The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic ...The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.展开更多
The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into ...The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N4-C)configuration to obtain Ni-X-N3-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N3-C(X:S,Se,and Te)SACs,Ni-Se-N3-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98%at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2)battery integrated with Ni-Se-N3-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm-2 and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N4-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N3-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of*COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.展开更多
Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2)reduction reaction and understanding the structure-property relationship.Herei...Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2)reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N2-bidentate(note that N2-bidentate site=N^N-bidentate site;N2¹dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N2-bidentate site,a Cu SAC with isolated undercoordinated Cu-N2 sites(Cu1.0/N2-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N2-GDY exhibits the highest Faradaic efficiency(FE)of 80.6%for CH4 in electrocatalytic reduction of CO_(2)at-0.96 V vs.RHE,and the partial current density of CH4 is 160 mA cm^(-2).The selectivity for CH4 is maintained above 70%when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N2-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N2 sites are more favorable in generating key*COOH and*CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N2 sites toward efficient electrocatalysis.展开更多
A fuel cell is an energy conversion device that can continuously input fuel and oxidant into the device through an electrochemical reaction to release electrical energy.Although noble metals show good activity in fuel...A fuel cell is an energy conversion device that can continuously input fuel and oxidant into the device through an electrochemical reaction to release electrical energy.Although noble metals show good activity in fuel cell-related electrochemical reactions,their ever-increasing price considerably hinders their industrial application.Improvement of atom utilization efficiency is considered one of the most effective strategies to improve the mass activity of catalysts,and this allows for the use of fewer catalysts,saving greatly on the cost.Thus,single-atom catalysts(SACs)with an atom utilization efficiency of 100%have been widely developed,which show remarkable performance in fuel cells.In this review,we will describe recent progress on the development of SACs for membrane electrode assembly of fuel cell applications.First,we will introduce several effective routes for the synthesis of SACs.The reaction mechanism of the involved reactions will also be introduced as it is highly determinant of the final activity.Then,we will systematically summarize the application of Pt group metal(PGM)and nonprecious group metal(non-PGM)catalysts in membrane electrode assembly of fuel cells.This review will offer numerous experiences for developing potential industrialized fuel cell catalysts in the future.展开更多
Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor select...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor selectivity and low current density due to its sluggish kinetics and multitudinous reaction pathways.Single-atom catalysts(SACs)demonstrate outstanding activity,excellent selectivity,and remarkable atom utilization efficiency,which give impetus to the search for electrocatalytic processes aiming at high selectivity.There appears significant activity in the development of efficient SACs for CO_(2)RR,while the density of the atomic sites remains a considerable barrier to be overcome.To construct high-metal-loading SACs,aggregation must be prevented,and thus novel strategies are required.The key to creating high-density atomically dispersed sites is designing enough anchoring sites,normally defects,to stabilize the highly mobile separated metal atoms.In this review,we summarized the advances in developing high-loading SACs through defect engineering,with a focus on the synthesis strategies to achieve high atomic site loading.Finally,the future opportunities and challenges for CO_(2)RR in the area of high-loading single-atom electrocatalysts are also discussed.展开更多
In this work,DFT calculations were used firstly to simulate the nitrogen coordinated metal single-atom catalysts(M-N_(x)SACs,M=Hg,Cu,Au,and Ru) to predict their catalytic activities in acetylene hydrochlorination.The ...In this work,DFT calculations were used firstly to simulate the nitrogen coordinated metal single-atom catalysts(M-N_(x)SACs,M=Hg,Cu,Au,and Ru) to predict their catalytic activities in acetylene hydrochlorination.The DFT results showed that Ru-N_(x)SACs had the best catalytic performance among the four catalysts,and Ru-N_(x)SACs could effectively inhibit the reduction of ruthenium cation.To verify the DFT results,Ru-N_(x)SACs were fabricated by pyrolyzing MOFs in-situ spatially confined metal precursors.The N coordination environment could be controlled by changing the pyrolysis temperature.Catalytic performance tests indicated that low N coordination number(Ru-N_(2),Ru-N_(3))exhibited excellent catalytic activity and stability compared to RuCl_(3)catalyst.DFT calculations further revealed that Ru-N_(2)and Ru-N_(3)had a tendency to activate HCl at the first step of reaction,whereas Ru-N4tended to activate C_(2)H_(2).These findings will serve as a reference for the design and control of metal active sites.展开更多
