With the ongoing depletion of fossil fuels,energy and environmental issues have become increasingly critical,necessitating the search for effective solutions.Catalysis,being one of the hallmarks of modern industry,off...With the ongoing depletion of fossil fuels,energy and environmental issues have become increasingly critical,necessitating the search for effective solutions.Catalysis,being one of the hallmarks of modern industry,offers a promising avenue for researchers.However,the question of how to significantly enhance the performance of catalysts has gradually drawn the attention of scholars.Defect engineering,a commonly employed and effective approach to improve catalyst activity,has become a significant research focus in the catalysis field in recent years.Nonmetal vacancies have received extensive attention due to their simple form.Consequently,exploration of metal vacancies has remained stagnant for a considerable period,resulting in a scarcity of comprehensive reviews on this topic.Therefore,based on the latest research findings,this paper summarizes and consolidates the construction strategies for metal vacancies,characterization techniques,and their roles in typical energy and environmental catalytic reactions.Additionally,it outlines potential challenges in the future,aiming to provide valuable references for researchers interested in investigating metal vacancies.展开更多
Iron-based metal matrix composites(IMMCs)have attracted significant research attention due to their high specific stiffness and strength,making them potentially suitable for various engineering applications.Microstruc...Iron-based metal matrix composites(IMMCs)have attracted significant research attention due to their high specific stiffness and strength,making them potentially suitable for various engineering applications.Microstructural design,including the selection of reinforcement and matrix phases,the reinforcement volume fraction,and the interface issues are essential factors determining the engineering performance of IMMCs.A variety of fabrication methods have been developed to manufacture IMMCs in recent years.This paper reviews the recent advances and development of IMMCs with particular focus on microstructure design,fabrication methods,and their engineering performance.The microstructure design issues of IMMC are firstly discussed,including the reinforcement and matrix phase selection criteria,interface geometry and characteristics,and the bonding mechanism.The fabrication methods,including liquid state,solid state,and gas-mixing processing are comprehensively reviewed and compared.The engineering performance of IMMCs in terms of elastic modulus,hardness and wear resistance,tensile and fracture behavior is reviewed.Finally,the current challenges of the IMMCs are highlighted,followed by the discussion and outlook of the future research directions of IMMCs.展开更多
1.Introduction Lithium-sulfur(Li-S)batteries are broadly considered as an outstanding candidate for the future sustainable energy storage pathway due to their high theoretical capacity,high energy density,and low cost...1.Introduction Lithium-sulfur(Li-S)batteries are broadly considered as an outstanding candidate for the future sustainable energy storage pathway due to their high theoretical capacity,high energy density,and low cost^([1,2]).However,their practical deployment has been hindered by the sluggish 16-electron conversion process and shuttle of lithium polysulfides(LiPSs),which result in the loss of active sulfu r species^([3,4]).展开更多
Photothermal catalysis is a synergetic process where photocatalysis and thermal catalysis work together to promote catalytic reactions,which compensates for the critical shortcomings of photocatalysis and thermal cata...Photothermal catalysis is a synergetic process where photocatalysis and thermal catalysis work together to promote catalytic reactions,which compensates for the critical shortcomings of photocatalysis and thermal catalysis,achieving an effect of 1+1>2.Previous reviews have summarized the mechanism of photothermal catalysis and its specific application in certain fields,but few have systematically analyzed the essential factors affecting the activity of photothermal catalysis,or provided a comprehensive summary of its application fields.In this review,the superiority of photothermal catalysis over individual photocatalysis and thermal catalysis will be comprehensively discussed with the aim to emphasize the importance of developing photothermal catalysis.After elucidating the basic mechanism of photothermal catalysis,an ample discussion on the factors influencing the catalytic activity of photothermal materials is provided from the following three perspectives:morphology,localized surface plasmon resonance,and defective structure of photothermal materials.Subsequently,this review summarizes the broad applications of photothermal catalysis in environmental management and energy conversion.Finally,this review discusses the challenges encountered in photothermal catalysis technology and proposes directions for future development.It provides new perspectives and a profound understanding of photothermal materials in photothermal environmental governance and energy conversion.展开更多
Environmental catalysis has been considered one of the important research topics.Some technologies(e.g.,photocatalysis and electrocatalysis)have been intensively developed with the advance of synthetic technologies of...Environmental catalysis has been considered one of the important research topics.Some technologies(e.g.,photocatalysis and electrocatalysis)have been intensively developed with the advance of synthetic technologies of catalytical materials.In 2019,we discussed the development trend of this field,and wrote a roadmap on this topic in Chinese Chemical Letters(30(2019)2065-2088).Nowadays,we discuss it again from a new viewpoint along this road.In this paper,several subtopics are discussed,e.g.,photocatalysis based on titanium dioxide,violet phosphorus,graphitic carbon and covalent organic frameworks,electrocatalysts based on carbon,metal-and covalent-organic framework.Finally,we hope that this roadmap can enrich the development of two-dimensional materials in environmental catalysis with novel understanding,and give useful inspiration to explore new catalysts for practical applications.展开更多
