Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor select...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor selectivity and low current density due to its sluggish kinetics and multitudinous reaction pathways.Single-atom catalysts(SACs)demonstrate outstanding activity,excellent selectivity,and remarkable atom utilization efficiency,which give impetus to the search for electrocatalytic processes aiming at high selectivity.There appears significant activity in the development of efficient SACs for CO_(2)RR,while the density of the atomic sites remains a considerable barrier to be overcome.To construct high-metal-loading SACs,aggregation must be prevented,and thus novel strategies are required.The key to creating high-density atomically dispersed sites is designing enough anchoring sites,normally defects,to stabilize the highly mobile separated metal atoms.In this review,we summarized the advances in developing high-loading SACs through defect engineering,with a focus on the synthesis strategies to achieve high atomic site loading.Finally,the future opportunities and challenges for CO_(2)RR in the area of high-loading single-atom electrocatalysts are also discussed.展开更多
The electronic structure of electrocatalysts plays a critical role in energy conversion,whereas for an efficient catalyst,it is challenging to modulate the orbitals.Herein,we present a new strategy to modulate the e_(...The electronic structure of electrocatalysts plays a critical role in energy conversion,whereas for an efficient catalyst,it is challenging to modulate the orbitals.Herein,we present a new strategy to modulate the e_(g) orbital occupancy of Pd by constructing composition-controllable Pd-Au metallic aerogels(MAs),optimizing the d-band center of Pd to achieve excellent performance for electrochemical carbon dioxide reduction reaction(CO_(2)RR).Specifically,Pd_(1)Au_(2) MAs achieve almost 100% Faraday efficiency(FE) of CO in the range of-0.40 to-0.80 V vs.reversible hydrogen electrode(RHE),as well as the long-term stability,being one of the best Pd-based materials for CO_(2)RR.The X-ray photoelectron spectroscopy(XPS) results and density functional theory(DFT) calculations demonstrate that the introduction of Au modulates the Pd e_(g) orbital occupancy,which significantly weakens *CO adsorption on Pd,reduces the CO_(2)RR energy barrier and consequently improves the electrocatalytic activity and stability for long-term applications.Our work highlights a new strategy for designing efficient electrocatalysts for CO_(2)RR and beyond.展开更多
Photocatalytic water splitting and carbon dioxide reduction provide us clean and sustainable energy resources. The carbon dioxide reduction is also the redemption of the greenhouse effect. MoS/TiOphotocatalysts based ...Photocatalytic water splitting and carbon dioxide reduction provide us clean and sustainable energy resources. The carbon dioxide reduction is also the redemption of the greenhouse effect. MoS/TiOphotocatalysts based on TiOnanoplates have been synthesized via a hydrothermal acidification route for water and carbon dioxide reduction reactions. This facile approach generates well dispersed Mo S3 with low crystallinity on the surface of TiOnanoplates. The as-synthesized MoS/TiOphotocatalyst showed considerable activity for both water reduction and carbon dioxide reduction. The thermal treatment effects of TiO, the loading percentage of MoSand the crystalline phase of TiOhave been investigated towards the photocatalytic performance. TiOnanoplate synthesized through hydrothermal reaction with the presence of HF acid is an ideal semiconductor material for the loading of MoSfor photocatalytic water and carbon dioxide reduction simultaneously in EDTA sacrificial solution.展开更多
Achieving carbon neutrality is an essential part of responding to climate change caused by the deforestation and over-exploitation of natural resources that have accompanied the development of human society.The carbon...Achieving carbon neutrality is an essential part of responding to climate change caused by the deforestation and over-exploitation of natural resources that have accompanied the development of human society.The carbon dioxide reduction reaction(CO_(2)RR)is a promising strategy to capture and convert carbon dioxide(CO_(2))into value-added chemical products.However,the traditional trial-and-error method makes it expensive and time-consuming to understand the deeper mechanism behind the reaction,discover novel catalysts with superior performance and lower cost,and determine optimal support structures and electrolytes for the CO_(2)RR.Emerging machine learning(ML)techniques provide an opportunity to integrate material science and artificial intelligence,which would enable chemists to extract the implicit knowledge behind data,be guided by the insights thereby gained,and be freed from performing repetitive experiments.In this perspective article,we focus on recent ad-vancements in ML-participated CO_(2)RR applications.After a brief introduction to ML techniques and the CO_(2)RR,we first focus on ML-accelerated property prediction for potential CO_(2)RR catalysts.Then we explore ML-aided prediction of catalytic activity and selectivity.This is followed by a discussion about ML-guided catalyst and electrode design.Next,the potential application of ML-assisted experimental synthesis for the CO_(2)RR is discussed.展开更多
Although converting the greenhouse gasses carbon dioxide(CO_(2))into solar fuels is regarded as a convenient means of solar energy storage,the intrinsic mechanism on how the high chemical inertness linear CO_(2)molecu...Although converting the greenhouse gasses carbon dioxide(CO_(2))into solar fuels is regarded as a convenient means of solar energy storage,the intrinsic mechanism on how the high chemical inertness linear CO_(2)molecules is activated and converted on a semiconductor oxide is still elusive.Herein,by creating the oxygen vacancies on the typical hexagonal tungsten oxide(WO3),we realize the continuous photoinduced CO_(2)reduction to selectively produce CO under light irradiation,which was verified by isotope labeling experiment.Detailed oxygen vacancies evolution investigation indicates that light irradiation can simultaneously induce the in-situ formation of oxygen vacancies on hexagonal WO3,and the oxygen vacancies promote the adsorption and activation of CO_(2)molecules,leading to the CO_(2)reduction to CO on the hexagonal WO3via an oxygen vacancies-involved process.Besides,the existence of water further promotes the formation of CO_(2)reduction intermediate,further promote the CO_(2)photoreduction.Our work provides insight on the mechanism for converting CO_(2)into CO under light irradiation.展开更多
Mixed metal oxide(MMO) represents a critical class of materials that can allow for obtaining a dynamic interface between its components:reduced metal and its metal oxide counterpart during an electrocatalytic reaction...Mixed metal oxide(MMO) represents a critical class of materials that can allow for obtaining a dynamic interface between its components:reduced metal and its metal oxide counterpart during an electrocatalytic reaction.Here,a synthetic method utilizing a MOF-derived micro/mesoporous carbon as a template to prepare sub-2 nm MMO catalysts for CO_(2) electro reduction is reported.Starting from the zeolite imidazolate framework(ZIF-8),the pyrolyzed derivatives were used to synthesize sub-2 nm Pd-Ni MMO with different compositions.The Ni-rich(Pd_(20)-Ni_(80)/ZC) catalyst exhibits unexpectedly superior performance for CO production with an improved Faradaic efficiency(FE) of 95.3% at the current density of 200 mA cm^(-2) at-0.56 V vs.reversible hydrogen electrode(RHE) compared to other Pd-Ni compositions.X-ray photoelectron spectroscopy(XPS) analysis confirms the presence of Ni^(2+) and Pd^(2+) in all compositions,demonstrating the presence of MMO.Density functional theory(DFT) calculation reveals that the lower CO binding energy on the surface of the Pd_(20)-Ni_(80) cluster eases CO desorption,thus increasing its production.This work provides a general synthetic strategy for MMO electrocatalysts and can pave a new way for screening multimetallic catalysts with a dynamic electrochemical interface.展开更多
