Single-atom catalysis,the catalysis by single-atom catalysts(SACs),has attracted considerable attention in recent years as a new frontier in the heterogeneous catalysis field.SACs have the advantages of both homogeneo...Single-atom catalysis,the catalysis by single-atom catalysts(SACs),has attracted considerable attention in recent years as a new frontier in the heterogeneous catalysis field.SACs have the advantages of both homogeneous catalysts(isolated active sites)and heterogeneous catalysts(stable and easy to separate),and are thus predicted to be able to bridge the homo-and heterogeneous catalysis.This prediction was first experimentally demonstrated in 2016.In this mini-review,we summarize the few homogeneous catalysis progresses reported recently where SACs have exhibited promising application:a)Rh/ZnO and Rh/CoO SAC have been used successfully in hydroformylation of olefin of which the activity are comparable to the homogeneous Wilkinson’s catalyst;b)a Pt/Al2O3 SAC has shown excellent performance in hydrosilylation reaction;and c)M-N-C SACs(M=Fe,Co etc.)have been applied in the activation of C–H bonds.All of these examples suggest that fabrication of suitable SACs could provide a new avenue for the heterogenization of homogeneous catalysts.These pioneering works shed new light on the recognition of single-atom catalysis in bridging the homo-and heterogeneous catalysis.展开更多
Metal-based catalysis,including homogeneous and heterogeneous catalysis,plays a significant role in the modern chemical industry.Heterogeneous catalysis is widely used due to the high efficiency,easy catalyst separati...Metal-based catalysis,including homogeneous and heterogeneous catalysis,plays a significant role in the modern chemical industry.Heterogeneous catalysis is widely used due to the high efficiency,easy catalyst separation and recycling.However,the metal-utilization efficiency for conventional heterogeneous catalysts needs further improvement compared to homogeneous catalyst.To tackle this,the pursing of heterogenizing homogeneous catalysts has always been attractive but challenging.As a recently emerging class of catalytic material,single-atom catalysts(SACs)are expected to bridge homogeneous and heterogeneous catalytic process in organic reactions and have arguably become the most active new frontier in catalysis field.In this review,a brief introduction and development history of single-atom catalysis and SACs involved organic reactions are documented.In addition,recent advances in SACs and their practical applications in organic reactions such as oxidation,reduction,addition,coupling reaction,and other organic reactions are thoroughly reviewed.To understand structure-property relationships of single-atom catalysis in organic reactions,active sites or coordination structure,metal atom-utilization efficiency(e.g.,turnover frequency,TOF calculated based on active metal)and catalytic performance(e.g.,conversion and selectivity)of SACs are comprehensively summarized.Furthermore,the application limitations,development trends,future challenges and perspective of SAC for organic reaction are discussed.展开更多
MgH2 is a promising and popular hydrogen storage material.In this work,the hydrogen desorption reactions of a single Pd atom adsorbed MgH2(110)surface are investigated by using first-principles density functional theo...MgH2 is a promising and popular hydrogen storage material.In this work,the hydrogen desorption reactions of a single Pd atom adsorbed MgH2(110)surface are investigated by using first-principles density functional theory calculations.We find that a single Pd atom adsorbed on the MgH2(110)surface can significantly lower the energy barrier of the hydrogen desorption reactions from 1.802 eV for pure MgH2(110)surface to 1.154 eV for Pd adsorbed MgH2(110)surface,indicating a strong Pd single-atom catalytic effect on the hydrogen desorption reactions.Furthermore,the Pd single-atom catalysis significantly reduces the hydrogen desorption temperature from 573K to 367K,which makes the hydrogen desorption reactions occur more easily and quickly on the MgH2(110)surface.We also discuss the microscopic process of the hydrogen desorption reactions through the reverse process of hydrogen spillover mechanism on the MgH2(110)surface.This study shows that Pd/MgH2 thin films can be used as good hydrogen storage materials in future experiments.展开更多
Water scarcity is an escalating global crisis,posing a severe threat to populations worldwide.Consequently,exploring various materials to remove emerging contaminants from freshwater sources has garnered significant a...Water scarcity is an escalating global crisis,posing a severe threat to populations worldwide.Consequently,exploring various materials to remove emerging contaminants from freshwater sources has garnered significant attention.In this regard,single-atom catalysis(SACs) has emerged as a catalyst of scientific progress in water purification and treatment methodologies during recent decades.SACs exhibit exceptional catalytic activity,selectivity and stability,due to their near-perfect atom utilization,highly unsaturated coordination environment and uniform reaction centers.However,a comprehensive and critical review encompassing the successful integration of SACs into water purification processes needs to be completed.This review aims to accentuate recent trends by presenting the synthesis,structure,and environment and energy application-relevant properties of SACs.The results show that a comprehensive and multi-perspective summary of the advantages of SACs in environmental remediation can have significant benefits,such as fast kinetics,costeffectiveness,selectivity.The oxidation and reduction processes of SACs and functional SACs materials in water purification were emphasized.Furthermore,the last section is devoted to the current research gaps and further perspectives on the application of SACs in water treatment,which are summarized and analyzed.展开更多
