The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecul...The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.展开更多
Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.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
All solid-state batteries(ASSBs)are the holy grails of rechargeable batteries,where extensive searches are ongoing in the pursuit of ideal solid-state electrolytes.Nevertheless,there is still a long way off to the sat...All solid-state batteries(ASSBs)are the holy grails of rechargeable batteries,where extensive searches are ongoing in the pursuit of ideal solid-state electrolytes.Nevertheless,there is still a long way off to the satisfactorily high(enough)ionic conductivity,long-term stability and especially being able to form compatible interfaces with the solid electrodes.Herein,we have explored ionic transport behavior and high mobility in the sub-nano pore networks in the framework structures.Macroscopically,the frameworked electrolyte behaves as a solid,and however in the(sub)-nano scales,the very limited number of solvent molecules in confinement makes them completely different from that in liquid electrolyte.Differentiated from a liquid-electrolyte counterpart,the interactions between the mobile ions and surrounding molecules are subject to dramatic changes,leading to a high ionic conductivity at room temperature with a low activation energy.Li+ions in the sub-nano cages of the network structure are highly mobile and diffuse rather independently,where the rate-limiting step of ions crossing cages is driven by the local concentration gradient and the electrostatic interactions between Li^(+)ions.This new class of frameworked electrolytes(FEs)with both high ionic conductivity and desirable interface with solid electrodes are demonstrated to work with Li-ion batteries,where the ASSB with LiFePO_(4)shows a highly stable electrochemical performance of over 450 cycles at 2℃ at room temperature,with an almost negligible capacity fade of 0.03‰ each cycle.In addition,the FE shows outstanding flexibility and anti-flammability,which are among the key requirements of large-scale applications.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
High-throughput transcriptomics has evolved from bulk RNA-seq to single-cell and spatial profiling,yet its clinical translation still depends on effective integration across diverse omics and data modalities.Emerging ...High-throughput transcriptomics has evolved from bulk RNA-seq to single-cell and spatial profiling,yet its clinical translation still depends on effective integration across diverse omics and data modalities.Emerging foundation models and multimodal learning frameworks are enabling scalable and transferable representations of cellular states,while advances in interpretability and real-world data integration are bridging the gap between discovery and clinical application.This paper outlines a concise roadmap for AI-driven,transcriptome-centered multi-omics integration in precision medicine(Figure 1).展开更多
Luminescent metal-organic frameworks(MOFs)have garnered significant attention due to their structural tunability and potential applications in solid-state lighting,bioimaging,sensing,anticounterfeiting,and other field...Luminescent metal-organic frameworks(MOFs)have garnered significant attention due to their structural tunability and potential applications in solid-state lighting,bioimaging,sensing,anticounterfeiting,and other fields.Nevertheless,due to the tendency of1,4-benzenedicarboxylic acid(BDC)to rotate within the framework,MOFs composed of it exhibit significant non-radiative energy dissipation and thus impair the emissive properties.In this study,efficient luminescence of MIL-140A nanocrystals(NCs)with BDC rotors as ligands is achieved by pressure treatment strategy.Pressure treatment effectively modulates the pore structure of the framework,enhancing the interactions between the N,N-dimethylformamide vip molecules and the BDC ligands.The enhanced host-vip interaction contributes to the structural rigidity of the MOF,thereby suppressing the rotation-induced excited-state energy loss.As a result,the pressure-treated MIL-140A NCs displayed bright blue-light emission,with the photoluminescence quantum yield increasing from an initial 6.8%to 69.2%.This study developed an effective strategy to improve the luminescence performance of rotor ligand MOFs,offers a new avenue for the rational design and synthesis of MOFs with superior luminescent properties.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
Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then...Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).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