The electrochemical reduction of CO_(2) is an extremely potential technique to achieve the goal of carbon neutrality,but the development of electrocatalysts with high activity,excellent product selectivity,and long-te...The electrochemical reduction of CO_(2) is an extremely potential technique to achieve the goal of carbon neutrality,but the development of electrocatalysts with high activity,excellent product selectivity,and long-term durability remains a great challenge.Herein,the role of metal-supports interaction(MSI)between different active sites(including single and bimetallic atom sites consisting of Cu and Ni atoms)and carbon-based supports(including C_(2) N,C_(3)N_(4),N-coordination graphene,and graphdiyne)on catalytic activity,prod-uct selectivity,and thermodynamic stability towards CO_(2) reduction reaction(CRR)is systematically investi-gated by first principles calculations.Our results show that MSI is mainly related to the charge transfer behavior from metal sites to supports,and different MSI leads to diverse magnetic moments and d-band centers.Subsequently,the adsorption and catalytic performance can be efficiently improved by tuning MSI.Notably,the bimetallic atom supported graphdiyne not only exhibits a better catalytic activity,higher product selec-tivity,and higher thermodynamic stability,but also effectively inhibits the hydrogen evolution reaction.This finding provides a new research idea and optimization strategy for the rational design of high-efficiency CRR catalysts.展开更多
Due to the burning of fossil fuels,the level of carbon dioxide(CO2)in the atmosphere gradually rises,leading to serious greenhouse effect and environmental problems.Electrocatalytic reduction of CO2 is currently an ef...Due to the burning of fossil fuels,the level of carbon dioxide(CO2)in the atmosphere gradually rises,leading to serious greenhouse effect and environmental problems.Electrocatalytic reduction of CO2 is currently an efficient way to convert CO2 to value-added products.Bismuth(Bi)-based nanomaterials have raised great interests due to their excellent activity and high selectivity to electrocatalytic CO2 reduction.In this review,the fundamental principles of electrochemical CO2 reduction reaction(CO2RR)are introduced at first.Moreover,the recent development of Bi-based electrocatalytic materials including Bi with various nanostructures(nanoparticle,nanosheet.etc.),Bi-based compounds(Bi oxide,bimetal chalcogenide,etc.),and Bi/C nanocomposites are summarized.In the end,the future prospects and challenges of electrocatalysts for CO2 reduction are discussed.展开更多
The precise control on the combination of multiple metal atoms in the structure of metal-organic frameworks(MOFs)endowed by reticular chemistry,allows the obtaining of materials with compositions that are programmed f...The precise control on the combination of multiple metal atoms in the structure of metal-organic frameworks(MOFs)endowed by reticular chemistry,allows the obtaining of materials with compositions that are programmed for achieving enhanced reactivity.The present work illustrates how through the transformation of MOFs with desired arrangements of metal cations,multi-metal spinel oxides with precise compositions can be obtained,and used as catalyst precursor for the reverse water-gas shift reaction.The differences in the spinel initial composition and structure,determined by neutron powder diffraction,influence the overall catalytic activity with changes in the process of in s itu formation of active,metal-oxide supported metal nanoparticles,which have been monitored and characterized with in situ X-ray diffraction and photoelectron spectroscopy studies.展开更多
Bismuth-based materials(e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO_(2) to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismu...Bismuth-based materials(e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO_(2) to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismuth oxides and subcarbonate encounter stability issues. This work is designated to exemplify that the operando synthesis can be an effective means to enhance the stability of electrocatalysts under operando CO_(2)RR conditions. A synthetic approach is developed to electrochemically convert Bi^(O)Cl into Cl-containing subcarbonate(Bi_(2)O_(2)(CO_(3))_(x)Cl_(y)) under operando CO_(2)RR conditions. The systematic operando spectroscopic studies depict that BiOCl is converted to Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) via a cathodic potential-promoted anion-exchange process. The operando synthesizedBi_(2)O_(2)(CO_(3))_(x)Cl_(y) can tolerate-1.0 V versus RHE, while for the wet-chemistry synthesized pure Bi_(2)O_(2)CO_(3),the formation of metallic Bio occurs at-0.6 V versus RHE. At-0.8 V versus RHE, Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) can readily attain a FEHCOO-of 97.9%,much higher than that of the pure Bi_(2)O_(2)CO_(3)(81.3%). DFT calculations indicate that differing from the pure Bi_(2)O_(2)CO_(3)-catalyzed CO_(2)RR, where formate is formed via a *OCHO intermediate step that requires a high energy input energy of 2.69 eV to proceed, the formation of H COO-over Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) has proceeded via a *COOH intermediate step that only requires low energy input of 2.56 eV.展开更多
Nb-containing catalysts have the potential to catalyze carbon dioxide(CO_(2))reduction due to their strong surface acidity and CO_(2)activation sites.Still,they have not been widely used in the development and design ...Nb-containing catalysts have the potential to catalyze carbon dioxide(CO_(2))reduction due to their strong surface acidity and CO_(2)activation sites.Still,they have not been widely used in the development and design of catalysts due to the theoretical/cost/safety limitations.Related advances have been continuously reported in the literature,demonstrating to some extent the promise of catalytic applications of Nb-containing catalysts in this area.In this minireview,we discuss the structure-activity relationships of Nb-containing catalysts for photo-,electro-,and thermocatalytic reduction of CO_(2).The engineering strategies of Nb-containing catalysts for enhancing the conversion and selectivity of CO_(2)reduction are discussed,ranging from Nb doping,noble metal decoration,surface acidity adjustment,oxygen vacancy engineering,and heterojunction construction to Nb or Nb_(2)O_(5) particle decoration.The theoretical calculation research for the possible reaction paths and product selectivity is also discussed.Finally,the prospects for designing and optimizing Nb-containing catalysts are proposed.With a deep understanding of catalytic activity and reaction mechanism,this minireview is expected to present the optimization of the Nb-containing catalysts for efficient and highly selective CO_(2)reduction.展开更多
