Nickel-catalyzed borylation of aryl nonaflates with B2pin2 could be realized,which proceeded effectively by means of C—O bond functionalization to afford a wide variety of valuable arylboronates in moderate to excell...Nickel-catalyzed borylation of aryl nonaflates with B2pin2 could be realized,which proceeded effectively by means of C—O bond functionalization to afford a wide variety of valuable arylboronates in moderate to excellent yields with good functionality compatibility.In addition,the gram-scale synthesis and the application of the approach in the late-stage elaboration of aryl nonaflate derived from pterostilbene could also be achieved.展开更多
Aerogels,renowned as ultra-lightweight solids with exceptional porosity and specific surface area,have emerged as pivotal materials for thermal insulation,catalysis,energy storage,and biomedicine.This review comprehen...Aerogels,renowned as ultra-lightweight solids with exceptional porosity and specific surface area,have emerged as pivotal materials for thermal insulation,catalysis,energy storage,and biomedicine.This review comprehensively evaluates the recent strides in sustainable,high-performance cellulose-based aerogels,emphasizing their fabrication,functionalization,and application prospects.It details the extraction of cellulose fromdiverse sources and its subsequent processing into nanocellulose(e.g.,cellulose nanofibrils and nanocrystals),which serves as the fundamental building block for aerogel synthesis.The critical sol-gel transition,solvent selection,and the pivotal role of drying techniques—freeze-drying,supercritical drying,and ambient pressure drying—in determining final aerogel architecture and properties are systematically analyzed.Special emphasis is placed on the advanced chemical modification of nanocellulose,including esterification,click chemistry,etherification,silanization,and amidation,which tailors surface chemistry to impart hydrophobicity,reactivity,or specific binding sites.The profound influence of cellulose source characteristics(aspect ratio,crystallinity,surface charge)on the pore-forming mechanism and aerogel performance is thoroughly discussed,bridging raw material selection with microstructure design.The review further elucidates the engineering of hybrid and composite aerogels by integrating silica,graphene,polymers,semiconductors,and metal-organic frameworks(MOFs),which synergistically enhance functionalities for targeted applications such as adsorption,photocatalysis,energy storage,sensing,and biomedical engineering.Despite significant progress,challenges remain in scalable green fabrication,balancing ultra-high porosity with mechanical robustness,and deepening the mechanistic understanding in complex applications.This work consolidates the current state-of-the-art,identifies key knowledge gaps,and provides a forward-looking perspective on the development of cellulose aerogels as versatile platforms for next-generation sustainable technologies.展开更多
Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/...Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.展开更多
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry,significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access thi...Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry,significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold.Catalyzed direct Csp^(2)-H functionalization provides an effective and costefficient approach to synthesizing carbazoles from simple and readily available starting materials,ensuring a promising path characterized by excellent atom and step economy.This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp^(2)-H functionalization techniques for synthesizing carbazoles.展开更多
Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous struct...Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous structure and intrinsic lithiophilic property.In this work,we introduce interface-engineered cellulose-based separators by converting intrinsic hydroxyl groups on cellulose nanofibers(CNFs)to nitrogen functionalities through a trace conducting polymer coating.Both experimental and theoretical results reveal that the nitrogen moieties disrupt the compact hydrogen bond network within hydroxyl cellulose,enabling multiple nitrogen-lithium interactions that enhance lithium ion transport.In addition to an extraordinary Li^(+)transference number of 0.86 and a high ionic conductivity of 1.1 mS cm^(-1),the nitrogen-functionalized CNF contributes to a uniform electric field and Li^(+)concentration distribution across the lithium metal surface.This facilitates the formation of a LiF-rich solid electrolyte interface and suppresses Li dendrite growth.Consequently,Li‖Li cells demonstrate stable plating/stripping cycles for approximately 3000 h at a current density of 1 mA cm^(-2) with a fixed capacity of 1 mAh cm^(-2),while maintaining a low overpotential of 15 mV.Our work provides valuable insights into the surface functionalization of natural biomass for advancing sustainable energy storage technologies.展开更多