Developing efficient electrocatalysts for converting dinitrogen to ammonia through electrocatalysis is of significance to the decentralized ammonia production. Here, through high-throughput density functional theory c...Developing efficient electrocatalysts for converting dinitrogen to ammonia through electrocatalysis is of significance to the decentralized ammonia production. Here, through high-throughput density functional theory calculations, we demonstrated that the interfacial modulation of hexagonal boron nitride/graphene(hBN-graphene) could sufficiently improve the catalytic activity of the single transition metal atom catalysts for nitrogen reduction reaction(NRR). It was revealed that Re@hBN-graphene and Os@hBN-graphene possessed remarkable NRR catalytic activity with low limiting potentials of 0.29 V and 0.33 V, respectively. Furthermore, the mechanism of the enhanced catalytic activity was investigated based on various descriptors of the adsorption energies of intermediates, where the synergistic effect of hBN and graphene in the hybrid substrate was found to play a key role. Motivated by the synergistic effect of hybrid substrate in single-atom catalysts, a novel strategy was proposed to efficiently design dual-atom catalysts by integrating the merits of both metal components. The as-designed dual-atom catalyst Fe-Mo@hBN exhibited more excellent NRR catalytic performance with a limiting potential of 0.17 V, manifesting the solidity of the design strategy. Our findings open new avenues for the search of heterostructure substrates for single-atom catalysts and the efficient design of dualatom catalysts for NRR.展开更多
The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.How...The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.However,one of the main obstacles of these systems is the poor reaction kinetics in the involved chemical reactions.Therefore,it is essential to incorporate suitable and efficient catalysts into the cell.These years,single-atom catalysts(SACs)are emerging as a frontier in catalysis due to their maximum atom efficiency and unique reaction selectivity.For SACs fabrication,metal-organic frameworks(MOFs)have been confirmed as promising templates or precursors due to their high metal loadings,structural adjustability,porosity,and tailorable catalytic site.In this review,we summarize effective strategies for fabricating SACs by MOFs with corresponding advanced characterization techniques and illustrate the key role of MOFs-based SACs in these batteries by explaining their reaction mechanisms and challenges.Finally,current applications,prospects,and opportunities for MOFs-based SACs in energy storage systems are discussed.展开更多
As a carbon-free energy carrier,hydrogen has become the pivot for future clean energy,while efficient hydrogen production and combustion still require precious metal-based catalysts.Single-atom catalysts(SACs)with hig...As a carbon-free energy carrier,hydrogen has become the pivot for future clean energy,while efficient hydrogen production and combustion still require precious metal-based catalysts.Single-atom catalysts(SACs)with high atomic utilization open up a desirable perspective for the scale applications of precious metals,but the general and facile preparation of various precious metal-based SACs remains challenging.Herein,a general movable printing method has been developed to synthesize various precious metal-based SACs,such as Pd,Pt,Rh,Ir,and Ru,and the features of highly dispersed single atoms with nitrogen coordination have been identified by comprehensive characterizations.More importantly,the synthesized Pt-and Ru-based SACs exhibit much higher activities than their corresponding nanoparticle counterparts for hydrogen oxidation reaction and hydrogen evolution reaction(HER).In addition,the Pd-based SAC delivers an excellent activity for photocatalytic hydrogen evolution.Especially for the superior mass activity of Ru-based SACs toward HER,density functional theory calculations confirmed that the adsorption of the hydrogen atom has a significant effect on the spin state and electronic structure of the catalysts.展开更多
The development of novel single-atom catalysts with optimal electron configuration and economical noble-metal cocatalyst for efficient photocatalytic hydrogen production is of great importance,but still challenging.He...The development of novel single-atom catalysts with optimal electron configuration and economical noble-metal cocatalyst for efficient photocatalytic hydrogen production is of great importance,but still challenging.Herein,we fabricate Pt and Co single-atom sites successively on polymeric carbon nitride(CN).In this Pt_(1)-Co_(1)/CN bimetallic single-atom catalyst,the noble-metal active sites are maximized,and the single-atomic Co_(1)N_4sites are tuned to Co_(1)N_3sites by photogenerated electrons arising from the introduced single-atomic Pt_(1)N_4sites.Mechanism studies and density functional theory(DFT)calculations reveal that the 3d orbitals of Co_(1)N_3single sites are filled with unpaired d-electrons,which lead to the improved visible-light response,carrier separation and charge migration for CN photocatalysts.Thereafter,the protons adsorption and activation are promoted.Taking this advantage of long-range electron synergy in bimetallic single atomic sites,the photocatalytic hydrogen evolution activity over Pt_(1)-Co_(1)/CN achieves 915.8 mmol g^(-1)Pt h^(-1),which is 19.8 times higher than Co_(1)/CN and 3.5 times higher to Pt_(1)/CN.While this electron-synergistic effect is not so efficient for Pt nanoclusters.These results demonstrate the synergistic effect at electron-level and provide electron-level guidance for the design of efficient photocatalysts.展开更多
Single-atom catalysts(SACs)have garnered increasingly growing attention in renewable energy scenarios,especially in electrocatalysis due to their unique high efficiency of atom utilization and flexible electronic stru...Single-atom catalysts(SACs)have garnered increasingly growing attention in renewable energy scenarios,especially in electrocatalysis due to their unique high efficiency of atom utilization and flexible electronic structure adjustability.The intensive efforts towards the rational design and synthesis of SACs with versatile local configurations have significantly accelerated the development of efficient and sustainable electrocatalysts for a wide range of electrochemical applications.As an emergent coordination avenue,intentionally breaking the planar symmetry of SACs by adding ligands in the axial direction of metal single atoms offers a novel approach for the tuning of both geometric and electronic structures,thereby enhancing electrocatalytic performance at active sites.In this review,we briefly outline the burgeoning research topic of axially coordinated SACs and provide a comprehensive summary of the recent advances in their synthetic strategies and electrocatalytic applications.Besides,the challenges and outlooks in this research field have also been emphasized.The present review provides an in-depth and comprehensive understanding of the axial coordination design of SACs,which could bring new perspectives and solutions for fine regulation of the electronic structures of SACs catering to high-performing energy electrocatalysis.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
