the high impact of production costs and attrition rates of the synthetic material.The synthetic oxygen carrier could break even with the natural ore in case of lower production costs and attrition rates,which could be reached by adapting the production process and recycling material.By comparison to state-of-the-art technologies,it is demonstrated that both routes are viable and the capture cost of CO_(2) could be reduced by implementing the chemical looping combustion technology.展开更多
High-temperature CO_(2)electrolysis via solid oxide electrolysis cells(CO_(2)-SOECs)has drawn special attention due to the high energy convention efficiency,fast electrode kinetics,and great potential in carbon cyclin...High-temperature CO_(2)electrolysis via solid oxide electrolysis cells(CO_(2)-SOECs)has drawn special attention due to the high energy convention efficiency,fast electrode kinetics,and great potential in carbon cycling.However,the development of cathode materials with high catalytic activity and chemical stability for pure CO_(2)electrolysis is still a great challenge.In this work,A-site cation deficient dual-phase material,namely(Pr_(0.4)Ca_(0.6))_(x)Fe_(0.8)Ni_(0.2)O_(3-δ)(PCFN,x=1,0.95,and 0.9),has been designed as the fuel electrode for a pure CO_(2)-SOEC,which presents superior electrochemical performance.Among all these compositions,(Pr_(0.4)Ca_(0.6))_(0.95)Fe_(0.8)Ni_(0.2)O_(3-δ)(PCFN95)exhibited the lowest polarization resistance of 0.458Ωcm^(2)at open-circuit voltage and 800℃.The application of PCFN95 as the cathode in a single cell yields an impressive electrolysis current density of 1.76 A cm^(-2)at 1.5 V and 800℃,which is 76%higher than that of single cells with stoichiometric Pr_(0.4)Ca_(0.6)Fe_(0.8)Ni_(0.2)O_(3-δ)(PCFN100)cathode.The effects of A-site deficiency on materials'phase structure and physicochemical properties are also systematically investigated.Such an enhancement in electrochemical performance is attributed to the promotion of effective CO_(2)adsorption,as well as the improved electrode kinetics resulting from the A-site deficiency.展开更多
Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have bee...Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have been proposed to address the challenges.Carbon capture and utilization(CCU) represents one of the approaches and thermochemical CO_(2) splitting driven by thermal energy is a subset of the CCU,which converts the captured CO_(2) into CO and makes it possible to achieve closed-loop carbon recirculation.Redox-active catalysts are among the most critical components of the thermochemical splitting cycles and perovskites are regarded as the most promising catalysts.Here we review the latest advancements in thermochemical cycles based on perovskites,covering thermodynamic principles,material modifications,reaction kinetics,oxygen pressure control,circular strategies,and demonstrations to provide a comprehensive overview of the topical area.Thermochemical cycles based on such materials require the consideration of trade-off between cost and efficiency,which is related to actual material used,operation mode,oxygen removal,and heat recovery.Lots of efforts have been made towards improving reaction rates,conversion efficiency and cycling stability,materials related research has been lacking-a key aspect affecting the performance across all above aspects.Double perovskites and composite perovskites arise recently as a potentially promising addition to material candidates.For such materials,more effective oxygen removal would be needed to enhance the overall efficiency,for which thermochemical or electrochemical oxygen pumps could contribute to efficient oxygen removal as well as serve as means for inert gas regeneration.The integration of thermochemical CO_(2) splitting process with downstream fuel production and other processes could reduce costs and increase efficiency of the technology.This represents one of the directions for the future research.展开更多
The magnitude and spatial variability of CO_(2)surface emissions and processes involving CO_(2)released to the atmosphere from the soils are relevant issues in the context of climate change.This work evaluated CO_(2)f...The magnitude and spatial variability of CO_(2)surface emissions and processes involving CO_(2)released to the atmosphere from the soils are relevant issues in the context of climate change.This work evaluated CO_(2)fluxes and^(13)C/^(12)C ratio of vegetation,organic matter,and soil gases from no disturbed soils of Chaco Pampean Plain(Argentina)with different soil properties and environmental conditions(PL and PA units).Soil organic decomposition from individual layers was accompanied byδ^(13)C of total organic carbon(δ^(13)C-TOC)values more enriched to depth.δ^(13)C-TOC values in the upper soil profile~ca.0–15 cm were like the plant community of this area(~−33 to−29‰)whileδ^(13)CTOC varied stronger bellow horizon A,till~−24‰.Bothδ^(13)C-TOC and soilδ^(13)C-CO_(2)were similar(~−24 to 26‰)at deeper horizons(~50–60 cm).Toward the superficial layers,δ^(13)C-TOC andδ^(13)C-CO_(2)showed more differences(till~4‰),due influence of the diffusion process.Horizon A layer(~0–20 cm)from both PL and PA units contained the most enrichedδ^(13)C-CO_(2)values(~−15–17‰)because atmospheric CO_(2)permeated the soil air.A simple two-component mixing model between sources(atmosphericδ^(13)C-CO_(2)and soil CO_(2))confirmed that process.Isotopically,CO_(2)fluxes reflected the biodegradation of C3 plants(source),diffusive transport,and CO_(2)exchange(atmosphere/soil).Soil moisture content appeared as a determining factor in the diffusion process and the magnitude of CO_(2)surface emissions(12–60 g·m^(−2)·d^(−1)).That condition was confirmed by CO_(2)diffusion coefficients estimated by air-filled porosity parameters and soil radon gradient model.展开更多