Vanadium-based materials have emerged as promising cathode candidates for aqueous zinc-ion batteries(AZIBs)due to their multivalent redox characteristics and diverse crystal structures,which enable high energy storage...Vanadium-based materials have emerged as promising cathode candidates for aqueous zinc-ion batteries(AZIBs)due to their multivalent redox characteristics and diverse crystal structures,which enable high energy storage capacity.Nevertheless,practical applications are hindered by several critical challenges,including vanadium species dissolution,side-product formation,sluggish Zn^(2+)diffusion kinetics,and low electrical conductivity.Organic functionalization,benefiting from its structural tunability and abundant functional groups,has been proven to be an effective strategy for enhancing the electrochemical performance of vanadium-based cathodes.This review systematically summarizes recent advances in organic-functionalized vanadium-based cathodes.First,the energy storage mechanism of vanadiumbased cathodes and the fundamental properties of organic compounds relevant to cathode optimization are outlined.Then,the functions of organic compounds are comprehensively analyzed from four key perspectives:capacity improvement,conductivity enhancement,Zn^(2+)diffusion kinetics optimization,and cycling stability promotion.Furthermore,the specific electrochemical performance modulation effects and practical application examples of this strategy are discussed in detail.Finally,current limitations and challenges in this field are highlighted,and corresponding solutions and future research directions are proposed,offering theoretical guidance and insights for the development of high-performance vanadium-based cathodes for AZIBs.展开更多
Quinoxalin-2(1H)-ones are unique nitrogen-containing organic compounds with wide applications in the agrochemical,pharmaceutical,and chemical industries as well as in material science.During the last decades,visible-l...Quinoxalin-2(1H)-ones are unique nitrogen-containing organic compounds with wide applications in the agrochemical,pharmaceutical,and chemical industries as well as in material science.During the last decades,visible-light-promoted photoredox catalysis has emerged as a versatile platform for constructing quinoxalin-2(1H)-one scaffolds under exceptionally mild conditions.In this review,we provide an overview of recent advances in photocatalytic direct C(3)–H functionalization of quinoxaline-2(1H)-ones,including the construction of C(3)–C bonds and C(3)–R_(F)/C/O/N/Cl/S/D bonds,as well as the related reaction mechanisms.We aim to enhance the methods for the reaction of quinoxalin-2(1H)-ones at the C-3 position,which have extensive applications in organic synthesis and medicinal chemistry.展开更多
Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal ...Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.展开更多
2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is a stoichiometric oxidant that is frequently used in traditional organic synthesis. Recently, the rapid development of organic electrochemistry has led to new advancem...2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is a stoichiometric oxidant that is frequently used in traditional organic synthesis. Recently, the rapid development of organic electrochemistry has led to new advancements in DDQ-catalyzed C—H bonds functionalization. Moreover, the challenging C—H functionalization of electron-deficient arenes has been achieved through the merger of electrochemical DDQ catalysis and photoirradiation. In addition, the synthetic utility of electrophotochemical DDQ catalysis was further demonstrated by the nucleophilic aromatic substitution (SNAr) reaction of unactivated aryl fluorides. The recent developments in electro- and electrophotochemical DDQ-catalyzed C—H/C—F func- tionalizations with attention to their strategies and mechanistic insights are summarized. It is hoped that this not only deepens the understanding of this field, but also helps relevant researchers expand the application scope of DDQ catalysis.展开更多
Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups in...Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.展开更多
Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to ...Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to the inevitable side reactions involving cycloaddition.Herein,the visible-light-mediated O-H functionalization reactions of alkenyl alcohols with diazo compounds were developed.This process competed favorably with the cycloaddition reaction.A series of multifunctional ethers were provided in low to high yields with aryldiazoacetates or 3-diazooxindoles.Biologically relevant spirooxindole-fused oxacycle could be easily accessed from the O-H functionalization product of alkenyl alcohol and 3-diazooxindole.展开更多
Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution o...Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.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
As naturally abundant and readily available starting materials,alcohols are frequently employed as synthetic building blocks in organic synthesis.The hydroxyl group,which serves as the characteristic functional group ...As naturally abundant and readily available starting materials,alcohols are frequently employed as synthetic building blocks in organic synthesis.The hydroxyl group,which serves as the characteristic functional group of alcohols,is the primary reactive site for these compounds.Consequently,dehydroxylative functionalization reaction is one of the representative transformations of alcohols and has demonstrated significant potential in constructing new chemical bonds.Over the past decade,this research field has received continuous and extensive attention.This review comprehensively summarizes the recent advances in the dehydroxylative functionalization of alcohols,discussing on the reaction methodologies and mechanisms for constructing carbon-heteroatom and carbon-carbon bonds from alcohols.展开更多
Increased human and industrial activities have exacerbated the release of toxic materials and acute envi-ronmental pollution in recent times.Biochar,a carbon-rich material produced from biomass,is gaining momentum as ...Increased human and industrial activities have exacerbated the release of toxic materials and acute envi-ronmental pollution in recent times.Biochar,a carbon-rich material produced from biomass,is gaining momentum as a versatile material for attaining a sustainable environment.The study reviews the application of functionalized biochar for energy storage,environmental remediation,catalysis,and sustainable agriculture,aiming to achieve a greener future.Thedeployment of crop residues as a renewable feedstock for biochar,and their properties,compositions,modification,and functionalization techniques are also discussed.Additionally,the avenues for applying functionalized biochar to achieve a greener future,future trends and innovations,challenges,and future research directions are highlighted.Despite the limitations of scalability,ecotoxicological risks,logistical issues,lack of characterization protocols,high production costs,poor social acceptance,and inadequate policy and regulatory frameworks,functionalized biochar offers a better surface area,improved porosity,enhanced functional groups,and higher recoverability,leading to improved performance,adsorption capacity,biodegradability,and applications in specialized fields.Future research should prioritize standardization,scalability,cost reduction strategies,expansion of application areas,integration of emerging tools such as artificial intelligence and predictive modeling,and the development of policy and regulatory frameworks,ensuring that biochar’s full potential is harnessed effectively to support a low-carbon,resource-efficient future and global sustainability goals.展开更多
In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especia...In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.展开更多
The transition metal-catalyzed C–H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step-and atom-economy,the abundan...The transition metal-catalyzed C–H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step-and atom-economy,the abundance of hydrocarbon compounds,and the potential for late-stage functionalization of complex organic molecules.The ortho-and meta-C-H activation and functionalization of aromatic compounds have been widely explored in recent years,however the distal para-C-H activation and functionalization has remained a significant challenge because of the difficulty in forming energetically favorable metallacyclic transition states.The utilization of appropriate directing groups or templates as well as the meticulous design of catalysts and ligands has proven to be effective in transition-metal-catalyzed remote para-C-H bonds activation and functionalization of aromatic compounds.This review aims to summarize the strategies for controlling para-selective C–H functionalization using the directing group,template engineering,and catalyst/ligand design under transition metals catalysis in recent years.展开更多
Organofluorines play a crucial role in medicine,agrochemicals,and materials science.Adding fluorine to molecules creates structures with specific beneficial properties or tunes properties through interactions with the...Organofluorines play a crucial role in medicine,agrochemicals,and materials science.Adding fluorine to molecules creates structures with specific beneficial properties or tunes properties through interactions with their environment.Many popular pharmaceuticals and agrochemicals contain fluorine because it enhances hydrogen bonding at protein’s active sites.展开更多
