Analyzes the three-phases——pre-task, task cycle, post-task and their rationale in task-based language teaching, designs corresponding teaching activities after adapting one text from New Horizon College English, so ...Analyzes the three-phases——pre-task, task cycle, post-task and their rationale in task-based language teaching, designs corresponding teaching activities after adapting one text from New Horizon College English, so that college English teachers can better understand and use this teaching approach, and then improve the teaching effect and college students’ comprehensive application abilities of language.展开更多
Since its proposal in the 1980s,Task-Based Language Teaching(TBLT)has become a pivotal direction for global foreign language teaching reform due to its philosophy of emphasizing“learning by doing”and focusing on lin...Since its proposal in the 1980s,Task-Based Language Teaching(TBLT)has become a pivotal direction for global foreign language teaching reform due to its philosophy of emphasizing“learning by doing”and focusing on linguistic meaning and communicative functions.China’s basic education English curriculum reform has also incorporated TBLT into curriculum standards and advocated its implementation in classrooms.However,after more than two decades of localized practice,TBLT has encountered numerous dilemmas in Chinese classrooms:the coexistence of theoretical advocacy and practical deviation,as well as formal imitation and substantive alienation.This paper systematically sorts out the theoretical core of TBLT,deeply analyzes the practical constraints it faces in China such as large class sizes,examination pressure,and teachers’professional competence,summarizes the specific manifestations of the dilemmas,combs through domestic scholars’attempts at localized improvement,and explores the possible paths for the integration of TBLT with China’s examination system.展开更多
Silicon possesses a high theoretical capacity,making it a potential contender for lithium-ion battery(LIB)anodes.Nonetheless,its practical usage is challenged by low electrical conductivity and significant volume expa...Silicon possesses a high theoretical capacity,making it a potential contender for lithium-ion battery(LIB)anodes.Nonetheless,its practical usage is challenged by low electrical conductivity and significant volume expansion during cycling.Here,we synthesized a novel silicon/carbon(Si/C)anode doped with ZnO via a template-derived method and high-temperature carbonization.The carbon structure,originated from metal-organic frameworks(MOFs)and ZnO doping,substantially enhanced the electrochemical properties of the composite material.It exhibited an initial capacity of 2100.3 mA h g-1at a current density of 0.2 A g-1and demonstrated excellent capacity retention over successive cycles.Moreover,the composite material displayed superior rate performance at higher current densities of 2 A g-1and 3 A g-1.To address the low initial Coulombic efficiency(ICE)of siliconbased materials,we adopted a direct contact prelithiation approach and optimized the lithiation process by controlling the prelithiation time.After 30 min of prelithiation,the ICE reached 97.9%,thereby reducing the initial irreversible capacity loss(ICL)and realizing stable discharge-charge in subsequent cycles.This rational design provides valuable insights for achieving high-performance silicon anode.展开更多
The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative p...The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.展开更多
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability...Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.展开更多
Alleviating the imbalance between urban and rural areas for regional coordinated development is an imperative response to the Sustainable Development Goal 10 of the United Nations.To track China’s urban-rural integra...Alleviating the imbalance between urban and rural areas for regional coordinated development is an imperative response to the Sustainable Development Goal 10 of the United Nations.To track China’s urban-rural integration progress and address the uneven issues in specific fields,this study constructed a novel seven-dimension index system of urban-rural integration,comprising free population mobility,efficient land transfer,interactive economic growth,highly-linked transportation,equal public services,joint environmental governance and unimpeded informatization between urban and rural areas.Based on a comprehensive measurement framework and multi-source panel data,we uncovered the spatial-temporal evolution of urban-rural integration in China’s 367 prefecture-level administrative units from 1980 to 2022.The results demonstrated that China’s urban-rural integration steadily increased from 27.51 to 57.35 with an average annual growth rate of 3.40%.Whereas,the overall urban-rural integration was relatively inferior in 2022,at the level of moderate integration whose proportion of China’s land area was 88.08%.The urban-rural integration level in eastern region and urban agglomerations was higher than that in mid-west and non-urban agglomerations.From the perspective of seven dimensions,interactive economic growth,joint environmental governance and unimpeded informatization made an obvious improvement and reached higher integration,while free population mobility,efficient land transfer,highly-linked transportation and equal public services maintained the stage of moderate integration in 2022.In the future,China should make targeted efforts for urban-rural integration in terms of population,land use,transportation and public services,and accelerate urban-rural common prosperity in the mid-west and economically underdeveloped areas.展开更多