Single-atom catalysts(SACs) with nitrogen-coordinated nonprecious metal sites have exhibited inimitable advantages in electrocatalysis.However,a large room for improving their activity and durability remains.Herein,we...Single-atom catalysts(SACs) with nitrogen-coordinated nonprecious metal sites have exhibited inimitable advantages in electrocatalysis.However,a large room for improving their activity and durability remains.Herein,we construct atomically dispersed Fe sites in N-doped carbon supports by secondary-atom-doped strategy.Upon the secondary doping,the density and coordination environment of active sites can be efficiently tuned,enabling the simultaneous improvement in the number and reactivity of the active site.Besides,structure optimizations in terms of the enlarged surface area and improved hydrophilicity can be achieved simultaneously.Due to the beneficial microstructure and abundant highly active FeN_5 moieties resulting from the secondary doping,the resultant catalyst exhibits an admirable half-wave potential of 0.81 V versus 0.83 V for Pt/C and much better stability than Pt/C in acidic media.This work would offer a general strategy for the design and preparation of highly active SACs for electrochemical energy devices.展开更多
Reducing the dimensions of metallic nanoparticles to isolated,single atom has attracted considerable attention in heterogeneous catalysis,because it significantly improves atomic utilization and often leads to distinc...Reducing the dimensions of metallic nanoparticles to isolated,single atom has attracted considerable attention in heterogeneous catalysis,because it significantly improves atomic utilization and often leads to distinct catalytic performance.Through extensive research,it has been recognized that the local coordination environment of single atoms has an important influence on their electronic structures and catalytic behaviors.In this review,we summarize a series of representative systems of single-atom catalysts,discussing their preparation,characterization,and structure-property relationship,with an emphasis on the correlation between the coordination spheres of isolated reactive centers and their intrinsic catalytic activities.We also share our perspectives on the current challenges and future research promises in the development of single-atom catalysis.With this article,we aim to highlight the possibility of finely tuning the catalytic performances by engineering the coordination spheres of single-atom sites and provide new insights into the further development for this emerging research field.展开更多
The continuous increase of global atmospheric CO_(2) concentrations brutally damages our environment. A series of methods have been developed to convert CO_(2) to valuable fuels and value-added chemicals to maintain t...The continuous increase of global atmospheric CO_(2) concentrations brutally damages our environment. A series of methods have been developed to convert CO_(2) to valuable fuels and value-added chemicals to maintain the equilibrium of carbon cycles. The electrochemical CO_(2) reduction reaction(CO_(2)RR) is one of the promising methods to produce fuels and chemicals, and it could offer sustainable paths to decrease carbon intensity and support renewable energy. Thus, significant research efforts and highly efficient catalysts are essential for converting CO_(2) into other valuable chemicals and fuels. Transition metal-based single atoms catalysts(TM-SACs) have recently received much attention and offer outstanding electrochemical applications with high activity and selectivity opportunities. By taking advantage of both heterogeneous and homogeneous catalysts, TM-SACs are the new rising star for electrochemical conversion of CO_(2) to the value-added product with high selectivity. In recent years, enormous research effort has been made to synthesize different TM-SACs with different M–Nxsites and study the electrochemical conversion of CO_(2) to CO. This review has discussed the development and characterization of different TMSACs with various catalytic sites, fundamental understanding of the electrochemical process in CO_(2) RR,intrinsic catalytic activity, and molecular strategics of SACs responsible for CO_(2)RR. Furthermore, we extensively review previous studies on 1 st-row transition metals TM-SACs(Ni, Co, Fe, Cu, Zn, Sn) and dual-atom catalysts(DACs) utilized for electrochemical CO_(2) conversions and highlight the opportunities and challenges.展开更多
Hydrogen,a renewable and outstanding energy carrier with zero carbon dioxide emission,is regarded as the best alternative to fossil fuels.The most preferred route to large-scale production of hydrogen is by water elec...Hydrogen,a renewable and outstanding energy carrier with zero carbon dioxide emission,is regarded as the best alternative to fossil fuels.The most preferred route to large-scale production of hydrogen is by water electrolysis from the intermittent sources(e.g.,wind,solar,hydro,and tidal energy).However,the efficiency of water electrolysis is very much dependent on the activity of electrocatalysts.Thus,designing high-effective,stable,and cheap materials for hydrogen evolution reaction(HER)could have a substantial impact on renewable energy technologies.Recently,single-atom catalysts(SACs)have emerged as a new frontier in catalysis science,because SACs have maximum atom-utilization efficiency and excellent catalytic reaction activity.Various synthesis methods and analytical techniques have been adopted to prepare and characterize these SACs.In this review,we discuss recent progress on SACs synthesis,characterization methods,and their catalytic applications.Particularly,we highlight their unique electrochemical characteristics toward HER.Finally,the current key challenges in SACs for HER are pointed out and some potential directions are proposed as well.展开更多
