Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
Two-dimensional conjugated metal-organic framework(2D c-MOF)nanosheets have garnered significant research interest owing to their suite of distinctive properties.Consequently,diverse synthetic methodologies have been ...Two-dimensional conjugated metal-organic framework(2D c-MOF)nanosheets have garnered significant research interest owing to their suite of distinctive properties.Consequently,diverse synthetic methodologies have been established for the fabrication of 2D c-MOFs exhibiting welldefined nanosheet morphology.In addition,the structural engineering of 2D c-MOF nanosheets for energy storage and conversion has emerged as a prominent research focus.This review comprehensively summarizes recent advancements in 2D c-MOF nanosheets.We commence with a concise overview of diverse synthesis strategies for these materials.Subsequently,progress in their utilization as electrode materials or catalysts for batteries,supercapacitors,and electrocatalysis/photocatalysis is systematically examined.Finally,prevailing challenges and prospective research directions are discussed.Collectively,this review aims to stimulate the development of sophisticated 2D c-MOF nanosheets for high-performance energy applications.展开更多
Ammonia plays a critical role in our society,not only as the source for fertilizers and other essential chemicals,but also as a promising hydrogen carrier due to its high energy density and ease of storage and transpo...Ammonia plays a critical role in our society,not only as the source for fertilizers and other essential chemicals,but also as a promising hydrogen carrier due to its high energy density and ease of storage and transportation.However,the conventional Haber-Bosch process is energy-intensive and costly.Developing a more energy efficient route for ammonia production is currently a holy grail in scientific society.This study reports a plasmonic semiconductor catalyst,molybdenum oxynitride(Mo2N/MoO_(2-x))nanosheet,that enables the ambient-pressure NH3 synthesis under light illumination.This catalyst achieves a remarkable NH3 production rate of 2338μmol·g^(-1)·h^(-1) at 400℃ and 857μmol·g^(-1)·h^(-1) at room temperature.Notably,we present the evidence for the coexistence of both nonthermal and photothermal effects,distinguishing this system from photothermally driven routes.This work demonstrates a viable pathway for NH3 production with low monetary and energetic investments and potential for distributed NH3 synthesis utilizing only water,air,and sunlight.展开更多
Atomically ordered precious intermetallic nanoparticles have garnered significant attention for diverse applications due to their well-defined surface atomic arrangements and exceptional electronic and geometric prope...Atomically ordered precious intermetallic nanoparticles have garnered significant attention for diverse applications due to their well-defined surface atomic arrangements and exceptional electronic and geometric properties.However,synthesizing non-precious ordered intermetallics that exhibit high stability under operating conditions remains a formidable challenge,primarily owing to their strong oxyphilicity,highly negative reduction potentials,and low corrosion resistance.In this work,we report a facile yet versatile seed-mediated solid-phase approach for fabricating uniform Ni_(3)Ga_(1) intermetallic nanocubes(NCs)fully encapsulated within N-doped carbon layers(denoted as Ni_(3)Ga_(1)@NC-800).Extensive characterization confirms the formation of a unique core-shell architecture,with atomic-resolution structural analysis and X-ray absorption fine structure measurements unequivocally verifying the atomically ordered Ni_(3)Ga_(1) intermetallic phase.The Ni_(3)Ga_(1)@NC-800 catalyst demonstrates exceptional performance in the 1,4-hydrogenation of α,β-unsaturated carbonyl compounds,exhibiting both remarkable activity and exclusive selectivity while maintaining high stability over multiple reaction cycles without observable performance decay.Combined experimental and theoretical calculations reveal that the strong interatomic p-d orbital hybridization facilitates electron transfer from Ga to Ni atoms,resulting in electron localization on ordered Ni atoms.This electronic configuration positively influences H_(2)activation and optimizes substrate adsorption strength,thereby substantially improving catalytic efficiency.Furthermore,this synthetic strategy proves generalizable,successfully extending to the synthesis of other non-precious ordered Ni_(1)Sn_(1) and Ni_(2)In_(3) intermetallics confined within N-doped carbon matrices.展开更多
Natural products,with their remarkable structural and biological diversity,have historically served as a vital bridge between chemistry,the life sciences,and medicine.They not only provide essential scaffolds for drug...Natural products,with their remarkable structural and biological diversity,have historically served as a vital bridge between chemistry,the life sciences,and medicine.They not only provide essential scaffolds for drug discovery but also inspire innovative strategies in drug development.The biomimetic synthesis of natural products employs principles from biomimicry,applying inspiration from biogenetic processes to design synthetic strategies that mimic biosynthetic processes.Biomimetic synthesis is a highly efficient approach in synthetic chemistry,as it addresses critical challenges in the synthesis of structurally complex natural products with significant biological and medicinal importance.It has gained widespread attention from researchers in chemistry,biology,pharmacy,and related fields,underscoring its interdisciplinary impact.In this perspective,we present recent advances and challenges in the biomimetic synthesis of natural products,along with the significance and prospects of this field,highlighting the transformative potential of biomimetic synthesis strategies for both chemical and biosynthetic approaches to natural product synthesis in the pursuit of novel therapeutic agents.展开更多