AgVO_(3)/ZIF-8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO_(3)and ZIF-8.X-ray diffraction(XRD),scanning electron microscopy(SEM),high-power transmission electron microscopy(...AgVO_(3)/ZIF-8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO_(3)and ZIF-8.X-ray diffraction(XRD),scanning electron microscopy(SEM),high-power transmission electron microscopy(HRTEM),X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectroscopy(UV-Vis DRS),photoluminescence(PL)spectroscopy,electron spin resonance(ESR)spectroscopy,transient photocurrent and electrochemical impedance spectroscopy(EIS)were used to characterize binary composites.Tetracycline(TC)was used as a substrate to study the performance efficiency of the degradation of photocatalysts under light conditions,and the degradation effect of TC was also evaluated under different mass concentrations and ionic contents.In addition,we further investigated the photocatalytic mechanism of the binary composite material AgVO_(3)/ZIF-8 and identified the key active components responsible for the catalytic degradation of this new photocatalyst.The experimental results show that the degradation efficiency of 10%-AZ,prepared with a molar ratio of 10%AgVO_(3)and ZIF-8 to TC,was 75.0%.This indicates that the photocatalytic activity can be maintained even under a certain ionic content,making it a suitable photocatalyst for optimal use.In addition,the photocatalytic mechanism of binary composites was further studied by the active species trapping experiment.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
The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic ...The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.展开更多
Metal-organic frameworks(MOFs)and their derivatives have gained significant attention in recent years for their ability to catalyze the advanced oxidation of persulfates.Cerium-doped MOFs,in particular,have shown prom...Metal-organic frameworks(MOFs)and their derivatives have gained significant attention in recent years for their ability to catalyze the advanced oxidation of persulfates.Cerium-doped MOFs,in particular,have shown promise due to their high catalytic efficiency,practical applicability,and cost-effectiveness.However,their structure,catalytic properties,and mechanisms are not yet fully understood.ZIF-8 was chosen as the raw material to prepare cerium-doped hollow carbon nano fibers(Ce-HCNFs)using the electrostatic spinning-calcination method.The objective is to investigate the structure,catalytic performance,and catalytic mechanism of Ce-HCNFs.The results show that Ce-HCNFs catalyzed the degradation of tetracycline(TC)by persulfate up to 76.9%,Quenching experiments and electron paramagnetic resonance experiments indicate the dominant role of single-linear oxygen.Furthermore,the experiments on the influence factor and cycling demonstrate the exceptional stability and recycling capability of Ce-HCNFs in real-world water environments.展开更多
Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to it...Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to its unique composition and bonding mode,which has advantages such as large specific surface area,high porosity,adjustable structure,and designable composition.Herein,MOF-derived MAMs are highlighted based on morphology and structure.The synthesis strategies of MOF-derived MAMs of different dimensions are discussed.On this basis,the structure-activity relationships can be deeply explored through the precise control of material structure and property by atomic engineering.Finally,perspectives are given for the existing problems of MOF-derived MAMs,which will open a new horizon and promote the development of MAMs.展开更多
The light-driven CO_(2)reduction reaction(CO_(2)RR)to CO is a very effective way to address global warming.To avoid competition with water photolysis,metal-free gas-solid CO_(2)RR catalysts should be investigated.Cova...The light-driven CO_(2)reduction reaction(CO_(2)RR)to CO is a very effective way to address global warming.To avoid competition with water photolysis,metal-free gas-solid CO_(2)RR catalysts should be investigated.Covalent organic frameworks(COFs)offer a promising approach for CO_(2)transformation but lack high efficiency and selectivity in the absence of metals.Here,we have incorporated a pyridine nitrogen component into the imine-COF conjugated structure(Tp Pym).This innovative system has set a record of producing a CO yield of 1565μmol g^(-1)within 6 h.The soft X-ray absorption fine structure measurement proves that Tp Pym has both better conjugation and electron cloud enrichment.The electronic structure distribution delays the charge-carrier recombination,as evidenced by femtosecond transient absorption spectroscopy.The energy band diagram and theoretical calculation show that the conduction-band potential of Tp Pym is lower and the reduction reaction of CO_(2)to CO is more likely to occur.展开更多
Water often presents significant challenges in catalysts by deactivating active sites,poisoning the reaction,and even degrading composite structure.These challenges are amplified when the water participates as a react...Water often presents significant challenges in catalysts by deactivating active sites,poisoning the reaction,and even degrading composite structure.These challenges are amplified when the water participates as a reactant and is fed as a liquid phase,such as trickle bed-type reactors in a hydrogen-water isotope exchange(HIE)reaction.The key balance in such multiphase reactions is the precise control of catalyst design to repel bulk liquid water while diffusing water vapor.Herein,a platinum-incorporated metal-organic framework(MIL-101)based bifunctional hydrophobic catalyst functionalized with long alkyl chains(C_(12),dodecylamine)and further manufactured with poly(vinylidene fluoride),Pt@MIL-101-12/PVDF,has been developed which can show dramatically improved catalytic activity under multi-phase reactions involving hydrogen gas and liquid water.Pt@MIL-101-12/PVDF demonstrates enhanced macroscopic water-blocking properties,with a notable reduction of over 65%in water adsorption capacity and newly introduced liquid water repellency.while exhibiting a negligible increase in mass transfer resistance,i.e.,bifunctional hydrophobicity.Excellent catalytic activity,evaluated via HIE reaction,and its durability underscore the impact of bifunctional hydrophobicity.In situ DRIFTS analysis elucidates water adsorption/desorption dynamics within the catalyst composite,highlighting reinforced water diffusion at the microscopic level,affirming the catalyst's bifunctionality in different length scales.With demonstrated radiation resistance,Pt@MIL-101-12/PVDF emerges as a promising candidate for isotope exchange reactions.展开更多