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis.It is the first time that allene was introduced into transition metal an...An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis.It is the first time that allene was introduced into transition metal and NHC synergetic catalysis,which demonstrated a versatile three-component reaction pattern,thus enabling two C-C bonds forged regioselectively in the reaction.The important reaction intermediates were successfully captured and characterized by HRMS analysis,and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.展开更多
Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strateg...Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strategy for the functionalization and conversion of C-H bonds of 1,4-naphthoquinones into C-N bonds,providing an effective route to synthesize 2-(N-substituted amino)-1,4-naphthoquinone with high yield under mild conditions.Additionally,the synergistic catalytic mechanism was investigated by 1H NMR titration experiments and LC-MS analysis,with experimental results sufficiently and consistently supporting the proposed mechanism of the catalytic cycle.展开更多
A binder-free Ru@NiMoS electrode was engineered by in situ growth of twodimensional NiMoS nanosheets on nickel foam.This process effectively promoted the electrostatic-driven aggregation of Ru(bpy)_(3)^(2+),harnessing...A binder-free Ru@NiMoS electrode was engineered by in situ growth of twodimensional NiMoS nanosheets on nickel foam.This process effectively promoted the electrostatic-driven aggregation of Ru(bpy)_(3)^(2+),harnessing the synergistic effect to enhance electrochemiluminescence(ECL)performance.The integration(Ru@NiMoS)achieved an impressive ECL efficiency of 70.1%,marking an impressive 36.9-fold enhancement over conventional Ru.Additionally,its ECL intensity was found to be remarkably 172.2 times greater than that of Ru.Within the Ru(bpy)_(3)^(2+)/TPA system,NiMoS emerged as a pivotal electrochemical catalyst,markedly boosting both the oxygen evolution reaction and the generation of reactive intermediates.Leveraging these distinctive properties,a highly efficient ECL sensor for lidocaine detection was developed.This sensor exhibited a linear response within the concentration range of 1 nM to 1μM and achieved a remarkably low detection limit of 0.22 nM,underlining its substantial potential for practical application.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
Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, d...Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, diverse photocatalysts, including ruthenium(II), iridium(Ⅲ), and organic dyes, have been most commonly applied.展开更多
Late-stage modification of complex molecules via site-selective hydrodefluorination is a challenging endeavor.The selective activation of carbon-fluorine(C-F) bonds in the presence of multiple C-F bonds is of importan...Late-stage modification of complex molecules via site-selective hydrodefluorination is a challenging endeavor.The selective activation of carbon-fluorine(C-F) bonds in the presence of multiple C-F bonds is of importance in organic synthesis and drug discovery.Herein,we describe the activation of C-F bonds via multiphoton photoredox catalysis to selectively produces a series of hydrodefluorinated compounds by simply tuning the reaction conditions.Moreover,this protocol was successfully applied to the late-stage functionalization of different drug-derivatives and the corresponding mono-,di-,and tri-defluorinated products were obtained in good to excellent yields.A detailed mechanistic investigation provides insight into the unprecedented hydrodefluorination pathway.展开更多
Hydrogen,as a cheap,clean,and cost-effective secondary energy source,performs an essential role in optimizing today’s energy structure.Magnesium hydride(Mg H_(2))represents an attractive hydrogen carrier for storage ...Hydrogen,as a cheap,clean,and cost-effective secondary energy source,performs an essential role in optimizing today’s energy structure.Magnesium hydride(Mg H_(2))represents an attractive hydrogen carrier for storage and transportation,however,the kinetic behavior and operating temperature remain undesirable.In this work,a dual-phase multi-site alloy(Ms A)anchored on carbon substrates was designed,and its superior catalytic effects on the hydrogen storage properties of MgH_(2) were reported.Mechanism analysis identified that multi-site Fe Ni_(3)/Ni Cu nanoalloys synergistically served as intrinsic drivers for the striking de/hydrogenation performance of the MgH_(2)-Ms A systems.Concretely,the unique multi-metallic site structure attached to the surface of MgH_(2)provided substantial reversible channels and accessible active sites conducive to the adsorption,activation,and nucleation of H atoms.In addition,the coupling system formed by FeNi_(3) and NiCu dual-phase alloys further enhanced the reactivity between Mg/MgH_(2) and H atoms.Hence,the onset dehydrogenation temperature of Mg H_(2)+5 wt%Ms A was reduced to 195℃ and the hydrogen desorption apparent activation energy was reduced to 83.6 k J/mol.5.08 wt%H_(2) could be released at 250℃ in 20 min,reaching a high dehydrogenation rate of 0.254 wt%H_(2)/min,yet that for MgH_(2) at a higher temperature of 335℃ was only 0.145 wt%H_(2)/min.Then,the dehydrogenated Mg H_(2)-Ms A sample could absorb hydrogen from room temperature(30℃)and charge 3.93 wt%H_(2) at 100℃ within20 min under 3.0 MPa H_(2) pressure.Benefiting from carbon substrates,the 5 wt%Ms A doped-MgH_(2) could still maintain 6.36 wt%hydrogen capacity after 20 cycles.In conclusion,this work provides experimental rationale and new insights for the design of efficient catalysts for magnesium-based solid-state hydrogen storage materials.展开更多