The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added valu...The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.展开更多
Developing bimetallic catalysts is an effective strategy for enhancing the activity and selectivity of electrochemical CO_(2) reduction reactions,where understanding the structure-activity relationship is essential fo...Developing bimetallic catalysts is an effective strategy for enhancing the activity and selectivity of electrochemical CO_(2) reduction reactions,where understanding the structure-activity relationship is essential for catalyst design.Herein,we prepared two Cu-Ag bimetallic catalysts with Ag nanoparticles attached to the top or the bottom of Cu nanowires.When tested in a flow cell,the Cu-Ag catalyst with Ag nanoparticles on the bottom achieved a faradaic efficiency of 54%for ethylene production,much higher than the catalyst with Ag nanoparticles on the top.The catalysts were further studied in the H-cell and zero-gap MEA cell.It was found that placing the two metals in the intensified reaction zone is crucial to triggering the tandem reaction of bimetallic catalysts.Our work elucidates the structure-activity relationship of bimetallic catalysts for CO_(2) reduction and demonstrates the importance of considering both catalyst structures and cell characteristics to achieve high activity and selectivity.展开更多
The electrocatalytic conversion of CO_(2) into valuable chemical feedstocks using renewable electricity offers a compelling strategy for closing the carbon loop.While copper-based materials are effective in catalyzing...The electrocatalytic conversion of CO_(2) into valuable chemical feedstocks using renewable electricity offers a compelling strategy for closing the carbon loop.While copper-based materials are effective in catalyzing CO_(2) to C_(2+)products,the instability of Cu^(+)species,which tend to reduce to Cu~0 at cathodic potentials during CO_(2) reduction,poses a significant challenge.Here,we report the development of SmCu_(2)O and investigate the influence of f-d orbital hybridization on the CO_(2) reduction reaction (CO_(2)RR).Supported by density functional theory (DFT) calculations,our experimental results demonstrate that hybridization between Sm^(3+)4f and Cu^(+)3d orbitals not only improves the adsorption of *CO intermediates and increases CO coverage to stabilize Cu^(+) but also facilitates CO_(2) activation and lowers the energy barriers for CAC coupling.Notably,Sm-Cu_(2)O achieves a Faradaic efficiency for C_(2)H_(4) that is 38%higher than that of undoped Cu_(2)O.Additionally,it sustains its catalytic activity over an extended operational period exceeding 7 h,compared to merely 2 h for the undoped sample.This research highlights the potential of fd orbital hybridization in enhancing the efficacy of copper-based catalysts for CO_(2)RR,pointing towards a promising direction for the development of durable,high-performance electrocatalysts for sustainable chemical synthesis.展开更多
The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great significance.Cu-based catalysts have been widely investigated for ECR due to their unique ab...The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great significance.Cu-based catalysts have been widely investigated for ECR due to their unique ability to generate various carbonaceous products,but directing selectivity toward one certain product and identifying the real active sites during ECR are still full of challenge.Here,after the incorporation of CdO into CuO,the Cu_(0.5)Cd_(0.5)-O catalyst achieves a 10.3-fold enhancement for CO selectivity in comparison with CuO,and a CO faradic efficiency nearly 90%with a current density around20 mA cm^(-2)could maintain at least 60 h.Interestingly,a wide CO/H_(2)ratio(0.07-10)is reached on Cu_(x)Cd_(1-x)-O catalysts by varying the Cu/Cd ratio,demonstrating the potential of syngas production using such catalysts.The results of ex situ XRD,XPS,and in situ Raman reveal that the real active sites of Cu_(0.5)Cd_(0.5)-O catalysts for CO production during ECR reaction are the reconstructed mixed phases of CuCd alloy and CdCO_(3).In situ FTIR and theoretical calculations further implicate the presence of Cd related species promotes the CO desorption and inhibits the H_(2)evolution,thus leading to an enhanced CO generation.展开更多
Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of...Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of how specific electrolyte influences Cu-based catalysts is lacking.This review addresses this gap by focusing on how electrolytes impact surface reconstruction and the CO_(2) reduction process on Cu-based electrocatalysts,identifying specific electrolyte compositions that enhance the density and stability of active sites,and providing insights into how different electrolyte environments modulate the selectivity and efficiency of C_(2+)product formation.The review begins by exploring how electrolytes induce favorable surface reconstruction in Cu-based catalysts,affecting surface roughness through dissolution-redeposition of Cu species and interactions with halogens and molecular additives.It also covers changes in crystalline facets of Cu and Cu_(2)O,and oxidation states,highlighting transitions from Cu^(0) to Cu^(δ+)and the stabilization of Cu^(+).The role of electrolytes in the C–C coupling process is examined,emphasizing their effects in modulating mass and charge transfer,CO_(2) adsorption,intermediate evolution,and product desorption.Subsequently,the mechanisms by non-aqueous electrolytes,including organic solvents,ionic liquids,and mixed electrolytes,affecting CO_(2) reduction are analyzed,highlighting the unique advantages and challenges of each type.The review concludes by addressing current challenges,proposing solutions,and research directions,such as optimizing electrolyte composition by integrating diverse cations and anions and employing advanced in-situ characterization techniques.These insights can significantly enhance CO_(2)reduction performance on Cu-based electrocatalysts,advancing efficient and sustainable green energy technologies.展开更多
Currently, the electrochemical CO_(2) reduction reaction (CO_(2) RR) can realize the resource conversion of CO_(2) , which is a promising approach to carbon resource use. Important advancements have been made in explo...Currently, the electrochemical CO_(2) reduction reaction (CO_(2) RR) can realize the resource conversion of CO_(2) , which is a promising approach to carbon resource use. Important advancements have been made in exploring the CO_(2) RR performance and mechanism because of the rational design of electrolyzer systems, such as H-cells, flow cells, and catalysts. Considering the future development direction of this technology and large-scale application needs, membrane electrode assembly (MEA) systems can improve energy use efficiency and achieve large-scale CO_(2) conversion, which is considered the most promising technology for industrial applications. This review will concentrate on the research progress and present situation of the MEA component structure. This paper begins with the composition and construction of a gas diff usion electrode. Then, the application of ion-exchange membranes in MEA is introduced. Furthermore, the eff ects of pH and the anion and cation of the anolyte on MEA performance are explored. Additionally, we present the anode reaction type in MEA. Finally, the challenges in this field are summarized, and upcoming trends are projected. This review should offer researchers a clearer picture of MEA systems and provide important, timely, and valuable insights into rational electrolyzer design to facilitate further development of CO_(2) electrochemical reduction.展开更多
Bismuth-based catalysts are highly promising for the electrochemical carbon dioxide reduction reaction(eCO_(2)RR)to formate product.However,achieving high activity and selectivity towards formate and ensuring long-ter...Bismuth-based catalysts are highly promising for the electrochemical carbon dioxide reduction reaction(eCO_(2)RR)to formate product.However,achieving high activity and selectivity towards formate and ensuring long-term stability remains challenging.This work reports the oxygen plasma inducing strategy to construct the abundant grain boundaries of Bi/BiO_x on ultrathin two-dimensional Bi nanosheets.The oxygen plasma-treated Bi nanosheet(OP-Bi)exhibits over 90%Faradaic efficiency(FE)for formate at a wide potential range from-0.5 to-1.1 V,and maintains a great stability catalytic performance without significant decay over 30 h in flow cell.Moreover,membrane electrode assembly(MEA)device with OPBi as catalyst sustains the robust current density of 100 mA cm^(-2)over 50 h,maintaining a formate FE above 90%.In addition,rechargeable Zn-CO_(2)battery presents the peak power density of1.22 mW cm^(-2)with OP-Bi as bifunctional catalyst.The mechanism experiments demonstrate that the high-density grain boundaries of OP-Bi provide more exposed active sites,faster electron transfer capacity,and the stronger intrinsic activity of Bi atoms.In situ spectroscopy and theo retical calculations further elucidate that the unsaturated Bi coordination atoms between the grain boundaries can effectively activate CO_(2)molecules through elongating the C-O bond,and reducing the formation energy barrier of the key intermediate(^(*)OCOH),thereby enhancing the catalytic performance of eCO_(2)RR to formate product.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22479097)the Shanghai Science and Technology Committee(Grant No.23ZR1433000)the National High-Level Talent Program for Young Scholars,the Start-up Fund(F.S.)from Shanghai Jiao Tong University.