Chemical recycling/upcycling of plastics has emerged as one of the most promising strategies for the plastic circular economy,enabling the depolymerization and functionalization of plastics into valuable monomers and ...Chemical recycling/upcycling of plastics has emerged as one of the most promising strategies for the plastic circular economy,enabling the depolymerization and functionalization of plastics into valuable monomers and chemicals.However,studies on the depolymerization and functionalization of challenging super engineering plastics have remained in early stage and underexplored.In this review,we would like to discuss the representative accomplishments and mechanism insights on chemical protocols achieved in depolymerization of super engineering plastics,especially for poly(phenylene sulfide)(PPS),poly(aryl ether)s including poly(ether ether ketone)(PEEK),polysulfone(PSU),polyphenylsulfone(PPSU)and polyethersulfone(PES).We anticipate that this review will provide an overall perspective on the current status and future trends of this emerging field.展开更多
Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor...Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor dispersion.Here,we report a strategy for the photosynergetic electrochemical functionalization of graphene(EFG).By using chloride ion(Cl^(-))as the intercalation anions and co-reactants,the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction,thus grasping crystallineperfect EFG.We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl,thus boosting the functionalization of graphene.Theoretical calculation and experimental results verified the oxygen evolution reaction(OER)on EFG has been improved by regulating the doping of chlorine atoms.In addition,the reduced interlayer distance and enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention.This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.展开更多
文摘Nickel-catalyzed borylation of aryl nonaflates with B2pin2 could be realized,which proceeded effectively by means of C—O bond functionalization to afford a wide variety of valuable arylboronates in moderate to excellent yields with good functionality compatibility.In addition,the gram-scale synthesis and the application of the approach in the late-stage elaboration of aryl nonaflate derived from pterostilbene could also be achieved.
基金funded by Basic Scientific Research Funds Project of Heilongjiang Universities of Department of Education,Heilongjiang Province,China,grant number 2025-KYYWF-ZR0763.
文摘Aerogels,renowned as ultra-lightweight solids with exceptional porosity and specific surface area,have emerged as pivotal materials for thermal insulation,catalysis,energy storage,and biomedicine.This review comprehensively evaluates the recent strides in sustainable,high-performance cellulose-based aerogels,emphasizing their fabrication,functionalization,and application prospects.It details the extraction of cellulose fromdiverse sources and its subsequent processing into nanocellulose(e.g.,cellulose nanofibrils and nanocrystals),which serves as the fundamental building block for aerogel synthesis.The critical sol-gel transition,solvent selection,and the pivotal role of drying techniques—freeze-drying,supercritical drying,and ambient pressure drying—in determining final aerogel architecture and properties are systematically analyzed.Special emphasis is placed on the advanced chemical modification of nanocellulose,including esterification,click chemistry,etherification,silanization,and amidation,which tailors surface chemistry to impart hydrophobicity,reactivity,or specific binding sites.The profound influence of cellulose source characteristics(aspect ratio,crystallinity,surface charge)on the pore-forming mechanism and aerogel performance is thoroughly discussed,bridging raw material selection with microstructure design.The review further elucidates the engineering of hybrid and composite aerogels by integrating silica,graphene,polymers,semiconductors,and metal-organic frameworks(MOFs),which synergistically enhance functionalities for targeted applications such as adsorption,photocatalysis,energy storage,sensing,and biomedical engineering.Despite significant progress,challenges remain in scalable green fabrication,balancing ultra-high porosity with mechanical robustness,and deepening the mechanistic understanding in complex applications.This work consolidates the current state-of-the-art,identifies key knowledge gaps,and provides a forward-looking perspective on the development of cellulose aerogels as versatile platforms for next-generation sustainable technologies.
基金supported by the National Natural Science Foundation of China(NSFC No.52271228)the Natural Science Foundation of Shaanxi Province(No.2023-JC-ZD-21)the Doctoral Dissertation Innovation Fund of Xi'an University of Technology(No.101-252072301)。
文摘Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.