Lithium-sulfur(Li-S)chemistry reaction opens a new battery era with high energy density;meanwhile,multiple electrons migration leads to the complex phase transition of sulfur species.To manipulate the binding strength...Lithium-sulfur(Li-S)chemistry reaction opens a new battery era with high energy density;meanwhile,multiple electrons migration leads to the complex phase transition of sulfur species.To manipulate the binding strength of multiple key intermediates more efficiently,the bimetallic TiVC MXene is utilized to realize multi-dimensional catalysis.Based on the macroscopic three-dimensional(3D)structure using two-dimensional(2D)MXene architecture,electron conductivity and sulfur utilization are improved.Microscopically,Ti-V catalytic systems regulate multiple reaction intermediates through intermetallic synergies customized surface properties and atomic scale coordination,thereby improving electronic and ionic conductivity.In-situ Raman spectroscopy and electrochemical analysis show that the conversion rate of polysulfides was accelerated during the charge-discharge process.The Ti-V interaction exhibits unique catalytic activity and regulates multiple continuous processes of sulfur species phase transformation,which are essential for the excellent energy performance of Li-S batteries.This study not only clarifies the catalytic mechanism of Ti-V at different dimensions but also proposes a promising strategy for the design of advanced catalytic systems in energy storage technology.展开更多
Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modificat...Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modification methods.Constructing defects on the surface of catalytic materials can effectively modulate the coordination environment of the active sites,affecting and changing the electrons,geometry,and other important properties at the catalytic active sites,thus altering the catalytic activity of the catalysts.However,the conformational relationship between defects and catalytic activity remains to be clarified.This dissertation focuses on an overview of recent advances in defect engineering in environmental catalysis.Based on defining the classification of defects in catalytic materials,defect construction methods,and characterization techniques are summarized and discussed.Focusing on an overview of the characteristics of the role of defects in electrocatalytic,photocatalytic,and thermal catalytic reactions and the mechanism of catalytic reactions.An elaborate link is given between the reaction activity and the structure of catalyst defects.Finally,the existing challenges and possible future directions for the application of defect engineering in environmental catalysis are discussed,which are expected to guide the design and development of efficient environmental catalysts and mechanism studies.展开更多
The photoinduced ligand-to-metal charge transfer(LMCT)process has been extensively investigated,however,the recovery of photocatalysts has remained a persistent challenge in the field.In light of this issue,a novel ap...The photoinduced ligand-to-metal charge transfer(LMCT)process has been extensively investigated,however,the recovery of photocatalysts has remained a persistent challenge in the field.In light of this issue,a novel approach involving the development of iron-based ionic liquids as photocatalysts has been pursued for the first time,with the goal of simultaneously facilitating the LMCT process and addressing the issue of photocatalyst recovery.Remarkably,the iron-based ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate(C_(4)mim-Fe Cl_(4))demonstrates exceptional recyclability and stability for the photocatalytic hydroacylation of olefins.This study will pave the way for new approaches to photocatalytic organic synthesis using ionic liquids as recyclable photocatalysts.展开更多
As important natural and pharmaceutical motifs,the catalytic construction of structurally diverse 3,3-disubstituted oxindoles often requires elaborate synthetic efforts on optimizations.Herein,we developed a simple an...As important natural and pharmaceutical motifs,the catalytic construction of structurally diverse 3,3-disubstituted oxindoles often requires elaborate synthetic efforts on optimizations.Herein,we developed a simple and divergent approach for constructing reverse-prenylated and prenylated oxindoles launched by Ni catalysis with bulk chemical isoprene.Using C3-unsubstituted oxindoles as starting materials,mono reverse-prenylation was demonstrated in high chemo-and regioselectivities facilitated by the combination of Ni(0)and monodentate phosphine ligand.Using the obtained reverse-prenylated oxindoles as versatile synthon,substitutions at the pseudobenzylic position with various electrophiles created vicinal quaternary centers in a concise way.With the help of additives(PPh3 and NaH),air could be directly used as green oxidant to construct prenylated and reverse-prenylatedα-hydroxy-oxindoles divergently from the same substrates.In situ esterification of prenylatedα-hydroxy-oxindoles allowed subsequent Friedel-Crafts substitutions with diverse nucleophiles to deliver prenyl substituted dimeric or spiro-oxindoles.This protocol provides a divergent synthetic approach for the construction of highly functionalized 3,3-disubstituted oxindoles,which have been otherwise difficult to access in a unified approach.展开更多