文摘Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.
基金funded by the National Natural Science Foundation of China,China (Nos.52272303 and 52073212)the General Program of Municipal Natural Science Foundation of Tianjin,China (Nos.17JCYBJC22700 and 17JCYBJC17000)the State Scholarship Fund of China Scholarship Council,China (Nos.201709345012 and 201706255009)。
文摘The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) (Grant Nos.2018R1A6A1A03024334,2019R1A2C1007637,2021M3I3A1082880,2021R1I1A1A01044174)the Basic Science Research Capacity Enhancement Project through Korea Basic Science Institute (Grant No.2019R1A6C1010024)。
文摘The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-based electrocatalyst was developed for use in gas-diffusion electrodes(GDE),and the effect of nitrogen(N)doping on the ECR activity of ZnO electrocatalysts was investigated.Initially,a ZnO nanosheet was prepared via the hydrothermal method,and nitridation was performed at different times to control the N-doping content.With an increase in the N-doping content,the morphological properties of the nanosheet changed significantly,namely,the 2D nanosheets transformed into irregularly shaped nanoparticles.Furthermore,the ECR performance of Zn O electrocatalysts with different N-doping content was assessed in 1.0 M KHCO_(3) electrolyte using a gas-diffusion electrode-based ECR cell.While the ECR activity increased after a small amount of N doping,it decreased for higher N doping content.Among them,the N:ZnO-1 h electrocatalysts showed the best CO selectivity,with a faradaic efficiency(FE_(CO))of 92.7%at-0.73 V vs.reversible hydrogen electrode(RHE),which was greater than that of an undoped Zn O electrocatalyst(FE_(CO)of 63.4%at-0.78 V_(RHE)).Also,the N:ZnO-1 h electrocatalyst exhibited outstanding durability for 16 h,with a partial current density of-92.1 mA cm^(-2).This improvement of N:ZnO-1 h electrocatalyst can be explained by density functional theory calculations,demonstrating that this improvement of N:ZnO-1 h electrocatalyst comes from(ⅰ)the optimized active sites lowering the free energy barrier for the rate-determining step(RDS),and(ⅱ)the modification of electronic structure enhancing the electron transfer rate by N doping.
基金financially supported by Outstanding Talent Research Fund of Zhengzhou University,China Postdoc toral Science Foundation(2020TQ0277,2020M682328)Central Plains Science and Technology Innovation Leader Project(214200510006)+1 种基金China Scholarship Council(No.202108410356)Postdoctoral Science Foundation of Henan province(202002010).
文摘Surface charge localization and inferior charge transfer efficiency seriously restrict the supply of reactive hydrogen and the reaction dynamics of CO_(2) photoreduction performance of photocatalysts.Herein,chemically bonded BiVO_(4)/Bi_(19)Cl_(3)S_(27)(BVO/BCS)S-scheme heterojunction with a strong internal electric field is designed.Experimental and density function theory calculation results confirm that the elaborated heterojunction accelerates the vectorial migration of photogenerated charges from BiVO_(4) to Bi_(19)Cl_(3)S_(27) via the interfacial chemical bonding interactions(i.e.,Bi-O and Bi-S bonds)between Bi atoms of BVO and S atoms of BCS or Bi atoms of BCS and O atoms of BVO under light irradiation,breaking the interfacial barrier and surface charge localization of Bi_(19)Cl_(3)S_(27),and further decreasing the energy of reactive hydrogen generation,CO_(2) absorption and activation.The separation efficiency of photogenerated carriers is much more efficient than that counterpart individual in BVO/BCS S-scheme heterojunction system.As a result,BVO/BCS heterojunction exhibits a significantly improved continuous photocatalytic performance for CO_(2) reduction and the 24 h CO yield reaches 678.27μmol⋅g^(-1).This work provides an atomic-level insight into charge transfer kinetics and CO_(2) reduction mechanism in S-scheme heterojunction.