The pursuit of heat-resistant energetic materials(HREMs)with thermal stability beyond 450℃ presents a significant challenge that has yet to be achieved.In this work,we develop an innovative electronic delocalization ...The pursuit of heat-resistant energetic materials(HREMs)with thermal stability beyond 450℃ presents a significant challenge that has yet to be achieved.In this work,we develop an innovative electronic delocalization strategy to design and synthesize a planar dizwitterionic diamino-bistriazolotetrazine,designated as TYX-1.The unique structural feature of TYX-1,including a nitrogen-rich fused ring system,planar conformation,and dizwitterionic configuration,combined with its hydrogen-bonded organic framework(HOF)structure,confer exceptional thermal stability(The onset temperature is 428℃,and the peak temperature is 473℃),high density(1.84 g/cm3),and remarkable detonation performance(detonation velocity:8616 m/s).Furthermore,TYX-1 exhibits an impressive insensitivity(impact sensitivity>40 J;friction sensitivity>360 N),surpassing all previously reported HREMs.Theoretical calculations and single-crystal clearly indicate that the delocalizedπelectrons within the dizwitterionic bistriazolotetrazine rings and the HOF structure of TYX-1 are pivotal in ensuring its high thermal stability and high energy density.The discovery of TYX-1 marks a significant advancement in the field of HREMs and is anticipated to catalyze substantial progress in various high-temperature applications reliant on energetic materials.展开更多
Photocatalytic carbon dioxide reduction reaction(CO2RR)is a carbon-neutral strategy to address global energy use and its impact on climate.Metal oxide and metal chalcogenide catalysts are the most investigated cata...Photocatalytic carbon dioxide reduction reaction(CO2RR)is a carbon-neutral strategy to address global energy use and its impact on climate.Metal oxide and metal chalcogenide catalysts are the most investigated catalysts for photocatalytic CO2RR.Unfortunately,low CO2adsorption ability and limited active sites of metal oxide and metal chalcogenide catalysts for CO2RR make them less competitive compared to their industrial counterparts.Inspired by applications of porphyrin-based metal-organic framework(MOF)catalysts for hydrogen evolution and photodynamic therapy,the investigations of these porphyrin-based MOFs,including pristine and composite porphyrin-based MOFs in photocatalytic CO2RR,have attracted significant attention in the last five years due to their excellent CO2adsorption capacities,high porosity,high stability,exceptional optoelectronic properties,and multi-functionality.However,due to the difference in photocatalytic CO2RR,several critical issues need to be addressed to achieve the rational design of advanced porphyrin-based MOF photocatalysts to improve activity,selectivity,and stability for CO2RR.Here,we review recent developments in the field of porphyrin-based MOF CO2RR photocatalysts,along with critical issues,challenges,and perspectives concerning porphyrin-based MOF catalysts for photocatalytic CO2RR.展开更多
Conventional hard carbon anodes,despite their high sodium storage capacity,suffer from two major limitations:sluggish ion diffusion kinetics due to tortuous micropore networks and significant volume expansion arising ...Conventional hard carbon anodes,despite their high sodium storage capacity,suffer from two major limitations:sluggish ion diffusion kinetics due to tortuous micropore networks and significant volume expansion arising from disordered carbon structures.These inherent defects collectively compromise rate capability and cycling stability.Herein,we devise a graphene oxide(GO)-directed templating approach to architect zeolitic imidazolate framework(ZIF)-derived carbon into a hierarchical nanoflower superstructure with radially aligned meso/macroporous nanosheets.This superstructure integrates three synergistic features:three-dimensional interconnected channels and graphitic domains enabling fast ion/electron transport,radially aligned nanosheets maximizing electrode-electrolyte contact while accommodating volume expansion,and nitrogen-doped defect sites providing preferential redox-active centers for sodium storage.The optimized ZIF-9@GO-6 achieves a high specific capacity of 521.8 mAh·g-1at 0.05 A·g-1with an initial Coulombic efficiency of 89.2%,and retains a specific capacity of 298.2 mAh·g-1after 500 cycles.This GO-directed morphological engineering strategy effectively resolves the intrinsic trade-offs between porosity,conductivity,and structural stability in conventional hard carbon anodes,paving the way for scalable,high-performance sodium-ion batteries.展开更多
The typical organic perylenetetracarboxylate(PTC)luminophore suffers from limited bio-application due to its aggregation-caused quenching(ACQ)induced undesirable electrochemiluminescence(ECL)efficiency in aqueous solu...The typical organic perylenetetracarboxylate(PTC)luminophore suffers from limited bio-application due to its aggregation-caused quenching(ACQ)induced undesirable electrochemiluminescence(ECL)efficiency in aqueous solution.Herein,the ECL emission of PTC was highly improved through the ingenious coordination of PTC(ligand)with Tb3+(metal ion)to prepare the Tb-PTC metal-organic framework(TbPTC MOF),which prevented theπ-πstacking and the aggregation of PTC molecules in a homogeneous phase.Moreover,we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology,pore size and electron transfer ability using different solvents during its synthesis procedure.Notably,under the mixture of DMF,Et OH,and H2O(v/v/v,1:1:1),a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity,which may be attributed to two reasons.Firstly,the mesopore and rough surface of Tb-PTC MOF(luminophore)provided abundant active sites and enlarged contact surfaces for S2O82–(coreactant).Secondly,Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission.Additionally,Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponinⅠ(cTnⅠ)detection,related to acute myocardial infarction.The constructed ECL immunosensor exhibited a satisfactory linear range(1 fg/m L-20 ng/mL)and a low detection limit of 0.48 fg/m L.This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance,broadening the scope for sensitive immunoassay in disease diagnosis.展开更多