In the context of the global pursuit of sustainable energy,dual-atom catalysts(DACs)have attracted widespread attention due to their unique structural and excellent catalytic performance.Unlike the single-atom catalys...In the context of the global pursuit of sustainable energy,dual-atom catalysts(DACs)have attracted widespread attention due to their unique structural and excellent catalytic performance.Unlike the single-atom catalysts,DACs possess two active metal centers,exhibiting intriguing synergistic effects that significantly enhance their efficiency in various electrochemical reactions.This comprehensive review provides an overview of the recent advances in the field of dual-atom catalysts,focusing on their innovative preparation methods and strategies.It further delves into the intrinsic connections between structure and performance,discussing the applications of DACs in hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,photocatalysis,carbon dioxide reduction reaction,and batteries.Lastly,a forward-looking perspective addresses the current challenges and outlines future directions.This review aims to deepen our understanding of DACs and stimulate further innovation in advanced catalysts for energy conversion systems.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
Catalysis has made great contributions to the productivity of human society. Therefore, the pursuit of new catalysts and research on catalytic processes has never stopped. Continuous and in-depth catalysis research si...Catalysis has made great contributions to the productivity of human society. Therefore, the pursuit of new catalysts and research on catalytic processes has never stopped. Continuous and in-depth catalysis research significantly increases the complexity of dynamic systems and multivariate optimization, thus posing higher challenges to research methodologies. Recently, the significant advancement of generative artificial intelligence (AI) provides new opportunities for catalysis research. Different from traditional discriminative AI, this state-of-the-art technique generates new samples based on existing data and accumulated knowledge, which endows it with attractive potential for catalysis research — a field featuring a vast exploration space, diverse data types and complex mapping relationships. Generative AI can greatly enhance both the efficiency and innovation capacity of catalysis research, subsequently fostering new scientific paradigms. This perspective covers the basic introduction, unique advantages of this powerful tool, and presents cases of generative AI implemented in various catalysis researches, including catalyst design and optimization, characterization technique enhancement and guidance for new research paradigms. These examples highlight its exceptional efficiency and general applicability. We further discuss the practical challenges in implementation and future development perspectives, ultimately aiming to promote better applications of generative AI in catalysis.展开更多
Deprivation of glucose and lactate provides an effective pathway to terminate the nutrients supplement for tumor growth.In this work,biomimetic nanozymes called m@BGLC are constructed for catalytic tumor inhibition th...Deprivation of glucose and lactate provides an effective pathway to terminate the nutrients supplement for tumor growth.In this work,biomimetic nanozymes called m@BGLC are constructed for catalytic tumor inhibition through nutrients deprivation and oxidative damage induction.Concretely,the catalytic enzymes of glucose oxidase(GOx),lactate oxidase(LOx)and chloroperoxidase(CPO)are precrosslinked with bovine serum albumin(BSA)to construct nanozymes,which are then biomimetic functionalized with cancer cell membrane to prepare m@BGLC.Benefiting from the biomimetic camouflage with homologous cell membrane,m@BGLC inherit homotypic binding and immune escape abilities,facilitating the tumor targeting accumulation and preferable cell internalization for improved drug delivery efficiency.Subsequently,under the cascade catalysis of nanozymes,m@BGLC consume glucose and lactate for tumor starvation therapy through nutrients deprivation,and meanwhile,the resulting hyprochloric acid(HClO)causes an oxidative damage of cells to synergistically inhibit tumor growth.In vitro and in vivo findings demonstrate a robust tumor eradication effect of m@BGLC without obvious adverse reactions via the targeted combination therapy.Such cascade catalytic nanomedicine may inspire the development of sophisticated strategies for tumor combination therapy under unfavorable tumor microenvironments.展开更多
基金financially supported by National Key R&D Program of China(2021YFB3500702)National Natural Science Foundation of China(Nos.21677010 and 51808037)Special fund of Beijing Key Laboratory of Indoor Air Quality Evaluation and Control(No.BZ0344KF21-04).
文摘With the ongoing depletion of fossil fuels,energy and environmental issues have become increasingly critical,necessitating the search for effective solutions.Catalysis,being one of the hallmarks of modern industry,offers a promising avenue for researchers.However,the question of how to significantly enhance the performance of catalysts has gradually drawn the attention of scholars.Defect engineering,a commonly employed and effective approach to improve catalyst activity,has become a significant research focus in the catalysis field in recent years.Nonmetal vacancies have received extensive attention due to their simple form.Consequently,exploration of metal vacancies has remained stagnant for a considerable period,resulting in a scarcity of comprehensive reviews on this topic.Therefore,based on the latest research findings,this paper summarizes and consolidates the construction strategies for metal vacancies,characterization techniques,and their roles in typical energy and environmental catalytic reactions.Additionally,it outlines potential challenges in the future,aiming to provide valuable references for researchers interested in investigating metal vacancies.