Cu catalysts can convert CO_(2) through an electrochemical reduction reaction into a variety of useful carbon-based products.However,this capability provides an obstacle to increasing the selectivity for a single prod...Cu catalysts can convert CO_(2) through an electrochemical reduction reaction into a variety of useful carbon-based products.However,this capability provides an obstacle to increasing the selectivity for a single product.Herein,we report a simple fabrication method for a Cu-Pd alloy catalyst for use in a membrane electrode assembly(MEA)-based CO_(2) electrolyzer for the electrochemical CO_(2) reduction reaction(ECRR)with high selectivity for CO production.When the composition of the Cu-Pd alloy catalyst was fabricated at 6:4,the selectivity for CO increased and the production of multi-carbon compounds and hydrogen is suppressed.Introducing a Cu-Pd alloy catalyst with 6:4 ratio as the cathode of the MEAbased CO_(2) electrolyzer showed a CO faradaic efficiency of 92.8%at 2.4 V_(cell).We assumed that these results contributed from the crystal planes on the surface of the Cu-Pd alloy.The phases of the Cu-Pd alloy catalyst were partially separated through annealing to fabricate a catalyst with high selectivity for CO at low voltage and C_(2)H_4 at high voltage.The results of CO-stripping testing confirmed that when Cu partially separates from the lattice of the Cu-Pd alloy,the desorption of~*CO is suppressed,suggesting that C-C coupling reaction is favored.展开更多
The electrochemical CO_(2) reduction reaction(CO_(2)RR) to controllable chemicals is considered as a promising pathway to store intermittent renewable energy. Herein, a set of catalysts based on copper-nitrogendoped c...The electrochemical CO_(2) reduction reaction(CO_(2)RR) to controllable chemicals is considered as a promising pathway to store intermittent renewable energy. Herein, a set of catalysts based on copper-nitrogendoped carbon xerogel(Cu-N-C) are successfully developed varying the copper amount and the nature of the copper precursor, for the efficient CO_(2)RR. The electrocatalytic performance of Cu-N-C materials is assessed by a rotating ring-disc electrode(RRDE), technique still rarely explored for CO_(2)RR. For comparison, products are also characterized by online gas chromatography in a H-cell. The as-synthesized Cu-NC catalysts are found to be active and highly CO selective at low overpotentials(from -0.6 to -0.8 V vs.RHE) in 0.1 M KHCO_(3), while H_(2) from the competitive water reduction appears at larger overpotentials(-0.9 V vs. RHE). The optimum copper acetate-derived catalyst containing Cu-N_(4) moieties exhibits a CO_(2)-to-CO turnover frequency of 997 h^(-1) at -0.9 V vs. RHE with a H_(2)/CO ratio of 1.8. These results demonstrate that RRDE configuration can be used as a feasible approach for identifying electrolysis products from CO_(2)RR.展开更多
Natural magnetite formed by the isomorphism substitutions of transition metals,including Fe,Ti,Co,etc.,was activated by mechanical grinding followed by H2 reduction.The temperature-programmed reduction of hydrogen(H2-...Natural magnetite formed by the isomorphism substitutions of transition metals,including Fe,Ti,Co,etc.,was activated by mechanical grinding followed by H2 reduction.The temperature-programmed reduction of hydrogen(H2-TPR)and temperature-programmed surface reaction of carbon dioxide(CO2-TPSR)were carried out to investigate the processes of oxygen loss and CO2 reduction.The samples were characterized by X-ray diffraction(XRD),field emission scanning electron microscopy(FE-SEM),and energy-dispersive X-ray spectroscopy(EDS).The results showed that the stability of spinel phases and oxygen-deficient degree significantly increased after natural magnetite was mechanically milled and reduced in H2 atmosphere.Meanwhile,the activity and selectivity of CO2 reduction into carbon were enhanced.The deposited carbon on the activated natural magnetite was confirmed as amorphous.The amount of carbon after CO2 reduction at 300°C for 90 min over the activated natural magnetite was 2.87wt%higher than that over the natural magnetite.展开更多
Carbon dioxide electrochemical reduction(CO_(2)RR)has been recognized as an efficient way to mitigate CO_(2)emissions and alleviate the pressure on global warming and associated environmental consequences.Gold(Au)is r...Carbon dioxide electrochemical reduction(CO_(2)RR)has been recognized as an efficient way to mitigate CO_(2)emissions and alleviate the pressure on global warming and associated environmental consequences.Gold(Au)is reported as stable and active electrocatalysts to convert CO_(2)to CO at low overpotential due to its moderate adsorption strength of^(*)COOH and^(*)CO.The request for improved catalytic performance,however,is motivated by current unsatisfied catalytic selectivity because of the side hydrogen evolution reaction.In this context,the design of Au based binary catalysts that can boost CO selectivity is of great interest.In the present work,we report that Au nanoparticles can be feasibly dispersed and anchored on silicon nanowires to form Au-Si binary nanomaterials.The Au-Si may stably drive CO_(2)RR with a CO Faraday efficiency of 95.6%at−0.6 V vs.RHE in 0.5 mol/L KHCO_(3)solution.Such selectivity outperforms Au particles by up to 61%.Controlled experiments illustrate that such catalytic enhancement can chiefly be ascribed to electronic effects of binary catalysts.Theoretical calculations reveal that spontaneously produced silicon oxide may not only inhibit hydrogen evolution reaction,but also stabilize the key intermediate^(*)COOH in CO formation.展开更多
Electrocatalytic carb on dioxide reducti on(CO_(2)R)presents a promising route to establish zero-e mission carb on cycle and store in termittent ren ewable energy into chemical fuels for steady energy supply.Methanol ...Electrocatalytic carb on dioxide reducti on(CO_(2)R)presents a promising route to establish zero-e mission carb on cycle and store in termittent ren ewable energy into chemical fuels for steady energy supply.Methanol is an ideal energy carrier as alternative fuels and one of the most important commodity chemicals.Nevertheless,methanol is currently mainly produced from fossil-based syngas,the production of which yields tremendous carb on emission globally.Direct CO_(2)R towards metha nol poses great potential to shift the paradigm of methanol production.In this perspective,we focus our discussions on producing methanol from electrochemical CO_(2)R,using metallomacrocyclic molecules as the model catalysts.We discuss the motivation of having methanol as the sole CO_(2)R product,the documented application of metallomacrocyclic catalysts for CO_(2)R,and recent advance in catalyzing CO_(2) to methanol with cobalt phthalocyanine-based catalysts.We attempt to understand the key factors in determining the activity,selectivity,and stability of electrocatalytic CO_(2)-to-methanol conversion,and to draw mechanistic insights from existing observations.Finally,we identify the challenges hindering methanol electrosynthesis directly from CO_(2) and some intriguing directions worthy of further investigation and exploration.展开更多
Recently,research on the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR)has attracted considerable attention due to its potential to resolve environmental problems caused by CO_(2) while utilizing clean energy a...Recently,research on the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR)has attracted considerable attention due to its potential to resolve environmental problems caused by CO_(2) while utilizing clean energy and producing high‐value‐added products.Considerable theoretical research in the lab has demonstrated its feasibility and prospect.However,industrialization is mandatory to realize the economic and social value of eCO_(2)RR.For industrial application of eCO_(2)RR,more criteria have been proposed for eCO_(2)RR research,including high current density(above 200 mA cm^(−2)),high product selectivity(above 90%),and long‐term stability.To fulfill these criteria,the eCO_(2)RR system needs to be systematically designed and optimized.In this review,recent research on eCO_(2)RR for industrial applications is summarized.The review starts with focus on potential industrial catalysts in eCO_(2)RR.Next,potential industrial products are proposed in eCO_(2)RR.These products,including carbon monoxide,formic acid,ethylene,and ethanol,all have high market demand,and have shown high current density and product selectivity in theoretical research.Notably,the innovative components and strategy for industrializing the eCO_(2)RR system are also highlighted here,including flow cells,seawater electrolytes,solid electrolytes,and a two‐step method.Finally,some instructions and possible future avenues are presented for the prospects of future industrial application of eCO_(2)RR.展开更多