In this study,a multifunctional aptamer-conjugated magnetic covalent organic framework(COF)-CuO/Au nanozyme(MCOF-CuO/Au@apt)was developed as a“three-in-one”platform for dual-signal colorimetric and fluorescent detec...In this study,a multifunctional aptamer-conjugated magnetic covalent organic framework(COF)-CuO/Au nanozyme(MCOF-CuO/Au@apt)was developed as a“three-in-one”platform for dual-signal colorimetric and fluorescent detection of Vibrio parahaemolyticus.The nanozyme integrated magnetic separation,peroxidase-like catalytic activity,and specific target recognition through an aptamer-based strategy.Upon binding to V.parahaemolyticus,the catalytic oxidation of tetra-aminophenylethylene(TPE-4A)by the nanozyme was selectively inhibited,resulting in distinct colorimetric and fluorescent signals that significantly enhanced the detection accuracy and reliability.The proposed method exhibited high sensitivity,with limits of detection(LOD)of 21 and 7 CFU/mL for the colorimetric and fluorescent assays,respectively.The performance of this method was validated using real seafood samples,including Penaeus vannamei,Mytilus coruscus,and Crassostrea gigas,which showed high recovery rates(101.11%-107.30%)and excellent reproducibility.The system also demonstrated strong specificity and accuracy under various conditions,confirming its robustness and practical applicability.Collectively,this innovative platform presents a promising solution for the rapid,versatile,and sensitive detection of V.parahaemolyticus in seafood,with considerable potential to advance food safety diagnosis and on-site monitoring.展开更多
Sedimentary facies modeling is a critical approach for understanding geological phenomena,yet the strong heterogeneity of reservoir systems poses a serious challenge for their refined characterization.In this study,we...Sedimentary facies modeling is a critical approach for understanding geological phenomena,yet the strong heterogeneity of reservoir systems poses a serious challenge for their refined characterization.In this study,we innovatively propose an interpretable attention-guided generative adversarial network framework with dual-domain learning,which achieves precise sedimentary facies modeling under the constraints of well facies and soft probability data.Specifically,we first effectively extract and preserve prior information of sedimentary facies models from both spatial and frequency domain perspectives.Then,during simulation,to enhance the capability of the network model for finely characterizing complex heterogeneous models,cross-spatial attention mechanisms are designed to effectively capture short-range and long-range dependencies between multi-scale pattern features.Additionally,through systematic feature map visualization analysis,we elucidate the processes of conditional fitting and complex sedimentary facies model reconstruction,intuitively demonstrating the functional mechanisms of each module.Finally,systematic experiments are conducted on multiple datasets to validate the effectiveness of the proposed method.The results demonstrate that the generated sedimentary facies models exhibit high consistency with training datasets in terms of visual realism and statistical indicators.Quantitative comparisons reveal remarkable performance of the method,achieving low Wasserstein distance(0.09),Kernel Inception Distance(0.0017)and Kernel Maximum Mean Discrepancy(0.21).These findings further confirm the high realism of the generated realizations regarding pattern features.This study offers a reliable and practical method for geological reservoir modeling,thereby advancing quantitative,precise geological research with broad application prospects.展开更多
Ion conduction in covalent-organic framework(COF)membranes is vital for energy conversion and storage.Conventional phenomenological methods based on the Arrhenius equation offer micrometer-scale cognition of ion condu...Ion conduction in covalent-organic framework(COF)membranes is vital for energy conversion and storage.Conventional phenomenological methods based on the Arrhenius equation offer micrometer-scale cognition of ion conduction,whereas they ignore atomic details of ion-pore interactions and sophisticated conduction mechanisms,leaving gaps in high-resolution and bottom-up understanding of ion conduction in a nanoconfined space.In this study,we develop a hierarchical approach by holistically synergizing electronic structure calculations,first-principles molecular dynamics simulations,and thermodynamic integration methods to investigate the conduction of chloride(Cl-)and hydroxide(OH-)ions in a COF membrane.It is revealed that Cl-ion with symmetric charge distribution undergoes weak solvation and tight ion-pore binding,which results in a tortuous conduction pathway,a high energy barrier,and slow diffusion based on the vehicular mechanism.In remarkable contrast,OH-ion with heterogeneous charge distribution features strong solvation and weak ion-pore binding,and it jumps frequently via a smooth pathway and a low energy barrier.Moreover,OH-ion conduction follows a mixed vehicular and Grotthuss mechanism,causing highly mutable ion identity and number,as well as superior dynamics due to proton transfer.This hierarchical approach provides sub-nanometer resolution insights into ion conduction,guiding intelligent membrane design and performance regulation to control ion conduction for emerging applications.展开更多