基金funding support from the National Natural Science Foundation of China(No.52101046)Shuangjie Chu appreciates the funding support from the National Key Research and Development Program of China(No.2022YFB3705600).
文摘Iron-based metal matrix composites(IMMCs)have attracted significant research attention due to their high specific stiffness and strength,making them potentially suitable for various engineering applications.Microstructural design,including the selection of reinforcement and matrix phases,the reinforcement volume fraction,and the interface issues are essential factors determining the engineering performance of IMMCs.A variety of fabrication methods have been developed to manufacture IMMCs in recent years.This paper reviews the recent advances and development of IMMCs with particular focus on microstructure design,fabrication methods,and their engineering performance.The microstructure design issues of IMMC are firstly discussed,including the reinforcement and matrix phase selection criteria,interface geometry and characteristics,and the bonding mechanism.The fabrication methods,including liquid state,solid state,and gas-mixing processing are comprehensively reviewed and compared.The engineering performance of IMMCs in terms of elastic modulus,hardness and wear resistance,tensile and fracture behavior is reviewed.Finally,the current challenges of the IMMCs are highlighted,followed by the discussion and outlook of the future research directions of IMMCs.
基金supported by the National Natural Science Foundation of China(52462027)the Natural Science Foundation of Guangxi(2022GXNSFAA035463)the Testing Technology Center of Materials and Devices,Tsinghua Shenzhen International Graduate School for instrumental support.
文摘1.Introduction Lithium-sulfur(Li-S)batteries are broadly considered as an outstanding candidate for the future sustainable energy storage pathway due to their high theoretical capacity,high energy density,and low cost^([1,2]).However,their practical deployment has been hindered by the sluggish 16-electron conversion process and shuttle of lithium polysulfides(LiPSs),which result in the loss of active sulfu r species^([3,4]).
基金supported by the National Natural Science Foundation of China(52161145409,21976116)State Administration of Foreign Experts Affairs(SAFEA)of China(“Belt and Road”Innovative Talent Exchange Foreign Expert Project,2023041004L+1 种基金Highend Foreign Expert Project,G2023041021L)Alexander-vonHumboldt Foundation of Germany(Group-Linkage Program)。
文摘Photothermal catalysis is a synergetic process where photocatalysis and thermal catalysis work together to promote catalytic reactions,which compensates for the critical shortcomings of photocatalysis and thermal catalysis,achieving an effect of 1+1>2.Previous reviews have summarized the mechanism of photothermal catalysis and its specific application in certain fields,but few have systematically analyzed the essential factors affecting the activity of photothermal catalysis,or provided a comprehensive summary of its application fields.In this review,the superiority of photothermal catalysis over individual photocatalysis and thermal catalysis will be comprehensively discussed with the aim to emphasize the importance of developing photothermal catalysis.After elucidating the basic mechanism of photothermal catalysis,an ample discussion on the factors influencing the catalytic activity of photothermal materials is provided from the following three perspectives:morphology,localized surface plasmon resonance,and defective structure of photothermal materials.Subsequently,this review summarizes the broad applications of photothermal catalysis in environmental management and energy conversion.Finally,this review discusses the challenges encountered in photothermal catalysis technology and proposes directions for future development.It provides new perspectives and a profound understanding of photothermal materials in photothermal environmental governance and energy conversion.
基金supported by the National Natural Science Foundation of China(Nos.52272290,21972030,52073119,and 52373210)the Natural Science Foundation of Jilin Province(No.20230101029JC)+1 种基金the Fundamental Research Program of Shanxi Province(No.202303021212159)the Monash University Malaysia–ASEAN grant(No.ASE-000010)。
文摘Environmental catalysis has been considered one of the important research topics.Some technologies(e.g.,photocatalysis and electrocatalysis)have been intensively developed with the advance of synthetic technologies of catalytical materials.In 2019,we discussed the development trend of this field,and wrote a roadmap on this topic in Chinese Chemical Letters(30(2019)2065-2088).Nowadays,we discuss it again from a new viewpoint along this road.In this paper,several subtopics are discussed,e.g.,photocatalysis based on titanium dioxide,violet phosphorus,graphitic carbon and covalent organic frameworks,electrocatalysts based on carbon,metal-and covalent-organic framework.Finally,we hope that this roadmap can enrich the development of two-dimensional materials in environmental catalysis with novel understanding,and give useful inspiration to explore new catalysts for practical applications.