Covalent organic frameworks(COFs)have great potential as adsorbents due to their customizable functionality,low density and high porosity.However,COFs powder exists with poor processing and recycling performance.Moreo...Covalent organic frameworks(COFs)have great potential as adsorbents due to their customizable functionality,low density and high porosity.However,COFs powder exists with poor processing and recycling performance.Moreover,due to the accumulation of COFs nanoparticles,it is not conducive to the full utilization of their surface functional groups.Currently,the strategy of COFs assembling into aerogel can be a good solution to this problem.Herein,we successfully synthesize composite aerogels(CSR)by in-situ self-assembly of two-dimensional COFs and graphene based on crosslinking of sodium alginate.Sodium alginate in the composite improves the mechanical properties of the aerogel,and graphene provides a template for the in-situ growth of COFs.Impressively,CSR aerogels with different COFs and sizes can be prepared by changing the moiety of the ligand and modulating the addition amount of COFs.The prepared CSR aerogels exhibit porous,low density,good processability and good mechanical properties.Among them,the density of CSR-N-1.6 is only 5 mg/cm3,which is the lowest density among the reported COF aerogels so far.Due to these remarkable properties,CSR aerogels perform excellent adsorption and recycling properties for the efficient and rapid removal of organic pollutants(organic dyes and antibiotics)from polluted water.In addition,it is also possible to visually recognize the presence of antibiotics by fluorescence detection.This work not only provides a new strategy for synthesizing COF aerogels,but also accelerates the practical application of COF aerogels and contributes to environmental remediation.展开更多
文摘The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.
基金Supported by the National Key Research and Development Program of China(2023YFB4104500,2023YFB4104502)the National Natural Science Foundation of China(22138013)the Taishan Scholar Project(ts201712020).
文摘Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.
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Singapore Ministry of Education,Grant/Award Number:A-8000186-01-00National Research Foundation(NRF)Singapore,Grant/Award Numbers:CRP NRF-CRP26-2021-0003,NRFCRP24-2020-0002A*STAR SERC CRF Award。
文摘All solid-state batteries(ASSBs)are the holy grails of rechargeable batteries,where extensive searches are ongoing in the pursuit of ideal solid-state electrolytes.Nevertheless,there is still a long way off to the satisfactorily high(enough)ionic conductivity,long-term stability and especially being able to form compatible interfaces with the solid electrodes.Herein,we have explored ionic transport behavior and high mobility in the sub-nano pore networks in the framework structures.Macroscopically,the frameworked electrolyte behaves as a solid,and however in the(sub)-nano scales,the very limited number of solvent molecules in confinement makes them completely different from that in liquid electrolyte.Differentiated from a liquid-electrolyte counterpart,the interactions between the mobile ions and surrounding molecules are subject to dramatic changes,leading to a high ionic conductivity at room temperature with a low activation energy.Li+ions in the sub-nano cages of the network structure are highly mobile and diffuse rather independently,where the rate-limiting step of ions crossing cages is driven by the local concentration gradient and the electrostatic interactions between Li^(+)ions.This new class of frameworked electrolytes(FEs)with both high ionic conductivity and desirable interface with solid electrodes are demonstrated to work with Li-ion batteries,where the ASSB with LiFePO_(4)shows a highly stable electrochemical performance of over 450 cycles at 2℃ at room temperature,with an almost negligible capacity fade of 0.03‰ each cycle.In addition,the FE shows outstanding flexibility and anti-flammability,which are among the key requirements of large-scale applications.
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.
文摘High-throughput transcriptomics has evolved from bulk RNA-seq to single-cell and spatial profiling,yet its clinical translation still depends on effective integration across diverse omics and data modalities.Emerging foundation models and multimodal learning frameworks are enabling scalable and transferable representations of cellular states,while advances in interpretability and real-world data integration are bridging the gap between discovery and clinical application.This paper outlines a concise roadmap for AI-driven,transcriptome-centered multi-omics integration in precision medicine(Figure 1).