基金National Natural Science Foundation of China,Grant/Award Numbers:52076209,52006224,52106285,22179027Foundation and Applied Foundation Research of Guangdong Province,Grant/Award Number:2022B1515020045+1 种基金Natural Science Foundation of Guangxi Province,Grant/Award Number:2021GXNSFAA075036Young Talent Support Project of Guangzhou Association for Science and Technology,Grant/Award Number:QT‐2023‐042。
文摘By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2) into CO.Generally,NiFe_(2_)O_(4) oxygen carriers have demonstrated remarkable efficiency in chemical looping CO_(2) conversion.Nevertheless,the intricate process of atomic migration and evolution within the internal structure of bimetallic oxygen carriers during continuous high‐temperature redox cycling remains unclear.Consequently,the lack of a fundamental understanding of the complex ionic migration and oxygen transfer associated with energy conversion processes hampers the design of high‐performance oxygen carriers.Thus,in this study,we employed in situ characterization techniques and theoretical calculations to investigate the ion migration behavior and structural evolution in the bulk of NiFe_(2_)O_(4) oxygen carriers during H_(2) reduction and CO_(2)/lab air oxidation cycles.We discovered that during the H_(2) reduction step,lattice oxygen rapidly migrates to vacancy layers to replenish consumed active oxygen species,while Ni leaches from the material and migrates to the surface.During the CO_(2) splitting step,Ni migrates toward the core of the bimetallic oxygen carrier,forming Fe–Ni alloys.During the air oxidation step,Fe–Ni migrates outward,creating a hollow structure owing to the Kirkendall effect triggered by the swift transfer of lattice oxygen.The metal atom migration paths depend on the oxygen transfer rates.These discoveries highlight the significance of regulating the release–recovery rate of lattice oxygen to uphold the structures and reactivity of oxygen carriers.This work offers a comprehensive understanding of the oxidation/reduction‐driven atomic interdiffusion behavior of bimetallic oxygen carriers.
文摘Chemical looping combustion has the potential to be an efficient and low-cost technology capable of contributing to the reduction of the atmospheric concentration of CO_(2) in order to reach the 1.5/2°C goal and mitigate climate change.In this process,a metal oxide is used as oxygen carrier in a dual fluidized bed to generate clean CO_(2) via combustion of biomass.Most commonly,natural ores or synthetic materials are used as oxygen carrier whereas both must meet special requirements for the conversion of solid fuels.Synthetic oxygen carriers are characterized by higher reactivity at the expense of higher costs versus the lower-cost natural ores.To determine the viability of both possibilities,a techno-economic comparison of a synthetic material based on manganese,iron,and copper to the natural ore ilmenite was conducted.The synthetic oxygen carrier was characterized and tested in a pilot plant,where high combustion efficiencies up to 98.4%and carbon capture rates up to 98.5%were reached.The techno-economic assessment resulted in CO_(2) capture costs of 75 and 40€/tCO_(2) for the synthetic and natural ore route respectively,whereas a sensitivity analysis showed the high impact of production costs and attrition rates of the synthetic material.The synthetic oxygen carrier could break even with the natural ore in case of lower production costs and attrition rates,which could be reached by adapting the production process and recycling material.By comparison to state-of-the-art technologies,it is demonstrated that both routes are viable and the capture cost of CO_(2) could be reduced by implementing the chemical looping combustion technology.
基金supported by the U.S.Department of Energy’s Office of Energy Efficiency and Renewable Energy(EERE)under the Industrial Efficiency&Decarbonization Office award number[DE-EE0009427]the funding support by the U.S.Department of Energy(USDOE),Office of Energy Efficiency and Renewable Energy(EERE),Advanced Manufacturing Office(AMO),under DOE Idaho Operations Office under Contract No.DEAC07-05ID14517
文摘High-temperature CO_(2)electrolysis via solid oxide electrolysis cells(CO_(2)-SOECs)has drawn special attention due to the high energy convention efficiency,fast electrode kinetics,and great potential in carbon cycling.However,the development of cathode materials with high catalytic activity and chemical stability for pure CO_(2)electrolysis is still a great challenge.In this work,A-site cation deficient dual-phase material,namely(Pr_(0.4)Ca_(0.6))_(x)Fe_(0.8)Ni_(0.2)O_(3-δ)(PCFN,x=1,0.95,and 0.9),has been designed as the fuel electrode for a pure CO_(2)-SOEC,which presents superior electrochemical performance.Among all these compositions,(Pr_(0.4)Ca_(0.6))_(0.95)Fe_(0.8)Ni_(0.2)O_(3-δ)(PCFN95)exhibited the lowest polarization resistance of 0.458Ωcm^(2)at open-circuit voltage and 800℃.The application of PCFN95 as the cathode in a single cell yields an impressive electrolysis current density of 1.76 A cm^(-2)at 1.5 V and 800℃,which is 76%higher than that of single cells with stoichiometric Pr_(0.4)Ca_(0.6)Fe_(0.8)Ni_(0.2)O_(3-δ)(PCFN100)cathode.The effects of A-site deficiency on materials'phase structure and physicochemical properties are also systematically investigated.Such an enhancement in electrochemical performance is attributed to the promotion of effective CO_(2)adsorption,as well as the improved electrode kinetics resulting from the A-site deficiency.