Hydrogen peroxide(H_(2)O_(2)),as a green oxidant,plays a vital role in various applications,including environmental remediation,disinfection,and chemical synthesis[1].The conventional anthraquinone process,despite its...Hydrogen peroxide(H_(2)O_(2)),as a green oxidant,plays a vital role in various applications,including environmental remediation,disinfection,and chemical synthesis[1].The conventional anthraquinone process,despite its industrial maturity and high yield,suffers from high energy consumption,carbon emissions,safety risks,and reliance on precious metals[2].Despite ongoing optimizations,a more sustainable alternative is urgently needed.The direct synthesis of hydrogen peroxide from water and oxygen has long been considered as an ideal alternative due to its theoretical 100%atom efficiency and environmental sustainability.展开更多
Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis...Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel,and also requires a large amount of poisonous solvents,which is generally not available for scaling-up production and commercial application.In recent years,great efforts have been made to explore simple,green,and efficient approaches for COFs synthesis.In this comprehensive review,we summarized the advances in emergent strategies by highlighting their distinct features.Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.展开更多
Ultrafast Joule heating(JH)has emerged as a powerful and scalable platform for rapid thermal processing of advanced nanomaterials.By delivering transient,high-intensity electrical pulses,JH induces ultrafast heating a...Ultrafast Joule heating(JH)has emerged as a powerful and scalable platform for rapid thermal processing of advanced nanomaterials.By delivering transient,high-intensity electrical pulses,JH induces ultrafast heating and cooling rates on the order of milliseconds,facilitating nonequilibrium phase transitions,defect modulation,and tailored nanostructural evolution.This technique offers unprecedented control over material synthesis and has been successfully applied to a broad spectrum of functional property-driven materials,including graphene,single-atom catalysts,transition metal carbides,oxides,nitrides,phosphides,and chalcogenides,as well as complex multicomponent frameworks such as high-entropy alloys.This review systematically explores the principles governing JH,highlights recent advances in its application to diverse materials systems,and critically assesses current limitations related to process uniformity,scalability,and mechanistic understanding.Particular attention is given to its intrinsic advantages,including energy efficiency,fast rate,environmental sustainability,and compatibility with sustainable manufacturing.Finally,we propose guidance for expanding the utility of JH for new materials discovery,including integration with in-situ diagnostics,theoretical compatibility and data-driven optimization of synthesis to effectively correlate structure-property relationships.展开更多
By investigating 17 peptide arylthioesters that were previously challenging to produce,this study reveals a clear correlation between increased ligation activity and decreased pKa values of their corresponding arylthi...By investigating 17 peptide arylthioesters that were previously challenging to produce,this study reveals a clear correlation between increased ligation activity and decreased pKa values of their corresponding arylthiols.The observed differences are attributed to variations in thioester bond strength and steric hindrance.These insights have led to the development of an improved one-pot chemical protein synthesis approach that leverages the reactivity differences between peptide arylthioesters with C-terminal Ala-SPh(4-NO_(2))and Ala-S-Ph(2,6-diCH_(3)).This approach eliminates the need for thiol-thioester exchange and additive removal steps while enabling in situ desulfurization,thereby significantly simplifying the protein synthesis process.展开更多
A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms.Compared to traditional poly...A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms.Compared to traditional polycyclic diterpenoids,their biosynthetic pathways are quite unique and diverse.Chemists have pinpointed a range of this type of unusual diterpenoids:cycloamphilectanes and isocycloamphilectanes,kempenes and rippertanes,hydropyrene and hydropyrenol,along with recently disclosed cephalotanes.This review describes developments in this field and discusses the challenges associated with synthesizing this class of highly complex compounds.展开更多
With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk che...With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).展开更多
Photoredox catalysis has made significant advances in stateof-the-art chemical synthesis,drawing energy from inexhaustible light and enabling various organic transformations to occur under mild reaction conditions.Ove...Photoredox catalysis has made significant advances in stateof-the-art chemical synthesis,drawing energy from inexhaustible light and enabling various organic transformations to occur under mild reaction conditions.Over the past few years,a variety of homogeneous and heterogeneous photocatalysts have been applied in the photoredox catalysis.Heterogeneous photoredox catalysis offers advantages such as easy separation and superior recyclability compared to homogeneous counterparts,although homogenous catalysts are usually associated with higher activities and selectivity.From a practical perspective,an optimal photoredox catalytic system would integrate the advantages of both homogeneous and heterogeneous cases.展开更多
Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge....Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge.We present a microwave-assisted approach for its continuous,large-scale production which enables synthesis at a rate of 0.6 g/h,with a yield of up to 90%.The synthesized GDY nanosheets have an average diameter of 246 nm and a thickness of 4 nm.We used GDY as a stable coating for potassium(K)metal anodes(K@GDY),taking advantage of its unique molecular structure to provide favorable paths for K-ion transport.This modification significantly inhibited dendrite formation and improved the cycling stability of K metal batteries.Full-cells with perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA)cathodes showed the clear superiority of the K@GDY anodes over bare K anodes in terms of performance,stability,and cycle life.The K@GDY maintained a stable voltage plateau and gave an excellent capacity retention after 600 cycles with nearly 100%Coulombic efficiency.This work not only provides a scalable and efficient way for GDY synthesis but also opens new possibilities for its use in energy storage and other advanced technologies.展开更多
Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive st...Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.展开更多
Converting CO_(2)with green hydrogen to methanol as a carbon-neutral liquid fuel is a promising route for the long-term storage and distribution of intermittent renewable energy.Nevertheless,attaining highly efficient...Converting CO_(2)with green hydrogen to methanol as a carbon-neutral liquid fuel is a promising route for the long-term storage and distribution of intermittent renewable energy.Nevertheless,attaining highly efficient methanol synthesis catalysts from the vast composition space remains a significant challenge.Here we present a machine learning framework for accelerating the development of high space-time yield(STY)methanol synthesis catalysts.A database of methanol synthesis catalysts has been compiled,consisting of catalyst composition,preparation parameters,structural characteristics,reaction conditions and their corresponding catalytic performance.A methodology for constructing catalyst features based on the intrinsic physicochemical properties of the catalyst components has been developed,which significantly reduced the data dimensionality and enhanced the efficiency of machine learning operations.Two high-precision machine learning prediction models for the activities and product selectivity of catalysts were trained and obtained.Using this machine learning framework,an efficient search was achieved within the catalyst composition space,leading to the successful identification of high STY multielement oxide methanol synthesis catalysts.Notably,the CuZnAlTi catalyst achieved high STYs of 0.49 and 0.65 g_(MeOH)/(g_(catalyst)h)for CO_(2)and CO hydrogenation to methanol at 250℃,respectively,and the STY was further increased to 2.63 g_(Me OH)/(g_(catalyst)h)in CO and CO_(2)co-hydrogenation.展开更多
Urbanization and industrialization have escalated water pollution,threatening ecosystems and human health.Water pollution not only degrades water quality but also poses long-term risks to human health through the food...Urbanization and industrialization have escalated water pollution,threatening ecosystems and human health.Water pollution not only degrades water quality but also poses long-term risks to human health through the food chain.The development of efficient wastewater detection and treatment methods is essential for mitigating this environmental hazard.Carbon dots(CDs),as emerging carbon-based nanomaterials,exhibit properties such as biocompatibility,photoluminescence(PL),water solubility,and strong adsorption,positioning them as promising candidates for environmental monitoring and management.Particularly in wastewater treatment,their optical and electron transfer properties make them ideal for pollutant detection and removal.Despite their potential,comprehensive reviews on CDs'role in wastewater treatment are scarce,often lacking detailed insights into their synthesis,PL mechanisms,and practical applications.This review systematically addresses the synthesis,PL mechanisms,and wastewater treatment applications of CDs,aiming to bridge existing research gaps.It begins with an overview of CDs structure and classification,essential for grasping their properties and uses.The paper then explores the pivotal PL mechanisms of CDs,crucial for their sensing capabilities.Next,comprehensive synthesis strategies are presented,encompassing both top-down and bottom-up strategies such as arc discharge,chemical oxidation,and hydrothermal/solvothermal synthesis.The diversity of these methods highlights the potential for tailored CDs production to suit specific environmental applications.Furthermore,the review systematically discusses the applications of CDs in wastewater treatment,including sensing,inorganic removal,and organic degradation.Finally,it delves into the research prospects and challenges of CDs,proposing future directions to enhance their role in wastewater treatment.展开更多
Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded...Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).展开更多
Ammonia is the cornerstone of modern agriculture,providing a critical nitrogen source for global food production and serving as a key raw material for numerous industrial chemicals.Electrocatalytic nitrate reduction,a...Ammonia is the cornerstone of modern agriculture,providing a critical nitrogen source for global food production and serving as a key raw material for numerous industrial chemicals.Electrocatalytic nitrate reduction,as an environmentally friendly method for synthesizing ammonia,not only mitigates the reliance on current ammonia synthesis processes fed by traditional fossil fuels but also effectively reduces nitrate pollution resulting from agricultural and industrial activities.This review explores the fundamental principles of electrocata lytic nitrate reduction,focusing on the key steps of electron transfer and ammonia formation.Additionally,it summarizes the critical factors influencing the performance and selectivity of the reaction,including the properties of the electrolyte,operating voltage,electrode materials,and design of the electrolytic cell.Further discussion of recent advances in electrocatalysts,including pure metal catalysts,metal oxide catalysts,non-metallic catalysts,and composite catalysts,highlights their significant roles in enhancing both the efficiency and selectivity of electrocata lytic nitrate to ammonia(NRA)reactions.Critical challenges for the industrial NRA trials and further outlooks are outlined to propel this strategy toward real-world applications.Overall,the review provides an in-depth overview and comprehensive understanding of electrocata lytic NRA technology,thereby promoting further advancements and innovations in this domain.展开更多