基金the National Natural Science Foundation of China(Nos.21831008,22025109,22101286)CAS Project for Young Scientists in Basic Research(No.YSBR-050)+1 种基金Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXXM-201901)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(No.KF2102)are gratefully acknowledged.
文摘An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis.It is the first time that allene was introduced into transition metal and NHC synergetic catalysis,which demonstrated a versatile three-component reaction pattern,thus enabling two C-C bonds forged regioselectively in the reaction.The important reaction intermediates were successfully captured and characterized by HRMS analysis,and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
基金2024 Special Talent Introduction Projects of Key R&D Program of Ningxia Hui Autonomous Region(2024BEH04049)the 2024 Guyuan City Innovation-Driven Achievement Transformation Project(2024BGTYF01-47)2025 Ningxia Natural Science Foundation Program(2025AAC030624).
文摘Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strategy for the functionalization and conversion of C-H bonds of 1,4-naphthoquinones into C-N bonds,providing an effective route to synthesize 2-(N-substituted amino)-1,4-naphthoquinone with high yield under mild conditions.Additionally,the synergistic catalytic mechanism was investigated by 1H NMR titration experiments and LC-MS analysis,with experimental results sufficiently and consistently supporting the proposed mechanism of the catalytic cycle.
基金supported by the Natural Science Foun-dation of Jilin Province(20200201238JC)the Science and Technology Development Program of Jilin Province(20200404147YY)+2 种基金Shenzhen Key Laboratory of Func-tional Aggregate Materials(ZDSYS20211021111400001)the Science Technology Innovation Commission of Shenzhen Municipality(KQTD20210811090142053,JCYJ20220818103007014)Tianjin Key Medical Disci-pline(Specialty)Construction Project.Thanks to the AIE Institute(www.aietech.org.cn)for providing some tech-nical assistance.
文摘A binder-free Ru@NiMoS electrode was engineered by in situ growth of twodimensional NiMoS nanosheets on nickel foam.This process effectively promoted the electrostatic-driven aggregation of Ru(bpy)_(3)^(2+),harnessing the synergistic effect to enhance electrochemiluminescence(ECL)performance.The integration(Ru@NiMoS)achieved an impressive ECL efficiency of 70.1%,marking an impressive 36.9-fold enhancement over conventional Ru.Additionally,its ECL intensity was found to be remarkably 172.2 times greater than that of Ru.Within the Ru(bpy)_(3)^(2+)/TPA system,NiMoS emerged as a pivotal electrochemical catalyst,markedly boosting both the oxygen evolution reaction and the generation of reactive intermediates.Leveraging these distinctive properties,a highly efficient ECL sensor for lidocaine detection was developed.This sensor exhibited a linear response within the concentration range of 1 nM to 1μM and achieved a remarkably low detection limit of 0.22 nM,underlining its substantial potential for practical application.
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.
文摘Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, diverse photocatalysts, including ruthenium(II), iridium(Ⅲ), and organic dyes, have been most commonly applied.
文摘Late-stage modification of complex molecules via site-selective hydrodefluorination is a challenging endeavor.The selective activation of carbon-fluorine(C-F) bonds in the presence of multiple C-F bonds is of importance in organic synthesis and drug discovery.Herein,we describe the activation of C-F bonds via multiphoton photoredox catalysis to selectively produces a series of hydrodefluorinated compounds by simply tuning the reaction conditions.Moreover,this protocol was successfully applied to the late-stage functionalization of different drug-derivatives and the corresponding mono-,di-,and tri-defluorinated products were obtained in good to excellent yields.A detailed mechanistic investigation provides insight into the unprecedented hydrodefluorination pathway.
基金financial supports from the National Key R&D Program of China(No.2020YFA0406204)the National Natural Science Foundation of China(No.51801078)。
文摘Hydrogen,as a cheap,clean,and cost-effective secondary energy source,performs an essential role in optimizing today’s energy structure.Magnesium hydride(Mg H_(2))represents an attractive hydrogen carrier for storage and transportation,however,the kinetic behavior and operating temperature remain undesirable.In this work,a dual-phase multi-site alloy(Ms A)anchored on carbon substrates was designed,and its superior catalytic effects on the hydrogen storage properties of MgH_(2) were reported.Mechanism analysis identified that multi-site Fe Ni_(3)/Ni Cu nanoalloys synergistically served as intrinsic drivers for the striking de/hydrogenation performance of the MgH_(2)-Ms A systems.Concretely,the unique multi-metallic site structure attached to the surface of MgH_(2)provided substantial reversible channels and accessible active sites conducive to the adsorption,activation,and nucleation of H atoms.In addition,the coupling system formed by FeNi_(3) and NiCu dual-phase alloys further enhanced the reactivity between Mg/MgH_(2) and H atoms.Hence,the onset dehydrogenation temperature of Mg H_(2)+5 wt%Ms A was reduced to 195℃ and the hydrogen desorption apparent activation energy was reduced to 83.6 k J/mol.5.08 wt%H_(2) could be released at 250℃ in 20 min,reaching a high dehydrogenation rate of 0.254 wt%H_(2)/min,yet that for MgH_(2) at a higher temperature of 335℃ was only 0.145 wt%H_(2)/min.Then,the dehydrogenated Mg H_(2)-Ms A sample could absorb hydrogen from room temperature(30℃)and charge 3.93 wt%H_(2) at 100℃ within20 min under 3.0 MPa H_(2) pressure.Benefiting from carbon substrates,the 5 wt%Ms A doped-MgH_(2) could still maintain 6.36 wt%hydrogen capacity after 20 cycles.In conclusion,this work provides experimental rationale and new insights for the design of efficient catalysts for magnesium-based solid-state hydrogen storage materials.