文摘Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have been proposed to address the challenges.Carbon capture and utilization(CCU) represents one of the approaches and thermochemical CO_(2) splitting driven by thermal energy is a subset of the CCU,which converts the captured CO_(2) into CO and makes it possible to achieve closed-loop carbon recirculation.Redox-active catalysts are among the most critical components of the thermochemical splitting cycles and perovskites are regarded as the most promising catalysts.Here we review the latest advancements in thermochemical cycles based on perovskites,covering thermodynamic principles,material modifications,reaction kinetics,oxygen pressure control,circular strategies,and demonstrations to provide a comprehensive overview of the topical area.Thermochemical cycles based on such materials require the consideration of trade-off between cost and efficiency,which is related to actual material used,operation mode,oxygen removal,and heat recovery.Lots of efforts have been made towards improving reaction rates,conversion efficiency and cycling stability,materials related research has been lacking-a key aspect affecting the performance across all above aspects.Double perovskites and composite perovskites arise recently as a potentially promising addition to material candidates.For such materials,more effective oxygen removal would be needed to enhance the overall efficiency,for which thermochemical or electrochemical oxygen pumps could contribute to efficient oxygen removal as well as serve as means for inert gas regeneration.The integration of thermochemical CO_(2) splitting process with downstream fuel production and other processes could reduce costs and increase efficiency of the technology.This represents one of the directions for the future research.
基金Financial support was provided through the Instituto de Geociencias Básicas,Aplicadas y Ambientales de Buenos Aires(IGEBA)and the Instituto de Geocronología y Geología Isotópica(INGEIS),both dependent of the Consejo Nacional de Investigaciones Científi cas y Técnicas(National Council for Scientific and Technological Research),and the Universidad de Buenos Aires(Buenos Aires University)of Argentinasupported by the Agencia Nacional de Promoción Científi ca y Tecnológica(National Agency for Scientific and Technological Promotion)projects PICT2010-0035 and PICT2010-2749。
文摘The magnitude and spatial variability of CO_(2)surface emissions and processes involving CO_(2)released to the atmosphere from the soils are relevant issues in the context of climate change.This work evaluated CO_(2)fluxes and^(13)C/^(12)C ratio of vegetation,organic matter,and soil gases from no disturbed soils of Chaco Pampean Plain(Argentina)with different soil properties and environmental conditions(PL and PA units).Soil organic decomposition from individual layers was accompanied byδ^(13)C of total organic carbon(δ^(13)C-TOC)values more enriched to depth.δ^(13)C-TOC values in the upper soil profile~ca.0–15 cm were like the plant community of this area(~−33 to−29‰)whileδ^(13)CTOC varied stronger bellow horizon A,till~−24‰.Bothδ^(13)C-TOC and soilδ^(13)C-CO_(2)were similar(~−24 to 26‰)at deeper horizons(~50–60 cm).Toward the superficial layers,δ^(13)C-TOC andδ^(13)C-CO_(2)showed more differences(till~4‰),due influence of the diffusion process.Horizon A layer(~0–20 cm)from both PL and PA units contained the most enrichedδ^(13)C-CO_(2)values(~−15–17‰)because atmospheric CO_(2)permeated the soil air.A simple two-component mixing model between sources(atmosphericδ^(13)C-CO_(2)and soil CO_(2))confirmed that process.Isotopically,CO_(2)fluxes reflected the biodegradation of C3 plants(source),diffusive transport,and CO_(2)exchange(atmosphere/soil).Soil moisture content appeared as a determining factor in the diffusion process and the magnitude of CO_(2)surface emissions(12–60 g·m^(−2)·d^(−1)).That condition was confirmed by CO_(2)diffusion coefficients estimated by air-filled porosity parameters and soil radon gradient model.
基金supported by the National Key R&D Program of China (2018YFA0901700)National Natural Science Foundation of China (22278241)+1 种基金a grant from the Institute Guo Qiang, Tsinghua University (2021GQG1016)Department of Chemical Engineering-iBHE Joint Cooperation Fund。
文摘The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.