Fischer-Tropsch synthesis offers a promising route to convert carbon-rich resources such as coal,natural gas,and biomass into clean fuels and high-value chemicals via syngas.Catalyst development is crucial for optimiz...Fischer-Tropsch synthesis offers a promising route to convert carbon-rich resources such as coal,natural gas,and biomass into clean fuels and high-value chemicals via syngas.Catalyst development is crucial for optimizing the process,with cobalt-and iron-based catalysts being widely used in industrial applications.Iron-based catalysts,in particular,are favored due to their low cost,broad temperature range,and high water-gas shift reaction activity,making them ideal for syngas derived from coal and biomass with a low H_(2)/CO ratio.However,despite their long history of industrial use,iron-based catalysts face two significant challenges.First,the presence of multiple iron phases-metallic iron,iron oxides,and iron carbides-complicates the understanding of the reaction mechanism due to dynamic phase transformations.Second,the high water-gas shift activity of these catalysts leads to increased CO_(2) selectivity,thereby reducing overall carbon efficiency.In Fischer-Tropsch synthesis,CO_(2) can arise as primary CO_(2) from CO disproportionation(the Boudouard reaction)and as secondary CO_(2) from the water-gas shift reaction.The accumulation of CO_(2) formation further compromises overall carbon efficiency,which is particularly undesirable given the current focus on minimizing carbon emissions and achieving carbon neutrality.This review focus on the ongoing advancements of iron-based catalysts for Fischer-Tropsch synthesis,with particular emphasis on overcoming these two critical challenges for iron-based catalysts:regulating the active phases and minimizing CO_(2) selectivity.Addressing these challenges is essential for enhancing the overall catalytic efficiency and selectivity of iron-based catalysts.In this review,recent efforts to suppress CO_(2) selectivity of iron-based catalysts,including catalyst hydrophobic modification and graphene confinement,are explored for their potential to stabilize active phases and prevent unwanted side reactions.This innovative approach offers new opportunities for developing catalysts with high activity,low CO_(2) selectivity,and enhanced stability,which are key factors for enhancing both the efficiency and sustainability for Fischer-Tropsch synthesis.Such advancements are crucial for advancing more efficient and sustainable Fischer-Tropsch synthesis technologies,supporting the global push for net-zero emissions goals,and contributing to carbon reduction efforts worldwide.展开更多
The goal of photocatalytic CO_(2)reduction is to obtain a single energy-bearing product with high efficiency and stability.Consequently,constructing highly selective photocatalysts with enhanced surface and optoelectr...The goal of photocatalytic CO_(2)reduction is to obtain a single energy-bearing product with high efficiency and stability.Consequently,constructing highly selective photocatalysts with enhanced surface and optoelectronic properties is crucial for achieving this objective.Here,we have developed a simple one-pot vulcanization method to synthesize a MIL-68(In)-derived Cd In_(2)S_(4)/In_(2)S_(3)heterojunction that exhibited stable and high selectivity.Multiple characterizations of the Cd In_(2)S_(4)/In_(2)S_(3)heterojunction revealed a hierarchical tubular structure with numerous surface reactive sites,a high visible-light utilization rate(λ<600 nm),efficient charge separation,and a prolonged charge-carrier lifetime.Moreover,an S-scheme charge transfer mechanism,based on the interleaved band between the two components,improved the reduction capability of the electrons.Benefiting from the compositional and structural synergy,the yield CO by Cd In_(2)S_(4)/In_(2)S_(3)-250(CI-250)reached 135.62μmol·g^(-1)·h^(-1),which was 49.32 times and 32.88 times higher than that of In_(2)S_(3)and Cd In_(2)S_(4),respectively.The Cd In_(2)S_(4)/In_(2)S_(3)heterojunction exhibited a quantum efficiency of 4.23%with a CO selectivity of 71%.Four cycle tests confirmed the good stability and recyclability of the CI-250.This work provides a new approach for designing and preparing high-performance hollow MOFsbased photocatalysts for scalable and sustainable CO_(2)reduction.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
基金supported by the National Natural Science Foundation of China(Nos.22205196 and 52371240)the Natural Science Foundation of Jiangsu Province(No.BK20210790)the start-up fundings from Yangzhou University.
文摘Two-dimensional conjugated metal-organic framework(2D c-MOF)nanosheets have garnered significant research interest owing to their suite of distinctive properties.Consequently,diverse synthetic methodologies have been established for the fabrication of 2D c-MOFs exhibiting welldefined nanosheet morphology.In addition,the structural engineering of 2D c-MOF nanosheets for energy storage and conversion has emerged as a prominent research focus.This review comprehensively summarizes recent advancements in 2D c-MOF nanosheets.We commence with a concise overview of diverse synthesis strategies for these materials.Subsequently,progress in their utilization as electrode materials or catalysts for batteries,supercapacitors,and electrocatalysis/photocatalysis is systematically examined.Finally,prevailing challenges and prospective research directions are discussed.Collectively,this review aims to stimulate the development of sophisticated 2D c-MOF nanosheets for high-performance energy applications.