基金the financial support provided by the National Natural Science Foundation of China(No.51932005)the Liaoning Revitalization Talents Program(No.XLYC1807175)+1 种基金the Development Plan of Science and Technology of Jilin Province,China(YDZJ202301ZYTS280)the Natural Science Foundation of Jilin Province(YDZJ202401316ZYTS)。
文摘Lithium-sulfur(Li-S)chemistry reaction opens a new battery era with high energy density;meanwhile,multiple electrons migration leads to the complex phase transition of sulfur species.To manipulate the binding strength of multiple key intermediates more efficiently,the bimetallic TiVC MXene is utilized to realize multi-dimensional catalysis.Based on the macroscopic three-dimensional(3D)structure using two-dimensional(2D)MXene architecture,electron conductivity and sulfur utilization are improved.Microscopically,Ti-V catalytic systems regulate multiple reaction intermediates through intermetallic synergies customized surface properties and atomic scale coordination,thereby improving electronic and ionic conductivity.In-situ Raman spectroscopy and electrochemical analysis show that the conversion rate of polysulfides was accelerated during the charge-discharge process.The Ti-V interaction exhibits unique catalytic activity and regulates multiple continuous processes of sulfur species phase transformation,which are essential for the excellent energy performance of Li-S batteries.This study not only clarifies the catalytic mechanism of Ti-V at different dimensions but also proposes a promising strategy for the design of advanced catalytic systems in energy storage technology.
基金supported by The National Key R&D Program of China(No.2021YFB3500700)National Natural Science Foundation of China(Nos.21677010 and 51808037)Special fund of Beijing Key Laboratory of Indoor Air Quality Evaluation and Control(No.BZ0344KF21-04)。
文摘Researchers have recently developed various surface engineering approaches to modify environmental catalysts and improve their catalytic activity.Defect engineering has proved to be one of the most promising modification methods.Constructing defects on the surface of catalytic materials can effectively modulate the coordination environment of the active sites,affecting and changing the electrons,geometry,and other important properties at the catalytic active sites,thus altering the catalytic activity of the catalysts.However,the conformational relationship between defects and catalytic activity remains to be clarified.This dissertation focuses on an overview of recent advances in defect engineering in environmental catalysis.Based on defining the classification of defects in catalytic materials,defect construction methods,and characterization techniques are summarized and discussed.Focusing on an overview of the characteristics of the role of defects in electrocatalytic,photocatalytic,and thermal catalytic reactions and the mechanism of catalytic reactions.An elaborate link is given between the reaction activity and the structure of catalyst defects.Finally,the existing challenges and possible future directions for the application of defect engineering in environmental catalysis are discussed,which are expected to guide the design and development of efficient environmental catalysts and mechanism studies.
基金financial support from the National Natural Science Foundation of China(Nos.22071222,22171249)the Natural Science Foundation of Henan Province(Nos.232300421363,242300420526)+2 种基金Key Research Projects of Universities in Henan Province(No.23A180010)Science&Technology Innovation Talents in Universities of Henan Province(No.23HASTIT003)Science and Technology Research and Development Plan Joint Fund of Henan Province(No.242301420006)。
文摘The photoinduced ligand-to-metal charge transfer(LMCT)process has been extensively investigated,however,the recovery of photocatalysts has remained a persistent challenge in the field.In light of this issue,a novel approach involving the development of iron-based ionic liquids as photocatalysts has been pursued for the first time,with the goal of simultaneously facilitating the LMCT process and addressing the issue of photocatalyst recovery.Remarkably,the iron-based ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate(C_(4)mim-Fe Cl_(4))demonstrates exceptional recyclability and stability for the photocatalytic hydroacylation of olefins.This study will pave the way for new approaches to photocatalytic organic synthesis using ionic liquids as recyclable photocatalysts.