The electrochemical carbon dioxide reduction reaction(CO_(2)RR)for highvalue-added products is a promising strategy to tackle excessive CO_(2) emissions.However,the activity of and selectivity for catalysts for CO_(2)...The electrochemical carbon dioxide reduction reaction(CO_(2)RR)for highvalue-added products is a promising strategy to tackle excessive CO_(2) emissions.However,the activity of and selectivity for catalysts for CO_(2)RR still need to be improved because of the competing reaction(hydrogen evolution reaction).In this study,for the first time,we have demonstrated dual atomic catalytic sites for CO_(2)RR from a core-shell hybrid of the covalent-organic framework and the metal-organic framework.Due to abundant dual atomic sites(with CoN_(4)O and ZnN_(4) of 2.47 and 11.05 wt.%,respectively)on hollow carbon,the catalyst promoted catalysis of CO_(2)RR,with the highest Faradic efficiency for CO of 92.6%at-0.8 V and a turnover frequency value of 1370.24 h^(-1) at-1.0 V.More importantly,the activity and selectivity of the catalyst were well retained for 30 h.The theoretical calculation further revealed that CoN_(4)O was the main site for CO_(2)RR,and the activity of and selectivity for Zn sites were also improved because of the synergetic roles.展开更多
Continuous accumulation and emission into the atmosphere of anthropogenic carbon dioxide(CO_(2)),a major greenhouse gas,has been recognized as a primary contributor to climate change associated with the global warming...Continuous accumulation and emission into the atmosphere of anthropogenic carbon dioxide(CO_(2)),a major greenhouse gas,has been recognized as a primary contributor to climate change associated with the global warming and acidification of oceans.This has led to drastic changes in the natural ecosystem,and hence an unhealthy ecological environment for human society.Thus,the effective mitigation of the ever increasing CO_(2)emission has been recognized as the most important global challenge.To achieve zero carbon footprint,novel materials and approaches are required for potentially reducing the CO_(2)release,while our current fossil-fuel-based energy must be replaced by renewable energy free from emissions.In this paper,porous carbons with hierarchical pore structures are promising for CO_(2)adsorption and electrochemical CO_(2)reduction owing to their high specific surface area,excellent catalytic performance,low cost and long-term stability.Since efficient gas-phased(electro)catalysis involves the access of reactants to active sites at the gas-liquid-solid triple phase,the hierarchical porous carbon materials possess multiple advantages for various CO_(2)-related applications with enhanced volumetric and gravimetric activities(e.g.,CO_(2)uptake and current density)for practical operations.Recent studies have demonstrated that porous carbon materials exhibited notable activities as CO_(2)adsorbents and provided facile conducting pathways and mass diffusion channels for efficient electrochemical CO_(2)reduction even under the high current operation conditions.Herein,we summarize recent advances in porous carbon materials for CO_(2)capture,storage,and electrochemical conversion.Prospectives and challenges on the rational design of porous carbon materials for scalable and practical CO_(2)capture and conversion are also discussed.展开更多
Electrocatalytic carbon dioxide reduction reaction(CO_(2) RR)is a promising method to solve current environment and energy issues.Copper-based catalysts have been widely studied for converting CO_(2) into value-added ...Electrocatalytic carbon dioxide reduction reaction(CO_(2) RR)is a promising method to solve current environment and energy issues.Copper-based catalysts have been widely studied for converting CO_(2) into value-added hy-drocarbon products.Cu monometallic catalyst has been proved to have some shortcomings,including relatively high energy barriers and diverse reaction pathways,leading to low reaction activities and poor product selec-tivity,respectively.Recently copper-based bimetallic tandem catalysts have attracted extensive attentions due to their special catalyst structure,which can be easily regulated to achieve high CO_(2) RR reactivity and product selectivity.With the development of quantum chemistry calculations and spectroscopic characterization methods,deep understandings of CO_(2) RR from the mechanism perspective provide a broad horizon for the design of effi-cient catalysts.This review offers a good summary of reaction mechanisms and product regulation strategies over copper-based bimetallic catalysts,along with a brief discussion on future directions towards their practical applications.展开更多
基金This project was supported by the National Natural Science Foundation of China(U19A2017,22272206,51976143)Natural Science Foundation of Hunan Province(S2021JJMSXM3153).
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor selectivity and low current density due to its sluggish kinetics and multitudinous reaction pathways.Single-atom catalysts(SACs)demonstrate outstanding activity,excellent selectivity,and remarkable atom utilization efficiency,which give impetus to the search for electrocatalytic processes aiming at high selectivity.There appears significant activity in the development of efficient SACs for CO_(2)RR,while the density of the atomic sites remains a considerable barrier to be overcome.To construct high-metal-loading SACs,aggregation must be prevented,and thus novel strategies are required.The key to creating high-density atomically dispersed sites is designing enough anchoring sites,normally defects,to stabilize the highly mobile separated metal atoms.In this review,we summarized the advances in developing high-loading SACs through defect engineering,with a focus on the synthesis strategies to achieve high atomic site loading.Finally,the future opportunities and challenges for CO_(2)RR in the area of high-loading single-atom electrocatalysts are also discussed.
基金financially supported by the National Natural Science Foundation of China (NSFC) (Grant No. 22105087)Natural Science Foundation of Jiangsu Province (Grant No. BK20210446)。
文摘The electronic structure of electrocatalysts plays a critical role in energy conversion,whereas for an efficient catalyst,it is challenging to modulate the orbitals.Herein,we present a new strategy to modulate the e_(g) orbital occupancy of Pd by constructing composition-controllable Pd-Au metallic aerogels(MAs),optimizing the d-band center of Pd to achieve excellent performance for electrochemical carbon dioxide reduction reaction(CO_(2)RR).Specifically,Pd_(1)Au_(2) MAs achieve almost 100% Faraday efficiency(FE) of CO in the range of-0.40 to-0.80 V vs.reversible hydrogen electrode(RHE),as well as the long-term stability,being one of the best Pd-based materials for CO_(2)RR.The X-ray photoelectron spectroscopy(XPS) results and density functional theory(DFT) calculations demonstrate that the introduction of Au modulates the Pd e_(g) orbital occupancy,which significantly weakens *CO adsorption on Pd,reduces the CO_(2)RR energy barrier and consequently improves the electrocatalytic activity and stability for long-term applications.Our work highlights a new strategy for designing efficient electrocatalysts for CO_(2)RR and beyond.