基金financially supported by the National Science Foundation(No.CHE-1954838)supported by the National Science Foundation(award number ECCS-2025064)as part of the National Nanotechnology Coordinated Infrastructure(NNCI).
文摘Ammonia plays a critical role in our society,not only as the source for fertilizers and other essential chemicals,but also as a promising hydrogen carrier due to its high energy density and ease of storage and transportation.However,the conventional Haber-Bosch process is energy-intensive and costly.Developing a more energy efficient route for ammonia production is currently a holy grail in scientific society.This study reports a plasmonic semiconductor catalyst,molybdenum oxynitride(Mo2N/MoO_(2-x))nanosheet,that enables the ambient-pressure NH3 synthesis under light illumination.This catalyst achieves a remarkable NH3 production rate of 2338μmol·g^(-1)·h^(-1) at 400℃ and 857μmol·g^(-1)·h^(-1) at room temperature.Notably,we present the evidence for the coexistence of both nonthermal and photothermal effects,distinguishing this system from photothermally driven routes.This work demonstrates a viable pathway for NH3 production with low monetary and energetic investments and potential for distributed NH3 synthesis utilizing only water,air,and sunlight.
基金financially supported by the program of the National Natural Science Foundation of Shandong Province(No.ZR2023ZD23)the Shandong Province Key Research and Development Plan(No.2023CXGC010607).
文摘Atomically ordered precious intermetallic nanoparticles have garnered significant attention for diverse applications due to their well-defined surface atomic arrangements and exceptional electronic and geometric properties.However,synthesizing non-precious ordered intermetallics that exhibit high stability under operating conditions remains a formidable challenge,primarily owing to their strong oxyphilicity,highly negative reduction potentials,and low corrosion resistance.In this work,we report a facile yet versatile seed-mediated solid-phase approach for fabricating uniform Ni_(3)Ga_(1) intermetallic nanocubes(NCs)fully encapsulated within N-doped carbon layers(denoted as Ni_(3)Ga_(1)@NC-800).Extensive characterization confirms the formation of a unique core-shell architecture,with atomic-resolution structural analysis and X-ray absorption fine structure measurements unequivocally verifying the atomically ordered Ni_(3)Ga_(1) intermetallic phase.The Ni_(3)Ga_(1)@NC-800 catalyst demonstrates exceptional performance in the 1,4-hydrogenation of α,β-unsaturated carbonyl compounds,exhibiting both remarkable activity and exclusive selectivity while maintaining high stability over multiple reaction cycles without observable performance decay.Combined experimental and theoretical calculations reveal that the strong interatomic p-d orbital hybridization facilitates electron transfer from Ga to Ni atoms,resulting in electron localization on ordered Ni atoms.This electronic configuration positively influences H_(2)activation and optimizes substrate adsorption strength,thereby substantially improving catalytic efficiency.Furthermore,this synthetic strategy proves generalizable,successfully extending to the synthesis of other non-precious ordered Ni_(1)Sn_(1) and Ni_(2)In_(3) intermetallics confined within N-doped carbon matrices.
基金financially supported by the National Key Research and Development Program of China(2023YFC3503902)the National Natural Science Foundation of China(82430108,82293681(82293680),and 82321004)+2 种基金the Guangdong Basic and Applied Basic Research Foundation(2022B1515120015 and 2024A1515030103)the Guangdong Major Project of Basic and Applied Basic Research(2023B0303000026)the Science and Technology Projects in Guangzhou(202102070001)。
文摘Natural products,with their remarkable structural and biological diversity,have historically served as a vital bridge between chemistry,the life sciences,and medicine.They not only provide essential scaffolds for drug discovery but also inspire innovative strategies in drug development.The biomimetic synthesis of natural products employs principles from biomimicry,applying inspiration from biogenetic processes to design synthetic strategies that mimic biosynthetic processes.Biomimetic synthesis is a highly efficient approach in synthetic chemistry,as it addresses critical challenges in the synthesis of structurally complex natural products with significant biological and medicinal importance.It has gained widespread attention from researchers in chemistry,biology,pharmacy,and related fields,underscoring its interdisciplinary impact.In this perspective,we present recent advances and challenges in the biomimetic synthesis of natural products,along with the significance and prospects of this field,highlighting the transformative potential of biomimetic synthesis strategies for both chemical and biosynthetic approaches to natural product synthesis in the pursuit of novel therapeutic agents.
文摘Hydrogen peroxide(H_(2)O_(2)),as a green oxidant,plays a vital role in various applications,including environmental remediation,disinfection,and chemical synthesis[1].The conventional anthraquinone process,despite its industrial maturity and high yield,suffers from high energy consumption,carbon emissions,safety risks,and reliance on precious metals[2].Despite ongoing optimizations,a more sustainable alternative is urgently needed.The direct synthesis of hydrogen peroxide from water and oxygen has long been considered as an ideal alternative due to its theoretical 100%atom efficiency and environmental sustainability.
