Photocatalytic carbon dioxide(CO_(2))reduction offers an alternative strategy for converting CO_(2)into high-value added gaseous fuels,thereby paving the way for the development of clean and renewable energy.Metal-org...Photocatalytic carbon dioxide(CO_(2))reduction offers an alternative strategy for converting CO_(2)into high-value added gaseous fuels,thereby paving the way for the development of clean and renewable energy.Metal-organic frameworks(MOFs),characterized by their highly porous structure,exceptional CO_(2)adsorption capacity,and tunable architecture,have emerged as promising candidates for photocatalytic CO_(2)reduction.This review systematically examines the recent advancement in MOFs-based photocatalysts for CO_(2)reduction to CO.It begins with the overview of the fundamental mechanisms and processes of MOFs towards photocatalytic CO_(2)reduction.Subsequently,common strategies for the modulation of MOFs-based photocatalysts are summarized,including metallic site modification,functionalized ligand incorporation,morphological control,defect engineering,and heterostructure construction.Notably,the review analyzes the critical factors contributing to the high selectivity of CO_(2)photoreduction to CO from both thermodynamic and kinetic perspectives.The conclusion addresses current challenges and future perspectives in designing highly efficient photocatalysts with abundant active sites,providing valuable insights for their continued development.展开更多
Photocatalytic CO_(2)cycloaddition reaction presents a promising CO_(2)conversion strategy to establish carbon neutrality.Among emerging catalysts,metal‑organic frameworks(MOFs)have been regarded as paradigmshifting p...Photocatalytic CO_(2)cycloaddition reaction presents a promising CO_(2)conversion strategy to establish carbon neutrality.Among emerging catalysts,metal‑organic frameworks(MOFs)have been regarded as paradigmshifting photocatalysts for their atomic precision in active site engineering,controllable porosity,and exceptional photochemical stability under ambient conditions.However,inherent limitations persist in conventional MOFs,including restricted solar spectrum utilization,inefficient charge carrier separation,and inadequate epoxide activation ability.Recent breakthroughs address these challenges through multiple strategies:ligand engineering,dopant incorporation,and composite construction.This review systematically maps the evolutionary trajectory of MOF‑based photocatalysts,providing mechanistic insights into structure‑activity relationships and providing insights and directions for the design of high‑performance MOF‑based photocatalysts.展开更多
Metal-Organic Frameworks(MOFs)have emerged as promising materials for gas adsorption and separation due to their exceptional surface area,tunable porosity,and versatility in functionalization.This paper explores the m...Metal-Organic Frameworks(MOFs)have emerged as promising materials for gas adsorption and separation due to their exceptional surface area,tunable porosity,and versatility in functionalization.This paper explores the mechanisms of gas adsorption in MOFs,including physical adsorption,chemisorption,and synergistic effects,which contribute to their efficiency in capturing and separating gases.The applications of MOFs in key areas such as carbon dioxide capture,hydrogen storage,natural gas separation,and air purification are discussed,highlighting their potential to address pressing environmental and energy challenges.Additionally,the use of MOFs in selective gas separation,membranes,and adsorption-based technologies like Pressure Swing Adsorption(PSA)and Vacuum Swing Adsorption(VSA)is explored,emphasizing their advantages over traditional materials.Despite challenges related to scalability,stability,and cost,MOFs hold great promise for advancing gas separation technologies in the near future,offering more efficient,sustainable,and environmentally friendly solutions.展开更多
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