基金support and funding by the European Union-Next Generation EU under the Italian Ministry of University and Research (MUR) National Innovation Ecosystem (No.ECS00000041-VITALITY and also “Ecosistema TECH4YOU-(Spoke 3-Goal 3.5)MUR is thanked for PRIN-PNRR 2022 project "P2022XKWH7-Circular Waste+3 种基金The University of Perugia is acknowledged for financial support to the university project “Fondo Ricerca di Ateneo,edizione 2022”The National Ph D program in Catalysis coordinated by the University of Perugia is also thankedthe financial supports of key research and development and technology transfer projects of Inner Mongolia Autonomous Region (No.2025KJHZ0008)major special projects of science and technology of Ordos (No.2022EEDSKJZDZX003)。
文摘Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry,significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold.Catalyzed direct Csp^(2)-H functionalization provides an effective and costefficient approach to synthesizing carbazoles from simple and readily available starting materials,ensuring a promising path characterized by excellent atom and step economy.This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp^(2)-H functionalization techniques for synthesizing carbazoles.
基金supported by the National Natural Science Foundation of China(Grant No.22479046,22461142135)。
文摘Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous structure and intrinsic lithiophilic property.In this work,we introduce interface-engineered cellulose-based separators by converting intrinsic hydroxyl groups on cellulose nanofibers(CNFs)to nitrogen functionalities through a trace conducting polymer coating.Both experimental and theoretical results reveal that the nitrogen moieties disrupt the compact hydrogen bond network within hydroxyl cellulose,enabling multiple nitrogen-lithium interactions that enhance lithium ion transport.In addition to an extraordinary Li^(+)transference number of 0.86 and a high ionic conductivity of 1.1 mS cm^(-1),the nitrogen-functionalized CNF contributes to a uniform electric field and Li^(+)concentration distribution across the lithium metal surface.This facilitates the formation of a LiF-rich solid electrolyte interface and suppresses Li dendrite growth.Consequently,Li‖Li cells demonstrate stable plating/stripping cycles for approximately 3000 h at a current density of 1 mA cm^(-2) with a fixed capacity of 1 mAh cm^(-2),while maintaining a low overpotential of 15 mV.Our work provides valuable insights into the surface functionalization of natural biomass for advancing sustainable energy storage technologies.
基金financial support from the National Natural Science Foundation of China(No.21676036)the Natural Science Foundation of Chongqing(No.CSTB2023NSCQMSX0580)the Large-scale Equipment Sharing Fund of Chongqing University(No.202403150240 and 202503150091)。
文摘Vanadium-based materials have emerged as promising cathode candidates for aqueous zinc-ion batteries(AZIBs)due to their multivalent redox characteristics and diverse crystal structures,which enable high energy storage capacity.Nevertheless,practical applications are hindered by several critical challenges,including vanadium species dissolution,side-product formation,sluggish Zn^(2+)diffusion kinetics,and low electrical conductivity.Organic functionalization,benefiting from its structural tunability and abundant functional groups,has been proven to be an effective strategy for enhancing the electrochemical performance of vanadium-based cathodes.This review systematically summarizes recent advances in organic-functionalized vanadium-based cathodes.First,the energy storage mechanism of vanadiumbased cathodes and the fundamental properties of organic compounds relevant to cathode optimization are outlined.Then,the functions of organic compounds are comprehensively analyzed from four key perspectives:capacity improvement,conductivity enhancement,Zn^(2+)diffusion kinetics optimization,and cycling stability promotion.Furthermore,the specific electrochemical performance modulation effects and practical application examples of this strategy are discussed in detail.Finally,current limitations and challenges in this field are highlighted,and corresponding solutions and future research directions are proposed,offering theoretical guidance and insights for the development of high-performance vanadium-based cathodes for AZIBs.
基金support from the National Natural Science Foundation of China(No.22101267)the China Postdoctoral Science Foundation(Nos.2021M692905 and 2024T170832)+2 种基金Natural Science Foundation of Henan Province,China(No.242300421123)Scientific Research Project of Hubei Provincial Education Department,China(No.Q20233104)Hubei Provincial Natural Science Foundation,China(No.2024AFB946).
