Solving the problems of carbon dioxide(CO_(2))emissions and energy scarcity by the development of highly selective,cost-effective,and reliable catalysts for the electrochemical reduction of CO_(2)to useful carbon-base...Solving the problems of carbon dioxide(CO_(2))emissions and energy scarcity by the development of highly selective,cost-effective,and reliable catalysts for the electrochemical reduction of CO_(2)to useful carbon-based products would be very helpful.We report the synthesis of an efficient graphene-supported bismuth single-atom catalyst(BiSA-G)featuring a BiN_(4)coordination structure for this purpose.The synthesis used tannic acid as a multifunctional ligand and ammonia as a nitrogen dopant.Using a scalable coordination chemistry approach,BiN_(4)sites were uniformly dispersed on the graphene substrate and were found to have an outstanding ability for the conversion of CO_(2)to CO,with a high Faradaic efficiency of 97.4%at−0.55 V(vs.RHE)and a high turnover frequency of 5230 h^(−1)along with outstanding stability.Density functional theory calculations confirmed that the BiN_(4)site serves as the dominant active center,simultaneously facilitating CO_(2)activation and the efficient formation of the crucial intermediate*COOH with a reduced free energy barrier.This discovery offers a new way for the atomic-scale design of high-efficiency catalysts for the electrochemical CO_(2)reduction reaction,potentially helping sustainable carbon use.展开更多
In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(...In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(x)-C)has been identified as the key active site in SACs.Although methods for preparing SACs have been extensively reported,a systematic summary of the direct construction of M-N_(x)-C,espe-cially unconventional metal-nitrogen-carbon(UM-N_(x)-C,x≠4),on SACs for PS non-radical activation has still not been reported.The role of the M-N_(x)-C active sites on PS non-radical activation is discussed and methods for the formation of M-N_(x)-C and UM-N_(x)-C active sites in SACs and the effect of catalyst carriers such as carbon nitride(g-C_(3)N_(4)),MOFs,COFs,and other car-bon materials are reviewed.Direct and indirect methods,especially for UM-N_(x)-C active site formation,are also elaborated.Factors affecting the formation of a M-N_(x)-C active site on SACs are also discussed.Prospects for the use of M-N_(x)-C active sites for the non-radical activation of PS by SACs to remove organic contaminants from wastewater are evaluated.展开更多
By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these c...The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.展开更多
Hydroisomerization of n-alkanes plays an important role in fuel and lubricants processing.Bifunctional catalysts with ultralow platinum loading have recently been reported successively for hydroisomerisation.Herein,th...Hydroisomerization of n-alkanes plays an important role in fuel and lubricants processing.Bifunctional catalysts with ultralow platinum loading have recently been reported successively for hydroisomerisation.Herein,the catalysts were prepared successfully with different methods to improve the catalytic performance.The conversion of 0.01%Pt1@CeOx/SAPO-11 prepared by co-calcination method(0.01%Pt1@CS-c)is 71.4%,25%higher than the other prepared by precipitation method.The turnover frequency per active surface platinum site(TOFPt)of 0.01%Ptl@CS-c is as high as 13115 h^(-1).Revealed by the X-ray photoelectron spectroscopy(XPS)results,the quality of phase boundary/intersurface between ceria and zeolite is found significantly different.The conjunction quality of phase boundary directly affects the spillover rate of intermediate species,which further leads to an apparent activity difference.In addition,the possible role of ceria in the reaction is discussed,rather than just as a carrier for the active metal atoms.展开更多
Precisely tailoring metal single-atoms within zeolite scaffolds and understanding the origin of the unique behavior of such atomically dispersed catalysts are pivotal and challenge in chemistry and catalysis.Herein,we...Precisely tailoring metal single-atoms within zeolite scaffolds and understanding the origin of the unique behavior of such atomically dispersed catalysts are pivotal and challenge in chemistry and catalysis.Herein,we have successfully fabricated Ni single-atoms within BEA zeolite(Ni_(1)@Beta)through a facile in situ two-step hydrothermal strategy,notably without using any chelating agent for stabilizing Ni species.With the aid of advanced characterization techniques,such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy,X-ray absorption spectroscopy,etc.,and combined with density functional theory calculations,the nature and micro-environment of isolated Ni species,which are incorporated within 6-membered rings and stabilized by four skeletal oxygens of Beta zeolite,have been identified.The as-obtained Ni1@Beta exhibits a superior performance in terms of activity(with a turnover frequency value up to 114.1 h^(-1))and stability(for 5 consecutive runs)in the selective hydrogenation of furfural,surpassing those of Ni nanoparticle analogues and previously reported Ni-based heterogeneous catalysts.This study provides an efficient strategy for the fabrication of non-noble metal single-atoms within zeolites,which could be of great help for the design of metal-zeolite combinations in the chemoselective reactions involved in biomass conversion and beyond.展开更多
The co-production of hydrogen and value-added biochemicals from lignocellulose utilizing solar energy has been regarded as one of the technologies most potentially able to alleviate the current energy crisis.Here,we d...The co-production of hydrogen and value-added biochemicals from lignocellulose utilizing solar energy has been regarded as one of the technologies most potentially able to alleviate the current energy crisis.Here,we demonstrate a cost-effective photoreforming strategy for lignocellulose valorization using a carbon nitride-supported platinum single-atom photocatalyst.An advanced H_(2) evolution rate of 6.34 mmol molPt^(-1) h^(-1) is achieved over the optimal catalyst,which is around 4.6 and 30.5 times higher compared with the nanosized Pt counterpart and pristine carbon nitride,respectively.Meanwhile,the monosaccharides are oxidized to value-added lactic acid with>99%conversion and extraordinary selectivity up to 97%.The theoretical calculations show that with Pt incorporation,the photogenerated holes are predominantly localized on the metal sites while the photogenerated electrons are concentrated on C_(3)N_(4),thus enhancing the effective separation of charge carriers.This work provides a promising avenue for the simultaneous production of green H2 and bio-based chemicals by biomass photorefinery.展开更多