Enhancing the activity of fragile enzymes is greatly useful for various purposes,including fabrication of enzyme-based immunosensors.Herein,we report a defect-engineering strategy for encapsulating enzymes within cova...Enhancing the activity of fragile enzymes is greatly useful for various purposes,including fabrication of enzyme-based immunosensors.Herein,we report a defect-engineering strategy for encapsulating enzymes within covalent organic frameworks(COFs),enabling the resulting immobilized enzymes with excellent catalytic activity and stability to construct high performance immunosensors.In this design,by consciously introducing monoaldehyde ligands into the imine-linked COFs structure,we have precisely customized the structural defects to improve enzyme loading capacity and conformational stability.Defect-engineering interaction modulation between enzymes and COFs drives the enhancement of catalytic performance.Compared to the pristine COFs,the enzyme@defective COFs composites with optimally tuned catalytic performance exhibit a 4.49-fold enhancement in enzymatic activity.Furthermore,it is demonstrated that the stable skeletons of COFs provide exceptional protection for the enzymes against external perturbations.Thereafter,the optimized enzyme@defective COFs are employed to fabricate immunosensor.We have successfully established a detection method for prostate-specific antigen(PSA),achieving a low detection limit of 0.09 ng/mL.More importantly,the developed immunosensor has successfully distinguished the prostate cancer patients from healthy individuals.This work establishes a novel paradigm for enzyme immobilization,ultimately empowering the construction of a PSA immunosensor with high sensitivity,remarkable operational stability,and great clinical application potential.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
Rechargeable Zn/Sn-air batteries have received considerable attention as promising energy storage devices.However,the electrochemical performance of these batteries is significantly constrained by the sluggish electro...Rechargeable Zn/Sn-air batteries have received considerable attention as promising energy storage devices.However,the electrochemical performance of these batteries is significantly constrained by the sluggish electrocatalytic reaction kinetics at the cathode.The integration of light energy into Zn/Sn-air batteries is a promising strategy for enhancing their performance.However,the photothermal and photoelectric effects generate heat in the battery under prolonged solar irradiation,leading to air cathode instability.This paper presents the first design and synthesis of Ni_(2)-1,5-diamino-4,8-dihydroxyanthraquinone(Ni_(2)DDA),an electronically conductiveπ-d conjugated metal-organic framework(MOF).Ni_(2)DDA exhibits both photoelectric and photothermal effects,with an optical band gap of~1.14 eV.Under illumination,Ni_(2)DDA achieves excellent oxygen evolution reaction performance(with an overpotential of 245 mV vs.reversible hydrogen electrode at 10 mA cm^(−2))and photothermal stability.These properties result from the synergy between the photoelectric and photothermal effects of Ni_(2)DDA.Upon integration into Zn/Sn-air batteries,Ni_(2)DDA ensures excellent cycling stability under light and exhibits remarkable performance in high-temperature environments up to 80℃.This study experimentally confirms the stable operation of photo-assisted Zn/Sn-air batteries under high-temperature conditions for the first time and provides novel insights into the application of electronically conductive MOFs in photoelectrocatalysis and photothermal catalysis.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
A series of dual-extended-polyhedral metal-organic frameworks(MOFs)was constructed based on the 14-coordinated Cu_(24)-MOP-1(MOP=metal-organic polyhedron)supermolecular building blocks(SBBs)with enhanced stability and...A series of dual-extended-polyhedral metal-organic frameworks(MOFs)was constructed based on the 14-coordinated Cu_(24)-MOP-1(MOP=metal-organic polyhedron)supermolecular building blocks(SBBs)with enhanced stability and tunable functionality for high water uptake efficiency and capacity.Exceptional water stability was demonstrated by the retention of chemical integrity and crystallinity of USC-CP-5(where USC-CP stands for University of South China coordination polymer)after exposure to boiling water for 24 h.Functionalization with-Cl,-OCH_(3),-OH,and-NH_(2)groups of USC-CP-5 resulted in water uptake capacities of 450,460,490,and 590 cm^(3)·g^(-1) at relative pressure(P/P_(0))=0.9,respectively.This performance is ascribed to both the increased hydrophilicity of the ligands and stronger hydrogen bonding.Intriguingly,high-temperature activated USC-5-NH_(2)exhibits a significant water uptake of 38.5 wt.%at P/P_(0)=0.3 and releases 0.44 L·kg^(-1) water between 25 and 65℃.This water release process is reversible for at least 100 cycles with minimal weight loss of only 1.6 wt.%.Consequently,USC-5-NH_(2)holds considerable potential for harvesting and releasing atmospheric water in arid desert regions,powered by solar energy.展开更多