文摘Quinoxalin-2(1H)-ones are unique nitrogen-containing organic compounds with wide applications in the agrochemical,pharmaceutical,and chemical industries as well as in material science.During the last decades,visible-light-promoted photoredox catalysis has emerged as a versatile platform for constructing quinoxalin-2(1H)-one scaffolds under exceptionally mild conditions.In this review,we provide an overview of recent advances in photocatalytic direct C(3)–H functionalization of quinoxaline-2(1H)-ones,including the construction of C(3)–C bonds and C(3)–R_(F)/C/O/N/Cl/S/D bonds,as well as the related reaction mechanisms.We aim to enhance the methods for the reaction of quinoxalin-2(1H)-ones at the C-3 position,which have extensive applications in organic synthesis and medicinal chemistry.
基金funded by the National Nature Science Foundation of China(62264006,62574102)“Thousand Talents Program”of Yunnan Province for Young Talents,Innovative Research Teams(in Science and Technology)in the University of Yunnan Province(IRTSTYN),XingDian Talent Support Program for Young Talents,and Frontier Research Team of Kunming University 2023,The Basic Research Project of Yunnan Province(Nos.202201AU070022)+2 种基金Kunming University Talent Introduction Fund(Nos.YJL20024)Yunnan Province Education Department Scientific Research Fund Project(Nos.2024Y759)Undergraduate Innovation and Entrepreneurship Training Program Project of Yunnan Provincial(202411393005)。
文摘Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.
文摘2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is a stoichiometric oxidant that is frequently used in traditional organic synthesis. Recently, the rapid development of organic electrochemistry has led to new advancements in DDQ-catalyzed C—H bonds functionalization. Moreover, the challenging C—H functionalization of electron-deficient arenes has been achieved through the merger of electrochemical DDQ catalysis and photoirradiation. In addition, the synthetic utility of electrophotochemical DDQ catalysis was further demonstrated by the nucleophilic aromatic substitution (SNAr) reaction of unactivated aryl fluorides. The recent developments in electro- and electrophotochemical DDQ-catalyzed C—H/C—F func- tionalizations with attention to their strategies and mechanistic insights are summarized. It is hoped that this not only deepens the understanding of this field, but also helps relevant researchers expand the application scope of DDQ catalysis.
文摘Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.
文摘Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to the inevitable side reactions involving cycloaddition.Herein,the visible-light-mediated O-H functionalization reactions of alkenyl alcohols with diazo compounds were developed.This process competed favorably with the cycloaddition reaction.A series of multifunctional ethers were provided in low to high yields with aryldiazoacetates or 3-diazooxindoles.Biologically relevant spirooxindole-fused oxacycle could be easily accessed from the O-H functionalization product of alkenyl alcohol and 3-diazooxindole.
文摘Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.
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Project supported by the Technology Program of Zhoukou(No.2023GG02054)the Natural Science Foundation of Shandong Province(No.ZR2024MB082)the Open Foundation Supported by Jiangsu Province Engineering Research Center of Precision Diagnostics and Therapeutics Development(No.SDGC2401)。
文摘As naturally abundant and readily available starting materials,alcohols are frequently employed as synthetic building blocks in organic synthesis.The hydroxyl group,which serves as the characteristic functional group of alcohols,is the primary reactive site for these compounds.Consequently,dehydroxylative functionalization reaction is one of the representative transformations of alcohols and has demonstrated significant potential in constructing new chemical bonds.Over the past decade,this research field has received continuous and extensive attention.This review comprehensively summarizes the recent advances in the dehydroxylative functionalization of alcohols,discussing on the reaction methodologies and mechanisms for constructing carbon-heteroatom and carbon-carbon bonds from alcohols.