基金supported by the Fundamental Research Funds for the Central Universities of Chinathe Starting Research Funds of Shaanxi Normal University for Mainstay Young Scholars+2 种基金the National Environment Agency of Singapore under the Environment Technology Research Programme(ETRP)through Project No.ETRP 1002 103Singapore National Research Foundation(NRF)through the Singapore-Berkeley Research Initiative for Sustainable Energy(SinBeRISE)Cambridge Centre for Carbon Reduction in Chemical Technology(C4T)CREATE Programmes
文摘Photocatalytic water splitting and carbon dioxide reduction provide us clean and sustainable energy resources. The carbon dioxide reduction is also the redemption of the greenhouse effect. MoS/TiOphotocatalysts based on TiOnanoplates have been synthesized via a hydrothermal acidification route for water and carbon dioxide reduction reactions. This facile approach generates well dispersed Mo S3 with low crystallinity on the surface of TiOnanoplates. The as-synthesized MoS/TiOphotocatalyst showed considerable activity for both water reduction and carbon dioxide reduction. The thermal treatment effects of TiO, the loading percentage of MoSand the crystalline phase of TiOhave been investigated towards the photocatalytic performance. TiOnanoplate synthesized through hydrothermal reaction with the presence of HF acid is an ideal semiconductor material for the loading of MoSfor photocatalytic water and carbon dioxide reduction simultaneously in EDTA sacrificial solution.
基金gratefully express gratitude to all parties who have contributed toward the success of this project,both financially and technically,especially the S&T Innovation 2025 Major Special Programme(Grant No.2018B10022)the Ningbo Commonweal Programme(Grant No.2022S122)funded by the Ningbo Science and Technology Bureau,China,as well as the UNNC FoSE Faculty Inspiration Grant,China+1 种基金the support from the Ningbo Municipal Key Laboratory on Clean Energy Conversion Technologies(2014A22010)as well as the Zhejiang Provincial Key Laboratory for Carbonaceous Wastes Processing and Process Intensification Research funded by the Zhejiang Provincial Department of Science and Technology(2020E10018)support from the ANU Futures Scheme(Q4601024).
文摘Achieving carbon neutrality is an essential part of responding to climate change caused by the deforestation and over-exploitation of natural resources that have accompanied the development of human society.The carbon dioxide reduction reaction(CO_(2)RR)is a promising strategy to capture and convert carbon dioxide(CO_(2))into value-added chemical products.However,the traditional trial-and-error method makes it expensive and time-consuming to understand the deeper mechanism behind the reaction,discover novel catalysts with superior performance and lower cost,and determine optimal support structures and electrolytes for the CO_(2)RR.Emerging machine learning(ML)techniques provide an opportunity to integrate material science and artificial intelligence,which would enable chemists to extract the implicit knowledge behind data,be guided by the insights thereby gained,and be freed from performing repetitive experiments.In this perspective article,we focus on recent ad-vancements in ML-participated CO_(2)RR applications.After a brief introduction to ML techniques and the CO_(2)RR,we first focus on ML-accelerated property prediction for potential CO_(2)RR catalysts.Then we explore ML-aided prediction of catalytic activity and selectivity.This is followed by a discussion about ML-guided catalyst and electrode design.Next,the potential application of ML-assisted experimental synthesis for the CO_(2)RR is discussed.
基金supported by National Natural Science Foundation of China(No.22088102)supported by National Natural Science Foundation of China(No.22090033)+1 种基金the support from Youth Innovation Promotion Association of Chinese Academy of SciencesDalian Institute of Chemical Physics,CAS。
文摘Although converting the greenhouse gasses carbon dioxide(CO_(2))into solar fuels is regarded as a convenient means of solar energy storage,the intrinsic mechanism on how the high chemical inertness linear CO_(2)molecules is activated and converted on a semiconductor oxide is still elusive.Herein,by creating the oxygen vacancies on the typical hexagonal tungsten oxide(WO3),we realize the continuous photoinduced CO_(2)reduction to selectively produce CO under light irradiation,which was verified by isotope labeling experiment.Detailed oxygen vacancies evolution investigation indicates that light irradiation can simultaneously induce the in-situ formation of oxygen vacancies on hexagonal WO3,and the oxygen vacancies promote the adsorption and activation of CO_(2)molecules,leading to the CO_(2)reduction to CO on the hexagonal WO3via an oxygen vacancies-involved process.Besides,the existence of water further promotes the formation of CO_(2)reduction intermediate,further promote the CO_(2)photoreduction.Our work provides insight on the mechanism for converting CO_(2)into CO under light irradiation.
基金supported by the National Research Foundation of Korea (NRF) Grant funded by the Korean Government (MSIT) (RS-2023-00210114)supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (NRF-2021R1C1C1004264 and NRF2021R1A4A1032114)+1 种基金supported by the National Research Foundation of Korea (NRF) Grant funded by the Korean Government (MSIT) (NRF-2022R1A4A1019296)supported by the National R&D Program through the National Research Foundation of Korea (NRF), funded by the Ministry of Science and ICT (2021M3D1A2051636)。
文摘Mixed metal oxide(MMO) represents a critical class of materials that can allow for obtaining a dynamic interface between its components:reduced metal and its metal oxide counterpart during an electrocatalytic reaction.Here,a synthetic method utilizing a MOF-derived micro/mesoporous carbon as a template to prepare sub-2 nm MMO catalysts for CO_(2) electro reduction is reported.Starting from the zeolite imidazolate framework(ZIF-8),the pyrolyzed derivatives were used to synthesize sub-2 nm Pd-Ni MMO with different compositions.The Ni-rich(Pd_(20)-Ni_(80)/ZC) catalyst exhibits unexpectedly superior performance for CO production with an improved Faradaic efficiency(FE) of 95.3% at the current density of 200 mA cm^(-2) at-0.56 V vs.reversible hydrogen electrode(RHE) compared to other Pd-Ni compositions.X-ray photoelectron spectroscopy(XPS) analysis confirms the presence of Ni^(2+) and Pd^(2+) in all compositions,demonstrating the presence of MMO.Density functional theory(DFT) calculation reveals that the lower CO binding energy on the surface of the Pd_(20)-Ni_(80) cluster eases CO desorption,thus increasing its production.This work provides a general synthetic strategy for MMO electrocatalysts and can pave a new way for screening multimetallic catalysts with a dynamic electrochemical interface.