基金supported by the National Key R&D Program of China(Grant No.2023YFA1406200)the National Natural Science Foundation of China(No.12274177 and 12304261)the China Postdoctoral Science Foundation(No.2024M751076)。
文摘Luminescent metal-organic frameworks(MOFs)have garnered significant attention due to their structural tunability and potential applications in solid-state lighting,bioimaging,sensing,anticounterfeiting,and other fields.Nevertheless,due to the tendency of1,4-benzenedicarboxylic acid(BDC)to rotate within the framework,MOFs composed of it exhibit significant non-radiative energy dissipation and thus impair the emissive properties.In this study,efficient luminescence of MIL-140A nanocrystals(NCs)with BDC rotors as ligands is achieved by pressure treatment strategy.Pressure treatment effectively modulates the pore structure of the framework,enhancing the interactions between the N,N-dimethylformamide vip molecules and the BDC ligands.The enhanced host-vip interaction contributes to the structural rigidity of the MOF,thereby suppressing the rotation-induced excited-state energy loss.As a result,the pressure-treated MIL-140A NCs displayed bright blue-light emission,with the photoluminescence quantum yield increasing from an initial 6.8%to 69.2%.This study developed an effective strategy to improve the luminescence performance of rotor ligand MOFs,offers a new avenue for the rational design and synthesis of MOFs with superior luminescent properties.
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.
文摘Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).
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AgVO_(3)/ZIF-8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO_(3)and ZIF-8.X-ray diffraction(XRD),scanning electron microscopy(SEM),high-power transmission electron microscopy(HRTEM),X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectroscopy(UV-Vis DRS),photoluminescence(PL)spectroscopy,electron spin resonance(ESR)spectroscopy,transient photocurrent and electrochemical impedance spectroscopy(EIS)were used to characterize binary composites.Tetracycline(TC)was used as a substrate to study the performance efficiency of the degradation of photocatalysts under light conditions,and the degradation effect of TC was also evaluated under different mass concentrations and ionic contents.In addition,we further investigated the photocatalytic mechanism of the binary composite material AgVO_(3)/ZIF-8 and identified the key active components responsible for the catalytic degradation of this new photocatalyst.The experimental results show that the degradation efficiency of 10%-AZ,prepared with a molar ratio of 10%AgVO_(3)and ZIF-8 to TC,was 75.0%.This indicates that the photocatalytic activity can be maintained even under a certain ionic content,making it a suitable photocatalyst for optimal use.In addition,the photocatalytic mechanism of binary composites was further studied by the active species trapping experiment.
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.
基金supported by the Natural Science Research Project of the Anhui Educational Committee,China(No.2022AH050827)the Open Research Fund Program of Anhui Province Key Laboratory of Specialty Polymers,Anhui University of Science and Technology,China(No.AHKLSP23-12)the Joint National-Local Engineering Research Center for Safe and Precise Coal Mining Fund,China(No.EC2022020)。
文摘The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.
基金Project supported by the National Natural Science Foundation of China(22206080)the Natural Science Foundation of Jiangsu(SBK2022041070)+1 种基金the Science and Technology Project of Henan Province(232102321050,232102321035)the International Science,Innovators,Technology Cooperation Projects of Henan Province(232102521009)。
文摘Metal-organic frameworks(MOFs)and their derivatives have gained significant attention in recent years for their ability to catalyze the advanced oxidation of persulfates.Cerium-doped MOFs,in particular,have shown promise due to their high catalytic efficiency,practical applicability,and cost-effectiveness.However,their structure,catalytic properties,and mechanisms are not yet fully understood.ZIF-8 was chosen as the raw material to prepare cerium-doped hollow carbon nano fibers(Ce-HCNFs)using the electrostatic spinning-calcination method.The objective is to investigate the structure,catalytic performance,and catalytic mechanism of Ce-HCNFs.The results show that Ce-HCNFs catalyzed the degradation of tetracycline(TC)by persulfate up to 76.9%,Quenching experiments and electron paramagnetic resonance experiments indicate the dominant role of single-linear oxygen.Furthermore,the experiments on the influence factor and cycling demonstrate the exceptional stability and recycling capability of Ce-HCNFs in real-world water environments.
基金supported by the National Natural Science Foundation of China(Nos.52373280,52177014 and 52273257).
文摘Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to its unique composition and bonding mode,which has advantages such as large specific surface area,high porosity,adjustable structure,and designable composition.Herein,MOF-derived MAMs are highlighted based on morphology and structure.The synthesis strategies of MOF-derived MAMs of different dimensions are discussed.On this basis,the structure-activity relationships can be deeply explored through the precise control of material structure and property by atomic engineering.Finally,perspectives are given for the existing problems of MOF-derived MAMs,which will open a new horizon and promote the development of MAMs.