Advancements in nanostructures and nanomaterials have significantly impacted both academic research and industry.Notable nanomaterials include carbon materials,polymeric nanoparticles,dendrimers,metal and metal oxide ...Advancements in nanostructures and nanomaterials have significantly impacted both academic research and industry.Notable nanomaterials include carbon materials,polymeric nanoparticles,dendrimers,metal and metal oxide nanoparticles,liposomes,zeolites,Metal-Organic Frameworks(MOFs),MXenes,molecular cages,and covalent organic frameworks(COFs).Their unique structures and properties make them suitable for diverse applications.Nano-structuration,which generates various nano-architectures with unique characteristics,influences the physical,chemical,and electrical properties of nanomaterials.This process is essential for achieving desired properties and maximizing application potential.Carbon materials,MOFs,and other nanomaterials have been classified based on their architectural dimensionality and the effects of nano-structuration on their applications.However,comprehensive studies on the synthesis and fabrication of COF nanostructures with desired architectures and dimensionalities are lacking.This review discusses the library of available nanostructures based on dimensionality,factors influencing nano-structuration,and the potential applications of nanomaterials like carbon materials,MOFs,and organic cage molecules.Additionally,it attempts to classify COFs based on architectural variation,specific synthetic strategies,and other factors influencing nano-structuration and applications.The aim is to develop novel synthetic methods for COF architectures across all dimensions,utilizing their morphological diversity for targeted applications based on their structure-property relationship,and to explore new methodologies for interconverting COF architectures through covalent and supramolecular self-assembly.展开更多
The evolution of cities into digitally managed environments requires computational systems that can operate in real time while supporting predictive and adaptive infrastructure management.Earlier approaches have often...The evolution of cities into digitally managed environments requires computational systems that can operate in real time while supporting predictive and adaptive infrastructure management.Earlier approaches have often advanced one dimension—such as Internet of Things(IoT)-based data acquisition,Artificial Intelligence(AI)-driven analytics,or digital twin visualization—without fully integrating these strands into a single operational loop.As a result,many existing solutions encounter bottlenecks in responsiveness,interoperability,and scalability,while also leaving concerns about data privacy unresolved.This research introduces a hybrid AI–IoT–Digital Twin framework that combines continuous sensing,distributed intelligence,and simulation-based decision support.The design incorporates multi-source sensor data,lightweight edge inference through Convolutional Neural Networks(CNN)and Long ShortTerm Memory(LSTM)models,and federated learning enhanced with secure aggregation and differential privacy to maintain confidentiality.A digital twin layer extends these capabilities by simulating city assets such as traffic flows and water networks,generating what-if scenarios,and issuing actionable control signals.Complementary modules,including model compression and synchronization protocols,are embedded to ensure reliability in bandwidth-constrained and heterogeneous urban environments.The framework is validated in two urban domains:traffic management,where it adapts signal cycles based on real-time congestion patterns,and pipeline monitoring,where it anticipates leaks through pressure and vibration data.Experimental results show a 28%reduction in response time,a 35%decrease in maintenance costs,and a marked reduction in false positives relative to conventional baselines.The architecture also demonstrates stability across 50+edge devices under federated training and resilience to uneven node participation.The proposed system provides a scalable and privacy-aware foundation for predictive urban infrastructure management.By closing the loop between sensing,learning,and control,it reduces operator dependence,enhances resource efficiency,and supports transparent governance models for emerging smart cities.展开更多
Covalent organic frameworks(COFs)have garnered significant attention in photocatalysis owing to their exceptional light absorption capacities,tunable band structures,and high specific surface areas.However,the rapid r...Covalent organic frameworks(COFs)have garnered significant attention in photocatalysis owing to their exceptional light absorption capacities,tunable band structures,and high specific surface areas.However,the rapid recombination of photogenerated carriers in COFs remains a critical bottleneck limiting their practical application.In this study,a novel S-scheme heterojunction was constructed by integrating a Ni-doped zeolitic imidazolate framework-8(Ni-ZIF-8)with Py-COF,effectively addressing this challenge.Through precisely controlled synthesis,the heterojunction achieves efficient and stable material combination,which not only significantly enhances photogenerated charge separation efficiency and markedly reduces recombination rates,but also demonstrates outstanding catalytic performance(162.77 mmol·h-1·g-1)and cycling stability in hydrogen evolution reaction.This study provides new insights into the design of efficient ZIF/COF-based heterojunction catalysts.This study provides an important theoretical foundation for the design of high-performance photocatalytic materials with broad application prospects.展开更多