Single-atom catalysts(SACS) have obtained a great deal of attention in many catalytic fields due to the high atom utilization efficiency and high catalytic activity.Recently,great achievements on S ACs have been made ...Single-atom catalysts(SACS) have obtained a great deal of attention in many catalytic fields due to the high atom utilization efficiency and high catalytic activity.Recently,great achievements on S ACs have been made for thermocatalysis,electrocatalysis,and photocatalysis which play an important role in obtaining value-added products.However,it remains a great challenge to fabricate S ACs with high metal loading and investigate their reaction mechanisms.Therefore,it is necessary to highlight the recent development of S ACs in these fields to guide future research.In this review,we overviewed the thermocatalysis applications of SACs in CO oxidation,preferential oxidation of CO,water-gas shift reaction,methane conversion,methanol steam reforming,aqueous-phase reforming of methanol,hydrogenation of alkynes and dienes,hydrogenation of CO,and hydrogenation of substituted nitroarenes.Moreover,the oxygen reduction reaction(ORR),hydrogen evolution reaction(HER),oxygen evolution reaction(OER),CO2 reduction reaction(CO2 RR),and N2 reduction reaction(N2 RR) for photocatalytic and electrocatalytic fields were also overviewed.Lastly,the opportunities and challenges of SACs were pointed out.展开更多
Currently,more than 86%of global energy consumption is still mainly dependent on traditional fossil fuels,which causes resource scarcity and even emission of high amounts of carbon dioxide(CO_(2)),resulting in a sever...Currently,more than 86%of global energy consumption is still mainly dependent on traditional fossil fuels,which causes resource scarcity and even emission of high amounts of carbon dioxide(CO_(2)),resulting in a severe“Greenhouse effect.”Considering this situation,the concept of“carbon neutrality”has been put forward by 125 countries one after another.To achieve the goals of“carbon neutrality,”two main strategies to reduce CO_(2) emissions and develop sustainable clean energy can be adopted.Notably,these are crucial for the synthesis of advanced single-atom catalysts(SACs)for energyrelated applications.In this review,we highlight unique SACs for conversion of CO_(2) into high-efficiency carbon energy,for example,through photocatalytic,electrocatalytic,and thermal catalytic hydrogenation technologies,to convert CO_(2) into hydrocarbon fuels(CO,CH_(4),HCOOH,CH_(3)OH,and multicarbon[C_(2+)]products).In addition,we introduce advanced energy conversion technologies and devices to replace traditional polluting fossil fuels,such as photocatalytic and electrocatalytic water splitting to produce hydrogen energy and a high-efficiency oxygen reduction reaction(ORR)for fuel cells.Impressively,several representative examples of SACs(including d-,ds-,p-,and f-blocks)for CO_(2) conversion,water splitting to H2,and ORR are discussed to describe synthesis methods,characterization,and corresponding catalytic activity.Finally,this review concludes with a description of the challenges and outlooks for future applications of SACs in contributing toward carbon neutrality.展开更多
The idea that single metal atoms dispersed on a solid support can act as an efficient heterogeneous catalyst was raised in2011when single Pt atoms on an FeOx surface were reported to be active for CO oxidation and pre...The idea that single metal atoms dispersed on a solid support can act as an efficient heterogeneous catalyst was raised in2011when single Pt atoms on an FeOx surface were reported to be active for CO oxidation and preferential oxidation of CO in H2.The last six years have witnessed tremendous progress in the field of single‐atom catalysis.Here we introduce the major achievements on this topic in2015and2016.Some particular aspects of single‐atom catalysis are discussed in depth,including new approaches in single‐atom catalyst(SAC)synthesis,stable gold SACs for various reactions,the high selectivity of Pt and Pd SACs in hydrogenation,and the superior performance of non‐noble metal SACs in electrochemistry.These accomplishments will encourage more efforts by researchers to achieve the controllable fabrication of SACs and explore their potential applications.展开更多
Single-atom catalysts(SACs),featuring a structure consisting of iso-lated metal atoms dispersed on solid supports,can provide the maximum atom utilization efficiency and great potential for bridging the gap be-tween h...Single-atom catalysts(SACs),featuring a structure consisting of iso-lated metal atoms dispersed on solid supports,can provide the maximum atom utilization efficiency and great potential for bridging the gap be-tween heterogeneous and homogeneous catalysis.Since Zhang and co-workers reported the single Pt atom on iron oxide for catalyzing CO oxidation in 2011,1 SACs have become a new frontier in catalysis sci-ences and have attracted numerous attention in various aspects,such as photocatalysis,electrocatalysis and thermal catalysis.2,3。展开更多
Single-atom catalysts(SACs)are among the most cutting-edge catalysts in the multiphase catalysis track due to their unique geometrical and electronic properties,the highest atom utilization efficiency,and uniform acti...Single-atom catalysts(SACs)are among the most cutting-edge catalysts in the multiphase catalysis track due to their unique geometrical and electronic properties,the highest atom utilization efficiency,and uniform active sites.SACs have been facing an unresolved problem in practical applications:the opposing contradiction of activity-stability.The successful development of single-atom nano-islands(SANIs)cleverly combines the ultra-high atom utilization efficiency of SACs with the confinement effect and structural stability of nano-island structures,realizing the“moving but not aggregation”of SACs,which fundamentally solves this inherent contradiction.Although research on the precise loading of single atoms on nano-islands continues to advance,existing reviews have not yet established a closed-loop cognitive framework encompassing“models-synthesis-high stability mechanisms-high activity essence-applications.”This work fills this critical gap by systematically integrating the basic conceptual models and cutting-edge synthesis strategies of SANIs,focusing on revealing the underlying mechanisms by which SANIs overcome the stability bottleneck of SACs,elucidating the role of nano-islands and their synergistic mechanisms to clarify the high activity essence,and establishing the structure-activity relationship between atomic confinement effects and macroscopic performance,ultimately achieving breakthrough validation across catalytic systems.This review aims to open new perspectives,drive a paradigm shift in understanding the multi-dimensional advantages of SANIs,and thereby spur breakthrough progress in this frontier field.展开更多