Constructing catalysts featuring an ordered structure,stable performance,and uniformly dispersed catalytic sites is vital for the epoxidation of small-molecular olefins.Here,we design catalysts by tracing the oxidatio...Constructing catalysts featuring an ordered structure,stable performance,and uniformly dispersed catalytic sites is vital for the epoxidation of small-molecular olefins.Here,we design catalysts by tracing the oxidationprocess origin and synthesize a series of highly dispersed metal porphyrin-based covalent organic frameworks(COFs)materials.The aim is to efficiently oxidize the C-H bonds of cumene by air to in-situ generate organic peroxides at a safe concentration,and integrate the multi-step oxidation method of cumene in industry into a one-step method for olefins’epoxidation.The carbonyl-ruthenium COF(Ru-COF-1)exhibits excellent performance,with 98% epoxide selectivity,1221.77 h^(-1) productivity,and over 95% selectivity after 9 cycles for 1-hexene.Analysis of structure-properties-catalytic relationships of Ru-COF-1 shows that,compared with Ru-porphyrins and metal-free COFs,the enhanced reaction performance mainly results from Ru metal introduction,which promotes benzylic proton transfer in cumene.Besides,Ru-COF-1’s porous,ordered structure aids oxygen enrichment,forming active peroxy radicals with the cumene carboncentered radicals formed on the catalyst surface.Ru-H sites then accelerate active oxygen transfer from peroxy radicals,enabling olefin tandem epoxidation.Density functional theory(DFT)calculations verify the reaction mechanism,and this work offers a reference for the design of catalysts for the green,safe,and efficient oxidation of olefins.展开更多
To meet the growing needs of flexible and wearable electronics,stretchable energy storage devices—especially supercapacitors(SCs)—have become a key focus in advanced energy storage research.However,achieving both me...To meet the growing needs of flexible and wearable electronics,stretchable energy storage devices—especially supercapacitors(SCs)—have become a key focus in advanced energy storage research.However,achieving both mechanical stretchability and high capacitance in SC still faces great challenges,and the crucial factors lie in creating superior electrode materials that exhibit high electrochemical performance as well as excellent mechanical stretchability.Covalent organic frameworks(COFs)possess considerable potential as electrode materials for SCs by virtue of stable organic frameworks,open channels and designable functional groups.Nevertheless,their applications in flexible SCs are greatly hindered by their rigid characteristics.Here a novel COFs@conductive polymer hydrogels(CPHs)@poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)complexes,which integrate the pseudocapacitance of PDITAPA COF,mechanical stretchability of hydrogels and high conductivity of PEDOT:PSS,has been developed as stretchable electrode of SCs.Physically cross-linked PEDOT nanofibers,with their interlinked and entangled architecture,collectively boost mechanical,electrical,and electrochemical performance.The COFs@CPHs@PEDOT:PSS simultaneously demonstrates outstanding mechanical stretchability,high electrical behaviors,and superior swelling characteristics.The resulting SC exhibits advantages of simple structures,facile assembly processes,high specific capacitance,excellent cycling stability,and arbitrary deformation,which holds great application prospects for wearable electronic products.Owing to its uncomplicated structure,ease of production,high energy storage capacity,robust cycling performance,and adaptability to deformation,this fabricated SC is well-suited for next-generation wearable technologies.展开更多