基金The authors acknowledge the financial support from the National Natural Science Foundation of China under Grant No.51371017the Major Subject Project of the University of Jinan(1420702).
文摘The electrochemical reduction of CO_(2) is an extremely potential technique to achieve the goal of carbon neutrality,but the development of electrocatalysts with high activity,excellent product selectivity,and long-term durability remains a great challenge.Herein,the role of metal-supports interaction(MSI)between different active sites(including single and bimetallic atom sites consisting of Cu and Ni atoms)and carbon-based supports(including C_(2) N,C_(3)N_(4),N-coordination graphene,and graphdiyne)on catalytic activity,prod-uct selectivity,and thermodynamic stability towards CO_(2) reduction reaction(CRR)is systematically investi-gated by first principles calculations.Our results show that MSI is mainly related to the charge transfer behavior from metal sites to supports,and different MSI leads to diverse magnetic moments and d-band centers.Subsequently,the adsorption and catalytic performance can be efficiently improved by tuning MSI.Notably,the bimetallic atom supported graphdiyne not only exhibits a better catalytic activity,higher product selec-tivity,and higher thermodynamic stability,but also effectively inhibits the hydrogen evolution reaction.This finding provides a new research idea and optimization strategy for the rational design of high-efficiency CRR catalysts.
基金Singapore MOE Tier2(Nos.MOE2017-T2-2-069,MOE2018-T2-1-010)the National Natural Science Foundation of China(No.21765016)+3 种基金the Ningxia Leading Scientific and Technological Innovation Talents Project,China(No.KJT2018002)the Natural Science Foundation of Ningxia,China(Nos.2018AAC03012,2018AAC03051)the College Students'Innovative and Entrepreneurship Training Program of Ningxia University,China(No.Q2020107490041)the National First-rate Discipline Construction Project of Ningxia,China(No.NXYLXK2017A04)。
文摘Due to the burning of fossil fuels,the level of carbon dioxide(CO2)in the atmosphere gradually rises,leading to serious greenhouse effect and environmental problems.Electrocatalytic reduction of CO2 is currently an efficient way to convert CO2 to value-added products.Bismuth(Bi)-based nanomaterials have raised great interests due to their excellent activity and high selectivity to electrocatalytic CO2 reduction.In this review,the fundamental principles of electrochemical CO2 reduction reaction(CO2RR)are introduced at first.Moreover,the recent development of Bi-based electrocatalytic materials including Bi with various nanostructures(nanoparticle,nanosheet.etc.),Bi-based compounds(Bi oxide,bimetal chalcogenide,etc.),and Bi/C nanocomposites are summarized.In the end,the future prospects and challenges of electrocatalysts for CO2 reduction are discussed.
基金We acknowledge Institut Laue-Langevin and Spanish initiatives on Neutron Scattering(ILL-SpINS)for beamtime at instrum ent D2B and G.Cuellofor assistance during data acquisition(10.5291/ILL-DATA.5-21-1114).We thank M.C.Capel for the TEM images and TEM-EDS analysis acquisition at Instituto de Catalisis y Petroleoquimica(CSIC).Funding:Work at Instituto de Ciencia de Materiales de Madrid-Consejo Superior de Instigaciones Cientfficas(CSIC)has been supported by the Spanish Research Agency(Agenda Estatal de Investigacion,AEI),Projects MAT2016-78465-R,CTQ2017-87262-R.This work was supported by the EU(ERC CoG HyMAP 648319)and Spanish MINECO(ENE2016-79608-C2-1-R).Authors also wish to thank to“Com unidad de Madrid”and European Structural Funds for their financial support to FotoArt-CM project(S2018/NMT-4367).F.G.acknowledges financial support from MINECO Ramon y Cajal program(RyC-2015-18384).
文摘The precise control on the combination of multiple metal atoms in the structure of metal-organic frameworks(MOFs)endowed by reticular chemistry,allows the obtaining of materials with compositions that are programmed for achieving enhanced reactivity.The present work illustrates how through the transformation of MOFs with desired arrangements of metal cations,multi-metal spinel oxides with precise compositions can be obtained,and used as catalyst precursor for the reverse water-gas shift reaction.The differences in the spinel initial composition and structure,determined by neutron powder diffraction,influence the overall catalytic activity with changes in the process of in s itu formation of active,metal-oxide supported metal nanoparticles,which have been monitored and characterized with in situ X-ray diffraction and photoelectron spectroscopy studies.
基金financially supported by Australian Research Council Discovery Project(DP200100965)。
文摘Bismuth-based materials(e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO_(2) to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismuth oxides and subcarbonate encounter stability issues. This work is designated to exemplify that the operando synthesis can be an effective means to enhance the stability of electrocatalysts under operando CO_(2)RR conditions. A synthetic approach is developed to electrochemically convert Bi^(O)Cl into Cl-containing subcarbonate(Bi_(2)O_(2)(CO_(3))_(x)Cl_(y)) under operando CO_(2)RR conditions. The systematic operando spectroscopic studies depict that BiOCl is converted to Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) via a cathodic potential-promoted anion-exchange process. The operando synthesizedBi_(2)O_(2)(CO_(3))_(x)Cl_(y) can tolerate-1.0 V versus RHE, while for the wet-chemistry synthesized pure Bi_(2)O_(2)CO_(3),the formation of metallic Bio occurs at-0.6 V versus RHE. At-0.8 V versus RHE, Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) can readily attain a FEHCOO-of 97.9%,much higher than that of the pure Bi_(2)O_(2)CO_(3)(81.3%). DFT calculations indicate that differing from the pure Bi_(2)O_(2)CO_(3)-catalyzed CO_(2)RR, where formate is formed via a *OCHO intermediate step that requires a high energy input energy of 2.69 eV to proceed, the formation of H COO-over Bi_(2)O_(2)(CO_(3))_(x)Cl_(y) has proceeded via a *COOH intermediate step that only requires low energy input of 2.56 eV.