Single-atom catalysts(SACs)have garnered significant attention in lithium-sulfur(Li-S)batteries for their potential to mitigate the severe polysulfide shuttle effect and sluggish redox kinetics.However,the development...Single-atom catalysts(SACs)have garnered significant attention in lithium-sulfur(Li-S)batteries for their potential to mitigate the severe polysulfide shuttle effect and sluggish redox kinetics.However,the development of highly efficient SACs and a comprehensive understanding of their structure-activity relationships remain enormously challenging.Herein,a novel kind of Fe-based SAC featuring an asymmetric FeN_(5)-TeN_(4) coordination structure was precisely designed by introducing Te atom adjacent to the Fe active center to enhance the catalytic activity.Theoretical calculations reveal that the neighboring Te atom modulates the local coordination environment of the central Fe site,elevating the d-band center closer to the Fermi level and strengthening the d-p orbital hybridization between the catalyst and sulfur species,thereby immobilizing polysulfides and improving the bidirectional catalysis of Li-S redox.Consequently,the Fe-Te atom pair catalyst endows Li-S batteries with exceptional rate performance,achieving a high specific capacity of 735 mAh g^(−1) at 5 C,and remarkable cycling stability with a low decay rate of 0.038%per cycle over 1000 cycles at 1 C.This work provides fundamental insights into the electronic structure modulation of SACs and establishes a clear correlation between precisely engineered atomic configurations and their enhanced catalytic performance in Li-S electrochemistry.展开更多
Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systemat...Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.展开更多
The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexit...The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexity of NO_(3)^(−)RR,yet challenges remain in optimizing performance and elucidating tandem mechanisms.Herein,we report a Cu@Co/CoFe-P tandem electrocatalyst featuring a phosphorus-doped heterostructure with dual active sites(Cu-P and Co/CoFe-P).This catalyst achieves an exceptional NH_(3)yield of 175.40 mg h^(−1)cm^(−2)and a record-high current density exceeding 2 A cm^(−2),with the electro-synthesized NH3 directly converted into NH4Cl.In situ spectroscopic analysis and density functional theory(DFT)calculations reveal a novel desorption-reactivation tandem mechanism:(1)the Cu-P domain preferentially reduces NO_(3)^(−)to*NO_(2),which desorbs as stable NO_(2)^(−);(2)the Co/CoFe-P domain subsequently reactivates NO_(2)^(−),and converts it efficiently into NH3.Moreover,phosphorus doping enhances*H supply,while Fe alloying with Co promotes NO_(2)^(−)hydrogenation,ensuring an efficient and synchronized tandem pathway for NO_(3)^(−)RR.The proposed*NO_(2)desorption-reactivation mechanism deepens the understanding of NO_(3)^(−)RR tandem process,thereby paving the way for designing more efficient tandem electrocatalysts.展开更多
The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasoni...The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu_(2)O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m^(−2)),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.展开更多
Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar.In this paper,a K_(2)FeO_(4)-involving hydrothermal oxidative magnetization w...Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar.In this paper,a K_(2)FeO_(4)-involving hydrothermal oxidative magnetization was explored to regulate multiple micro-structures for manufacture magnetic hydrochar(MHC)for Fenton-like degradation of tetracycline in aqueous solution.Diverse shapes of Fe_(3)O_(4) and nano zero-valent iron(nZVI)were doped with abundant oxygen containing groups and persistent free radicals(PFRs).Multiple catalysis sites including iron species,PFRs,oxygen containing groups,and graphite defects contributed to accelerate the Fenton-like degradation with synergistic effect.Notably,MHC achieved a tetracycline removal rate of 99% within 60 min at 50 mg/L,with a total organic carbon(TOC)removal rate of 35%.Furthermore,after four cycles of reuse,the degradation efficiency slightly decreased to 93%.This study highlights the potential of magnetic hydrochar with multiple catalytic sites in the effective and sustainable degradation of pollutants.展开更多
Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent c...Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.展开更多
The reduction of N2 to NH_(3) is an important reaction for the industrial production of ammonia gas.Here,we theoretically study the thermal synthesis of ammonia catalyzed by Ru1@Mo_(2)CO_(x)single-atom catalyst(SAC),w...The reduction of N2 to NH_(3) is an important reaction for the industrial production of ammonia gas.Here,we theoretically study the thermal synthesis of ammonia catalyzed by Ru1@Mo_(2)CO_(x)single-atom catalyst(SAC),where Ru atoms are anchored on the oxygen vacancy of the defective Mo2COx.The results show that Ru1@Mo_(2)CO_(x)exhibits excellent stability,and can effectively adsorb and activate N2,owing to up to0.87|e|charge transfer from it to N2.The optimal pathway of N2-to-NH_(3) conversion is association pathway I,of which the rate-determining step is*NH_(2)→*NH_(3) with the barrier energy of 1.26 eV.Especially,the Mo_(2)CO_(x)center functions as an electron reservoir,donating electrons to the NxHy species,while the Ru single atom serves as a charge transfer pathway,thereby enhancing the reaction activity.This finding provides a theoretical foundation for the rational design of MXene-based SACs for thermal catalytic NH_(3) synthesis.展开更多
This article systematically reviewed the applications of single-atom catalysts(SACs)in the domain of photocatalytic reactions,with a particular emphasis on the indispensable role of H_(2)O in these processes.SACs,due ...This article systematically reviewed the applications of single-atom catalysts(SACs)in the domain of photocatalytic reactions,with a particular emphasis on the indispensable role of H_(2)O in these processes.SACs,due to their distinct active sites and superior catalytic efficacy,found their applications in the fields of energy conversion and environmental protection.The review elaborated on the potential carriers,preparation methods,and characterization techniques for single-atom photocatalysts.Subsequently,the article provided an in-depth explanation of the crucial role of H_(2)O in photocatalytic reactions,serving as an important green solvent and an oxygen/proton source.The adsorption of water could also change the surface energy structure and charge distribution of the photocatalyst.Conversely,the presence of H_(2)O might also inhibit the target reaction.Additionally,the distinct roles of water in both liquid and gas phases were discussed.Furthermore,the review systematically summarized the applications of single-atom photocatalysts in H_(2)generation,CO_(2)reduction,N2fixation,H_(2)O_(2)production,and environmentalremediation.It delved into the mechanisms by which water molecules participated in photocatalytic processes and their interactions with competing pathways,thereby revealing the complexity and critical importance of water in photocatalytic reactions.Finally,the article discusses the opportunities and challenges of SACs in photocatalytic reactions with H_(2)O.This article provides a comprehensive perspective for understanding the role of SACs in waterinvolved photocatalytic reactions.展开更多