Electrochemical water splitting is regarded as the most promising approach to produce hydrogen.However,the sluggish electrochemical reactions occurring at the anode and cathode,namely,the oxygen evolution reaction(OER...Electrochemical water splitting is regarded as the most promising approach to produce hydrogen.However,the sluggish electrochemical reactions occurring at the anode and cathode,namely,the oxygen evolution reaction(OER)and the hydrogen evolution reaction(HER),respectively,consume a tremendous amount of energy,seriously hampering its wide application.Recently,single-atom catalysts(SACs)have been proposed to effectively enhance the kinetics of these two reactions.In this minireview,we focus on the recent progress in SACs for OER and HER applications.Three classes of SACs have been reviewed,i.e.,alloy-based SACs,carbon-based SACs and SACs supported on other compounds.Different factors affecting the activities of SACs are also highlighted,including the inherent element property,the coordination environment,the geometric structure and the loading amount of metal atoms.Finally,we summarize the current problems and directions for future development in SACs.展开更多
Water splitting by electrolysis is an appealing pathway for sustainable hydrogen production. The practical performance of water splitting is highly dependent on the efficiency of electrocatalysts, which can promote th...Water splitting by electrolysis is an appealing pathway for sustainable hydrogen production. The practical performance of water splitting is highly dependent on the efficiency of electrocatalysts, which can promote the anodic oxygen evolution reaction(OER) or cathodic hydrogen evolution reaction(HER). Downsizing the metal nanostructures to atomic level to construct single-atom catalysts(SACs) has attracted enormous attention due to its distinct advantages in maximizing the efficiency of metal atom utilization and enhancing activity over corresponding metal nanoparticles. Research on SACs towards electrochemical water splitting application is an emerging field and intensive investigations have been focused on their rational syntheses and applications in HER/OER. In this review, we focus on the wet chemical method developed to prepare non-noble metal based SACs with an emphasis on the synthetic strategies and structure-activity relationship between single metal atoms and catalytic activity. Finally, the challenges and future opportunities for application of single-atom catalysts in water splitting are briefly addressed.展开更多
Single-atom site catalysts(SACs)have made great achievements due to their nearly 100%atomic utilization and uniform active sites.Regulating the surrounding environment of active sites,including electron structure and ...Single-atom site catalysts(SACs)have made great achievements due to their nearly 100%atomic utilization and uniform active sites.Regulating the surrounding environment of active sites,including electron structure and coordination environment via atom-level interface regulation,to design and construct an advanced SACs is of great significance for boosting electrocatalytic reactions.In this review,we systemically summarized the fundamental understandings and intrinsic mechanisms of SACs for electrocatalytic applications based on the interface site regulations.We elaborated the several different regulation strategies of SACs to demonstrate their ascendancy in electrocatalytic applications.Firstly,the interfacial electronic interaction was presented to reveal the electron transfer behavior of active sites.Secondly,the different coordination structures of metal active center coordinated with two or three non-metal elements were also summarized.In addition,other atom-level interfaces of SACs,including metal atom–atom interface,metal atom-X-atom interface(X:non-metal element),metal atom-particle interface,were highlighted and the corresponding promoting effect towards electrocatalysis was disclosed.Finally,we outlooked the limitations,perspectives and challenges of SACs based on atomic interface regulation.展开更多
Metal-sulfur batteries are recognized as a promising candidate for next generation electrochemical energy storage systems owing to their high theoretical energy density,low cost and environmental friendliness.However,...Metal-sulfur batteries are recognized as a promising candidate for next generation electrochemical energy storage systems owing to their high theoretical energy density,low cost and environmental friendliness.However,sluggish redox kinetics of sulfur species and the shuttle effect lead to large polarization and severe capacity decay.Numerous approaches from physical barrier,chemical adsorption strategies to electrocatalysts have been tried to solve these issues and pushed the rate and cycle performance of sulfur electrodes to higher levels.Most recently,single-atom catalysts(SACs)with high catalytic efficiency have been introduced into metal-sulfur systems to achieve fast redox kinetics of sulfur conversion.In this review,we systematically summarize the current progress on SACs for sulfur electrodes from aspects of synthesis,characterization and electrochemical performance.Challenges and potential solutions for designing SACs for high-performance sulfur electrodes are discussed.展开更多
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(NRF,2021R1C1C1013953,2022K1A4A7A04094394,2022K1A4A7A04095890)。
文摘The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.
文摘The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N4-C)configuration to obtain Ni-X-N3-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N3-C(X:S,Se,and Te)SACs,Ni-Se-N3-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98%at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2)battery integrated with Ni-Se-N3-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm-2 and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N4-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N3-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of*COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.
文摘Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2)reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N2-bidentate(note that N2-bidentate site=N^N-bidentate site;N2¹dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N2-bidentate site,a Cu SAC with isolated undercoordinated Cu-N2 sites(Cu1.0/N2-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N2-GDY exhibits the highest Faradaic efficiency(FE)of 80.6%for CH4 in electrocatalytic reduction of CO_(2)at-0.96 V vs.RHE,and the partial current density of CH4 is 160 mA cm^(-2).The selectivity for CH4 is maintained above 70%when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N2-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N2 sites are more favorable in generating key*COOH and*CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N2 sites toward efficient electrocatalysis.