With the rapid advancement of portable energy devices and sensor technologies,enhancing their catalytic performance,sensing capabilities,and application reliability has become a critical challenge in the fields of mat...With the rapid advancement of portable energy devices and sensor technologies,enhancing their catalytic performance,sensing capabilities,and application reliability has become a critical challenge in the fields of materials and energy science.Single-atom catalysts(SACs),owing to their high atomic utilization,outstanding catalytic activity,and precisely engineered structures enabled by density functional theory and enhanced by artificial intelligence,have shown tremendous potential in advancing portable energy and sensing technologies.While existing reviews predominantly focus on the application of SACs in individual portable devices,systematic discussions on their overall development prospects and challenges within portable energy and sensor fields remain scarce.Therefore,this review comprehensively explores the application potential and recent advancements of SACs in portable zinc-air batteries,proton exchange membrane fuel cells,and sensor technologies.The article highlights the influence of key factors such as material design,structural optimization,and packaging integration on device performance,while also addressing the primary bottlenecks and challenges encountered in current practical applications.Furthermore,it suggests possible future development directions,aiming to offer theoretical insights and engineering guidance for the large-scale deployment of SACs in wearable electronic devices,portable energy systems,and smart sensing technologies.展开更多
Propane dehydrogenation(PDH)has emerged as a key on-purpose technology for the production of propylene,but it often depends on toxic chromium and expensive platinum catalysts,highlighting the need for environmentally ...Propane dehydrogenation(PDH)has emerged as a key on-purpose technology for the production of propylene,but it often depends on toxic chromium and expensive platinum catalysts,highlighting the need for environmentally friendly and cost-effective alternatives.In this study,we developed a facile impregnation method to fabricate unsaturated Co single-atoms with a tricoordinated Co_(1)O_(3)H_(x) structure by regulating silanol nests in purely siliceous Beta zeolites.Detailed PDH catalytic tests and characterizations revealed a positive correlation between the presence of silanol nests and enhanced catalytic activity.Additionally,the unsaturated Co single-atoms exhibited a carbon deposition rate more than an order of magnitude slower than that of Co nanoparticles.Notably,the optimized Co_(0.3%)/deAl-meso-Beta catalyst achieved a record-high propylene formation rate of 21.2 mmol_(C3H6) g_(cat)^(-1) h^(-1),with an exceptional propylene selectivity of 99.1%at 550℃.Moreover,the Co_(0.3%)/deAl-meso-Beta catalyst demonstrated excellent stability,with negligible deactivation after 5 consecutive regeneration cycles.This study emphasizes the pivotal role of silanol nests of zeolites in stabilizing and modulating the coordination environment of metallic active sites,providing valuable insights for the design of high-activity,high-stability,and low-cost PDH catalysts.展开更多
Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stab...Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites,thus meeting fundamental requirements for practical application.The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts(SACs)prepared based on silicon-based materials(mesoporous silica,silicon-based minerals,and organosilicon materials)has unique advantages such as structural stability(especially important under strong oxidation conditions)and environmental protection.In this paper,the preparation strategies for the silicon-based SACs were assessed first,and the structural characteristics of various silicon-based SACs are systematically discussed,their application process and mechanism in Fenton-like process to achieve water purification are investigated,and the progress of Fenton-like process in density functional theory(DFT)of siliconbased derived single atom catalysts is summarized.In this paper,the preparation strategies and applications of silicon-based derived SACs are analyzed in depth,and their oxidation activities and pathways to different pollutants in water are reviewed.In addition,this paper also summarizes the device design and application of silicon-based derived SACs,and prospects the future development of silicon-based SACs in Fenton-like applications.展开更多
As environmental pollutants pose a serious threat to socioeconomic and environmental health,the development of simple,efficient,accurate and costeffective methods for pollution monitoring and control remains a major c...As environmental pollutants pose a serious threat to socioeconomic and environmental health,the development of simple,efficient,accurate and costeffective methods for pollution monitoring and control remains a major challenge,but it is an unavoidable issue.In the past decade,the artificial nanozymes have been widely used for environmental pollutant monitoring and control,because of their low cost,high stability,easy mass production,etc.However,the conventional nanozyme technology faces significant challenges in terms of difficulty in regulating the exposed crystal surface,complex composition,low catalytic activity,etc.In contrast,the emerging single-atom nanozymes(SANs)have attracted much attention in the field of environmental monitoring and control,due to their multiple advantages of atomically dispersed active sites,high atom utilization efficiency,tunable coordination environment,etc.To date,the insufficient efforts have been made to comprehensively characterize the applications of SANs in the monitoring and control of environmental pollutants.Building on the recent advances in the field,this review systematically summarizes the main synthesis methods of SANs and highlights their advances in the monitoring and control of environmental pollutants.Finally,we critically evaluate the limitations and challenges of SANs,and provide the insights into their future prospects for the monitoring and control of environmental pollutants.展开更多
Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,c...Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,curvature-induced strain has been extensively demonstrated as a powerful tool for modulating the catalytic performance of M-N-C catalysts.However,identifying optimal strain patterns using density functional theory(DFT)is computationally intractable due to the high-dimensional search space.Here,we developed a graph neural network(GNN)integrated with an advanced topological data analysis tool-persistent homology-to predict the adsorption energy response of adsorbate under proposed curvature patterns,using nitric oxide electroreduction(NORR)as an example.Our machine learning model achieves high accuracy in predicting the adsorption energy response to curvature,with a mean absolute error(MAE)of 0.126 eV.Furthermore,we elucidate general trends in curvature-modulated adsorption energies of intermediates across various metals and coordination environments.We recommend several promising catalysts for NORR that exhibit significant potential for performance optimization via curvature modulation.This methodology can be readily extended to describe other non-bonded interactions,such as lattice strain and surface stress,providing a versatile approach for advanced catalyst design.展开更多
The single-atom M-N-C(M typically being Co or Fe)is a prominent material with exceptional reactivity in areas of catalysis for sustainable energy.However,the formation of metal nanoparticles in M-N-C materials is coup...The single-atom M-N-C(M typically being Co or Fe)is a prominent material with exceptional reactivity in areas of catalysis for sustainable energy.However,the formation of metal nanoparticles in M-N-C materials is coupled with hightemperature calcination conditions,limiting the density of M-Nx active sites and thus restricting the catalytic performance of such catalysts.Herein,we describe an effective decoupling strategy to construct high-density M-Nx active sites by generating polyfurfuryl alcohol in the MOF precursor,effectively preventing the formation of metal nanoparticles even with up to 6.377%cobalt loading.This catalyst showed a high H_(2) production rate of 778mLgcat^(−1) h^(−1) when used in the dehydrogenation reaction of formic acid.In addition to the high density of the active site,a curved carbon surface in the structure is also thought to be the reason for the high performance of the catalyst.展开更多
Photoreforming of formic acid(FA)represents a compelling technology for green hydrogen(H_(2))production,but the application is limited by the relatively low activity and selectivity.Recent advancements have introduced...Photoreforming of formic acid(FA)represents a compelling technology for green hydrogen(H_(2))production,but the application is limited by the relatively low activity and selectivity.Recent advancements have introduced transition-metal nitrides(TMNs)as a new class of co-catalysts for photocatalytic FA reforming,showing impressive performance but still having the disadvantage of suboptimal H_(2)selectivity.Here,we present a novel Cu-W_(2)N_(3)cocatalyst with abundant Cu single-atom sites.On combining with a CdS photocatalyst,the CdS/Cu-W_(2)N_(3)system demonstrated an elevated H_(2)generation rate of 172.69μmol·h^(-1) and superior H_(2)selectivity in comparison to CdS/W_(2)N_(3).Comprehensive experimental and theoretical investigations indicate that the introduction of Cu single-atom sites in Cu-W_(2)N_(3)leads to a robust interaction with CdS,which optimizes the charge transfer.More significantly,the Cu single-atom sites modify the inert surface of the W_(2)N_(3)cocatalyst,creating conducive electron transfer channels and leading to an abundance of active sites favorable for hydrogen evolution reaction(HER),consequently resulting in higher H_(2)selectivity than pristine W_(2)N_(3).This study provides a promising approach to achieving an efficient photoreforming reaction with specific selectivity via the design of novel cocatalysts with specialized active sites.展开更多
Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds.However,challenges remain to develop both cost-effective and efficient catalysts.In this study,we developed a...Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds.However,challenges remain to develop both cost-effective and efficient catalysts.In this study,we developed a Ru-Co/ZrO_(2)single-atom alloy catalyst which afforded diverse primary amines from alcohols in the presence of ammonia and hydrogen with exceptional conversion(up to 90%)and selectivity(80%)under mild conditions(0.7 MPa NH_(3),0.3 MPa H_(2),160℃)and exhibited satisfactory stability upon regeneration.The turnover rate was approximately 8.4 times higher than that observed over the Co/ZrO_(2)catalyst.Characterizations indicated that the alloyed Ru facilitated the reduction of Co,strengthened the interaction with H_(2)and mitigated the over-strong adsorption of aldehyde intermediates.These combined effects contributed significantly to the enhanced catalytic performances.This work presents a promising strategy for the development of advanced catalysts in the amination of alcohols.展开更多
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein...The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein,an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy(Co-O_(V))on the Co/BiOCl-O_(V)photocatalyst was developed for photocatalytic degradation of glyphosate(GLP)wastewater of high performance/selectivity.Under full-spectrum-light irradiation,a high GLP degradation rate of 99.8%with over 90%C-P bond-breaking selectivity was achieved within 2 h,while effectively circumventing toxicant residues such as aminomethylphosphonic acid(AMPA).X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-O_(V)carrier and photothermal/pyroelectric effect.The oriented formation of more•O_(2)^(−)on Co/BiOCl-O_(V)could be achieved with the Co-O_(V)coupled center that had excellent O2 adsorption/activation capacity,as demonstrated by quantum calculations.The formed unique Co-O_(V)active sites could largely decrease the C-P bond-breaking energy barrier,thus greatly improving the selectivity toward the initial C-P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP.The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C-X bonds.展开更多
Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined acti...Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined active sites and high loadings under precise control has become a hotly debated topic in scientific research.Metal-organic frameworks(MOFs),with their exceptional properties such as ultrahigh specific surface areas,precisely controllable structural de-signs,and highly flexible functional cus-tomization capabilities,are regarded as one of the ideal matrices for supporting and sta-bilizing SACs.This review provides an in-sightful overview of the diverse preparation strategies for MOFs-derived SACs.It comprehen-sively analyzes the unique advantages and challenges of each method in achieving efficient synthesis of SACs,emphasizing the crucial role of optimized processes in unlocking the antici-pated performance of SACs.Furthermore,this review delves into a series of advanced charac-terization techniques,including aberration-corrected scanning transmission electron mi-croscopy(AC-STEM),electron energy loss spectroscopy(EELS),X-ray absorption spec-troscopy(XAS),and infrared absorption spectroscopy(IRAS),offering valuable insights into the atomic-scale fine structures and properties of SACs,significantly advancing the under-standing of SAC mechanisms.Moreover,this review focuses on exploring the potential appli-cations of MOFs-derived SACs in electrocatalysis frontier fields.This comprehensive exami-nation lays a solid theoretical foundation and provides a directional guidance for the rational design and controllable synthesis of high-performance MOFs-derived SACs.展开更多
Perfluoroalkyl and polyfluoroalkyl substances(PFASs)pollution with their toxicity,carcinogenicity,and persistence has been concerned worldwide.Research into novel materials for detecting and removing PFASs has increas...Perfluoroalkyl and polyfluoroalkyl substances(PFASs)pollution with their toxicity,carcinogenicity,and persistence has been concerned worldwide.Research into novel materials for detecting and removing PFASs has increased rapidly,particularly in regard to the emergence of well-characterized single-atom materials(SAMs).Owing to the high selectivity,high atom utilization,and abundant active sites of SAMs,these materials exhibit remarkable efficacy in the detection and removal of PFASs.In this work,recent advances in the synthesis of SAMs for the detection and removal PFASs are reviewed.In-depth discussions of the structure-activity relationship and reaction mechanisms have demonstrated the high efficiency,activity,and selectivity of SAMs for the detection,adsorption,and degradation of PFASs.To optimize the application of SAMs in PFASs remediation,this review comprehensively surveys SAMs applications for PFASs and analyzes potential design strategies based on synthesis methods and corresponding properties.Synthesis strategies such as wet-chemistry,which offer ease of operation and high potential for large-scale production,are recommended for the further exploration of specific SAMs for the detection and removal of PFASs.Finally,this review identifies the challenges and opportunities for development of SAMs for the detection and remediation of PFASs,providing an outlook on strategic goals for a green economy and sustainable development.展开更多
Lithium-sulfur batteries(LSBs)have become a favorable contender for next-generation electrochemical energy storage systems due to their outstanding features such as high energy density,low cost,and environmental frien...Lithium-sulfur batteries(LSBs)have become a favorable contender for next-generation electrochemical energy storage systems due to their outstanding features such as high energy density,low cost,and environmental friendliness.However,the commercialization of LSBs is still characterized by critical issues such as low sulfur utilization,short cycle life,and poor rate performance,which need to be resolved.Single-atom catalysts,with their outstanding features such as ultra-high atom utilization rate close to 100%and adjustable coordination configuration,have received extensive attention in the field of lithium-sulfur battery research.In this paper,the preparation and characterization of single-atom catalysts for Li-S batteries are briefly introduced,and the latest research progress of single-atom catalysts for Li-S batteries is reviewed from three aspects:cathode,separator and anode.Finally,the key technical problems and future research directions of single-atom catalysts for lithium-sulfur batteries are also prospected,with a view to promoting the further development of commercialized LSBs.展开更多
Lithium-sulfur(Li-S)batteries are regarded as the most formidable competitor to lithium-ion batteries due to their superior theoretical capacity.However,the negative impact of soluble lithium polysulfide(LiPSs)and slo...Lithium-sulfur(Li-S)batteries are regarded as the most formidable competitor to lithium-ion batteries due to their superior theoretical capacity.However,the negative impact of soluble lithium polysulfide(LiPSs)and slow redox reaction kinetics seriously hamper the commercialization of Li-S batteries.In this study,a defect-rich single-atom catalyst with an oversaturated asymmetric Fe-N_(5)coordination structure anchored in defective g-C_(3)N_(4)(C_(3)N_(4)-Fe@rGO)is designed via an absorption-pyrolysis strategy.The two-dimensional(2D)conducting C_(3)N_(4)@graphene structure with abundant defect sites accelerates the trans-fer and transportation of lithium ions and electrons.The oversaturated asymmetric Fe-N_(5)coordination structure effectively improves the adsorbility of LiPSs and accelerates the redox kinetics of sulfur species.Hence,the Li-S cell with a C_(3)N_(4)-Fe@rGO modified separator reveals a high initial capacity(1197.1 mAh g^(-1) at 0.2 C)and a low capacity decay rate(0.037%per cycle after 900 cycles at 1 C).Even at high sulfur loading and extreme temperatures of 0℃,it also shows good cycling performance.This work creates ideas for synthesizing oversaturated single-atom coordination environments and an efficient route to the practical realization of the Li-S batteries.展开更多
文摘Solving the problems of carbon dioxide(CO_(2))emissions and energy scarcity by the development of highly selective,cost-effective,and reliable catalysts for the electrochemical reduction of CO_(2)to useful carbon-based products would be very helpful.We report the synthesis of an efficient graphene-supported bismuth single-atom catalyst(BiSA-G)featuring a BiN_(4)coordination structure for this purpose.The synthesis used tannic acid as a multifunctional ligand and ammonia as a nitrogen dopant.Using a scalable coordination chemistry approach,BiN_(4)sites were uniformly dispersed on the graphene substrate and were found to have an outstanding ability for the conversion of CO_(2)to CO,with a high Faradaic efficiency of 97.4%at−0.55 V(vs.RHE)and a high turnover frequency of 5230 h^(−1)along with outstanding stability.Density functional theory calculations confirmed that the BiN_(4)site serves as the dominant active center,simultaneously facilitating CO_(2)activation and the efficient formation of the crucial intermediate*COOH with a reduced free energy barrier.This discovery offers a new way for the atomic-scale design of high-efficiency catalysts for the electrochemical CO_(2)reduction reaction,potentially helping sustainable carbon use.