High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carb...High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody(Ab1)and ferrocene(Fc),and used for electrochemical detection of AFP.Due to the small,homogeneous pore size of the COF,Ab1 with a big size was immobilized on the surface of the COF,while Fc with a small size was covalently modified both on the surface and in the pores of COF.The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers.Meanwhile,the enriched Fc molecules not only improved the conductivity of the COF,but also effectively transferred and amplified the electrochemical signal.This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL(S/N of 3:1)and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations.Furthermore,this immunosensor showed excellent selectivity,stability and reproducibility in the testing of real samples.This study presents an innovative prototype for construction of a precious metal-free,antibody-directly-immobilized,simple and stable electrochemical immunoprobe.展开更多
Vinylene-linked covalent organic frameworks(COFs)are renowned for their excellent organic semiconducting properties,attributed to their in-planeπ-conjugated and robust structures.However,their synthesis remains chall...Vinylene-linked covalent organic frameworks(COFs)are renowned for their excellent organic semiconducting properties,attributed to their in-planeπ-conjugated and robust structures.However,their synthesis remains challenging due to the complexity of reaction pathways and the limited availability of building units containing reactive methyl groups,which hinders their practical application.Herein,two vinylene-linked benzotristhiazole-based 2D COFs with high crystallinity were constructed via Aldol condensation reaction.Notably,the incorporation of fluorine atoms into the COF framework significantly enhanced its photocatalytic activity.Specifically,the fluorinated COF(BTZ-F)exhibited substantially improved performance in the selective oxidation of organic sulfides compared to its non-fluorinated counterpart(BTZ-H).A synergistic combination of experimental characterization and theoretical calculations revealed that fluorination significantly modulates the electronic structure of the framework,thereby promoting efficient charge separation and transfer.Further mechanistic investigations revealed that both electron-transfer and energy-transfer pathways are involved in the oxidation of phenyl methyl sulfide,providing deeper insights into the enhanced photocatalytic efficiency of the fluorinated framework.展开更多
The conversion of nitric oxide(NO),a gaseous pollutant with an intermediate nitrogen oxidation state,into value-added ammonium nitrate(NH4NO3)via redox processes offers a sustainable alternative to conventional ...The conversion of nitric oxide(NO),a gaseous pollutant with an intermediate nitrogen oxidation state,into value-added ammonium nitrate(NH4NO3)via redox processes offers a sustainable alternative to conventional disposal methods,which are hampered by competing pathways that yield undesirable byproducts.Herein,we decouple the synthesis of NH4NO3into electrochemical NO oxidation(NOOR)and reduction(NORR)by employing H-terminated and Cu-metallated porphyrinic metal-organic framework catalysts(H-PMOF and Cu-PMOF,respectively),leveraging their tailored coordination environments and varied NO adsorption configurations.The H-PMOF favors O-atom adsorption via hydrogen bonding,whereas the Cu-PMOF strengthens N-atom adsorption through Cu-N interactions.They promote NOOR tand NORR to N,respectively,achieving greater Faradaic efficiencies and yield rates compared to their respective counterparts.When integrated in one electrolyzer,they enable direct synthesis of NH4NO3by generating 662.4μmol of Nand 409.5μmol of NH4+hourly.Molecular dynamics simulations reveal differences in adsorption modes,while computational results identify the ratedetermining dehydrogenation(*HNO3→*NO3for NOOR)and hydrogenation steps(*NO→~*NHO for NORR),with both catalysts exhibiting reduced energy barriers.This work presents a strategy for directing NO redox reactions through coordination engineering,paving the way for sustainable nitrogen valorization.展开更多
The photogenerated carrier separation efficiency and material wettability are of critical importance for aqueous-phase photocatalytic reactions,achieving both simultaneously poses a significant challenge owing to the ...The photogenerated carrier separation efficiency and material wettability are of critical importance for aqueous-phase photocatalytic reactions,achieving both simultaneously poses a significant challenge owing to the inherent interdependencies and trade-offs involved.In this work,a series of isoreticular benzotrithiophene-based covalent organic frameworks(COFs)were successfully synthesized by incorporating diverse hydrophobic and hydrophilic functional groups(-OH,-F,-H)onto their skeletons,thereby modulating their characteristic charge separation and transport as well as their wettability,and systematically studied their photocatalytic H2O2 production performance in O2-saturated water under visible-light irradiation.Remarkably,the synthesized hydrophilic BTT-BD-OH-COF demonstrates the highest H2O2 production rate of 6105μmol g-1 h-1 in the absence of any sacrificial agent in pure water,attributed to its extended light absorption range,improved hydrophilicity,and enhanced photo-induced charge separation and transport efficiency.Combined experimental results and the density functional theory calculations elucidate the reaction mechanism,revealing the overall H2O2 photosynthesis via both oxygen reduction reaction and water oxidation reaction dual pathways.This study demonstrates that functional-group-mediated linker engineering is a powerful approach for significantly enhancing the efficiency of COF-based photocatalysts.展开更多
摘要Analyzes the three-phases——pre-task, task cycle, post-task and their rationale in task-based language teaching, designs corresponding teaching activities after adapting one text from New Horizon College English, so that college English teachers can better understand and use this teaching approach, and then improve the teaching effect and college students’ comprehensive application abilities of language.