基金National Natural Science Foundation of China,Grant/Award Numbers:22075203,22279079,21905179Guangdong Science and Technology Department Program,Grant/Award Number:2021QN02L252+1 种基金Shenzhen Science and Technology Department Program,Grant/Award Numbers:20220810133521001,20220809165014001Natural Science Foundation of SZU,Grant/Award Numbers:000002111605,000002112215。
文摘A fuel cell is an energy conversion device that can continuously input fuel and oxidant into the device through an electrochemical reaction to release electrical energy.Although noble metals show good activity in fuel cell-related electrochemical reactions,their ever-increasing price considerably hinders their industrial application.Improvement of atom utilization efficiency is considered one of the most effective strategies to improve the mass activity of catalysts,and this allows for the use of fewer catalysts,saving greatly on the cost.Thus,single-atom catalysts(SACs)with an atom utilization efficiency of 100%have been widely developed,which show remarkable performance in fuel cells.In this review,we will describe recent progress on the development of SACs for membrane electrode assembly of fuel cell applications.First,we will introduce several effective routes for the synthesis of SACs.The reaction mechanism of the involved reactions will also be introduced as it is highly determinant of the final activity.Then,we will systematically summarize the application of Pt group metal(PGM)and nonprecious group metal(non-PGM)catalysts in membrane electrode assembly of fuel cells.This review will offer numerous experiences for developing potential industrialized fuel cell catalysts in the future.
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supported by the National Natural Science Foundation of China (NSFC,22172082,21978137,22102074,and 21878162)Natural Science Foundation of Tianjin (20JCZDJC00770)+1 种基金Postdoctoral Research Foundation of China (2021M701776)NCC Fund (NCC2020FH05)。
文摘In this work,DFT calculations were used firstly to simulate the nitrogen coordinated metal single-atom catalysts(M-N_(x)SACs,M=Hg,Cu,Au,and Ru) to predict their catalytic activities in acetylene hydrochlorination.The DFT results showed that Ru-N_(x)SACs had the best catalytic performance among the four catalysts,and Ru-N_(x)SACs could effectively inhibit the reduction of ruthenium cation.To verify the DFT results,Ru-N_(x)SACs were fabricated by pyrolyzing MOFs in-situ spatially confined metal precursors.The N coordination environment could be controlled by changing the pyrolysis temperature.Catalytic performance tests indicated that low N coordination number(Ru-N_(2),Ru-N_(3))exhibited excellent catalytic activity and stability compared to RuCl_(3)catalyst.DFT calculations further revealed that Ru-N_(2)and Ru-N_(3)had a tendency to activate HCl at the first step of reaction,whereas Ru-N4tended to activate C_(2)H_(2).These findings will serve as a reference for the design and control of metal active sites.
基金the financial support from the National Natural Science Foundation of China (52076045)the Ministry of Science and Technology of China (2019YFC1906700, 2018YFC1902600)the support from “Zhishan Scholar” of Southeast University。
文摘Developing efficient electrocatalysts for converting dinitrogen to ammonia through electrocatalysis is of significance to the decentralized ammonia production. Here, through high-throughput density functional theory calculations, we demonstrated that the interfacial modulation of hexagonal boron nitride/graphene(hBN-graphene) could sufficiently improve the catalytic activity of the single transition metal atom catalysts for nitrogen reduction reaction(NRR). It was revealed that Re@hBN-graphene and Os@hBN-graphene possessed remarkable NRR catalytic activity with low limiting potentials of 0.29 V and 0.33 V, respectively. Furthermore, the mechanism of the enhanced catalytic activity was investigated based on various descriptors of the adsorption energies of intermediates, where the synergistic effect of hBN and graphene in the hybrid substrate was found to play a key role. Motivated by the synergistic effect of hybrid substrate in single-atom catalysts, a novel strategy was proposed to efficiently design dual-atom catalysts by integrating the merits of both metal components. The as-designed dual-atom catalyst Fe-Mo@hBN exhibited more excellent NRR catalytic performance with a limiting potential of 0.17 V, manifesting the solidity of the design strategy. Our findings open new avenues for the search of heterostructure substrates for single-atom catalysts and the efficient design of dualatom catalysts for NRR.
基金Financial support was provided by the Guangdong College Students’Innovative Project(202110580014)the Guangdong “Climbing”Program for Research Items(pdjh2021b0544)。
文摘The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.However,one of the main obstacles of these systems is the poor reaction kinetics in the involved chemical reactions.Therefore,it is essential to incorporate suitable and efficient catalysts into the cell.These years,single-atom catalysts(SACs)are emerging as a frontier in catalysis due to their maximum atom efficiency and unique reaction selectivity.For SACs fabrication,metal-organic frameworks(MOFs)have been confirmed as promising templates or precursors due to their high metal loadings,structural adjustability,porosity,and tailorable catalytic site.In this review,we summarize effective strategies for fabricating SACs by MOFs with corresponding advanced characterization techniques and illustrate the key role of MOFs-based SACs in these batteries by explaining their reaction mechanisms and challenges.Finally,current applications,prospects,and opportunities for MOFs-based SACs in energy storage systems are discussed.