文摘In recent years,numer-ous single-atom catalysts(SACs)have been synthesized to activate persulfate(PS)by a non-radical pathway because of its high se-lectivity,and activity for the cata-lyst.Metal-nitrogen-carbon(M-N_(x)-C)has been identified as the key active site in SACs.Although methods for preparing SACs have been extensively reported,a systematic summary of the direct construction of M-N_(x)-C,espe-cially unconventional metal-nitrogen-carbon(UM-N_(x)-C,x≠4),on SACs for PS non-radical activation has still not been reported.The role of the M-N_(x)-C active sites on PS non-radical activation is discussed and methods for the formation of M-N_(x)-C and UM-N_(x)-C active sites in SACs and the effect of catalyst carriers such as carbon nitride(g-C_(3)N_(4)),MOFs,COFs,and other car-bon materials are reviewed.Direct and indirect methods,especially for UM-N_(x)-C active site formation,are also elaborated.Factors affecting the formation of a M-N_(x)-C active site on SACs are also discussed.Prospects for the use of M-N_(x)-C active sites for the non-radical activation of PS by SACs to remove organic contaminants from wastewater are evaluated.
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
基金supported by Shanxi Province Science Foundation for Youths(202203021212300)Taiyuan University of Science and Technology Scientific Research Initial Funding(20212064)Outstanding Doctoral Award Fund in Shanxi Province(20222060).
文摘The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.
基金Project supported by National Natural Science Foundation of China(22078159,U19B2001)。
文摘Hydroisomerization of n-alkanes plays an important role in fuel and lubricants processing.Bifunctional catalysts with ultralow platinum loading have recently been reported successively for hydroisomerisation.Herein,the catalysts were prepared successfully with different methods to improve the catalytic performance.The conversion of 0.01%Pt1@CeOx/SAPO-11 prepared by co-calcination method(0.01%Pt1@CS-c)is 71.4%,25%higher than the other prepared by precipitation method.The turnover frequency per active surface platinum site(TOFPt)of 0.01%Ptl@CS-c is as high as 13115 h^(-1).Revealed by the X-ray photoelectron spectroscopy(XPS)results,the quality of phase boundary/intersurface between ceria and zeolite is found significantly different.The conjunction quality of phase boundary directly affects the spillover rate of intermediate species,which further leads to an apparent activity difference.In addition,the possible role of ceria in the reaction is discussed,rather than just as a carrier for the active metal atoms.
文摘Precisely tailoring metal single-atoms within zeolite scaffolds and understanding the origin of the unique behavior of such atomically dispersed catalysts are pivotal and challenge in chemistry and catalysis.Herein,we have successfully fabricated Ni single-atoms within BEA zeolite(Ni_(1)@Beta)through a facile in situ two-step hydrothermal strategy,notably without using any chelating agent for stabilizing Ni species.With the aid of advanced characterization techniques,such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy,X-ray absorption spectroscopy,etc.,and combined with density functional theory calculations,the nature and micro-environment of isolated Ni species,which are incorporated within 6-membered rings and stabilized by four skeletal oxygens of Beta zeolite,have been identified.The as-obtained Ni1@Beta exhibits a superior performance in terms of activity(with a turnover frequency value up to 114.1 h^(-1))and stability(for 5 consecutive runs)in the selective hydrogenation of furfural,surpassing those of Ni nanoparticle analogues and previously reported Ni-based heterogeneous catalysts.This study provides an efficient strategy for the fabrication of non-noble metal single-atoms within zeolites,which could be of great help for the design of metal-zeolite combinations in the chemoselective reactions involved in biomass conversion and beyond.
文摘The co-production of hydrogen and value-added biochemicals from lignocellulose utilizing solar energy has been regarded as one of the technologies most potentially able to alleviate the current energy crisis.Here,we demonstrate a cost-effective photoreforming strategy for lignocellulose valorization using a carbon nitride-supported platinum single-atom photocatalyst.An advanced H_(2) evolution rate of 6.34 mmol molPt^(-1) h^(-1) is achieved over the optimal catalyst,which is around 4.6 and 30.5 times higher compared with the nanosized Pt counterpart and pristine carbon nitride,respectively.Meanwhile,the monosaccharides are oxidized to value-added lactic acid with>99%conversion and extraordinary selectivity up to 97%.The theoretical calculations show that with Pt incorporation,the photogenerated holes are predominantly localized on the metal sites while the photogenerated electrons are concentrated on C_(3)N_(4),thus enhancing the effective separation of charge carriers.This work provides a promising avenue for the simultaneous production of green H2 and bio-based chemicals by biomass photorefinery.