With high energy density and low material cost,lithium sulfur batteries(LSBs)emerge quite expeditiously as a fascinating energy storage system over the past decade.Broad applications of LSBs ranging from electric vehi...With high energy density and low material cost,lithium sulfur batteries(LSBs)emerge quite expeditiously as a fascinating energy storage system over the past decade.Broad applications of LSBs ranging from electric vehicles to stationary grid storage seem rather bright in recent literatures.However,there still exist many pressing challenges to be addressed because we do not yet fully understand and control the electrode-electrolyte interface chemistries during battery operation,such as polysulide shuttling and poor utilization of active sulfur.Single-atom catalysts(SACs)pave new possibilities of tackling the tough issues due to their decent applicability in the atomic-level identification of structure-activity relationships and reaction mechanism,as well as their structural tunability with atomic precision.This review comprehensively summarizes the very recent advances in utilization of highly active SACs for LSBs by stating and discussing the related publications,which involves catalyst synthesis routes,battery pertormance,catalytic mechanisms,optimization strategies,and promises to achieve long-lite,high-energy LSBs.We see that endeavors to employ SACs to modify sulfur cathode have allowed efficient polysulfide conversion and confinement,leading to the minimization of shuttle effect.Parallel efforts are being devoted to extending the scope of SACs to cell separator and lithium metal anode in order to unlock the full potential of LSBs.We also obtain mechanistic insights into battery chemistries and nature of SACs in their strong interactions with polysulfides through advanced in situ characterizations documented.Overall,acceleration in the development of LSBs by introducing SACs is noticeable,and this cutting edge needs more attentions to further promoting the design of better LSBs.展开更多
As a class of nanomaterials with natural enzyme-like characteristics, nanozymes have shown their great potential in various applications. Reducible metal oxides featured with defect structures, and single-atom catalys...As a class of nanomaterials with natural enzyme-like characteristics, nanozymes have shown their great potential in various applications. Reducible metal oxides featured with defect structures, and single-atom catalysts with isolated metal sites are regarded as two of the most promising nanozymes. However, the strategies to construct highly performed nanozymes by combining these advantages are rarely reported. Herein, we report the coordination-unsaturated single-atomic Cu species supported on sintered CeO_(2), which combines the advantages of defect engineering and single-atom catalysis, exhibiting a largely enhanced peroxidase(POD)-like activity. The high-temperature calcination induces the transformation of inert Cu_(1)O_(4) species into coordination-unsaturated Cu_(1)O_(3) sites. This novel Cu_(1)O_(3) active sites with an unsaturated coordination work as a new type of defect sites to greatly activate the isolated Cu atoms and accelerate the dissociation of H_(2)O_(2) to form hydroxyl radicals(·OH). The obtained nanozyme with a high POD-like activity possesses low cytotoxicity, showing potential applications for the tumor inhibition in vitro and in vivo.展开更多
Rare earth metals are strategic resources with potential applications in optics,metallurgy and catalysis.In recent years,single-atom site catalysts(SASCs) have attracted increasing attention owing to their 100%atom ef...Rare earth metals are strategic resources with potential applications in optics,metallurgy and catalysis.In recent years,single-atom site catalysts(SASCs) have attracted increasing attention owing to their 100%atom efficiency and unique catalytic performances.Over the past decade,rare earth elements,including rare earth metals and their oxides,have shown great potential in SASCs.However,systematic analyses of data are still handful.In this mini-review,the use of rare earth metals and their oxides in SASCs was summarized and the results are discussed.A particular focus was paid to the synthetic strategies,characterization of rare earth-containing SASCs,and applications as catalysis supports,promoters and active sites.Current issues faced by rare-earth metals and their oxides in SASCs,as well as future prospects were also provided.展开更多
基金supported by National Natural Science Foundation of China(21606222,21776270)Postdoctoral Science Foundation(2017M621170,2016M601350)~~
文摘Single-atom catalysis,the catalysis by single-atom catalysts(SACs),has attracted considerable attention in recent years as a new frontier in the heterogeneous catalysis field.SACs have the advantages of both homogeneous catalysts(isolated active sites)and heterogeneous catalysts(stable and easy to separate),and are thus predicted to be able to bridge the homo-and heterogeneous catalysis.This prediction was first experimentally demonstrated in 2016.In this mini-review,we summarize the few homogeneous catalysis progresses reported recently where SACs have exhibited promising application:a)Rh/ZnO and Rh/CoO SAC have been used successfully in hydroformylation of olefin of which the activity are comparable to the homogeneous Wilkinson’s catalyst;b)a Pt/Al2O3 SAC has shown excellent performance in hydrosilylation reaction;and c)M-N-C SACs(M=Fe,Co etc.)have been applied in the activation of C–H bonds.All of these examples suggest that fabrication of suitable SACs could provide a new avenue for the heterogenization of homogeneous catalysts.These pioneering works shed new light on the recognition of single-atom catalysis in bridging the homo-and heterogeneous catalysis.
