Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully construct...Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.展开更多
CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organ...CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.展开更多
The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative p...The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.展开更多
Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fund...Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.展开更多
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability...Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.展开更多
Accelerating the development of new quality productive forces(NQPF),with innovation at its core,has become essential for firm growth in the new era.Drawing on financial data from China's A-share listed companies s...Accelerating the development of new quality productive forces(NQPF),with innovation at its core,has become essential for firm growth in the new era.Drawing on financial data from China's A-share listed companies spanning the period 2010–2023,this study empirically investigates the impact of entrepreneurial spirit on firm-level NQPF.The results indicate that entrepreneurial spirit significantly promotes firm-level NQPF.Mechanism analysis indicates that entrepreneurial effort—underpinned by technological capital accumulation,effective incentive and constraint mechanisms,and a competitive market environment—plays a mediating role in this relationship.Further heterogeneity analysis reveals that,amid China's economic transition,the positive effects of entrepreneurial spirit are more pronounced in non-state-owned enterprises,high-tech firms,and newly established firms.Accordingly,systematic efforts should be pursued across the technological,organizational,and environmental(TOE)dimensions to optimize the cultivation of entrepreneurial spirit.In particular,greater emphasis should be placed on productive entrepreneurial spirit and the constructive role of entrepreneurial effort,so as to fully leverage their contribution to the advancement of firm-level NQPF.展开更多
The Ordos Basin is a large superimposed hydrocarbon-bearing basin in China,and further research on the sedimentary characteristics and sedimentary evolution of the sequence framework of target layers is of great theor...The Ordos Basin is a large superimposed hydrocarbon-bearing basin in China,and further research on the sedimentary characteristics and sedimentary evolution of the sequence framework of target layers is of great theoretical and practical significance for guiding oil and gas exploration.The sedimentary facies and sedimentary evolution of the high-resolution sequence framework of the Carboniferous Taiyuan Formation in the Hangjinqi area have been systematically analyzed for the first time by drilling,logging and seismic data.The results show that four types of sequence interfaces can be identified in the Taiyuan Formation:regional unconformity surfaces,scour surfaces,lithologic-lithofacies transformation surfaces and flooding surfaces.According to the sedimentary response caused by the upward and downward movements of the base level at different levels,the Taiyuan Formation can be divided into 2 long-term cycles(LSC_(1)-LSC_(2)),4 mid-term cycles(MSC_(1)-MSC4)and 7 short-term cycles(SSC_(1)-SSC7).The long-and mid-term cycles correspond to members T_(1)and T_(2)and layers T_(1)-1,T_(1-2),T_(2-1),and T_(2)-2,respectively.Long-term cycles are dominated by C_(1);mid-term cycles are dominated by C_(1)and C_(2),followed by A2;and short-term cycles are dominated by C_(1),C_(2),A1 and A2.Under the high-resolution sequence stratigraphic framework,the Hangjinqi area underwent a transformation of fan delta and tidal flat depositional systems during the Taiyuan Formation sedimentary period.In the MSC_(1)-MSC_(2)stage,owing to a large-scale paleocontinent,the fan delta sedimentary body,which was limited in scale and scope,developed only in the southeastern corner and gradually transitioned basinward to tidal flat facies.In the MSC3-MSC4 stage,as the paleocontinent continuously decreased and the sedimentary range expanded,fan-delta plain sedimentation began in the study area.Several braided distributary channels with poor connectivity developed on the fan-delta plain,and between them were floodplains and peat swamps.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by ca...The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.展开更多
The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Coval...The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Covalent organic frameworks(COFs) are ideal adsorbents for gold recovery owing to their large surface area,good stability,easily functionalized ability,periodic structures,and definitive nanopores.Herein,a cyano-functionalized COF(COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold.The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance,which possesses fast adsorption kinetics,high cycling stability,and adsorption capacity up to 663.67 mg/g.Excitingly,COF-CN showed extremely high selectivity for gold ions,even in the presence of various competing cations and anions.The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE.The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.展开更多