文摘With the rapid advancement of portable energy devices and sensor technologies,enhancing their catalytic performance,sensing capabilities,and application reliability has become a critical challenge in the fields of materials and energy science.Single-atom catalysts(SACs),owing to their high atomic utilization,outstanding catalytic activity,and precisely engineered structures enabled by density functional theory and enhanced by artificial intelligence,have shown tremendous potential in advancing portable energy and sensing technologies.While existing reviews predominantly focus on the application of SACs in individual portable devices,systematic discussions on their overall development prospects and challenges within portable energy and sensor fields remain scarce.Therefore,this review comprehensively explores the application potential and recent advancements of SACs in portable zinc-air batteries,proton exchange membrane fuel cells,and sensor technologies.The article highlights the influence of key factors such as material design,structural optimization,and packaging integration on device performance,while also addressing the primary bottlenecks and challenges encountered in current practical applications.Furthermore,it suggests possible future development directions,aiming to offer theoretical insights and engineering guidance for the large-scale deployment of SACs in wearable electronic devices,portable energy systems,and smart sensing technologies.
文摘Propane dehydrogenation(PDH)has emerged as a key on-purpose technology for the production of propylene,but it often depends on toxic chromium and expensive platinum catalysts,highlighting the need for environmentally friendly and cost-effective alternatives.In this study,we developed a facile impregnation method to fabricate unsaturated Co single-atoms with a tricoordinated Co_(1)O_(3)H_(x) structure by regulating silanol nests in purely siliceous Beta zeolites.Detailed PDH catalytic tests and characterizations revealed a positive correlation between the presence of silanol nests and enhanced catalytic activity.Additionally,the unsaturated Co single-atoms exhibited a carbon deposition rate more than an order of magnitude slower than that of Co nanoparticles.Notably,the optimized Co_(0.3%)/deAl-meso-Beta catalyst achieved a record-high propylene formation rate of 21.2 mmol_(C3H6) g_(cat)^(-1) h^(-1),with an exceptional propylene selectivity of 99.1%at 550℃.Moreover,the Co_(0.3%)/deAl-meso-Beta catalyst demonstrated excellent stability,with negligible deactivation after 5 consecutive regeneration cycles.This study emphasizes the pivotal role of silanol nests of zeolites in stabilizing and modulating the coordination environment of metallic active sites,providing valuable insights for the design of high-activity,high-stability,and low-cost PDH catalysts.
基金supported by National Natural Science Foundation of China(No.52170086)Natural Science Foundation of Shandong Province(No.ZR2021ME013)+1 种基金Natural science Foundation of Shaanxi province(No.2024JC-YBQN-0252)Special Scientific Research Project of Hanzhong City-Shaanxi University of Technology Co-construction State Key Laboratory(No.SXJ2106)。
文摘Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites,thus meeting fundamental requirements for practical application.The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts(SACs)prepared based on silicon-based materials(mesoporous silica,silicon-based minerals,and organosilicon materials)has unique advantages such as structural stability(especially important under strong oxidation conditions)and environmental protection.In this paper,the preparation strategies for the silicon-based SACs were assessed first,and the structural characteristics of various silicon-based SACs are systematically discussed,their application process and mechanism in Fenton-like process to achieve water purification are investigated,and the progress of Fenton-like process in density functional theory(DFT)of siliconbased derived single atom catalysts is summarized.In this paper,the preparation strategies and applications of silicon-based derived SACs are analyzed in depth,and their oxidation activities and pathways to different pollutants in water are reviewed.In addition,this paper also summarizes the device design and application of silicon-based derived SACs,and prospects the future development of silicon-based SACs in Fenton-like applications.
基金supported by the National Natural Science Foundation of China(22422604,32472435)the National Key Research and Development Program of China(2021YFD1700300)+1 种基金the Agricultural Science and Technology Innovation Program of CAAS(CAAS-ASTIP-IQSTAP-04)the State Key Laboratory of Analytical Chemistry for Life Science。
文摘As environmental pollutants pose a serious threat to socioeconomic and environmental health,the development of simple,efficient,accurate and costeffective methods for pollution monitoring and control remains a major challenge,but it is an unavoidable issue.In the past decade,the artificial nanozymes have been widely used for environmental pollutant monitoring and control,because of their low cost,high stability,easy mass production,etc.However,the conventional nanozyme technology faces significant challenges in terms of difficulty in regulating the exposed crystal surface,complex composition,low catalytic activity,etc.In contrast,the emerging single-atom nanozymes(SANs)have attracted much attention in the field of environmental monitoring and control,due to their multiple advantages of atomically dispersed active sites,high atom utilization efficiency,tunable coordination environment,etc.To date,the insufficient efforts have been made to comprehensively characterize the applications of SANs in the monitoring and control of environmental pollutants.Building on the recent advances in the field,this review systematically summarizes the main synthesis methods of SANs and highlights their advances in the monitoring and control of environmental pollutants.Finally,we critically evaluate the limitations and challenges of SANs,and provide the insights into their future prospects for the monitoring and control of environmental pollutants.
基金supported by the Natural Science Foundation of Xiamen,China(3502Z202472001)the National Natural Science Foundation of China(22402163,22021001,21925404,T2293692,and 22361132532)。
文摘Metal-nitrogen-carbon(M-N-C)single-atom catalysts are widely utilized in various energy-related catalytic processes,offering a highly efficient and cost-effective catalytic system with significant potential.Recently,curvature-induced strain has been extensively demonstrated as a powerful tool for modulating the catalytic performance of M-N-C catalysts.However,identifying optimal strain patterns using density functional theory(DFT)is computationally intractable due to the high-dimensional search space.Here,we developed a graph neural network(GNN)integrated with an advanced topological data analysis tool-persistent homology-to predict the adsorption energy response of adsorbate under proposed curvature patterns,using nitric oxide electroreduction(NORR)as an example.Our machine learning model achieves high accuracy in predicting the adsorption energy response to curvature,with a mean absolute error(MAE)of 0.126 eV.Furthermore,we elucidate general trends in curvature-modulated adsorption energies of intermediates across various metals and coordination environments.We recommend several promising catalysts for NORR that exhibit significant potential for performance optimization via curvature modulation.This methodology can be readily extended to describe other non-bonded interactions,such as lattice strain and surface stress,providing a versatile approach for advanced catalyst design.