基金National Natural Science Foundation of China,Grant/Award Numbers:62105083,22109034,22109035,52164028Start-up Research Foundation of Hainan University,Grant/Award Numbers:KYQD(ZR)-20008,KYQD(ZR)-20082,KYQD(ZR)-20083,KYQD(ZR)-20084,KYQD(ZR)-21065,KYQD(ZR)-21124,KYQD(ZR)-21125+4 种基金Basic and Applied Basic Research Foundation of Guangdong Province,Grant/Award Number:2019A1515110558Hainan Provincial Postdoctoral Science Foundation,Grant/Award Number:RZ2100007123Hainan Province Science and Technology Special Fund,Grant/Award Numbers:ZDYF2020037,ZDYF2020207Hainan Provincial Natural Science Foundation,Grant/Award Numbers:222MS009,222RC548The specific research fund of The Innovation Platform for Academicians of Hainan Province。
文摘As a carbon-free energy carrier,hydrogen has become the pivot for future clean energy,while efficient hydrogen production and combustion still require precious metal-based catalysts.Single-atom catalysts(SACs)with high atomic utilization open up a desirable perspective for the scale applications of precious metals,but the general and facile preparation of various precious metal-based SACs remains challenging.Herein,a general movable printing method has been developed to synthesize various precious metal-based SACs,such as Pd,Pt,Rh,Ir,and Ru,and the features of highly dispersed single atoms with nitrogen coordination have been identified by comprehensive characterizations.More importantly,the synthesized Pt-and Ru-based SACs exhibit much higher activities than their corresponding nanoparticle counterparts for hydrogen oxidation reaction and hydrogen evolution reaction(HER).In addition,the Pd-based SAC delivers an excellent activity for photocatalytic hydrogen evolution.Especially for the superior mass activity of Ru-based SACs toward HER,density functional theory calculations confirmed that the adsorption of the hydrogen atom has a significant effect on the spin state and electronic structure of the catalysts.
基金the support of the National Natural Science Foundation of China (22002118,22208262,52271228,52202298,52201279,51834009,51801151)the Natural Science Foundation of Shaanxi Province (2021JQ-468,2020JZ-47)+2 种基金the Natural Science Foundation of Shaanxi Provincial Department of Education (21JP086)the Postdoctoral Research Foundation of China (2020 M683528,2020TQ0245,2018M633643XB)the Hundred Talent Program of Shaanxi Province。
文摘The development of novel single-atom catalysts with optimal electron configuration and economical noble-metal cocatalyst for efficient photocatalytic hydrogen production is of great importance,but still challenging.Herein,we fabricate Pt and Co single-atom sites successively on polymeric carbon nitride(CN).In this Pt_(1)-Co_(1)/CN bimetallic single-atom catalyst,the noble-metal active sites are maximized,and the single-atomic Co_(1)N_4sites are tuned to Co_(1)N_3sites by photogenerated electrons arising from the introduced single-atomic Pt_(1)N_4sites.Mechanism studies and density functional theory(DFT)calculations reveal that the 3d orbitals of Co_(1)N_3single sites are filled with unpaired d-electrons,which lead to the improved visible-light response,carrier separation and charge migration for CN photocatalysts.Thereafter,the protons adsorption and activation are promoted.Taking this advantage of long-range electron synergy in bimetallic single atomic sites,the photocatalytic hydrogen evolution activity over Pt_(1)-Co_(1)/CN achieves 915.8 mmol g^(-1)Pt h^(-1),which is 19.8 times higher than Co_(1)/CN and 3.5 times higher to Pt_(1)/CN.While this electron-synergistic effect is not so efficient for Pt nanoclusters.These results demonstrate the synergistic effect at electron-level and provide electron-level guidance for the design of efficient photocatalysts.
基金The authors acknowledge financial support from the National Key R&D Program of China(2022YFA1505700)National Natural Science Foundation of China(22205232,51971157 and 21601187)Shenzhen Science and Technology Program(JCYJ20210324115412035 and ZDSYS20210813095534001).
文摘Single-atom catalysts(SACs)have garnered increasingly growing attention in renewable energy scenarios,especially in electrocatalysis due to their unique high efficiency of atom utilization and flexible electronic structure adjustability.The intensive efforts towards the rational design and synthesis of SACs with versatile local configurations have significantly accelerated the development of efficient and sustainable electrocatalysts for a wide range of electrochemical applications.As an emergent coordination avenue,intentionally breaking the planar symmetry of SACs by adding ligands in the axial direction of metal single atoms offers a novel approach for the tuning of both geometric and electronic structures,thereby enhancing electrocatalytic performance at active sites.In this review,we briefly outline the burgeoning research topic of axially coordinated SACs and provide a comprehensive summary of the recent advances in their synthetic strategies and electrocatalytic applications.Besides,the challenges and outlooks in this research field have also been emphasized.The present review provides an in-depth and comprehensive understanding of the axial coordination design of SACs,which could bring new perspectives and solutions for fine regulation of the electronic structures of SACs catering to high-performing energy electrocatalysis.