基金financially supported by the National Natural Science Foundation of China(Nos.22322801,22108010,22278124)Fundamental Research Funds for the Central Universities(No.buctrc202135)。
文摘Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel,and also requires a large amount of poisonous solvents,which is generally not available for scaling-up production and commercial application.In recent years,great efforts have been made to explore simple,green,and efficient approaches for COFs synthesis.In this comprehensive review,we summarized the advances in emergent strategies by highlighting their distinct features.Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.
基金supported by the National Natural Science Foundation of China(Grant No.22402030)the Fujian Province Young and Middle-Aged Teacher Education Research Project(JZ240012)+1 种基金I.S.A.acknowledges funding support from Research Ireland under the SFI-IRC Pathway Program(Grant no:22/PATH-S/10725)the SFI Industry RD&I Fellowship Program(Grant no:21/IRDIF/9876).
文摘Ultrafast Joule heating(JH)has emerged as a powerful and scalable platform for rapid thermal processing of advanced nanomaterials.By delivering transient,high-intensity electrical pulses,JH induces ultrafast heating and cooling rates on the order of milliseconds,facilitating nonequilibrium phase transitions,defect modulation,and tailored nanostructural evolution.This technique offers unprecedented control over material synthesis and has been successfully applied to a broad spectrum of functional property-driven materials,including graphene,single-atom catalysts,transition metal carbides,oxides,nitrides,phosphides,and chalcogenides,as well as complex multicomponent frameworks such as high-entropy alloys.This review systematically explores the principles governing JH,highlights recent advances in its application to diverse materials systems,and critically assesses current limitations related to process uniformity,scalability,and mechanistic understanding.Particular attention is given to its intrinsic advantages,including energy efficiency,fast rate,environmental sustainability,and compatibility with sustainable manufacturing.Finally,we propose guidance for expanding the utility of JH for new materials discovery,including integration with in-situ diagnostics,theoretical compatibility and data-driven optimization of synthesis to effectively correlate structure-property relationships.
基金CAMS Innovation Fund for Medical Sciences(CIFMS,No.2021-I2M-1-026)the National Key R&D Program of China(No.2018YFE0111400)+6 种基金the NIH Research Project Grant Program(No.R01 EB025892)the National Natural Science Foundation of China(the Training Program of the Major Research Plan,No.91853120)the National Major Scientific and Technological Special Project of China(Nos.2018ZX09711001-005 and 2018ZX09711001-013)the State Key Laboratory of Bioactive Substance and Function of Natural Medicines,Institute of Materia Medicathe Biomedical High Performance Computing Platform,Chinese Academy of Medical Sciencesthe Chinese Academy of Medical SciencesPeking Union Medical College for funding and support.
文摘By investigating 17 peptide arylthioesters that were previously challenging to produce,this study reveals a clear correlation between increased ligation activity and decreased pKa values of their corresponding arylthiols.The observed differences are attributed to variations in thioester bond strength and steric hindrance.These insights have led to the development of an improved one-pot chemical protein synthesis approach that leverages the reactivity differences between peptide arylthioesters with C-terminal Ala-SPh(4-NO_(2))and Ala-S-Ph(2,6-diCH_(3)).This approach eliminates the need for thiol-thioester exchange and additive removal steps while enabling in situ desulfurization,thereby significantly simplifying the protein synthesis process.
基金the National Natural Science Foundation of China(No.22471224)。
文摘A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms.Compared to traditional polycyclic diterpenoids,their biosynthetic pathways are quite unique and diverse.Chemists have pinpointed a range of this type of unusual diterpenoids:cycloamphilectanes and isocycloamphilectanes,kempenes and rippertanes,hydropyrene and hydropyrenol,along with recently disclosed cephalotanes.This review describes developments in this field and discusses the challenges associated with synthesizing this class of highly complex compounds.
基金supported by the National Natural Science Foundation of China(Nos.22175174 and 52332007).
文摘With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).
基金the National Natural Science Foundation of China(No.22271060),The Department of Chemistry at Fudan University and College of Chemistry and Chemical Engineering at Ningxia University is gratefully acknowledged.
文摘Photoredox catalysis has made significant advances in stateof-the-art chemical synthesis,drawing energy from inexhaustible light and enabling various organic transformations to occur under mild reaction conditions.Over the past few years,a variety of homogeneous and heterogeneous photocatalysts have been applied in the photoredox catalysis.Heterogeneous photoredox catalysis offers advantages such as easy separation and superior recyclability compared to homogeneous counterparts,although homogenous catalysts are usually associated with higher activities and selectivity.From a practical perspective,an optimal photoredox catalytic system would integrate the advantages of both homogeneous and heterogeneous cases.