摘要Since its proposal in the 1980s,Task-Based Language Teaching(TBLT)has become a pivotal direction for global foreign language teaching reform due to its philosophy of emphasizing“learning by doing”and focusing on linguistic meaning and communicative functions.China’s basic education English curriculum reform has also incorporated TBLT into curriculum standards and advocated its implementation in classrooms.However,after more than two decades of localized practice,TBLT has encountered numerous dilemmas in Chinese classrooms:the coexistence of theoretical advocacy and practical deviation,as well as formal imitation and substantive alienation.This paper systematically sorts out the theoretical core of TBLT,deeply analyzes the practical constraints it faces in China such as large class sizes,examination pressure,and teachers’professional competence,summarizes the specific manifestations of the dilemmas,combs through domestic scholars’attempts at localized improvement,and explores the possible paths for the integration of TBLT with China’s examination system.
基金supported by the National Key R&D Program of China(No.2022YFA1504100)the Anhui Provincial Major Science and Technology Project(No.202203a05020017)+4 种基金the National Natural Science Foundation of China(Nos.52222210,51925207,U1910210,52161145101,51972067,51902062,and 52002083)the“Transformational Technologies for Clean Energy and Demonstration”Strategic Priority Research Program of Chinese Academy of Sciences(No.XDA21000000)the National Synchrotron Radiation Laboratory(No.KY2060000173)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(No.YLU-DNL Fund 2021002)the Fundamental Research Funds for the Central Universities(No.WK2060140026)。
摘要Silicon possesses a high theoretical capacity,making it a potential contender for lithium-ion battery(LIB)anodes.Nonetheless,its practical usage is challenged by low electrical conductivity and significant volume expansion during cycling.Here,we synthesized a novel silicon/carbon(Si/C)anode doped with ZnO via a template-derived method and high-temperature carbonization.The carbon structure,originated from metal-organic frameworks(MOFs)and ZnO doping,substantially enhanced the electrochemical properties of the composite material.It exhibited an initial capacity of 2100.3 mA h g-1at a current density of 0.2 A g-1and demonstrated excellent capacity retention over successive cycles.Moreover,the composite material displayed superior rate performance at higher current densities of 2 A g-1and 3 A g-1.To address the low initial Coulombic efficiency(ICE)of siliconbased materials,we adopted a direct contact prelithiation approach and optimized the lithiation process by controlling the prelithiation time.After 30 min of prelithiation,the ICE reached 97.9%,thereby reducing the initial irreversible capacity loss(ICL)and realizing stable discharge-charge in subsequent cycles.This rational design provides valuable insights for achieving high-performance silicon anode.
基金supported by the National Natural Science Foundation of China(No.52304329)the Yunnan Fundamental Research Projects(No.202201BE070001-003),Guo Lin would like to acknowledge Xing Dian talent support program of Yunnan Province.
摘要The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.
基金The National Natural Science Foundation of China (NSFC,Nos.92256201,52273006,22071041,92356302,and 21971052)Natural Science Foundation of Jilin Province (No.20240101181JC) are gratefully appreciated for financial the supportssupported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
摘要Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.
基金supported by the Innovative Research Group Project of the National Natural Science Foundation of China(Grant No.42121001).
摘要Alleviating the imbalance between urban and rural areas for regional coordinated development is an imperative response to the Sustainable Development Goal 10 of the United Nations.To track China’s urban-rural integration progress and address the uneven issues in specific fields,this study constructed a novel seven-dimension index system of urban-rural integration,comprising free population mobility,efficient land transfer,interactive economic growth,highly-linked transportation,equal public services,joint environmental governance and unimpeded informatization between urban and rural areas.Based on a comprehensive measurement framework and multi-source panel data,we uncovered the spatial-temporal evolution of urban-rural integration in China’s 367 prefecture-level administrative units from 1980 to 2022.The results demonstrated that China’s urban-rural integration steadily increased from 27.51 to 57.35 with an average annual growth rate of 3.40%.Whereas,the overall urban-rural integration was relatively inferior in 2022,at the level of moderate integration whose proportion of China’s land area was 88.08%.The urban-rural integration level in eastern region and urban agglomerations was higher than that in mid-west and non-urban agglomerations.From the perspective of seven dimensions,interactive economic growth,joint environmental governance and unimpeded informatization made an obvious improvement and reached higher integration,while free population mobility,efficient land transfer,highly-linked transportation and equal public services maintained the stage of moderate integration in 2022.In the future,China should make targeted efforts for urban-rural integration in terms of population,land use,transportation and public services,and accelerate urban-rural common prosperity in the mid-west and economically underdeveloped areas.
基金supported by the National Natural Science Foundation of China(Grant Nos.22105156,22175139,22505195,22171136,22405207 and 22302156)the China National Science Fund for Distinguished Young Scholars(Grant No.22325504)。
摘要The pursuit of heat-resistant energetic materials(HREMs)with thermal stability beyond 450℃ presents a significant challenge that has yet to be achieved.In this work,we develop an innovative electronic delocalization strategy to design and synthesize a planar dizwitterionic diamino-bistriazolotetrazine,designated as TYX-1.The unique structural feature of TYX-1,including a nitrogen-rich fused ring system,planar conformation,and dizwitterionic configuration,combined with its hydrogen-bonded organic framework(HOF)structure,confer exceptional thermal stability(The onset temperature is 428℃,and the peak temperature is 473℃),high density(1.84 g/cm3),and remarkable detonation performance(detonation velocity:8616 m/s).Furthermore,TYX-1 exhibits an impressive insensitivity(impact sensitivity>40 J;friction sensitivity>360 N),surpassing all previously reported HREMs.Theoretical calculations and single-crystal clearly indicate that the delocalizedπelectrons within the dizwitterionic bistriazolotetrazine rings and the HOF structure of TYX-1 are pivotal in ensuring its high thermal stability and high energy density.The discovery of TYX-1 marks a significant advancement in the field of HREMs and is anticipated to catalyze substantial progress in various high-temperature applications reliant on energetic materials.