The intrinsic pressure framework,which treats self-propelling force as an external force,provides a convenient and consistent description of mechanical equilibrium in active matter.However,direct experimental evidence...The intrinsic pressure framework,which treats self-propelling force as an external force,provides a convenient and consistent description of mechanical equilibrium in active matter.However,direct experimental evidence is still lacking.To validate this framework,here we employ a programmable robotic platform,where a single light-controlled wheeled robot travels in an activity landscape.Our experiments quantitatively demonstrate that the intrinsic pressure difference across the activity interface is balanced by the emerged polarization force.This result unambiguously confirms the theoretical predictions,thus validating the intrinsic pressure framework and laying the experimental foundation for the intrinsic pressure-based mechanical description of dry active matter.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
The rare earth metal-organic frameworks （Ln-MOFs） materials, Ln（BTC）（H2O）-（DMF）, were synthesized using the rare earth metal （Ln=Sm, Eu, Tb, Y） and 1,3,5-trirnesic acid （BTC） as a metal ion center and liga...The rare earth metal-organic frameworks （Ln-MOFs） materials, Ln（BTC）（H2O）-（DMF）, were synthesized using the rare earth metal （Ln=Sm, Eu, Tb, Y） and 1,3,5-trirnesic acid （BTC） as a metal ion center and ligand, respectively. X-ray diffraction （XRD） and infrared spectroscopy （FT-IR） were employed to characterize the Ln-MOFs structural features. The property of adsorption desul- furization of Ln-MOFs materials was evaluated with thiophene/n-octane as model oil. The results showed that Ln-MOFs with rare earth metals Sm, Eu, Tb and Y had perfect crystalline and good adsorption desulfurization ability. Y（BTC）（H2O）-（DMF） material had a comparatively better activity for the adsorption desulfurization with desulfurization rate up to 80.7% and the sulfur adsorption ca- pacity was found 30.7 mgS/g（Y-MOFs）. The Ln-MOFs materials had excellent reusability.展开更多
基金supported by the National Key Research and Development Program of China(No.2021YFC2901100)the National Natural Science Foundation of China(No.22478425).
文摘Photocatalytic carbon dioxide(CO_(2))reduction offers an alternative strategy for converting CO_(2)into high-value added gaseous fuels,thereby paving the way for the development of clean and renewable energy.Metal-organic frameworks(MOFs),characterized by their highly porous structure,exceptional CO_(2)adsorption capacity,and tunable architecture,have emerged as promising candidates for photocatalytic CO_(2)reduction.This review systematically examines the recent advancement in MOFs-based photocatalysts for CO_(2)reduction to CO.It begins with the overview of the fundamental mechanisms and processes of MOFs towards photocatalytic CO_(2)reduction.Subsequently,common strategies for the modulation of MOFs-based photocatalysts are summarized,including metallic site modification,functionalized ligand incorporation,morphological control,defect engineering,and heterostructure construction.Notably,the review analyzes the critical factors contributing to the high selectivity of CO_(2)photoreduction to CO from both thermodynamic and kinetic perspectives.The conclusion addresses current challenges and future perspectives in designing highly efficient photocatalysts with abundant active sites,providing valuable insights for their continued development.
文摘Photocatalytic CO_(2)cycloaddition reaction presents a promising CO_(2)conversion strategy to establish carbon neutrality.Among emerging catalysts,metal‑organic frameworks(MOFs)have been regarded as paradigmshifting photocatalysts for their atomic precision in active site engineering,controllable porosity,and exceptional photochemical stability under ambient conditions.However,inherent limitations persist in conventional MOFs,including restricted solar spectrum utilization,inefficient charge carrier separation,and inadequate epoxide activation ability.Recent breakthroughs address these challenges through multiple strategies:ligand engineering,dopant incorporation,and composite construction.This review systematically maps the evolutionary trajectory of MOF‑based photocatalysts,providing mechanistic insights into structure‑activity relationships and providing insights and directions for the design of high‑performance MOF‑based photocatalysts.