Purpose-This paper provides a comprehensive analysis of the Brazilian freight railway system,examining the efficacy of the current concession renewal model in light of persistent structural problems such as market con...Purpose-This paper provides a comprehensive analysis of the Brazilian freight railway system,examining the efficacy of the current concession renewal model in light of persistent structural problems such as market concentration,cargo dependence on export commodities and underutilization of the network.Situating Brazil within the broader international debate on railway reforms,the paper evaluates whether the ongoing early renewal of concessions can deliver a more diversified and competitive freight system.Design/methodology/approach-The study adopts a sequential mixed-methods research design that integrates longitudinal quantitative analysis with qualitative institutional and policy evaluation.The quantitative component examines time-series indicators published by ANTT,DNIT and INFRA S.A.from 1999 to 2023 to identify structural patterns in traffic growth,investment,safety and market concentration.The qualitative component employs a process-tracing logic to reconstruct the evolution of concession renewals and the implementation of Railway Law 14.273/2021,drawing on concepts from regulatory economics,institutional theory and industrial organization.These empirical streams are synthesized through an analytical framework that connects three dimensions-regulatory design,market structure and system performance-allowing for a systematic assessment of how Brazil’s institutional configuration shapes incentives,competitive dynamics and network utilization.Findings-The analysis confirms that the early renewal of concessions has successfully secured substantial private investment for capacity expansion on existing trunk lines.However,it has perpetuated the vertically integrated model,reinforcing the market power of incumbent operators and failing to significantly promote intramodal competition or cargo diversification.The system remains dominated by iron ore and agricultural commodities,with general cargo representing a minuscule share.The new authorization regime and short-line railway policies present a viable pathway for market opening but face significant operational and institutional barriers to implementation.Originality/value-This research offers a timely and critical assessment of a pivotal moment in Brazilian railway policy.It moves beyond a simplistic evaluation of volume growth to a structural analysis of market failures and the interplay between concession renewal and regulatory innovation.The findings provide actionable insights for policymakers in Brazil and other emerging economies seeking to balance private investment with public interest goals in railway infrastructure,highlighting the necessity of complementary,pro-competitive measures alongside financial investment.展开更多
The evolution of cities into digitally managed environments requires computational systems that can operate in real time while supporting predictive and adaptive infrastructure management.Earlier approaches have often...The evolution of cities into digitally managed environments requires computational systems that can operate in real time while supporting predictive and adaptive infrastructure management.Earlier approaches have often advanced one dimension—such as Internet of Things(IoT)-based data acquisition,Artificial Intelligence(AI)-driven analytics,or digital twin visualization—without fully integrating these strands into a single operational loop.As a result,many existing solutions encounter bottlenecks in responsiveness,interoperability,and scalability,while also leaving concerns about data privacy unresolved.This research introduces a hybrid AI–IoT–Digital Twin framework that combines continuous sensing,distributed intelligence,and simulation-based decision support.The design incorporates multi-source sensor data,lightweight edge inference through Convolutional Neural Networks(CNN)and Long ShortTerm Memory(LSTM)models,and federated learning enhanced with secure aggregation and differential privacy to maintain confidentiality.A digital twin layer extends these capabilities by simulating city assets such as traffic flows and water networks,generating what-if scenarios,and issuing actionable control signals.Complementary modules,including model compression and synchronization protocols,are embedded to ensure reliability in bandwidth-constrained and heterogeneous urban environments.The framework is validated in two urban domains:traffic management,where it adapts signal cycles based on real-time congestion patterns,and pipeline monitoring,where it anticipates leaks through pressure and vibration data.Experimental results show a 28%reduction in response time,a 35%decrease in maintenance costs,and a marked reduction in false positives relative to conventional baselines.The architecture also demonstrates stability across 50+edge devices under federated training and resilience to uneven node participation.The proposed system provides a scalable and privacy-aware foundation for predictive urban infrastructure management.By closing the loop between sensing,learning,and control,it reduces operator dependence,enhances resource efficiency,and supports transparent governance models for emerging smart cities.展开更多
Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and effic...Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and efficient energy technologies,are constrained in their performance enhancement by the sluggish oxygen reduction reaction(ORR)kinetics at the cathode,anode CO poisoning(e.g.,from methanol crossover)and intricate water management dilemmas[1].展开更多
Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have e...Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have exploded in popularity in the field of biomaterials as excellent protective materials with the advantages of conformational flexibility,thermal and chemical stability,and functional controllability.With these superior properties,the applications of ZIF-based materials in combination with various therapies for cancer treatment have grown rapidly in recent years,showing remarkable achievements and great potential.This review elucidates the recent advancements in the use of ZIFs as drug delivery agents for cancer therapy.The structures,synthesis methods,properties,and various modifiers of ZIFs used in oncotherapy are presented.Recent advances in the application of ZIF-based nanoparticles as single or combination tumor treatments are reviewed.Furthermore,the future prospects,potential limitations,and challenges of the application of ZIF-based nanomaterials in cancer treatment are discussed.We except to fully explore the potential of ZIF-based materials to present a clear outline for their application as an effective cancer treatment to help them achieve early clinical application.展开更多
Structured design helps to play out the coordination advantage and optimize the performance of electro-chemical reactions.In this work,hierarchical hollow microspheres(Co_(3)S_(4)@NiCo_(2)S_(4)) with unique core-shell...Structured design helps to play out the coordination advantage and optimize the performance of electro-chemical reactions.In this work,hierarchical hollow microspheres(Co_(3)S_(4)@NiCo_(2)S_(4)) with unique core-shell heterostructure were successfully prepared through simple template and solvothermal methods.Thanks to the hollow structure,cross-linked nanowire arrays,and in-situ coating of zeolite imidazole framework(ZIF),Co_(3)S_(4)@NiCo_(2)S_(4) demonstrated excellent electrochemical performance with a specific ca-pacitance of up to 2697.7 F g^(-1)at 1 A g^(-1) and cycling stability of 80.5% after 5000 cycles.The covalent organic framework(COF)derived nano carbon,which had undergone secondary calcination and ZnCl_(2) activation,also exhibited excellent double-layer energy storage performance.Compared to a single calci-nation,the incredible increase in capacitance was up to 208.5 times greater,reaching 291.9 F g^(-1)at 1 A g^(-1)while maintaining ultra-high rate performance(81.0%at 20 A g^(-1)).The hybrid supercapacitor,assem-bled with Co_(3)S_(4)@NiCo_(2)S_(4)as the cathode and COF-derived carbon as the anode,exhibited an extremely high energy density(79.7 Wh kg^(-1)at 693.5 W kg^(-1))and excellent cyclic stability(maintained 79.3%after 10,000 cycles of 20 A g^(-1)),further explaining the reliable and practical characteristics.This work provided reference for the structural optimization of transition metal sulfides and the high-temperature activation of COF-derived carbon.展开更多
As a class of crystalline porous materials,metal-organic frameworks(MOFs)have shown unique advantages in the fields of catalysis,gas storage and separation,but their inherent microporous structure(pore diameter<2 n...As a class of crystalline porous materials,metal-organic frameworks(MOFs)have shown unique advantages in the fields of catalysis,gas storage and separation,but their inherent microporous structure(pore diameter<2 nm)severely limits their application in scenarios such as macromolecular mass transfer and so on.In order to overcome this re-striction,mesoporous MOFs(meso-MOFs)with a larger aperture(2-50 nm)have attracted much attention due to their potential applications in biological macromolecular catalysis,energy storage and other fields.To date,how to accurately regulate its mesopore topology and pore ordering still faces important technical challenges.展开更多
Strained bridged rings bicyclo[3.2.1]octane and tricyclo[3.2.1.0^(2,7)]octane are prevalent in natural products known for their significant biological activities.However,strategies for efficiently synthesizing these c...Strained bridged rings bicyclo[3.2.1]octane and tricyclo[3.2.1.0^(2,7)]octane are prevalent in natural products known for their significant biological activities.However,strategies for efficiently synthesizing these complex frameworks from simple starting materials via de novo synthesis remain underexplored.This article presents an efficient strategy that combines phosphine catalysis and photocatalysis to execute a stepwise tandem reaction involving allenoates and α-cyano cinnamaldehydes,including[3+2]cyclization,[5+2]cyclization,acyl transfer,and decarboxylation reactions,synthesizing a series of functional bicyclo[3.2.1]octa-2,6-diene and tricyclo[3.2.1.0^(2,7)]oct-3-ene skeleton derivatives with excellent chemoselectivity demonstrated throughout the process.Meanwhile,the reaction can also be performed via a onepot,scalable phosphine/photocatalytic cascade process,efficiently yielding the bridged products which can serve as versatile intermediates for further applications.展开更多
(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under...(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.展开更多
Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nano...Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.展开更多
文摘Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.
文摘CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.
基金supported by the National Natural Science Foundation of China(No.52304329)the Yunnan Fundamental Research Projects(No.202201BE070001-003),Guo Lin would like to acknowledge Xing Dian talent support program of Yunnan Province.
文摘The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.
基金supported by National Natural Science Foundation of China(32494793).
文摘Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.