基金the funding support from the National Key Research and Development Program of China(2019YFE0123400)the Tianjin Distinguished Young Scholars Fund(20JCJQJC00260)+4 种基金the Major Science and Technology Project of Anhui Province(202203f07020007)the Anhui Conch Group Co.,Ltdthe“111”Project(B16027)the funding support from the Natural Science Foundation of China(22209081)the fellowship of China Postdoctoral Science Foundation(2021M690082)。
文摘Developing bimetallic catalysts is an effective strategy for enhancing the activity and selectivity of electrochemical CO_(2) reduction reactions,where understanding the structure-activity relationship is essential for catalyst design.Herein,we prepared two Cu-Ag bimetallic catalysts with Ag nanoparticles attached to the top or the bottom of Cu nanowires.When tested in a flow cell,the Cu-Ag catalyst with Ag nanoparticles on the bottom achieved a faradaic efficiency of 54%for ethylene production,much higher than the catalyst with Ag nanoparticles on the top.The catalysts were further studied in the H-cell and zero-gap MEA cell.It was found that placing the two metals in the intensified reaction zone is crucial to triggering the tandem reaction of bimetallic catalysts.Our work elucidates the structure-activity relationship of bimetallic catalysts for CO_(2) reduction and demonstrates the importance of considering both catalyst structures and cell characteristics to achieve high activity and selectivity.
基金Financial support from the National Natural Science Foundation of China(grant nos.22379006,21575016,U20A20154,22279005)from the National Program for Support of Top-notch Young Professionals is gratefully acknowledged。
文摘The electrocatalytic conversion of CO_(2) into valuable chemical feedstocks using renewable electricity offers a compelling strategy for closing the carbon loop.While copper-based materials are effective in catalyzing CO_(2) to C_(2+)products,the instability of Cu^(+)species,which tend to reduce to Cu~0 at cathodic potentials during CO_(2) reduction,poses a significant challenge.Here,we report the development of SmCu_(2)O and investigate the influence of f-d orbital hybridization on the CO_(2) reduction reaction (CO_(2)RR).Supported by density functional theory (DFT) calculations,our experimental results demonstrate that hybridization between Sm^(3+)4f and Cu^(+)3d orbitals not only improves the adsorption of *CO intermediates and increases CO coverage to stabilize Cu^(+) but also facilitates CO_(2) activation and lowers the energy barriers for CAC coupling.Notably,Sm-Cu_(2)O achieves a Faradaic efficiency for C_(2)H_(4) that is 38%higher than that of undoped Cu_(2)O.Additionally,it sustains its catalytic activity over an extended operational period exceeding 7 h,compared to merely 2 h for the undoped sample.This research highlights the potential of fd orbital hybridization in enhancing the efficacy of copper-based catalysts for CO_(2)RR,pointing towards a promising direction for the development of durable,high-performance electrocatalysts for sustainable chemical synthesis.
基金financially supported by the National Natural Science Foundation of China with grant number of 22172082 and 21978137。
文摘The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great significance.Cu-based catalysts have been widely investigated for ECR due to their unique ability to generate various carbonaceous products,but directing selectivity toward one certain product and identifying the real active sites during ECR are still full of challenge.Here,after the incorporation of CdO into CuO,the Cu_(0.5)Cd_(0.5)-O catalyst achieves a 10.3-fold enhancement for CO selectivity in comparison with CuO,and a CO faradic efficiency nearly 90%with a current density around20 mA cm^(-2)could maintain at least 60 h.Interestingly,a wide CO/H_(2)ratio(0.07-10)is reached on Cu_(x)Cd_(1-x)-O catalysts by varying the Cu/Cd ratio,demonstrating the potential of syngas production using such catalysts.The results of ex situ XRD,XPS,and in situ Raman reveal that the real active sites of Cu_(0.5)Cd_(0.5)-O catalysts for CO production during ECR reaction are the reconstructed mixed phases of CuCd alloy and CdCO_(3).In situ FTIR and theoretical calculations further implicate the presence of Cd related species promotes the CO desorption and inhibits the H_(2)evolution,thus leading to an enhanced CO generation.