基金National Natural Science Foundation of China,Grant/Award Numbers:21603054,31671930Innovation and entrepreneurship training program for college students of Hebei Agricultural University,Grant/Award Numbers:2019085,s202010086046+2 种基金Scientific Research Development Fund project of Hebei Agricultural University,Grant/Award Number:JY2020028the Natural Science Foundation of Hebei Province,Grant/Award Numbers:B2016204131,B2016204136Young Topnotch Talents Foundation of Hebei Provincial Universities,Grant/Award Number:BJ2016027.
文摘The single-atom M-N-C(M typically being Co or Fe)is a prominent material with exceptional reactivity in areas of catalysis for sustainable energy.However,the formation of metal nanoparticles in M-N-C materials is coupled with hightemperature calcination conditions,limiting the density of M-Nx active sites and thus restricting the catalytic performance of such catalysts.Herein,we describe an effective decoupling strategy to construct high-density M-Nx active sites by generating polyfurfuryl alcohol in the MOF precursor,effectively preventing the formation of metal nanoparticles even with up to 6.377%cobalt loading.This catalyst showed a high H_(2) production rate of 778mLgcat^(−1) h^(−1) when used in the dehydrogenation reaction of formic acid.In addition to the high density of the active site,a curved carbon surface in the structure is also thought to be the reason for the high performance of the catalyst.
基金supported by the National Natural Science Foundation of China(Grant Nos.52488201,52376209,and 22108218)the China Postdoctoral Science Foundation(Grant Nos.2020M673386,and 2020T130503)the Fundamental Research Funds for the Central Universities。
文摘Photoreforming of formic acid(FA)represents a compelling technology for green hydrogen(H_(2))production,but the application is limited by the relatively low activity and selectivity.Recent advancements have introduced transition-metal nitrides(TMNs)as a new class of co-catalysts for photocatalytic FA reforming,showing impressive performance but still having the disadvantage of suboptimal H_(2)selectivity.Here,we present a novel Cu-W_(2)N_(3)cocatalyst with abundant Cu single-atom sites.On combining with a CdS photocatalyst,the CdS/Cu-W_(2)N_(3)system demonstrated an elevated H_(2)generation rate of 172.69μmol·h^(-1) and superior H_(2)selectivity in comparison to CdS/W_(2)N_(3).Comprehensive experimental and theoretical investigations indicate that the introduction of Cu single-atom sites in Cu-W_(2)N_(3)leads to a robust interaction with CdS,which optimizes the charge transfer.More significantly,the Cu single-atom sites modify the inert surface of the W_(2)N_(3)cocatalyst,creating conducive electron transfer channels and leading to an abundance of active sites favorable for hydrogen evolution reaction(HER),consequently resulting in higher H_(2)selectivity than pristine W_(2)N_(3).This study provides a promising approach to achieving an efficient photoreforming reaction with specific selectivity via the design of novel cocatalysts with specialized active sites.
文摘Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds.However,challenges remain to develop both cost-effective and efficient catalysts.In this study,we developed a Ru-Co/ZrO_(2)single-atom alloy catalyst which afforded diverse primary amines from alcohols in the presence of ammonia and hydrogen with exceptional conversion(up to 90%)and selectivity(80%)under mild conditions(0.7 MPa NH_(3),0.3 MPa H_(2),160℃)and exhibited satisfactory stability upon regeneration.The turnover rate was approximately 8.4 times higher than that observed over the Co/ZrO_(2)catalyst.Characterizations indicated that the alloyed Ru facilitated the reduction of Co,strengthened the interaction with H_(2)and mitigated the over-strong adsorption of aldehyde intermediates.These combined effects contributed significantly to the enhanced catalytic performances.This work presents a promising strategy for the development of advanced catalysts in the amination of alcohols.
基金supported by the National Natural Science Foundation of China(No.22368014)Guizhou Provincial S&T Project(Nos.GCC[2023]011,ZK[2022]011)Guizhou Provincial Higher Education Institution Program(No.Qianjiaoji[2023]082).
文摘The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein,an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy(Co-O_(V))on the Co/BiOCl-O_(V)photocatalyst was developed for photocatalytic degradation of glyphosate(GLP)wastewater of high performance/selectivity.Under full-spectrum-light irradiation,a high GLP degradation rate of 99.8%with over 90%C-P bond-breaking selectivity was achieved within 2 h,while effectively circumventing toxicant residues such as aminomethylphosphonic acid(AMPA).X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-O_(V)carrier and photothermal/pyroelectric effect.The oriented formation of more•O_(2)^(−)on Co/BiOCl-O_(V)could be achieved with the Co-O_(V)coupled center that had excellent O2 adsorption/activation capacity,as demonstrated by quantum calculations.The formed unique Co-O_(V)active sites could largely decrease the C-P bond-breaking energy barrier,thus greatly improving the selectivity toward the initial C-P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP.The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C-X bonds.