文摘Metal-Organic Frameworks(MOFs)have emerged as promising materials for gas adsorption and separation due to their exceptional surface area,tunable porosity,and versatility in functionalization.This paper explores the mechanisms of gas adsorption in MOFs,including physical adsorption,chemisorption,and synergistic effects,which contribute to their efficiency in capturing and separating gases.The applications of MOFs in key areas such as carbon dioxide capture,hydrogen storage,natural gas separation,and air purification are discussed,highlighting their potential to address pressing environmental and energy challenges.Additionally,the use of MOFs in selective gas separation,membranes,and adsorption-based technologies like Pressure Swing Adsorption(PSA)and Vacuum Swing Adsorption(VSA)is explored,emphasizing their advantages over traditional materials.Despite challenges related to scalability,stability,and cost,MOFs hold great promise for advancing gas separation technologies in the near future,offering more efficient,sustainable,and environmentally friendly solutions.
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.
基金supported by the Nanjing Second Hospital talent lifting project(No.RCZD23001)the Jiangsu Province traditional Chinese medicine science and technology development general program(No.MS2023063)+1 种基金Medical Science and Technology Development Foundation,Nanjing Department of Health(No.ZKX20033)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX25_0240).
文摘Enhancing the activity of fragile enzymes is greatly useful for various purposes,including fabrication of enzyme-based immunosensors.Herein,we report a defect-engineering strategy for encapsulating enzymes within covalent organic frameworks(COFs),enabling the resulting immobilized enzymes with excellent catalytic activity and stability to construct high performance immunosensors.In this design,by consciously introducing monoaldehyde ligands into the imine-linked COFs structure,we have precisely customized the structural defects to improve enzyme loading capacity and conformational stability.Defect-engineering interaction modulation between enzymes and COFs drives the enhancement of catalytic performance.Compared to the pristine COFs,the enzyme@defective COFs composites with optimally tuned catalytic performance exhibit a 4.49-fold enhancement in enzymatic activity.Furthermore,it is demonstrated that the stable skeletons of COFs provide exceptional protection for the enzymes against external perturbations.Thereafter,the optimized enzyme@defective COFs are employed to fabricate immunosensor.We have successfully established a detection method for prostate-specific antigen(PSA),achieving a low detection limit of 0.09 ng/mL.More importantly,the developed immunosensor has successfully distinguished the prostate cancer patients from healthy individuals.This work establishes a novel paradigm for enzyme immobilization,ultimately empowering the construction of a PSA immunosensor with high sensitivity,remarkable operational stability,and great clinical application potential.
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supported by the National Natural Science Foundation of China(No.62464010)Spring City Plan-Special Program for Young Talents(K202005007)+2 种基金Yunnan Talents Support Plan for Young Talents(XDYC-QNRC-2022-0482)Yunnan Local Colleges Applied Basic Research Projects(202101BA070001-138)Frontier Research Team of Kunming University 2023.
文摘Rechargeable Zn/Sn-air batteries have received considerable attention as promising energy storage devices.However,the electrochemical performance of these batteries is significantly constrained by the sluggish electrocatalytic reaction kinetics at the cathode.The integration of light energy into Zn/Sn-air batteries is a promising strategy for enhancing their performance.However,the photothermal and photoelectric effects generate heat in the battery under prolonged solar irradiation,leading to air cathode instability.This paper presents the first design and synthesis of Ni_(2)-1,5-diamino-4,8-dihydroxyanthraquinone(Ni_(2)DDA),an electronically conductiveπ-d conjugated metal-organic framework(MOF).Ni_(2)DDA exhibits both photoelectric and photothermal effects,with an optical band gap of~1.14 eV.Under illumination,Ni_(2)DDA achieves excellent oxygen evolution reaction performance(with an overpotential of 245 mV vs.reversible hydrogen electrode at 10 mA cm^(−2))and photothermal stability.These properties result from the synergy between the photoelectric and photothermal effects of Ni_(2)DDA.Upon integration into Zn/Sn-air batteries,Ni_(2)DDA ensures excellent cycling stability under light and exhibits remarkable performance in high-temperature environments up to 80℃.This study experimentally confirms the stable operation of photo-assisted Zn/Sn-air batteries under high-temperature conditions for the first time and provides novel insights into the application of electronically conductive MOFs in photoelectrocatalysis and photothermal catalysis.