基金supported by the National Natural Science Foundation of China(Nos.22375031,22202037,22472023)the Fundamental Research Funds for the Central Universities(Nos.2412023YQ001,2412023QD019,2412024QD014)+1 种基金supported by grants from the seventh batch of Jilin Province Youth Science and Technology Talent Lifting Project(No.QT202305)Science and Technology Development Plan Project of Jilin Province,China(No.20240101192JC)。
文摘The light-driven CO_(2)reduction reaction(CO_(2)RR)to CO is a very effective way to address global warming.To avoid competition with water photolysis,metal-free gas-solid CO_(2)RR catalysts should be investigated.Covalent organic frameworks(COFs)offer a promising approach for CO_(2)transformation but lack high efficiency and selectivity in the absence of metals.Here,we have incorporated a pyridine nitrogen component into the imine-COF conjugated structure(Tp Pym).This innovative system has set a record of producing a CO yield of 1565μmol g^(-1)within 6 h.The soft X-ray absorption fine structure measurement proves that Tp Pym has both better conjugation and electron cloud enrichment.The electronic structure distribution delays the charge-carrier recombination,as evidenced by femtosecond transient absorption spectroscopy.The energy band diagram and theoretical calculation show that the conduction-band potential of Tp Pym is lower and the reduction reaction of CO_(2)to CO is more likely to occur.
基金supported by grants from the National Research Foundation of Korea(NRF)under grant No.RS-2022-00155422 and No.2021R1C1C102014。
文摘Water often presents significant challenges in catalysts by deactivating active sites,poisoning the reaction,and even degrading composite structure.These challenges are amplified when the water participates as a reactant and is fed as a liquid phase,such as trickle bed-type reactors in a hydrogen-water isotope exchange(HIE)reaction.The key balance in such multiphase reactions is the precise control of catalyst design to repel bulk liquid water while diffusing water vapor.Herein,a platinum-incorporated metal-organic framework(MIL-101)based bifunctional hydrophobic catalyst functionalized with long alkyl chains(C_(12),dodecylamine)and further manufactured with poly(vinylidene fluoride),Pt@MIL-101-12/PVDF,has been developed which can show dramatically improved catalytic activity under multi-phase reactions involving hydrogen gas and liquid water.Pt@MIL-101-12/PVDF demonstrates enhanced macroscopic water-blocking properties,with a notable reduction of over 65%in water adsorption capacity and newly introduced liquid water repellency.while exhibiting a negligible increase in mass transfer resistance,i.e.,bifunctional hydrophobicity.Excellent catalytic activity,evaluated via HIE reaction,and its durability underscore the impact of bifunctional hydrophobicity.In situ DRIFTS analysis elucidates water adsorption/desorption dynamics within the catalyst composite,highlighting reinforced water diffusion at the microscopic level,affirming the catalyst's bifunctionality in different length scales.With demonstrated radiation resistance,Pt@MIL-101-12/PVDF emerges as a promising candidate for isotope exchange reactions.
基金the financial support provided by the National Natural Science Foundation of China(Nos.22175094,21971113)。
文摘Covalent organic frameworks(COFs)have great potential as adsorbents due to their customizable functionality,low density and high porosity.However,COFs powder exists with poor processing and recycling performance.Moreover,due to the accumulation of COFs nanoparticles,it is not conducive to the full utilization of their surface functional groups.Currently,the strategy of COFs assembling into aerogel can be a good solution to this problem.Herein,we successfully synthesize composite aerogels(CSR)by in-situ self-assembly of two-dimensional COFs and graphene based on crosslinking of sodium alginate.Sodium alginate in the composite improves the mechanical properties of the aerogel,and graphene provides a template for the in-situ growth of COFs.Impressively,CSR aerogels with different COFs and sizes can be prepared by changing the moiety of the ligand and modulating the addition amount of COFs.The prepared CSR aerogels exhibit porous,low density,good processability and good mechanical properties.Among them,the density of CSR-N-1.6 is only 5 mg/cm3,which is the lowest density among the reported COF aerogels so far.Due to these remarkable properties,CSR aerogels perform excellent adsorption and recycling properties for the efficient and rapid removal of organic pollutants(organic dyes and antibiotics)from polluted water.In addition,it is also possible to visually recognize the presence of antibiotics by fluorescence detection.This work not only provides a new strategy for synthesizing COF aerogels,but also accelerates the practical application of COF aerogels and contributes to environmental remediation.