基金The National Natural Science Foundation of China (NSFC,Nos.92256201,52273006,22071041,92356302,and 21971052)Natural Science Foundation of Jilin Province (No.20240101181JC) are gratefully appreciated for financial the supportssupported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
文摘Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.
基金Liaoning Provincial Social Science Fund Key Disciplines Development Project,Research on the New Supply Function of Entrepreneurs Based on Innovation Ecosystems Driven by Data(Grant No.L22ZD061)。
文摘Accelerating the development of new quality productive forces(NQPF),with innovation at its core,has become essential for firm growth in the new era.Drawing on financial data from China's A-share listed companies spanning the period 2010–2023,this study empirically investigates the impact of entrepreneurial spirit on firm-level NQPF.The results indicate that entrepreneurial spirit significantly promotes firm-level NQPF.Mechanism analysis indicates that entrepreneurial effort—underpinned by technological capital accumulation,effective incentive and constraint mechanisms,and a competitive market environment—plays a mediating role in this relationship.Further heterogeneity analysis reveals that,amid China's economic transition,the positive effects of entrepreneurial spirit are more pronounced in non-state-owned enterprises,high-tech firms,and newly established firms.Accordingly,systematic efforts should be pursued across the technological,organizational,and environmental(TOE)dimensions to optimize the cultivation of entrepreneurial spirit.In particular,greater emphasis should be placed on productive entrepreneurial spirit and the constructive role of entrepreneurial effort,so as to fully leverage their contribution to the advancement of firm-level NQPF.
基金supported by the Fundamental Research Funds for the Liaoning Universities(Grant No.LJ202410166012).
文摘The Ordos Basin is a large superimposed hydrocarbon-bearing basin in China,and further research on the sedimentary characteristics and sedimentary evolution of the sequence framework of target layers is of great theoretical and practical significance for guiding oil and gas exploration.The sedimentary facies and sedimentary evolution of the high-resolution sequence framework of the Carboniferous Taiyuan Formation in the Hangjinqi area have been systematically analyzed for the first time by drilling,logging and seismic data.The results show that four types of sequence interfaces can be identified in the Taiyuan Formation:regional unconformity surfaces,scour surfaces,lithologic-lithofacies transformation surfaces and flooding surfaces.According to the sedimentary response caused by the upward and downward movements of the base level at different levels,the Taiyuan Formation can be divided into 2 long-term cycles(LSC_(1)-LSC_(2)),4 mid-term cycles(MSC_(1)-MSC4)and 7 short-term cycles(SSC_(1)-SSC7).The long-and mid-term cycles correspond to members T_(1)and T_(2)and layers T_(1)-1,T_(1-2),T_(2-1),and T_(2)-2,respectively.Long-term cycles are dominated by C_(1);mid-term cycles are dominated by C_(1)and C_(2),followed by A2;and short-term cycles are dominated by C_(1),C_(2),A1 and A2.Under the high-resolution sequence stratigraphic framework,the Hangjinqi area underwent a transformation of fan delta and tidal flat depositional systems during the Taiyuan Formation sedimentary period.In the MSC_(1)-MSC_(2)stage,owing to a large-scale paleocontinent,the fan delta sedimentary body,which was limited in scale and scope,developed only in the southeastern corner and gradually transitioned basinward to tidal flat facies.In the MSC3-MSC4 stage,as the paleocontinent continuously decreased and the sedimentary range expanded,fan-delta plain sedimentation began in the study area.Several braided distributary channels with poor connectivity developed on the fan-delta plain,and between them were floodplains and peat swamps.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2023-00217581)supported by the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(RS-2024-00406724)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(RS-2025-25430676)。
文摘The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.