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the financial support of the Fundamental Research Funds for the Central Universities (CCNU20QN007, CCNU20TS013)the Program of Introducing Talents of Discipline to Universities of China (111 program, B17019)the Recruitment Program of Global Youth Experts of China。
文摘Single-atom catalysts(SACs) with nitrogen-coordinated nonprecious metal sites have exhibited inimitable advantages in electrocatalysis.However,a large room for improving their activity and durability remains.Herein,we construct atomically dispersed Fe sites in N-doped carbon supports by secondary-atom-doped strategy.Upon the secondary doping,the density and coordination environment of active sites can be efficiently tuned,enabling the simultaneous improvement in the number and reactivity of the active site.Besides,structure optimizations in terms of the enlarged surface area and improved hydrophilicity can be achieved simultaneously.Due to the beneficial microstructure and abundant highly active FeN_5 moieties resulting from the secondary doping,the resultant catalyst exhibits an admirable half-wave potential of 0.81 V versus 0.83 V for Pt/C and much better stability than Pt/C in acidic media.This work would offer a general strategy for the design and preparation of highly active SACs for electrochemical energy devices.
基金This work is supported by NSFC(21773242,21935010)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)+1 种基金National Key Research and Development Program of China(2018YFA0208600)King Abdullah University of Science and Technology.J.Dong acknowledges financial support from Youth Innovation Promotion Association of Chinese Academy of Sciences(2018017).
文摘Reducing the dimensions of metallic nanoparticles to isolated,single atom has attracted considerable attention in heterogeneous catalysis,because it significantly improves atomic utilization and often leads to distinct catalytic performance.Through extensive research,it has been recognized that the local coordination environment of single atoms has an important influence on their electronic structures and catalytic behaviors.In this review,we summarize a series of representative systems of single-atom catalysts,discussing their preparation,characterization,and structure-property relationship,with an emphasis on the correlation between the coordination spheres of isolated reactive centers and their intrinsic catalytic activities.We also share our perspectives on the current challenges and future research promises in the development of single-atom catalysis.With this article,we aim to highlight the possibility of finely tuning the catalytic performances by engineering the coordination spheres of single-atom sites and provide new insights into the further development for this emerging research field.
基金BRNS,Mumbai,India(No-2013/37P/67/BRNS),MNRE,New Delhi,India(No-102/87/2011-NT),and CSIR,New Delhi,India{YSP-02(P-81-113),OLP-95}for the financial supportUGC,New Delhi,for a fellowship。
文摘The continuous increase of global atmospheric CO_(2) concentrations brutally damages our environment. A series of methods have been developed to convert CO_(2) to valuable fuels and value-added chemicals to maintain the equilibrium of carbon cycles. The electrochemical CO_(2) reduction reaction(CO_(2)RR) is one of the promising methods to produce fuels and chemicals, and it could offer sustainable paths to decrease carbon intensity and support renewable energy. Thus, significant research efforts and highly efficient catalysts are essential for converting CO_(2) into other valuable chemicals and fuels. Transition metal-based single atoms catalysts(TM-SACs) have recently received much attention and offer outstanding electrochemical applications with high activity and selectivity opportunities. By taking advantage of both heterogeneous and homogeneous catalysts, TM-SACs are the new rising star for electrochemical conversion of CO_(2) to the value-added product with high selectivity. In recent years, enormous research effort has been made to synthesize different TM-SACs with different M–Nxsites and study the electrochemical conversion of CO_(2) to CO. This review has discussed the development and characterization of different TMSACs with various catalytic sites, fundamental understanding of the electrochemical process in CO_(2) RR,intrinsic catalytic activity, and molecular strategics of SACs responsible for CO_(2)RR. Furthermore, we extensively review previous studies on 1 st-row transition metals TM-SACs(Ni, Co, Fe, Cu, Zn, Sn) and dual-atom catalysts(DACs) utilized for electrochemical CO_(2) conversions and highlight the opportunities and challenges.
基金financially supported by the Natural Sciences and Engineering Research Council of Canada(NSERC)Institut National de la Recherche Scientifique(INRS)the National Natural Science Foundation of China(516722040)
文摘Hydrogen,a renewable and outstanding energy carrier with zero carbon dioxide emission,is regarded as the best alternative to fossil fuels.The most preferred route to large-scale production of hydrogen is by water electrolysis from the intermittent sources(e.g.,wind,solar,hydro,and tidal energy).However,the efficiency of water electrolysis is very much dependent on the activity of electrocatalysts.Thus,designing high-effective,stable,and cheap materials for hydrogen evolution reaction(HER)could have a substantial impact on renewable energy technologies.Recently,single-atom catalysts(SACs)have emerged as a new frontier in catalysis science,because SACs have maximum atom-utilization efficiency and excellent catalytic reaction activity.Various synthesis methods and analytical techniques have been adopted to prepare and characterize these SACs.In this review,we discuss recent progress on SACs synthesis,characterization methods,and their catalytic applications.Particularly,we highlight their unique electrochemical characteristics toward HER.Finally,the current key challenges in SACs for HER are pointed out and some potential directions are proposed as well.