基金financially supported by the National Natural Science Foundation of China(No.22305009)the Science and Technology Development Fund,Macao SAR(File no.FDCT-0125/2022/A and FDCT-0006/2023/RIB1)Hong Kong Research Grant Council(RGC)General Research Fund(GRF)City U 11305419,11306920,CityU 11308721,CityU 11316522,and SIRG7020022。
摘要Photocatalytic carbon dioxide reduction reaction(CO2RR)is a carbon-neutral strategy to address global energy use and its impact on climate.Metal oxide and metal chalcogenide catalysts are the most investigated catalysts for photocatalytic CO2RR.Unfortunately,low CO2adsorption ability and limited active sites of metal oxide and metal chalcogenide catalysts for CO2RR make them less competitive compared to their industrial counterparts.Inspired by applications of porphyrin-based metal-organic framework(MOF)catalysts for hydrogen evolution and photodynamic therapy,the investigations of these porphyrin-based MOFs,including pristine and composite porphyrin-based MOFs in photocatalytic CO2RR,have attracted significant attention in the last five years due to their excellent CO2adsorption capacities,high porosity,high stability,exceptional optoelectronic properties,and multi-functionality.However,due to the difference in photocatalytic CO2RR,several critical issues need to be addressed to achieve the rational design of advanced porphyrin-based MOF photocatalysts to improve activity,selectivity,and stability for CO2RR.Here,we review recent developments in the field of porphyrin-based MOF CO2RR photocatalysts,along with critical issues,challenges,and perspectives concerning porphyrin-based MOF catalysts for photocatalytic CO2RR.
基金supported by the National Natural Science Foundation of China(No.22478236)the Fundamental Research Program of Shanxi Province,China(No.202403021221146)。
摘要Conventional hard carbon anodes,despite their high sodium storage capacity,suffer from two major limitations:sluggish ion diffusion kinetics due to tortuous micropore networks and significant volume expansion arising from disordered carbon structures.These inherent defects collectively compromise rate capability and cycling stability.Herein,we devise a graphene oxide(GO)-directed templating approach to architect zeolitic imidazolate framework(ZIF)-derived carbon into a hierarchical nanoflower superstructure with radially aligned meso/macroporous nanosheets.This superstructure integrates three synergistic features:three-dimensional interconnected channels and graphitic domains enabling fast ion/electron transport,radially aligned nanosheets maximizing electrode-electrolyte contact while accommodating volume expansion,and nitrogen-doped defect sites providing preferential redox-active centers for sodium storage.The optimized ZIF-9@GO-6 achieves a high specific capacity of 521.8 mAh·g-1at 0.05 A·g-1with an initial Coulombic efficiency of 89.2%,and retains a specific capacity of 298.2 mAh·g-1after 500 cycles.This GO-directed morphological engineering strategy effectively resolves the intrinsic trade-offs between porosity,conductivity,and structural stability in conventional hard carbon anodes,paving the way for scalable,high-performance sodium-ion batteries.
基金financially supported by National Natural Science Foundation of China(Nos.22077105,22374122,22204129,22176153 and 22174113)the Natural Science Foundation of Chongqing(No.CSTB2022NSCQ-MSX0613)Fundamental Research Funds for the Central Universities(No.SWU-KR22017)。
摘要The typical organic perylenetetracarboxylate(PTC)luminophore suffers from limited bio-application due to its aggregation-caused quenching(ACQ)induced undesirable electrochemiluminescence(ECL)efficiency in aqueous solution.Herein,the ECL emission of PTC was highly improved through the ingenious coordination of PTC(ligand)with Tb3+(metal ion)to prepare the Tb-PTC metal-organic framework(TbPTC MOF),which prevented theπ-πstacking and the aggregation of PTC molecules in a homogeneous phase.Moreover,we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology,pore size and electron transfer ability using different solvents during its synthesis procedure.Notably,under the mixture of DMF,Et OH,and H2O(v/v/v,1:1:1),a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity,which may be attributed to two reasons.Firstly,the mesopore and rough surface of Tb-PTC MOF(luminophore)provided abundant active sites and enlarged contact surfaces for S2O82–(coreactant).Secondly,Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission.Additionally,Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponinⅠ(cTnⅠ)detection,related to acute myocardial infarction.The constructed ECL immunosensor exhibited a satisfactory linear range(1 fg/m L-20 ng/mL)and a low detection limit of 0.48 fg/m L.This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance,broadening the scope for sensitive immunoassay in disease diagnosis.