文摘Increased human and industrial activities have exacerbated the release of toxic materials and acute envi-ronmental pollution in recent times.Biochar,a carbon-rich material produced from biomass,is gaining momentum as a versatile material for attaining a sustainable environment.The study reviews the application of functionalized biochar for energy storage,environmental remediation,catalysis,and sustainable agriculture,aiming to achieve a greener future.Thedeployment of crop residues as a renewable feedstock for biochar,and their properties,compositions,modification,and functionalization techniques are also discussed.Additionally,the avenues for applying functionalized biochar to achieve a greener future,future trends and innovations,challenges,and future research directions are highlighted.Despite the limitations of scalability,ecotoxicological risks,logistical issues,lack of characterization protocols,high production costs,poor social acceptance,and inadequate policy and regulatory frameworks,functionalized biochar offers a better surface area,improved porosity,enhanced functional groups,and higher recoverability,leading to improved performance,adsorption capacity,biodegradability,and applications in specialized fields.Future research should prioritize standardization,scalability,cost reduction strategies,expansion of application areas,integration of emerging tools such as artificial intelligence and predictive modeling,and the development of policy and regulatory frameworks,ensuring that biochar’s full potential is harnessed effectively to support a low-carbon,resource-efficient future and global sustainability goals.
文摘In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.
基金support from the National Natural Science Foundation of China(No.21901206)Postdoctoral Science Foundation of China(No.2022M712589)+2 种基金General Key R&D Projects in Shaanxi Province(No.2023-YBGY-321)Natural Science Foundation of Chongqing(No.CSTB2022NSCQ-MSX0826)National&Local Joint Engineering Research Center for mineral Salt Deep Utilization,Huaiyin Institute of Technology(No.SF202407)for financial support。
文摘The transition metal-catalyzed C–H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step-and atom-economy,the abundance of hydrocarbon compounds,and the potential for late-stage functionalization of complex organic molecules.The ortho-and meta-C-H activation and functionalization of aromatic compounds have been widely explored in recent years,however the distal para-C-H activation and functionalization has remained a significant challenge because of the difficulty in forming energetically favorable metallacyclic transition states.The utilization of appropriate directing groups or templates as well as the meticulous design of catalysts and ligands has proven to be effective in transition-metal-catalyzed remote para-C-H bonds activation and functionalization of aromatic compounds.This review aims to summarize the strategies for controlling para-selective C–H functionalization using the directing group,template engineering,and catalyst/ligand design under transition metals catalysis in recent years.
文摘Organofluorines play a crucial role in medicine,agrochemicals,and materials science.Adding fluorine to molecules creates structures with specific beneficial properties or tunes properties through interactions with their environment.Many popular pharmaceuticals and agrochemicals contain fluorine because it enhances hydrogen bonding at protein’s active sites.
基金supported by the National Natural Science Foundation of China(Nos.22125103 and 22301077)STCSM(22JC140100)Shanghai Pujiang Program(No.22PJ1403200)。
文摘Chemical recycling/upcycling of plastics has emerged as one of the most promising strategies for the plastic circular economy,enabling the depolymerization and functionalization of plastics into valuable monomers and chemicals.However,studies on the depolymerization and functionalization of challenging super engineering plastics have remained in early stage and underexplored.In this review,we would like to discuss the representative accomplishments and mechanism insights on chemical protocols achieved in depolymerization of super engineering plastics,especially for poly(phenylene sulfide)(PPS),poly(aryl ether)s including poly(ether ether ketone)(PEEK),polysulfone(PSU),polyphenylsulfone(PPSU)and polyethersulfone(PES).We anticipate that this review will provide an overall perspective on the current status and future trends of this emerging field.
基金supported by the Natural Science Foundation of Guangxi Province(2021GXNSFBA220077,GUIKE AD23026050)National Natural Science Foundation of China(22102035 and 22162006)Innovation Project of Guangxi Graduate Education(XYCBZ2024021).
文摘Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor dispersion.Here,we report a strategy for the photosynergetic electrochemical functionalization of graphene(EFG).By using chloride ion(Cl^(-))as the intercalation anions and co-reactants,the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction,thus grasping crystallineperfect EFG.We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl,thus boosting the functionalization of graphene.Theoretical calculation and experimental results verified the oxygen evolution reaction(OER)on EFG has been improved by regulating the doping of chlorine atoms.In addition,the reduced interlayer distance and enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention.This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.