基金financially supported by the Key Research and Development Program of Hubei Province(No.2022BAA026)the Major Project of Hubei Provincial Department of Education(No.D20211502)+1 种基金the Open/Innovation Project of Key Laboratory of Novel Biomass-Based Environmental and Energy Materials in Petroleum and Chemical Industry(No.2022BEEA06)support by the Postgraduate Innovation Foundation from Wuhan Institute of Technology(No.CX2021364)。
文摘Metal-based catalysis,including homogeneous and heterogeneous catalysis,plays a significant role in the modern chemical industry.Heterogeneous catalysis is widely used due to the high efficiency,easy catalyst separation and recycling.However,the metal-utilization efficiency for conventional heterogeneous catalysts needs further improvement compared to homogeneous catalyst.To tackle this,the pursing of heterogenizing homogeneous catalysts has always been attractive but challenging.As a recently emerging class of catalytic material,single-atom catalysts(SACs)are expected to bridge homogeneous and heterogeneous catalytic process in organic reactions and have arguably become the most active new frontier in catalysis field.In this review,a brief introduction and development history of single-atom catalysis and SACs involved organic reactions are documented.In addition,recent advances in SACs and their practical applications in organic reactions such as oxidation,reduction,addition,coupling reaction,and other organic reactions are thoroughly reviewed.To understand structure-property relationships of single-atom catalysis in organic reactions,active sites or coordination structure,metal atom-utilization efficiency(e.g.,turnover frequency,TOF calculated based on active metal)and catalytic performance(e.g.,conversion and selectivity)of SACs are comprehensively summarized.Furthermore,the application limitations,development trends,future challenges and perspective of SAC for organic reaction are discussed.
基金supported by the National Key Basic Research Program(No.2011CB921404)National Natural Science Foundation of China(No.21421063,No.91021004,No.21233007,No.21803066)+2 种基金Strategic Priority Research Program of Chinese Academy of Sciences(No.XDC01000000)Research Start-Up Grants(No.KY2340000094)from University of Science and Technology of Chinathe Chinese Academy of Sciences Pioneer Hundred Talents Program
文摘MgH2 is a promising and popular hydrogen storage material.In this work,the hydrogen desorption reactions of a single Pd atom adsorbed MgH2(110)surface are investigated by using first-principles density functional theory calculations.We find that a single Pd atom adsorbed on the MgH2(110)surface can significantly lower the energy barrier of the hydrogen desorption reactions from 1.802 eV for pure MgH2(110)surface to 1.154 eV for Pd adsorbed MgH2(110)surface,indicating a strong Pd single-atom catalytic effect on the hydrogen desorption reactions.Furthermore,the Pd single-atom catalysis significantly reduces the hydrogen desorption temperature from 573K to 367K,which makes the hydrogen desorption reactions occur more easily and quickly on the MgH2(110)surface.We also discuss the microscopic process of the hydrogen desorption reactions through the reverse process of hydrogen spillover mechanism on the MgH2(110)surface.This study shows that Pd/MgH2 thin films can be used as good hydrogen storage materials in future experiments.
基金financially supported by the National Natural Science Foundation of China (No.52200055)the Natural Science Foundation of Jiangsu Province (No.BK20210483)+1 种基金China Postdoctoral Science Foundation (No.2022T150271)the Natural Science Research of Jiangsu Higher Education Institutions of China (No.23KJB610001)。
文摘Water scarcity is an escalating global crisis,posing a severe threat to populations worldwide.Consequently,exploring various materials to remove emerging contaminants from freshwater sources has garnered significant attention.In this regard,single-atom catalysis(SACs) has emerged as a catalyst of scientific progress in water purification and treatment methodologies during recent decades.SACs exhibit exceptional catalytic activity,selectivity and stability,due to their near-perfect atom utilization,highly unsaturated coordination environment and uniform reaction centers.However,a comprehensive and critical review encompassing the successful integration of SACs into water purification processes needs to be completed.This review aims to accentuate recent trends by presenting the synthesis,structure,and environment and energy application-relevant properties of SACs.The results show that a comprehensive and multi-perspective summary of the advantages of SACs in environmental remediation can have significant benefits,such as fast kinetics,costeffectiveness,selectivity.The oxidation and reduction processes of SACs and functional SACs materials in water purification were emphasized.Furthermore,the last section is devoted to the current research gaps and further perspectives on the application of SACs in water treatment,which are summarized and analyzed.
基金financially supported by the National Natural Science Foundation of China(Nos.11675051,51302079,51702138,51702297,51633006,51725304,51733004,51703159,and 51903186)the Natural Science Foundation of Hunan Province(No.2017JJ1008)+1 种基金the Key Research and Development Program of Hunan Province of China(No.2018GK2031)the Ministry of Science and Technology of China(Nos.2017YFA0204503 and 2016YFB0401100)。
文摘Single-atom catalysts(SACS) have obtained a great deal of attention in many catalytic fields due to the high atom utilization efficiency and high catalytic activity.Recently,great achievements on S ACs have been made for thermocatalysis,electrocatalysis,and photocatalysis which play an important role in obtaining value-added products.However,it remains a great challenge to fabricate S ACs with high metal loading and investigate their reaction mechanisms.Therefore,it is necessary to highlight the recent development of S ACs in these fields to guide future research.In this review,we overviewed the thermocatalysis applications of SACs in CO oxidation,preferential oxidation of CO,water-gas shift reaction,methane conversion,methanol steam reforming,aqueous-phase reforming of methanol,hydrogenation of alkynes and dienes,hydrogenation of CO,and hydrogenation of substituted nitroarenes.Moreover,the oxygen reduction reaction(ORR),hydrogen evolution reaction(HER),oxygen evolution reaction(OER),CO2 reduction reaction(CO2 RR),and N2 reduction reaction(N2 RR) for photocatalytic and electrocatalytic fields were also overviewed.Lastly,the opportunities and challenges of SACs were pointed out.