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supported by the National Natural Science Foundation of China(Nos.11375082,22271189,12405385,92356301,and 21522105)the Hunan Provincial Natural Science Foundation of China(No.2021JJ30565)+5 种基金the Science and Technology Commission of Shanghai Municipality(Nos.21XD1402300,21JC1401700,and 21DZ2260400)the supports by the Double First-Class Initiative Fund of ShanghaiTech University(No.SYLDX0052022)the Analytical Instrumentation Center(No.SPST-AIC10112914)for adsorption measurementthe staff at BL17B1 beamline of the National Facility for Protein Science in Shanghai(NFPS),Shanghai Advanced Research Institute,CAS,for providing beamtime for single-crystal X-ray diffraction data collectionthe project CICECO-Aveiro Institute of Materials,Grants(Nos.UIDB/50011/2020,UIDP/50011/2020,and LA/P/0006/2020)financed by national funds through the FCT/MEC(PIDDAC).
文摘A series of dual-extended-polyhedral metal-organic frameworks(MOFs)was constructed based on the 14-coordinated Cu_(24)-MOP-1(MOP=metal-organic polyhedron)supermolecular building blocks(SBBs)with enhanced stability and tunable functionality for high water uptake efficiency and capacity.Exceptional water stability was demonstrated by the retention of chemical integrity and crystallinity of USC-CP-5(where USC-CP stands for University of South China coordination polymer)after exposure to boiling water for 24 h.Functionalization with-Cl,-OCH_(3),-OH,and-NH_(2)groups of USC-CP-5 resulted in water uptake capacities of 450,460,490,and 590 cm^(3)·g^(-1) at relative pressure(P/P_(0))=0.9,respectively.This performance is ascribed to both the increased hydrophilicity of the ligands and stronger hydrogen bonding.Intriguingly,high-temperature activated USC-5-NH_(2)exhibits a significant water uptake of 38.5 wt.%at P/P_(0)=0.3 and releases 0.44 L·kg^(-1) water between 25 and 65℃.This water release process is reversible for at least 100 cycles with minimal weight loss of only 1.6 wt.%.Consequently,USC-5-NH_(2)holds considerable potential for harvesting and releasing atmospheric water in arid desert regions,powered by solar energy.
基金financially supported by the National Natural Science Foundation of China(No.22508360)Zhejiang Provincial Natural Science Foundation of China(No.QN26B060028)+1 种基金the National Key Research and Development Program Nanotechnology Specific Project(No.2020YFA0210900)Innovative Team Project of Guang-dong Ordinary University(No.2019KCXTD002).
文摘Constructing catalysts featuring an ordered structure,stable performance,and uniformly dispersed catalytic sites is vital for the epoxidation of small-molecular olefins.Here,we design catalysts by tracing the oxidationprocess origin and synthesize a series of highly dispersed metal porphyrin-based covalent organic frameworks(COFs)materials.The aim is to efficiently oxidize the C-H bonds of cumene by air to in-situ generate organic peroxides at a safe concentration,and integrate the multi-step oxidation method of cumene in industry into a one-step method for olefins’epoxidation.The carbonyl-ruthenium COF(Ru-COF-1)exhibits excellent performance,with 98% epoxide selectivity,1221.77 h^(-1) productivity,and over 95% selectivity after 9 cycles for 1-hexene.Analysis of structure-properties-catalytic relationships of Ru-COF-1 shows that,compared with Ru-porphyrins and metal-free COFs,the enhanced reaction performance mainly results from Ru metal introduction,which promotes benzylic proton transfer in cumene.Besides,Ru-COF-1’s porous,ordered structure aids oxygen enrichment,forming active peroxy radicals with the cumene carboncentered radicals formed on the catalyst surface.Ru-H sites then accelerate active oxygen transfer from peroxy radicals,enabling olefin tandem epoxidation.Density functional theory(DFT)calculations verify the reaction mechanism,and this work offers a reference for the design of catalysts for the green,safe,and efficient oxidation of olefins.