基金financially supported by the National Natural Science Foundation of China (No.51972302)。
文摘The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Covalent organic frameworks(COFs) are ideal adsorbents for gold recovery owing to their large surface area,good stability,easily functionalized ability,periodic structures,and definitive nanopores.Herein,a cyano-functionalized COF(COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold.The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance,which possesses fast adsorption kinetics,high cycling stability,and adsorption capacity up to 663.67 mg/g.Excitingly,COF-CN showed extremely high selectivity for gold ions,even in the presence of various competing cations and anions.The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE.The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
文摘Purpose-This paper provides a comprehensive analysis of the Brazilian freight railway system,examining the efficacy of the current concession renewal model in light of persistent structural problems such as market concentration,cargo dependence on export commodities and underutilization of the network.Situating Brazil within the broader international debate on railway reforms,the paper evaluates whether the ongoing early renewal of concessions can deliver a more diversified and competitive freight system.Design/methodology/approach-The study adopts a sequential mixed-methods research design that integrates longitudinal quantitative analysis with qualitative institutional and policy evaluation.The quantitative component examines time-series indicators published by ANTT,DNIT and INFRA S.A.from 1999 to 2023 to identify structural patterns in traffic growth,investment,safety and market concentration.The qualitative component employs a process-tracing logic to reconstruct the evolution of concession renewals and the implementation of Railway Law 14.273/2021,drawing on concepts from regulatory economics,institutional theory and industrial organization.These empirical streams are synthesized through an analytical framework that connects three dimensions-regulatory design,market structure and system performance-allowing for a systematic assessment of how Brazil’s institutional configuration shapes incentives,competitive dynamics and network utilization.Findings-The analysis confirms that the early renewal of concessions has successfully secured substantial private investment for capacity expansion on existing trunk lines.However,it has perpetuated the vertically integrated model,reinforcing the market power of incumbent operators and failing to significantly promote intramodal competition or cargo diversification.The system remains dominated by iron ore and agricultural commodities,with general cargo representing a minuscule share.The new authorization regime and short-line railway policies present a viable pathway for market opening but face significant operational and institutional barriers to implementation.Originality/value-This research offers a timely and critical assessment of a pivotal moment in Brazilian railway policy.It moves beyond a simplistic evaluation of volume growth to a structural analysis of market failures and the interplay between concession renewal and regulatory innovation.The findings provide actionable insights for policymakers in Brazil and other emerging economies seeking to balance private investment with public interest goals in railway infrastructure,highlighting the necessity of complementary,pro-competitive measures alongside financial investment.
基金The researchers would like to thank the Deanship of Graduate Studies and Scientific Research at Qassim University for financial support(QU-APC-2025)。
文摘The evolution of cities into digitally managed environments requires computational systems that can operate in real time while supporting predictive and adaptive infrastructure management.Earlier approaches have often advanced one dimension—such as Internet of Things(IoT)-based data acquisition,Artificial Intelligence(AI)-driven analytics,or digital twin visualization—without fully integrating these strands into a single operational loop.As a result,many existing solutions encounter bottlenecks in responsiveness,interoperability,and scalability,while also leaving concerns about data privacy unresolved.This research introduces a hybrid AI–IoT–Digital Twin framework that combines continuous sensing,distributed intelligence,and simulation-based decision support.The design incorporates multi-source sensor data,lightweight edge inference through Convolutional Neural Networks(CNN)and Long ShortTerm Memory(LSTM)models,and federated learning enhanced with secure aggregation and differential privacy to maintain confidentiality.A digital twin layer extends these capabilities by simulating city assets such as traffic flows and water networks,generating what-if scenarios,and issuing actionable control signals.Complementary modules,including model compression and synchronization protocols,are embedded to ensure reliability in bandwidth-constrained and heterogeneous urban environments.The framework is validated in two urban domains:traffic management,where it adapts signal cycles based on real-time congestion patterns,and pipeline monitoring,where it anticipates leaks through pressure and vibration data.Experimental results show a 28%reduction in response time,a 35%decrease in maintenance costs,and a marked reduction in false positives relative to conventional baselines.The architecture also demonstrates stability across 50+edge devices under federated training and resilience to uneven node participation.The proposed system provides a scalable and privacy-aware foundation for predictive urban infrastructure management.By closing the loop between sensing,learning,and control,it reduces operator dependence,enhances resource efficiency,and supports transparent governance models for emerging smart cities.
文摘Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and efficient energy technologies,are constrained in their performance enhancement by the sluggish oxygen reduction reaction(ORR)kinetics at the cathode,anode CO poisoning(e.g.,from methanol crossover)and intricate water management dilemmas[1].
基金National Natural Science Foundation of China(52073278)the“Medical Science+X”Cross-innovation Team of the Norman Bethune Health Science of Jilin University(2022JBGS10)+2 种基金the Jilin Province Science and Technology Development Program(20190201044JC20230101045JC)the Education Department of Jilin Province(JJKH20231205KJ).