基金National Key R&D Program of China,Grant/Award Number:2018YFA0702003National Natural Science Foundation of China,Grant/Award Numbers:21890383,21871159Science and Technology Key Project of Guangdong Province of China,Grant/Award Number:2020B010188002。
文摘Currently,more than 86%of global energy consumption is still mainly dependent on traditional fossil fuels,which causes resource scarcity and even emission of high amounts of carbon dioxide(CO_(2)),resulting in a severe“Greenhouse effect.”Considering this situation,the concept of“carbon neutrality”has been put forward by 125 countries one after another.To achieve the goals of“carbon neutrality,”two main strategies to reduce CO_(2) emissions and develop sustainable clean energy can be adopted.Notably,these are crucial for the synthesis of advanced single-atom catalysts(SACs)for energyrelated applications.In this review,we highlight unique SACs for conversion of CO_(2) into high-efficiency carbon energy,for example,through photocatalytic,electrocatalytic,and thermal catalytic hydrogenation technologies,to convert CO_(2) into hydrocarbon fuels(CO,CH_(4),HCOOH,CH_(3)OH,and multicarbon[C_(2+)]products).In addition,we introduce advanced energy conversion technologies and devices to replace traditional polluting fossil fuels,such as photocatalytic and electrocatalytic water splitting to produce hydrogen energy and a high-efficiency oxygen reduction reaction(ORR)for fuel cells.Impressively,several representative examples of SACs(including d-,ds-,p-,and f-blocks)for CO_(2) conversion,water splitting to H2,and ORR are discussed to describe synthesis methods,characterization,and corresponding catalytic activity.Finally,this review concludes with a description of the challenges and outlooks for future applications of SACs in contributing toward carbon neutrality.
基金supported by the National Natural Science Foundation of China(21606222,21303184,21573232)China Postdoctoral Science Foundation(2016M601350)+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020100)National Key Projects for Fundamental Research and Development of China(2016YFA0202801)Department of Science and Technology of Liaoning Province(2015020086-101)~~
文摘The idea that single metal atoms dispersed on a solid support can act as an efficient heterogeneous catalyst was raised in2011when single Pt atoms on an FeOx surface were reported to be active for CO oxidation and preferential oxidation of CO in H2.The last six years have witnessed tremendous progress in the field of single‐atom catalysis.Here we introduce the major achievements on this topic in2015and2016.Some particular aspects of single‐atom catalysis are discussed in depth,including new approaches in single‐atom catalyst(SAC)synthesis,stable gold SACs for various reactions,the high selectivity of Pt and Pd SACs in hydrogenation,and the superior performance of non‐noble metal SACs in electrochemistry.These accomplishments will encourage more efforts by researchers to achieve the controllable fabrication of SACs and explore their potential applications.
文摘Single-atom catalysts(SACs),featuring a structure consisting of iso-lated metal atoms dispersed on solid supports,can provide the maximum atom utilization efficiency and great potential for bridging the gap be-tween heterogeneous and homogeneous catalysis.Since Zhang and co-workers reported the single Pt atom on iron oxide for catalyzing CO oxidation in 2011,1 SACs have become a new frontier in catalysis sci-ences and have attracted numerous attention in various aspects,such as photocatalysis,electrocatalysis and thermal catalysis.2,3。
基金supported by the National Key Research and Development Program of China(No.2022YFD1700801-3)Key Laboratory of Jiangxi Province for Persistent Pollutants Prevention Control and Resource Reuse(No.2023SSY02061)support of the projects and research platform support provided by the laboratory.
文摘Single-atom catalysts(SACs)are among the most cutting-edge catalysts in the multiphase catalysis track due to their unique geometrical and electronic properties,the highest atom utilization efficiency,and uniform active sites.SACs have been facing an unresolved problem in practical applications:the opposing contradiction of activity-stability.The successful development of single-atom nano-islands(SANIs)cleverly combines the ultra-high atom utilization efficiency of SACs with the confinement effect and structural stability of nano-island structures,realizing the“moving but not aggregation”of SACs,which fundamentally solves this inherent contradiction.Although research on the precise loading of single atoms on nano-islands continues to advance,existing reviews have not yet established a closed-loop cognitive framework encompassing“models-synthesis-high stability mechanisms-high activity essence-applications.”This work fills this critical gap by systematically integrating the basic conceptual models and cutting-edge synthesis strategies of SANIs,focusing on revealing the underlying mechanisms by which SANIs overcome the stability bottleneck of SACs,elucidating the role of nano-islands and their synergistic mechanisms to clarify the high activity essence,and establishing the structure-activity relationship between atomic confinement effects and macroscopic performance,ultimately achieving breakthrough validation across catalytic systems.This review aims to open new perspectives,drive a paradigm shift in understanding the multi-dimensional advantages of SANIs,and thereby spur breakthrough progress in this frontier field.
基金supported by the National Natural Science Foundation(52302284,22002086,22204096)Shanghai Sailing Program(23YF1412200)the Fundamental Research Funds for the Central Universities(22120240314).
文摘Single-atom catalysts(SACs)have garnered significant attention in lithium-sulfur(Li-S)batteries for their potential to mitigate the severe polysulfide shuttle effect and sluggish redox kinetics.However,the development of highly efficient SACs and a comprehensive understanding of their structure-activity relationships remain enormously challenging.Herein,a novel kind of Fe-based SAC featuring an asymmetric FeN_(5)-TeN_(4) coordination structure was precisely designed by introducing Te atom adjacent to the Fe active center to enhance the catalytic activity.Theoretical calculations reveal that the neighboring Te atom modulates the local coordination environment of the central Fe site,elevating the d-band center closer to the Fermi level and strengthening the d-p orbital hybridization between the catalyst and sulfur species,thereby immobilizing polysulfides and improving the bidirectional catalysis of Li-S redox.Consequently,the Fe-Te atom pair catalyst endows Li-S batteries with exceptional rate performance,achieving a high specific capacity of 735 mAh g^(−1) at 5 C,and remarkable cycling stability with a low decay rate of 0.038%per cycle over 1000 cycles at 1 C.This work provides fundamental insights into the electronic structure modulation of SACs and establishes a clear correlation between precisely engineered atomic configurations and their enhanced catalytic performance in Li-S electrochemistry.