基金the financial support from the Discovery Early Career Researcher Award (Grant No. DE220101074), Australian Research Council
文摘Nb-containing catalysts have the potential to catalyze carbon dioxide(CO_(2))reduction due to their strong surface acidity and CO_(2)activation sites.Still,they have not been widely used in the development and design of catalysts due to the theoretical/cost/safety limitations.Related advances have been continuously reported in the literature,demonstrating to some extent the promise of catalytic applications of Nb-containing catalysts in this area.In this minireview,we discuss the structure-activity relationships of Nb-containing catalysts for photo-,electro-,and thermocatalytic reduction of CO_(2).The engineering strategies of Nb-containing catalysts for enhancing the conversion and selectivity of CO_(2)reduction are discussed,ranging from Nb doping,noble metal decoration,surface acidity adjustment,oxygen vacancy engineering,and heterojunction construction to Nb or Nb_(2)O_(5) particle decoration.The theoretical calculation research for the possible reaction paths and product selectivity is also discussed.Finally,the prospects for designing and optimizing Nb-containing catalysts are proposed.With a deep understanding of catalytic activity and reaction mechanism,this minireview is expected to present the optimization of the Nb-containing catalysts for efficient and highly selective CO_(2)reduction.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government MSIT(2021R1A2C2093358,2021R1A4A3027878,2022M3I3A1081901)financial support from the Lotte Chemical Company。
文摘Cu catalysts can convert CO_(2) through an electrochemical reduction reaction into a variety of useful carbon-based products.However,this capability provides an obstacle to increasing the selectivity for a single product.Herein,we report a simple fabrication method for a Cu-Pd alloy catalyst for use in a membrane electrode assembly(MEA)-based CO_(2) electrolyzer for the electrochemical CO_(2) reduction reaction(ECRR)with high selectivity for CO production.When the composition of the Cu-Pd alloy catalyst was fabricated at 6:4,the selectivity for CO increased and the production of multi-carbon compounds and hydrogen is suppressed.Introducing a Cu-Pd alloy catalyst with 6:4 ratio as the cathode of the MEAbased CO_(2) electrolyzer showed a CO faradaic efficiency of 92.8%at 2.4 V_(cell).We assumed that these results contributed from the crystal planes on the surface of the Cu-Pd alloy.The phases of the Cu-Pd alloy catalyst were partially separated through annealing to fabricate a catalyst with high selectivity for CO at low voltage and C_(2)H_4 at high voltage.The results of CO-stripping testing confirmed that when Cu partially separates from the lattice of the Cu-Pd alloy,the desorption of~*CO is suppressed,suggesting that C-C coupling reaction is favored.
基金Grant PID2020-115848RB-C21 "STORELEC" projectTED2021-129694B-C22 "DEFY-CO2" project funded by MCIN/AEI/10.13039/501100011033+3 种基金LMP253_ (2)1 project funded by Gobierno de AragónGrant IJC2019-041874-I funded by the MCIN/AEI/10.13039/501100011033CSIC for her JAE Intro ICU 2021-ICB-04 grantthe Y2020/EMT-6419 "CEOTRES" project funded by the Comunidad Autonoma de Madrid。
文摘The electrochemical CO_(2) reduction reaction(CO_(2)RR) to controllable chemicals is considered as a promising pathway to store intermittent renewable energy. Herein, a set of catalysts based on copper-nitrogendoped carbon xerogel(Cu-N-C) are successfully developed varying the copper amount and the nature of the copper precursor, for the efficient CO_(2)RR. The electrocatalytic performance of Cu-N-C materials is assessed by a rotating ring-disc electrode(RRDE), technique still rarely explored for CO_(2)RR. For comparison, products are also characterized by online gas chromatography in a H-cell. The as-synthesized Cu-NC catalysts are found to be active and highly CO selective at low overpotentials(from -0.6 to -0.8 V vs.RHE) in 0.1 M KHCO_(3), while H_(2) from the competitive water reduction appears at larger overpotentials(-0.9 V vs. RHE). The optimum copper acetate-derived catalyst containing Cu-N_(4) moieties exhibits a CO_(2)-to-CO turnover frequency of 997 h^(-1) at -0.9 V vs. RHE with a H_(2)/CO ratio of 1.8. These results demonstrate that RRDE configuration can be used as a feasible approach for identifying electrolysis products from CO_(2)RR.
基金This work was supported by the National Key Research and Development Program of China(No.2016YFB 0600904).The authors gratefully acknowledge the support of the Analytical and Test Center of Sichuan University.
文摘Natural magnetite formed by the isomorphism substitutions of transition metals,including Fe,Ti,Co,etc.,was activated by mechanical grinding followed by H2 reduction.The temperature-programmed reduction of hydrogen(H2-TPR)and temperature-programmed surface reaction of carbon dioxide(CO2-TPSR)were carried out to investigate the processes of oxygen loss and CO2 reduction.The samples were characterized by X-ray diffraction(XRD),field emission scanning electron microscopy(FE-SEM),and energy-dispersive X-ray spectroscopy(EDS).The results showed that the stability of spinel phases and oxygen-deficient degree significantly increased after natural magnetite was mechanically milled and reduced in H2 atmosphere.Meanwhile,the activity and selectivity of CO2 reduction into carbon were enhanced.The deposited carbon on the activated natural magnetite was confirmed as amorphous.The amount of carbon after CO2 reduction at 300°C for 90 min over the activated natural magnetite was 2.87wt%higher than that over the natural magnetite.
基金supported by the National Key Research and Development Program of China (No. 2020YFA0406103)National Natural Science Foundation of China (Nos. 51902217 and 21771134)+4 种基金National Key Research and Development Program of China(No. 2017YFA0204800)National MCF Energy R&D Program (No. 2018YFE0306105)the Suzhou Key Laboratory of Functional Nano & Soft Materials, Collaborative Innovation Center of Suzhou Nano Science & Technologythe 111 ProjectJoint International Research Laboratory of Carbon-Based Functional Materials and Devices
文摘Carbon dioxide electrochemical reduction(CO_(2)RR)has been recognized as an efficient way to mitigate CO_(2)emissions and alleviate the pressure on global warming and associated environmental consequences.Gold(Au)is reported as stable and active electrocatalysts to convert CO_(2)to CO at low overpotential due to its moderate adsorption strength of^(*)COOH and^(*)CO.The request for improved catalytic performance,however,is motivated by current unsatisfied catalytic selectivity because of the side hydrogen evolution reaction.In this context,the design of Au based binary catalysts that can boost CO selectivity is of great interest.In the present work,we report that Au nanoparticles can be feasibly dispersed and anchored on silicon nanowires to form Au-Si binary nanomaterials.The Au-Si may stably drive CO_(2)RR with a CO Faraday efficiency of 95.6%at−0.6 V vs.RHE in 0.5 mol/L KHCO_(3)solution.Such selectivity outperforms Au particles by up to 61%.Controlled experiments illustrate that such catalytic enhancement can chiefly be ascribed to electronic effects of binary catalysts.Theoretical calculations reveal that spontaneously produced silicon oxide may not only inhibit hydrogen evolution reaction,but also stabilize the key intermediate^(*)COOH in CO formation.
基金financial support through the StartUp Fund for Outstanding Talent with grant number A1098531023601307the National University of Singapore and Ministry of Education in Singapore for its financial support through Tier-1 projects with grant numbers R-279000-622-133 and R-279-000-622-731.