基金granted by the National Natural Science Foundation of China(Nos.52533008,21835003,62274097,and 62004106)National Key Research and Development Program of China(Nos.2024YFB3612500,2024YFB3612600,and 2023YFB3608900)+2 种基金Basic Research Program of Jiangsu Province(No.BK20243057)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX25_1213)the Natural Science Foundation of Nanjing Universityof Posts and Telecommunications(No.NY225135).
文摘To meet the growing needs of flexible and wearable electronics,stretchable energy storage devices—especially supercapacitors(SCs)—have become a key focus in advanced energy storage research.However,achieving both mechanical stretchability and high capacitance in SC still faces great challenges,and the crucial factors lie in creating superior electrode materials that exhibit high electrochemical performance as well as excellent mechanical stretchability.Covalent organic frameworks(COFs)possess considerable potential as electrode materials for SCs by virtue of stable organic frameworks,open channels and designable functional groups.Nevertheless,their applications in flexible SCs are greatly hindered by their rigid characteristics.Here a novel COFs@conductive polymer hydrogels(CPHs)@poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)complexes,which integrate the pseudocapacitance of PDITAPA COF,mechanical stretchability of hydrogels and high conductivity of PEDOT:PSS,has been developed as stretchable electrode of SCs.Physically cross-linked PEDOT nanofibers,with their interlinked and entangled architecture,collectively boost mechanical,electrical,and electrochemical performance.The COFs@CPHs@PEDOT:PSS simultaneously demonstrates outstanding mechanical stretchability,high electrical behaviors,and superior swelling characteristics.The resulting SC exhibits advantages of simple structures,facile assembly processes,high specific capacitance,excellent cycling stability,and arbitrary deformation,which holds great application prospects for wearable electronic products.Owing to its uncomplicated structure,ease of production,high energy storage capacity,robust cycling performance,and adaptability to deformation,this fabricated SC is well-suited for next-generation wearable technologies.
基金supported by the National Natural Science Foundation of China (Grant Nos.T2325027,12274448,T2350007,12404239,12174041,12325405,12090054,and T2221001)the National Key R&D Program of China (Grant No.2022YFF0503504)。
文摘The intrinsic pressure framework,which treats self-propelling force as an external force,provides a convenient and consistent description of mechanical equilibrium in active matter.However,direct experimental evidence is still lacking.To validate this framework,here we employ a programmable robotic platform,where a single light-controlled wheeled robot travels in an activity landscape.Our experiments quantitatively demonstrate that the intrinsic pressure difference across the activity interface is balanced by the emerged polarization force.This result unambiguously confirms the theoretical predictions,thus validating the intrinsic pressure framework and laying the experimental foundation for the intrinsic pressure-based mechanical description of dry active matter.
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.
基金supported by the National Natural Science Foundation of China(21136001,21173018)
文摘The rare earth metal-organic frameworks （Ln-MOFs） materials, Ln（BTC）（H2O）-（DMF）, were synthesized using the rare earth metal （Ln=Sm, Eu, Tb, Y） and 1,3,5-trirnesic acid （BTC） as a metal ion center and ligand, respectively. X-ray diffraction （XRD） and infrared spectroscopy （FT-IR） were employed to characterize the Ln-MOFs structural features. The property of adsorption desul- furization of Ln-MOFs materials was evaluated with thiophene/n-octane as model oil. The results showed that Ln-MOFs with rare earth metals Sm, Eu, Tb and Y had perfect crystalline and good adsorption desulfurization ability. Y（BTC）（H2O）-（DMF） material had a comparatively better activity for the adsorption desulfurization with desulfurization rate up to 80.7% and the sulfur adsorption ca- pacity was found 30.7 mgS/g（Y-MOFs）. The Ln-MOFs materials had excellent reusability.