基金support of the National Natural Science Foundation of China(22075131 and 22078265)the Shaanxi Fundamental Science Research Project for Mathematics and Physics under Grants(No.22JSZ005)the State-Key Laboratory of Multiphase Complex Systems(No.MPCS-2021-A).
文摘Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.
基金supported financially by the Key Project of the National Ministry of Science and Technology (No.2022YFC3705005)the Open Foundation of Key Laboratory of Industrial Ecology and Environmental Engineering,MOE (KLIEEE-22-05)
文摘The electrocatalytic reduction of nitrate to ammonia(NO_(3)^(−)RR)offers a sustainable alternative to energy-intensive industrial NH3 synthesis.Tandem catalysis has shown promise in overcoming the multi-step complexity of NO_(3)^(−)RR,yet challenges remain in optimizing performance and elucidating tandem mechanisms.Herein,we report a Cu@Co/CoFe-P tandem electrocatalyst featuring a phosphorus-doped heterostructure with dual active sites(Cu-P and Co/CoFe-P).This catalyst achieves an exceptional NH_(3)yield of 175.40 mg h^(−1)cm^(−2)and a record-high current density exceeding 2 A cm^(−2),with the electro-synthesized NH3 directly converted into NH4Cl.In situ spectroscopic analysis and density functional theory(DFT)calculations reveal a novel desorption-reactivation tandem mechanism:(1)the Cu-P domain preferentially reduces NO_(3)^(−)to*NO_(2),which desorbs as stable NO_(2)^(−);(2)the Co/CoFe-P domain subsequently reactivates NO_(2)^(−),and converts it efficiently into NH3.Moreover,phosphorus doping enhances*H supply,while Fe alloying with Co promotes NO_(2)^(−)hydrogenation,ensuring an efficient and synchronized tandem pathway for NO_(3)^(−)RR.The proposed*NO_(2)desorption-reactivation mechanism deepens the understanding of NO_(3)^(−)RR tandem process,thereby paving the way for designing more efficient tandem electrocatalysts.
基金supported by Yunnan Major Scientific and Technological Projects(Grant No.202402AB080004)Yunnan Provincial Education Department Universities Serve Key Industry Science and Technology Projects(Grant No:FWCY-BSPY2024043)+1 种基金Top Innovative Talents for Graduate Students of KUST(Grant No:CA24163M116A)Analysis and Testing Fund of KUST(Grant No:2024P20233102006).The authors extend their gratitude to Mr.Kong Qingyuan from Scientific Compass(www.shiyanjia.com)for providing invaluable assistance with scientific research.
文摘The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu_(2)O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m^(−2)),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.
基金supported byHainan Provincial Natural Science Foundation of China(Nos.422RC600,519QN175)National Natural Science Foundation ofChina(Nos.52160018,21801053,52400206,52500209)High-Level Talent Program of Hainan Province(Nos.XJ2400008202,XJ2400011473).
文摘Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar.In this paper,a K_(2)FeO_(4)-involving hydrothermal oxidative magnetization was explored to regulate multiple micro-structures for manufacture magnetic hydrochar(MHC)for Fenton-like degradation of tetracycline in aqueous solution.Diverse shapes of Fe_(3)O_(4) and nano zero-valent iron(nZVI)were doped with abundant oxygen containing groups and persistent free radicals(PFRs).Multiple catalysis sites including iron species,PFRs,oxygen containing groups,and graphite defects contributed to accelerate the Fenton-like degradation with synergistic effect.Notably,MHC achieved a tetracycline removal rate of 99% within 60 min at 50 mg/L,with a total organic carbon(TOC)removal rate of 35%.Furthermore,after four cycles of reuse,the degradation efficiency slightly decreased to 93%.This study highlights the potential of magnetic hydrochar with multiple catalytic sites in the effective and sustainable degradation of pollutants.
文摘Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.
基金the financial support from National Natural Science Foundation of China(22479032,22363001 and 22250710677)the NSFC Center for Single-Atom Catalysis(22388102)+2 种基金the National Key R&D Project(2022YFA1503900)the Natural Science Special Foundation of Guizhou University(No.202140)Guizhou Provincial Key Laboratory Platform Project(ZSYS[2025]008).
文摘The reduction of N2 to NH_(3) is an important reaction for the industrial production of ammonia gas.Here,we theoretically study the thermal synthesis of ammonia catalyzed by Ru1@Mo_(2)CO_(x)single-atom catalyst(SAC),where Ru atoms are anchored on the oxygen vacancy of the defective Mo2COx.The results show that Ru1@Mo_(2)CO_(x)exhibits excellent stability,and can effectively adsorb and activate N2,owing to up to0.87|e|charge transfer from it to N2.The optimal pathway of N2-to-NH_(3) conversion is association pathway I,of which the rate-determining step is*NH_(2)→*NH_(3) with the barrier energy of 1.26 eV.Especially,the Mo_(2)CO_(x)center functions as an electron reservoir,donating electrons to the NxHy species,while the Ru single atom serves as a charge transfer pathway,thereby enhancing the reaction activity.This finding provides a theoretical foundation for the rational design of MXene-based SACs for thermal catalytic NH_(3) synthesis.