文摘As important natural and pharmaceutical motifs,the catalytic construction of structurally diverse 3,3-disubstituted oxindoles often requires elaborate synthetic efforts on optimizations.Herein,we developed a simple and divergent approach for constructing reverse-prenylated and prenylated oxindoles launched by Ni catalysis with bulk chemical isoprene.Using C3-unsubstituted oxindoles as starting materials,mono reverse-prenylation was demonstrated in high chemo-and regioselectivities facilitated by the combination of Ni(0)and monodentate phosphine ligand.Using the obtained reverse-prenylated oxindoles as versatile synthon,substitutions at the pseudobenzylic position with various electrophiles created vicinal quaternary centers in a concise way.With the help of additives(PPh3 and NaH),air could be directly used as green oxidant to construct prenylated and reverse-prenylatedα-hydroxy-oxindoles divergently from the same substrates.In situ esterification of prenylatedα-hydroxy-oxindoles allowed subsequent Friedel-Crafts substitutions with diverse nucleophiles to deliver prenyl substituted dimeric or spiro-oxindoles.This protocol provides a divergent synthetic approach for the construction of highly functionalized 3,3-disubstituted oxindoles,which have been otherwise difficult to access in a unified approach.
基金supported by the China Postdoctoral Science Foundation(Nos.2021M700981,2022M711787,2021M691759 and 2021TQ0169)Shuimu Tsinghua Scholar program(No.2021SM071)Beijing Natural Science Foundation(No.2224103).
文摘In the context of the global pursuit of sustainable energy,dual-atom catalysts(DACs)have attracted widespread attention due to their unique structural and excellent catalytic performance.Unlike the single-atom catalysts,DACs possess two active metal centers,exhibiting intriguing synergistic effects that significantly enhance their efficiency in various electrochemical reactions.This comprehensive review provides an overview of the recent advances in the field of dual-atom catalysts,focusing on their innovative preparation methods and strategies.It further delves into the intrinsic connections between structure and performance,discussing the applications of DACs in hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,photocatalysis,carbon dioxide reduction reaction,and batteries.Lastly,a forward-looking perspective addresses the current challenges and outlines future directions.This review aims to deepen our understanding of DACs and stimulate further innovation in advanced catalysts for energy conversion systems.
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supported by the National Natural Science Foundation of China(T2441001)the National Key Research&Development Program of China(2023YFB4104503).
文摘Catalysis has made great contributions to the productivity of human society. Therefore, the pursuit of new catalysts and research on catalytic processes has never stopped. Continuous and in-depth catalysis research significantly increases the complexity of dynamic systems and multivariate optimization, thus posing higher challenges to research methodologies. Recently, the significant advancement of generative artificial intelligence (AI) provides new opportunities for catalysis research. Different from traditional discriminative AI, this state-of-the-art technique generates new samples based on existing data and accumulated knowledge, which endows it with attractive potential for catalysis research — a field featuring a vast exploration space, diverse data types and complex mapping relationships. Generative AI can greatly enhance both the efficiency and innovation capacity of catalysis research, subsequently fostering new scientific paradigms. This perspective covers the basic introduction, unique advantages of this powerful tool, and presents cases of generative AI implemented in various catalysis researches, including catalyst design and optimization, characterization technique enhancement and guidance for new research paradigms. These examples highlight its exceptional efficiency and general applicability. We further discuss the practical challenges in implementation and future development perspectives, ultimately aiming to promote better applications of generative AI in catalysis.
基金financial support of Guangdong Basic and Applied Basic Research Foundation(No.2022B1515020095)National Natural Science Foundation of China(No.52073140)。
文摘Deprivation of glucose and lactate provides an effective pathway to terminate the nutrients supplement for tumor growth.In this work,biomimetic nanozymes called m@BGLC are constructed for catalytic tumor inhibition through nutrients deprivation and oxidative damage induction.Concretely,the catalytic enzymes of glucose oxidase(GOx),lactate oxidase(LOx)and chloroperoxidase(CPO)are precrosslinked with bovine serum albumin(BSA)to construct nanozymes,which are then biomimetic functionalized with cancer cell membrane to prepare m@BGLC.Benefiting from the biomimetic camouflage with homologous cell membrane,m@BGLC inherit homotypic binding and immune escape abilities,facilitating the tumor targeting accumulation and preferable cell internalization for improved drug delivery efficiency.Subsequently,under the cascade catalysis of nanozymes,m@BGLC consume glucose and lactate for tumor starvation therapy through nutrients deprivation,and meanwhile,the resulting hyprochloric acid(HClO)causes an oxidative damage of cells to synergistically inhibit tumor growth.In vitro and in vivo findings demonstrate a robust tumor eradication effect of m@BGLC without obvious adverse reactions via the targeted combination therapy.Such cascade catalytic nanomedicine may inspire the development of sophisticated strategies for tumor combination therapy under unfavorable tumor microenvironments.