基金supported by the Hubei Provincial Natural Science Foundation of China (2023AFB0049)the Scientific Research Fund Project of Wuhan Institute of Technology (No.K2024006)the Graduate Education Innovation Fund of Wuhan Institute of Technology (No. CX2023091)。
文摘Electrocatalytic reduction of CO_(2)is crucial for environmental sustainability and renewable energy storage,with Cu-based catalysts excelling in producing high-value C_(2+)products.However,a comprehensive analysis of how specific electrolyte influences Cu-based catalysts is lacking.This review addresses this gap by focusing on how electrolytes impact surface reconstruction and the CO_(2) reduction process on Cu-based electrocatalysts,identifying specific electrolyte compositions that enhance the density and stability of active sites,and providing insights into how different electrolyte environments modulate the selectivity and efficiency of C_(2+)product formation.The review begins by exploring how electrolytes induce favorable surface reconstruction in Cu-based catalysts,affecting surface roughness through dissolution-redeposition of Cu species and interactions with halogens and molecular additives.It also covers changes in crystalline facets of Cu and Cu_(2)O,and oxidation states,highlighting transitions from Cu^(0) to Cu^(δ+)and the stabilization of Cu^(+).The role of electrolytes in the C–C coupling process is examined,emphasizing their effects in modulating mass and charge transfer,CO_(2) adsorption,intermediate evolution,and product desorption.Subsequently,the mechanisms by non-aqueous electrolytes,including organic solvents,ionic liquids,and mixed electrolytes,affecting CO_(2) reduction are analyzed,highlighting the unique advantages and challenges of each type.The review concludes by addressing current challenges,proposing solutions,and research directions,such as optimizing electrolyte composition by integrating diverse cations and anions and employing advanced in-situ characterization techniques.These insights can significantly enhance CO_(2)reduction performance on Cu-based electrocatalysts,advancing efficient and sustainable green energy technologies.
基金The financial assistance for this work was provided by the National Natural Science Foundation of China (Nos. 51773092, 21975124, 20210283, and 22109070)the Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure (No. SKL201911SIC).
文摘Currently, the electrochemical CO_(2) reduction reaction (CO_(2) RR) can realize the resource conversion of CO_(2) , which is a promising approach to carbon resource use. Important advancements have been made in exploring the CO_(2) RR performance and mechanism because of the rational design of electrolyzer systems, such as H-cells, flow cells, and catalysts. Considering the future development direction of this technology and large-scale application needs, membrane electrode assembly (MEA) systems can improve energy use efficiency and achieve large-scale CO_(2) conversion, which is considered the most promising technology for industrial applications. This review will concentrate on the research progress and present situation of the MEA component structure. This paper begins with the composition and construction of a gas diff usion electrode. Then, the application of ion-exchange membranes in MEA is introduced. Furthermore, the eff ects of pH and the anion and cation of the anolyte on MEA performance are explored. Additionally, we present the anode reaction type in MEA. Finally, the challenges in this field are summarized, and upcoming trends are projected. This review should offer researchers a clearer picture of MEA systems and provide important, timely, and valuable insights into rational electrolyzer design to facilitate further development of CO_(2) electrochemical reduction.
基金supported by the Hainan Province Science and Technology Special Fund(ZDYF2024SHFZ074,ZDYF2024SHFZ072,ZDYF2022SHFZ299)the National Natural Science Foundation of China(22109035,22202053,52164028,52274297,22309037)+4 种基金the Start-up Research Foundation of Hainan University(KYQD(ZR)-20008,20083,20084,21125,23035)the collaborative Innovation Center of Marine Science and Technology,Hainan University(XTCX2022HYC04,XTCX2022HYC05)the Innovative Research Projects for Graduate Students of Hainan Province(Qhyb2022-89,Qhyb2022-87,Qhys2022-174)the Scientific Research Program Funded by Shaanxi Provincial Education Department(Program No.23JK0439)the specific research fund of The Innovation Platform for Academicians of Hainan Province(YSPTZX202315)。
文摘Bismuth-based catalysts are highly promising for the electrochemical carbon dioxide reduction reaction(eCO_(2)RR)to formate product.However,achieving high activity and selectivity towards formate and ensuring long-term stability remains challenging.This work reports the oxygen plasma inducing strategy to construct the abundant grain boundaries of Bi/BiO_x on ultrathin two-dimensional Bi nanosheets.The oxygen plasma-treated Bi nanosheet(OP-Bi)exhibits over 90%Faradaic efficiency(FE)for formate at a wide potential range from-0.5 to-1.1 V,and maintains a great stability catalytic performance without significant decay over 30 h in flow cell.Moreover,membrane electrode assembly(MEA)device with OPBi as catalyst sustains the robust current density of 100 mA cm^(-2)over 50 h,maintaining a formate FE above 90%.In addition,rechargeable Zn-CO_(2)battery presents the peak power density of1.22 mW cm^(-2)with OP-Bi as bifunctional catalyst.The mechanism experiments demonstrate that the high-density grain boundaries of OP-Bi provide more exposed active sites,faster electron transfer capacity,and the stronger intrinsic activity of Bi atoms.In situ spectroscopy and theo retical calculations further elucidate that the unsaturated Bi coordination atoms between the grain boundaries can effectively activate CO_(2)molecules through elongating the C-O bond,and reducing the formation energy barrier of the key intermediate(^(*)OCOH),thereby enhancing the catalytic performance of eCO_(2)RR to formate product.