基金supported by Henan Province Key Research and Development and Promotion of Science and Technology Project(No.25A150001)the National Natural Science Foundation of China(Nos.22409171,22125303,92361302,and 92061203).
文摘Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined active sites and high loadings under precise control has become a hotly debated topic in scientific research.Metal-organic frameworks(MOFs),with their exceptional properties such as ultrahigh specific surface areas,precisely controllable structural de-signs,and highly flexible functional cus-tomization capabilities,are regarded as one of the ideal matrices for supporting and sta-bilizing SACs.This review provides an in-sightful overview of the diverse preparation strategies for MOFs-derived SACs.It comprehen-sively analyzes the unique advantages and challenges of each method in achieving efficient synthesis of SACs,emphasizing the crucial role of optimized processes in unlocking the antici-pated performance of SACs.Furthermore,this review delves into a series of advanced charac-terization techniques,including aberration-corrected scanning transmission electron mi-croscopy(AC-STEM),electron energy loss spectroscopy(EELS),X-ray absorption spec-troscopy(XAS),and infrared absorption spectroscopy(IRAS),offering valuable insights into the atomic-scale fine structures and properties of SACs,significantly advancing the under-standing of SAC mechanisms.Moreover,this review focuses on exploring the potential appli-cations of MOFs-derived SACs in electrocatalysis frontier fields.This comprehensive exami-nation lays a solid theoretical foundation and provides a directional guidance for the rational design and controllable synthesis of high-performance MOFs-derived SACs.
基金supported by Shenzhen Science and Technology Program(NO.JCYJ20210324094000001).
文摘Perfluoroalkyl and polyfluoroalkyl substances(PFASs)pollution with their toxicity,carcinogenicity,and persistence has been concerned worldwide.Research into novel materials for detecting and removing PFASs has increased rapidly,particularly in regard to the emergence of well-characterized single-atom materials(SAMs).Owing to the high selectivity,high atom utilization,and abundant active sites of SAMs,these materials exhibit remarkable efficacy in the detection and removal of PFASs.In this work,recent advances in the synthesis of SAMs for the detection and removal PFASs are reviewed.In-depth discussions of the structure-activity relationship and reaction mechanisms have demonstrated the high efficiency,activity,and selectivity of SAMs for the detection,adsorption,and degradation of PFASs.To optimize the application of SAMs in PFASs remediation,this review comprehensively surveys SAMs applications for PFASs and analyzes potential design strategies based on synthesis methods and corresponding properties.Synthesis strategies such as wet-chemistry,which offer ease of operation and high potential for large-scale production,are recommended for the further exploration of specific SAMs for the detection and removal of PFASs.Finally,this review identifies the challenges and opportunities for development of SAMs for the detection and remediation of PFASs,providing an outlook on strategic goals for a green economy and sustainable development.
基金supported by the Shenzhen Key Basic Research Project:Ionic Liquid-Assisted Synthesis of Single Catalyst and Its Applications in Lithium Sulfur Batteries(GXWD20220817125846003)Major Instrument Project of National Natural Science Foundation of China(62127807)Shenzhen Sustainable Development Special Project(KCXFZ20201221173000001).
文摘Lithium-sulfur batteries(LSBs)have become a favorable contender for next-generation electrochemical energy storage systems due to their outstanding features such as high energy density,low cost,and environmental friendliness.However,the commercialization of LSBs is still characterized by critical issues such as low sulfur utilization,short cycle life,and poor rate performance,which need to be resolved.Single-atom catalysts,with their outstanding features such as ultra-high atom utilization rate close to 100%and adjustable coordination configuration,have received extensive attention in the field of lithium-sulfur battery research.In this paper,the preparation and characterization of single-atom catalysts for Li-S batteries are briefly introduced,and the latest research progress of single-atom catalysts for Li-S batteries is reviewed from three aspects:cathode,separator and anode.Finally,the key technical problems and future research directions of single-atom catalysts for lithium-sulfur batteries are also prospected,with a view to promoting the further development of commercialized LSBs.
基金supported by the National Natural Science Foundation of China(Nos.U21A2060 and 22178116)the Natural Science Foundation of Shanghai(No.22ZR1417400)the Fundamental Research Funds for the Central Universities(Nos.222201817001,50321041918013,JKA01221601,JKD01241701).
文摘Lithium-sulfur(Li-S)batteries are regarded as the most formidable competitor to lithium-ion batteries due to their superior theoretical capacity.However,the negative impact of soluble lithium polysulfide(LiPSs)and slow redox reaction kinetics seriously hamper the commercialization of Li-S batteries.In this study,a defect-rich single-atom catalyst with an oversaturated asymmetric Fe-N_(5)coordination structure anchored in defective g-C_(3)N_(4)(C_(3)N_(4)-Fe@rGO)is designed via an absorption-pyrolysis strategy.The two-dimensional(2D)conducting C_(3)N_(4)@graphene structure with abundant defect sites accelerates the trans-fer and transportation of lithium ions and electrons.The oversaturated asymmetric Fe-N_(5)coordination structure effectively improves the adsorbility of LiPSs and accelerates the redox kinetics of sulfur species.Hence,the Li-S cell with a C_(3)N_(4)-Fe@rGO modified separator reveals a high initial capacity(1197.1 mAh g^(-1) at 0.2 C)and a low capacity decay rate(0.037%per cycle after 900 cycles at 1 C).Even at high sulfur loading and extreme temperatures of 0℃,it also shows good cycling performance.This work creates ideas for synthesizing oversaturated single-atom coordination environments and an efficient route to the practical realization of the Li-S batteries.