基金financially supported by Guangdong Basic and Applied Basic Research Foundation(No.2024A1515010976)Shenzhen Peacock Plan(No.20210802524B)+3 种基金the Postdoctoral Research Foundation of China(Nos.GZC20241085,GZC20230562,GZC20230564)China Postdoctoral Science Foundation(No.2024M760583)the National Natural Science Foundation of China(No.52402234)Shenzhen Key Laboratory of 2D Metamaterials for Information Technology
文摘This article systematically reviewed the applications of single-atom catalysts(SACs)in the domain of photocatalytic reactions,with a particular emphasis on the indispensable role of H_(2)O in these processes.SACs,due to their distinct active sites and superior catalytic efficacy,found their applications in the fields of energy conversion and environmental protection.The review elaborated on the potential carriers,preparation methods,and characterization techniques for single-atom photocatalysts.Subsequently,the article provided an in-depth explanation of the crucial role of H_(2)O in photocatalytic reactions,serving as an important green solvent and an oxygen/proton source.The adsorption of water could also change the surface energy structure and charge distribution of the photocatalyst.Conversely,the presence of H_(2)O might also inhibit the target reaction.Additionally,the distinct roles of water in both liquid and gas phases were discussed.Furthermore,the review systematically summarized the applications of single-atom photocatalysts in H_(2)generation,CO_(2)reduction,N2fixation,H_(2)O_(2)production,and environmentalremediation.It delved into the mechanisms by which water molecules participated in photocatalytic processes and their interactions with competing pathways,thereby revealing the complexity and critical importance of water in photocatalytic reactions.Finally,the article discusses the opportunities and challenges of SACs in photocatalytic reactions with H_(2)O.This article provides a comprehensive perspective for understanding the role of SACs in waterinvolved photocatalytic reactions.
基金the National Key R&D Program of China(No.2018YFA0702003)the National Natural Science Foundation of China(Nos.21890383,21671117,21871159)+1 种基金the China Postdoctoral Science Foundation(No.2019M660607)Z.C.Z.acknowledges support from the Shuimu Isinghua Scholar Program.
文摘With high energy density and low material cost,lithium sulfur batteries(LSBs)emerge quite expeditiously as a fascinating energy storage system over the past decade.Broad applications of LSBs ranging from electric vehicles to stationary grid storage seem rather bright in recent literatures.However,there still exist many pressing challenges to be addressed because we do not yet fully understand and control the electrode-electrolyte interface chemistries during battery operation,such as polysulide shuttling and poor utilization of active sulfur.Single-atom catalysts(SACs)pave new possibilities of tackling the tough issues due to their decent applicability in the atomic-level identification of structure-activity relationships and reaction mechanism,as well as their structural tunability with atomic precision.This review comprehensively summarizes the very recent advances in utilization of highly active SACs for LSBs by stating and discussing the related publications,which involves catalyst synthesis routes,battery pertormance,catalytic mechanisms,optimization strategies,and promises to achieve long-lite,high-energy LSBs.We see that endeavors to employ SACs to modify sulfur cathode have allowed efficient polysulfide conversion and confinement,leading to the minimization of shuttle effect.Parallel efforts are being devoted to extending the scope of SACs to cell separator and lithium metal anode in order to unlock the full potential of LSBs.We also obtain mechanistic insights into battery chemistries and nature of SACs in their strong interactions with polysulfides through advanced in situ characterizations documented.Overall,acceleration in the development of LSBs by introducing SACs is noticeable,and this cutting edge needs more attentions to further promoting the design of better LSBs.
基金supported by the National Key Research and Development Program of China (2021YFA1501103)the National Science Fund for Distinguished Young Scholars of China (22225110)+3 种基金the National Natural Science Foundation of China (22102088)the foundation of Key Laboratory of Colloid and Interface Chemistry (Shandong University), Ministry of Education (202202)the Taishan Scholar Project of Shandong Province of Chinathe Young Scholars Program of Shandong University。
文摘As a class of nanomaterials with natural enzyme-like characteristics, nanozymes have shown their great potential in various applications. Reducible metal oxides featured with defect structures, and single-atom catalysts with isolated metal sites are regarded as two of the most promising nanozymes. However, the strategies to construct highly performed nanozymes by combining these advantages are rarely reported. Herein, we report the coordination-unsaturated single-atomic Cu species supported on sintered CeO_(2), which combines the advantages of defect engineering and single-atom catalysis, exhibiting a largely enhanced peroxidase(POD)-like activity. The high-temperature calcination induces the transformation of inert Cu_(1)O_(4) species into coordination-unsaturated Cu_(1)O_(3) sites. This novel Cu_(1)O_(3) active sites with an unsaturated coordination work as a new type of defect sites to greatly activate the isolated Cu atoms and accelerate the dissociation of H_(2)O_(2) to form hydroxyl radicals(·OH). The obtained nanozyme with a high POD-like activity possesses low cytotoxicity, showing potential applications for the tumor inhibition in vitro and in vivo.
基金Project supported by the China Postdoctoral Science Foundation(2020M670355)the National Key R&D Program of China(2016YFC0204305)National Natural Science Foundation of China(21777004)。
文摘Rare earth metals are strategic resources with potential applications in optics,metallurgy and catalysis.In recent years,single-atom site catalysts(SASCs) have attracted increasing attention owing to their 100%atom efficiency and unique catalytic performances.Over the past decade,rare earth elements,including rare earth metals and their oxides,have shown great potential in SASCs.However,systematic analyses of data are still handful.In this mini-review,the use of rare earth metals and their oxides in SASCs was summarized and the results are discussed.A particular focus was paid to the synthetic strategies,characterization of rare earth-containing SASCs,and applications as catalysis supports,promoters and active sites.Current issues faced by rare-earth metals and their oxides in SASCs,as well as future prospects were also provided.