基金supported by National Natural Science Foundation of China(52302034,52402060,52202201,52021006)Beijing National Laboratory for Molecular Sciences(BNLMS-CXTD202001)+1 种基金Shenzhen Science and Technology Innovation Commission(KQTD20221101115627004)China Postdoctoral Science Foundation(2024T170972)。
文摘Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge.We present a microwave-assisted approach for its continuous,large-scale production which enables synthesis at a rate of 0.6 g/h,with a yield of up to 90%.The synthesized GDY nanosheets have an average diameter of 246 nm and a thickness of 4 nm.We used GDY as a stable coating for potassium(K)metal anodes(K@GDY),taking advantage of its unique molecular structure to provide favorable paths for K-ion transport.This modification significantly inhibited dendrite formation and improved the cycling stability of K metal batteries.Full-cells with perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA)cathodes showed the clear superiority of the K@GDY anodes over bare K anodes in terms of performance,stability,and cycle life.The K@GDY maintained a stable voltage plateau and gave an excellent capacity retention after 600 cycles with nearly 100%Coulombic efficiency.This work not only provides a scalable and efficient way for GDY synthesis but also opens new possibilities for its use in energy storage and other advanced technologies.
基金Joint Project of Dalian University of Technology-Dalian Institute of Chemical Physics (HX20230236)。
文摘Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(LDT23E06012E06)National Key R&D Program of China(2023YFC3710800)+3 种基金the National EnergySaving and Low-Carbon Materials Production and Application Demonstration Platform Program(TC220H06N)Pioneer R&D Program of Zhejiang Province-China(2024SSYS0066,2023C03016)National Natural Science Foundation of China(42341208)Zhejiang Energy Group Research Fund(ZNKJ-2023-100)。
文摘Converting CO_(2)with green hydrogen to methanol as a carbon-neutral liquid fuel is a promising route for the long-term storage and distribution of intermittent renewable energy.Nevertheless,attaining highly efficient methanol synthesis catalysts from the vast composition space remains a significant challenge.Here we present a machine learning framework for accelerating the development of high space-time yield(STY)methanol synthesis catalysts.A database of methanol synthesis catalysts has been compiled,consisting of catalyst composition,preparation parameters,structural characteristics,reaction conditions and their corresponding catalytic performance.A methodology for constructing catalyst features based on the intrinsic physicochemical properties of the catalyst components has been developed,which significantly reduced the data dimensionality and enhanced the efficiency of machine learning operations.Two high-precision machine learning prediction models for the activities and product selectivity of catalysts were trained and obtained.Using this machine learning framework,an efficient search was achieved within the catalyst composition space,leading to the successful identification of high STY multielement oxide methanol synthesis catalysts.Notably,the CuZnAlTi catalyst achieved high STYs of 0.49 and 0.65 g_(MeOH)/(g_(catalyst)h)for CO_(2)and CO hydrogenation to methanol at 250℃,respectively,and the STY was further increased to 2.63 g_(Me OH)/(g_(catalyst)h)in CO and CO_(2)co-hydrogenation.
基金supported by the Natural Science Foundation of Hebei Province(No.E2022208046)National Science Foundation of China(No.52004080)+2 种基金Key project of National Natural Science Foundation of China(No.U20A20130)Key research and development project of Hebei Province(No.22373704D)2023 Central Government Guide Local Science and Technology Development Fund Project(No.236Z1812 G)。
文摘Urbanization and industrialization have escalated water pollution,threatening ecosystems and human health.Water pollution not only degrades water quality but also poses long-term risks to human health through the food chain.The development of efficient wastewater detection and treatment methods is essential for mitigating this environmental hazard.Carbon dots(CDs),as emerging carbon-based nanomaterials,exhibit properties such as biocompatibility,photoluminescence(PL),water solubility,and strong adsorption,positioning them as promising candidates for environmental monitoring and management.Particularly in wastewater treatment,their optical and electron transfer properties make them ideal for pollutant detection and removal.Despite their potential,comprehensive reviews on CDs'role in wastewater treatment are scarce,often lacking detailed insights into their synthesis,PL mechanisms,and practical applications.This review systematically addresses the synthesis,PL mechanisms,and wastewater treatment applications of CDs,aiming to bridge existing research gaps.It begins with an overview of CDs structure and classification,essential for grasping their properties and uses.The paper then explores the pivotal PL mechanisms of CDs,crucial for their sensing capabilities.Next,comprehensive synthesis strategies are presented,encompassing both top-down and bottom-up strategies such as arc discharge,chemical oxidation,and hydrothermal/solvothermal synthesis.The diversity of these methods highlights the potential for tailored CDs production to suit specific environmental applications.Furthermore,the review systematically discusses the applications of CDs in wastewater treatment,including sensing,inorganic removal,and organic degradation.Finally,it delves into the research prospects and challenges of CDs,proposing future directions to enhance their role in wastewater treatment.
基金supported by the National Key Research and Development Program of China(2019YFA0905100)the National Natural Science Foundation of China(21991102,22378227).
文摘Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).