文摘Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have exploded in popularity in the field of biomaterials as excellent protective materials with the advantages of conformational flexibility,thermal and chemical stability,and functional controllability.With these superior properties,the applications of ZIF-based materials in combination with various therapies for cancer treatment have grown rapidly in recent years,showing remarkable achievements and great potential.This review elucidates the recent advancements in the use of ZIFs as drug delivery agents for cancer therapy.The structures,synthesis methods,properties,and various modifiers of ZIFs used in oncotherapy are presented.Recent advances in the application of ZIF-based nanoparticles as single or combination tumor treatments are reviewed.Furthermore,the future prospects,potential limitations,and challenges of the application of ZIF-based nanomaterials in cancer treatment are discussed.We except to fully explore the potential of ZIF-based materials to present a clear outline for their application as an effective cancer treatment to help them achieve early clinical application.
基金the College Students Innovative Practice Fund of Jiangsu University Industrial Center(ZXJG2023047)for funding this research.
文摘Structured design helps to play out the coordination advantage and optimize the performance of electro-chemical reactions.In this work,hierarchical hollow microspheres(Co_(3)S_(4)@NiCo_(2)S_(4)) with unique core-shell heterostructure were successfully prepared through simple template and solvothermal methods.Thanks to the hollow structure,cross-linked nanowire arrays,and in-situ coating of zeolite imidazole framework(ZIF),Co_(3)S_(4)@NiCo_(2)S_(4) demonstrated excellent electrochemical performance with a specific ca-pacitance of up to 2697.7 F g^(-1)at 1 A g^(-1) and cycling stability of 80.5% after 5000 cycles.The covalent organic framework(COF)derived nano carbon,which had undergone secondary calcination and ZnCl_(2) activation,also exhibited excellent double-layer energy storage performance.Compared to a single calci-nation,the incredible increase in capacitance was up to 208.5 times greater,reaching 291.9 F g^(-1)at 1 A g^(-1)while maintaining ultra-high rate performance(81.0%at 20 A g^(-1)).The hybrid supercapacitor,assem-bled with Co_(3)S_(4)@NiCo_(2)S_(4)as the cathode and COF-derived carbon as the anode,exhibited an extremely high energy density(79.7 Wh kg^(-1)at 693.5 W kg^(-1))and excellent cyclic stability(maintained 79.3%after 10,000 cycles of 20 A g^(-1)),further explaining the reliable and practical characteristics.This work provided reference for the structural optimization of transition metal sulfides and the high-temperature activation of COF-derived carbon.
基金support from the National Natural Science Foundation of China(22088101,21733003,22365021,22305132)the Inner Mongolia Autonomous Region“Grassland Talents”Project(2024098)+3 种基金the Inner Mongolia Natural Science Foundation Youth Fund(2023QN02014)The Local Talent Project of Inner Mongolia(12000-15042222)the Basic Research Expenses Supported under 45 Years Old of Inner Mongolia(10000-23112101/036)the“Young Academic Talents”Program of Inner Mongolia University 23600-5233706.
文摘As a class of crystalline porous materials,metal-organic frameworks(MOFs)have shown unique advantages in the fields of catalysis,gas storage and separation,but their inherent microporous structure(pore diameter<2 nm)severely limits their application in scenarios such as macromolecular mass transfer and so on.In order to overcome this re-striction,mesoporous MOFs(meso-MOFs)with a larger aperture(2-50 nm)have attracted much attention due to their potential applications in biological macromolecular catalysis,energy storage and other fields.To date,how to accurately regulate its mesopore topology and pore ordering still faces important technical challenges.
基金financial support from National Natural Science Foundation of China(Nos.82374020 and 22401025)Science&Technology Department of Sichuan Province(No.2024NSFTD0023)Xinglin Scholar Research Promotion Project of Chengdu University of TCM。
文摘Strained bridged rings bicyclo[3.2.1]octane and tricyclo[3.2.1.0^(2,7)]octane are prevalent in natural products known for their significant biological activities.However,strategies for efficiently synthesizing these complex frameworks from simple starting materials via de novo synthesis remain underexplored.This article presents an efficient strategy that combines phosphine catalysis and photocatalysis to execute a stepwise tandem reaction involving allenoates and α-cyano cinnamaldehydes,including[3+2]cyclization,[5+2]cyclization,acyl transfer,and decarboxylation reactions,synthesizing a series of functional bicyclo[3.2.1]octa-2,6-diene and tricyclo[3.2.1.0^(2,7)]oct-3-ene skeleton derivatives with excellent chemoselectivity demonstrated throughout the process.Meanwhile,the reaction can also be performed via a onepot,scalable phosphine/photocatalytic cascade process,efficiently yielding the bridged products which can serve as versatile intermediates for further applications.
文摘(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.
文摘Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.