文摘Electrochemical water splitting is regarded as the most promising approach to produce hydrogen.However,the sluggish electrochemical reactions occurring at the anode and cathode,namely,the oxygen evolution reaction(OER)and the hydrogen evolution reaction(HER),respectively,consume a tremendous amount of energy,seriously hampering its wide application.Recently,single-atom catalysts(SACs)have been proposed to effectively enhance the kinetics of these two reactions.In this minireview,we focus on the recent progress in SACs for OER and HER applications.Three classes of SACs have been reviewed,i.e.,alloy-based SACs,carbon-based SACs and SACs supported on other compounds.Different factors affecting the activities of SACs are also highlighted,including the inherent element property,the coordination environment,the geometric structure and the loading amount of metal atoms.Finally,we summarize the current problems and directions for future development in SACs.
基金the financial support from start-up fund of Linyi University (40619025)the Natural Science Foundation of Shandong Province (ZR2018BB060)+1 种基金Zhejiang Provincial Natural Science Foundation of China (LR17B060003)Natural Science Foundation of China (21676246)。
文摘Water splitting by electrolysis is an appealing pathway for sustainable hydrogen production. The practical performance of water splitting is highly dependent on the efficiency of electrocatalysts, which can promote the anodic oxygen evolution reaction(OER) or cathodic hydrogen evolution reaction(HER). Downsizing the metal nanostructures to atomic level to construct single-atom catalysts(SACs) has attracted enormous attention due to its distinct advantages in maximizing the efficiency of metal atom utilization and enhancing activity over corresponding metal nanoparticles. Research on SACs towards electrochemical water splitting application is an emerging field and intensive investigations have been focused on their rational syntheses and applications in HER/OER. In this review, we focus on the wet chemical method developed to prepare non-noble metal based SACs with an emphasis on the synthetic strategies and structure-activity relationship between single metal atoms and catalytic activity. Finally, the challenges and future opportunities for application of single-atom catalysts in water splitting are briefly addressed.
基金supported by the National Key R&D Program of China(2018YFA0702003)the National Natural Science Foundation of China(21890383,21871159)the Science and Technology Key Project of Guangdong Province of China(2020B010188002)。
文摘Single-atom site catalysts(SACs)have made great achievements due to their nearly 100%atomic utilization and uniform active sites.Regulating the surrounding environment of active sites,including electron structure and coordination environment via atom-level interface regulation,to design and construct an advanced SACs is of great significance for boosting electrocatalytic reactions.In this review,we systemically summarized the fundamental understandings and intrinsic mechanisms of SACs for electrocatalytic applications based on the interface site regulations.We elaborated the several different regulation strategies of SACs to demonstrate their ascendancy in electrocatalytic applications.Firstly,the interfacial electronic interaction was presented to reveal the electron transfer behavior of active sites.Secondly,the different coordination structures of metal active center coordinated with two or three non-metal elements were also summarized.In addition,other atom-level interfaces of SACs,including metal atom–atom interface,metal atom-X-atom interface(X:non-metal element),metal atom-particle interface,were highlighted and the corresponding promoting effect towards electrocatalysis was disclosed.Finally,we outlooked the limitations,perspectives and challenges of SACs based on atomic interface regulation.
基金supported by the National Natural Science Foundation of China(No.51972313,51525206 and 51927803)the Ministry of Science and Technology of China(2016YFA0200100 and 2016YFB0100100)+7 种基金the Strategic Priority Research Program of Chinese Academy of Science(No.XDA22010602)Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.Y201942)the Key Research Program of Chinese Academy of Sciences(No.KGZD-EW-T06)the Special Projects of the Central Government in Guidance of Local Science and Technology Development(No.2020JH6/10500024)the Program for Guangdong Introducing Innovative and Entrepreneurial Teamsthe Development and Reform Commission of Shenzhen Municipality for the development of the “Low-Dimensional Materials and Devices”discipline and the EconomicThe Bureau of Industry and Information Technology of Shenzhen for the“2017 Graphene Manufacturing Innovation Center Project”(No.201901171523)China Petrochemical Cooperation(No.218025)。
文摘Metal-sulfur batteries are recognized as a promising candidate for next generation electrochemical energy storage systems owing to their high theoretical energy density,low cost and environmental friendliness.However,sluggish redox kinetics of sulfur species and the shuttle effect lead to large polarization and severe capacity decay.Numerous approaches from physical barrier,chemical adsorption strategies to electrocatalysts have been tried to solve these issues and pushed the rate and cycle performance of sulfur electrodes to higher levels.Most recently,single-atom catalysts(SACs)with high catalytic efficiency have been introduced into metal-sulfur systems to achieve fast redox kinetics of sulfur conversion.In this review,we systematically summarize the current progress on SACs for sulfur electrodes from aspects of synthesis,characterization and electrochemical performance.Challenges and potential solutions for designing SACs for high-performance sulfur electrodes are discussed.