基金supported by the National Key Research and Development Program of China(2023YFE0120900)the National Natural Science Foundation of China(52377160)+2 种基金the National Natural Science Foundation of China National Young Talents Project(GYKP010)Shaanxi Provincial Natural Science Program(2023-JCYB-425)Xi’an Jiaotong University Young Top Talents Program。
文摘Ammonia is the cornerstone of modern agriculture,providing a critical nitrogen source for global food production and serving as a key raw material for numerous industrial chemicals.Electrocatalytic nitrate reduction,as an environmentally friendly method for synthesizing ammonia,not only mitigates the reliance on current ammonia synthesis processes fed by traditional fossil fuels but also effectively reduces nitrate pollution resulting from agricultural and industrial activities.This review explores the fundamental principles of electrocata lytic nitrate reduction,focusing on the key steps of electron transfer and ammonia formation.Additionally,it summarizes the critical factors influencing the performance and selectivity of the reaction,including the properties of the electrolyte,operating voltage,electrode materials,and design of the electrolytic cell.Further discussion of recent advances in electrocatalysts,including pure metal catalysts,metal oxide catalysts,non-metallic catalysts,and composite catalysts,highlights their significant roles in enhancing both the efficiency and selectivity of electrocata lytic nitrate to ammonia(NRA)reactions.Critical challenges for the industrial NRA trials and further outlooks are outlined to propel this strategy toward real-world applications.Overall,the review provides an in-depth overview and comprehensive understanding of electrocata lytic NRA technology,thereby promoting further advancements and innovations in this domain.
文摘Fischer-Tropsch synthesis offers a promising route to convert carbon-rich resources such as coal,natural gas,and biomass into clean fuels and high-value chemicals via syngas.Catalyst development is crucial for optimizing the process,with cobalt-and iron-based catalysts being widely used in industrial applications.Iron-based catalysts,in particular,are favored due to their low cost,broad temperature range,and high water-gas shift reaction activity,making them ideal for syngas derived from coal and biomass with a low H_(2)/CO ratio.However,despite their long history of industrial use,iron-based catalysts face two significant challenges.First,the presence of multiple iron phases-metallic iron,iron oxides,and iron carbides-complicates the understanding of the reaction mechanism due to dynamic phase transformations.Second,the high water-gas shift activity of these catalysts leads to increased CO_(2) selectivity,thereby reducing overall carbon efficiency.In Fischer-Tropsch synthesis,CO_(2) can arise as primary CO_(2) from CO disproportionation(the Boudouard reaction)and as secondary CO_(2) from the water-gas shift reaction.The accumulation of CO_(2) formation further compromises overall carbon efficiency,which is particularly undesirable given the current focus on minimizing carbon emissions and achieving carbon neutrality.This review focus on the ongoing advancements of iron-based catalysts for Fischer-Tropsch synthesis,with particular emphasis on overcoming these two critical challenges for iron-based catalysts:regulating the active phases and minimizing CO_(2) selectivity.Addressing these challenges is essential for enhancing the overall catalytic efficiency and selectivity of iron-based catalysts.In this review,recent efforts to suppress CO_(2) selectivity of iron-based catalysts,including catalyst hydrophobic modification and graphene confinement,are explored for their potential to stabilize active phases and prevent unwanted side reactions.This innovative approach offers new opportunities for developing catalysts with high activity,low CO_(2) selectivity,and enhanced stability,which are key factors for enhancing both the efficiency and sustainability for Fischer-Tropsch synthesis.Such advancements are crucial for advancing more efficient and sustainable Fischer-Tropsch synthesis technologies,supporting the global push for net-zero emissions goals,and contributing to carbon reduction efforts worldwide.
基金financially supported by the Program for the Development of Science and Technology of Jilin Province(Nos.20240601047RC and YDZJ202201ZYTS629)Hainan Province Science and Technology Special Fund(No.ZDYF2022SHFZ090)+1 种基金the National Natural Science Foundation(Nos.22466017 and 22061014)the specific research fund of the Innovation Platform for Academicians of Hainan Province。
文摘The goal of photocatalytic CO_(2)reduction is to obtain a single energy-bearing product with high efficiency and stability.Consequently,constructing highly selective photocatalysts with enhanced surface and optoelectronic properties is crucial for achieving this objective.Here,we have developed a simple one-pot vulcanization method to synthesize a MIL-68(In)-derived Cd In_(2)S_(4)/In_(2)S_(3)heterojunction that exhibited stable and high selectivity.Multiple characterizations of the Cd In_(2)S_(4)/In_(2)S_(3)heterojunction revealed a hierarchical tubular structure with numerous surface reactive sites,a high visible-light utilization rate(λ<600 nm),efficient charge separation,and a prolonged charge-carrier lifetime.Moreover,an S-scheme charge transfer mechanism,based on the interleaved band between the two components,improved the reduction capability of the electrons.Benefiting from the compositional and structural synergy,the yield CO by Cd In_(2)S_(4)/In_(2)S_(3)-250(CI-250)reached 135.62μmol·g^(-1)·h^(-1),which was 49.32 times and 32.88 times higher than that of In_(2)S_(3)and Cd In_(2)S_(4),respectively.The Cd In_(2)S_(4)/In_(2)S_(3)heterojunction exhibited a quantum efficiency of 4.23%with a CO selectivity of 71%.Four cycle tests confirmed the good stability and recyclability of the CI-250.This work provides a new approach for designing and preparing high-performance hollow MOFsbased photocatalysts for scalable and sustainable CO_(2)reduction.