文摘Electrocatalytic carb on dioxide reducti on(CO_(2)R)presents a promising route to establish zero-e mission carb on cycle and store in termittent ren ewable energy into chemical fuels for steady energy supply.Methanol is an ideal energy carrier as alternative fuels and one of the most important commodity chemicals.Nevertheless,methanol is currently mainly produced from fossil-based syngas,the production of which yields tremendous carb on emission globally.Direct CO_(2)R towards metha nol poses great potential to shift the paradigm of methanol production.In this perspective,we focus our discussions on producing methanol from electrochemical CO_(2)R,using metallomacrocyclic molecules as the model catalysts.We discuss the motivation of having methanol as the sole CO_(2)R product,the documented application of metallomacrocyclic catalysts for CO_(2)R,and recent advance in catalyzing CO_(2) to methanol with cobalt phthalocyanine-based catalysts.We attempt to understand the key factors in determining the activity,selectivity,and stability of electrocatalytic CO_(2)-to-methanol conversion,and to draw mechanistic insights from existing observations.Finally,we identify the challenges hindering methanol electrosynthesis directly from CO_(2) and some intriguing directions worthy of further investigation and exploration.
基金supported by the National Natural Science Foundation of China(Grant Nos.51873085,52071171)Liaoning Revitalization Talents Program-Pan Deng Scholars(XLYC2007056,XLYC1802005)+9 种基金the Liaoning BaiQianWan Talents Program(LNBQW2018B0048)the Natural Science Fund of Liaoning Province for Excellent Young Scholars(2019-YQ-04)the Key Project of Scientific Research of the Education Department of Liaoning Province(LZD201902)the Shenyang Science and Technology Project(21-108-9-04)the Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)the Linkage Project(LP210100467,LP210200504,LP210200345)Industrial Transformation Training Centre(IC180100005)schemesthe CSIRO Energy Centrethe Kick-Start Project.
文摘Recently,research on the electrocatalytic CO_(2) reduction reaction(eCO_(2)RR)has attracted considerable attention due to its potential to resolve environmental problems caused by CO_(2) while utilizing clean energy and producing high‐value‐added products.Considerable theoretical research in the lab has demonstrated its feasibility and prospect.However,industrialization is mandatory to realize the economic and social value of eCO_(2)RR.For industrial application of eCO_(2)RR,more criteria have been proposed for eCO_(2)RR research,including high current density(above 200 mA cm^(−2)),high product selectivity(above 90%),and long‐term stability.To fulfill these criteria,the eCO_(2)RR system needs to be systematically designed and optimized.In this review,recent research on eCO_(2)RR for industrial applications is summarized.The review starts with focus on potential industrial catalysts in eCO_(2)RR.Next,potential industrial products are proposed in eCO_(2)RR.These products,including carbon monoxide,formic acid,ethylene,and ethanol,all have high market demand,and have shown high current density and product selectivity in theoretical research.Notably,the innovative components and strategy for industrializing the eCO_(2)RR system are also highlighted here,including flow cells,seawater electrolytes,solid electrolytes,and a two‐step method.Finally,some instructions and possible future avenues are presented for the prospects of future industrial application of eCO_(2)RR.
基金Q.Xu acknowledges financial support from the Natural Science Foundation of Shanghai(20ZR1464000)G.Zeng is grateful for the support from the National Natural Science Foundation of China(21878322,22075309)the Science and Technology Commission of Shanghai(19ZR1479200).The authors also thank the Shanghai Synchrotron Radiation Facility for XAFS measurements at Beamline BL14w1.
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR)for highvalue-added products is a promising strategy to tackle excessive CO_(2) emissions.However,the activity of and selectivity for catalysts for CO_(2)RR still need to be improved because of the competing reaction(hydrogen evolution reaction).In this study,for the first time,we have demonstrated dual atomic catalytic sites for CO_(2)RR from a core-shell hybrid of the covalent-organic framework and the metal-organic framework.Due to abundant dual atomic sites(with CoN_(4)O and ZnN_(4) of 2.47 and 11.05 wt.%,respectively)on hollow carbon,the catalyst promoted catalysis of CO_(2)RR,with the highest Faradic efficiency for CO of 92.6%at-0.8 V and a turnover frequency value of 1370.24 h^(-1) at-1.0 V.More importantly,the activity and selectivity of the catalyst were well retained for 30 h.The theoretical calculation further revealed that CoN_(4)O was the main site for CO_(2)RR,and the activity of and selectivity for Zn sites were also improved because of the synergetic roles.
基金he Australian Research Council for financial support(ARC,DE190100965,FL190100126 and CE230100032).
文摘Continuous accumulation and emission into the atmosphere of anthropogenic carbon dioxide(CO_(2)),a major greenhouse gas,has been recognized as a primary contributor to climate change associated with the global warming and acidification of oceans.This has led to drastic changes in the natural ecosystem,and hence an unhealthy ecological environment for human society.Thus,the effective mitigation of the ever increasing CO_(2)emission has been recognized as the most important global challenge.To achieve zero carbon footprint,novel materials and approaches are required for potentially reducing the CO_(2)release,while our current fossil-fuel-based energy must be replaced by renewable energy free from emissions.In this paper,porous carbons with hierarchical pore structures are promising for CO_(2)adsorption and electrochemical CO_(2)reduction owing to their high specific surface area,excellent catalytic performance,low cost and long-term stability.Since efficient gas-phased(electro)catalysis involves the access of reactants to active sites at the gas-liquid-solid triple phase,the hierarchical porous carbon materials possess multiple advantages for various CO_(2)-related applications with enhanced volumetric and gravimetric activities(e.g.,CO_(2)uptake and current density)for practical operations.Recent studies have demonstrated that porous carbon materials exhibited notable activities as CO_(2)adsorbents and provided facile conducting pathways and mass diffusion channels for efficient electrochemical CO_(2)reduction even under the high current operation conditions.Herein,we summarize recent advances in porous carbon materials for CO_(2)capture,storage,and electrochemical conversion.Prospectives and challenges on the rational design of porous carbon materials for scalable and practical CO_(2)capture and conversion are also discussed.
基金financial support from National Na-ture Science Foundation of China(Nos.22078232 and 21938008)the Science and Technology Major Project of Tianjin(Nos.19ZXNCGX00030 and 20JCYBJC00870)Seed Foundation of Tianjin University(2022XJS-0051).
文摘Electrocatalytic carbon dioxide reduction reaction(CO_(2) RR)is a promising method to solve current environment and energy issues.Copper-based catalysts have been widely studied for converting CO_(2) into value-added hy-drocarbon products.Cu monometallic catalyst has been proved to have some shortcomings,including relatively high energy barriers and diverse reaction pathways,leading to low reaction activities and poor product selec-tivity,respectively.Recently copper-based bimetallic tandem catalysts have attracted extensive attentions due to their special catalyst structure,which can be easily regulated to achieve high CO_(2) RR reactivity and product selectivity.With the development of quantum chemistry calculations and spectroscopic characterization methods,deep understandings of CO_(2) RR from the mechanism perspective provide a broad horizon for the design of effi-cient catalysts.This review offers a good summary of reaction mechanisms and product regulation strategies over copper-based bimetallic catalysts,along with a brief discussion on future directions towards their practical applications.