摘要In this study,a multifunctional aptamer-conjugated magnetic covalent organic framework(COF)-CuO/Au nanozyme(MCOF-CuO/Au@apt)was developed as a“three-in-one”platform for dual-signal colorimetric and fluorescent detection of Vibrio parahaemolyticus.The nanozyme integrated magnetic separation,peroxidase-like catalytic activity,and specific target recognition through an aptamer-based strategy.Upon binding to V.parahaemolyticus,the catalytic oxidation of tetra-aminophenylethylene(TPE-4A)by the nanozyme was selectively inhibited,resulting in distinct colorimetric and fluorescent signals that significantly enhanced the detection accuracy and reliability.The proposed method exhibited high sensitivity,with limits of detection(LOD)of 21 and 7 CFU/mL for the colorimetric and fluorescent assays,respectively.The performance of this method was validated using real seafood samples,including Penaeus vannamei,Mytilus coruscus,and Crassostrea gigas,which showed high recovery rates(101.11%-107.30%)and excellent reproducibility.The system also demonstrated strong specificity and accuracy under various conditions,confirming its robustness and practical applicability.Collectively,this innovative platform presents a promising solution for the rapid,versatile,and sensitive detection of V.parahaemolyticus in seafood,with considerable potential to advance food safety diagnosis and on-site monitoring.
基金supported by National Science and Technology Major Project"CO2 Flooding for Significantly Enhancing Recovery Rate and Long-Term Sequestration Technology"(No.2024ZD1406601)National Natural Science Foundation of China(Nos.42272186,42472179,42302128,42202109)+1 种基金Frontier Interdisciplinary Exploration Research Program of China University of Petroleum,Beijing(No.2462024XKQY003)Science Foundation of China University of Petroleum(Beijing)(Nos.2462023BJRC024,and 2462023YJRC039)。
摘要Sedimentary facies modeling is a critical approach for understanding geological phenomena,yet the strong heterogeneity of reservoir systems poses a serious challenge for their refined characterization.In this study,we innovatively propose an interpretable attention-guided generative adversarial network framework with dual-domain learning,which achieves precise sedimentary facies modeling under the constraints of well facies and soft probability data.Specifically,we first effectively extract and preserve prior information of sedimentary facies models from both spatial and frequency domain perspectives.Then,during simulation,to enhance the capability of the network model for finely characterizing complex heterogeneous models,cross-spatial attention mechanisms are designed to effectively capture short-range and long-range dependencies between multi-scale pattern features.Additionally,through systematic feature map visualization analysis,we elucidate the processes of conditional fitting and complex sedimentary facies model reconstruction,intuitively demonstrating the functional mechanisms of each module.Finally,systematic experiments are conducted on multiple datasets to validate the effectiveness of the proposed method.The results demonstrate that the generated sedimentary facies models exhibit high consistency with training datasets in terms of visual realism and statistical indicators.Quantitative comparisons reveal remarkable performance of the method,achieving low Wasserstein distance(0.09),Kernel Inception Distance(0.0017)and Kernel Maximum Mean Discrepancy(0.21).These findings further confirm the high realism of the generated realizations regarding pattern features.This study offers a reliable and practical method for geological reservoir modeling,thereby advancing quantitative,precise geological research with broad application prospects.
基金supported by the National Science Foundation for Distinguished Young Scholars,China(No.52025065)the Key Research and Development Program of Shaanxi,China(No.2023GXLH-016)+3 种基金A*STAR LCER-FI,Singapore projects(LCERFI010015 U2102d2004 and LCERFI01-0033 U2102d2006)the National Research Foundation Singapore(NRF-CRP26-2021RS0002)the China Scholarship Council Program,China(Project ID:202306280178)for financial supportthe support of the Computing Center in Xi’an。
摘要Ion conduction in covalent-organic framework(COF)membranes is vital for energy conversion and storage.Conventional phenomenological methods based on the Arrhenius equation offer micrometer-scale cognition of ion conduction,whereas they ignore atomic details of ion-pore interactions and sophisticated conduction mechanisms,leaving gaps in high-resolution and bottom-up understanding of ion conduction in a nanoconfined space.In this study,we develop a hierarchical approach by holistically synergizing electronic structure calculations,first-principles molecular dynamics simulations,and thermodynamic integration methods to investigate the conduction of chloride(Cl-)and hydroxide(OH-)ions in a COF membrane.It is revealed that Cl-ion with symmetric charge distribution undergoes weak solvation and tight ion-pore binding,which results in a tortuous conduction pathway,a high energy barrier,and slow diffusion based on the vehicular mechanism.In remarkable contrast,OH-ion with heterogeneous charge distribution features strong solvation and weak ion-pore binding,and it jumps frequently via a smooth pathway and a low energy barrier.Moreover,OH-ion conduction follows a mixed vehicular and Grotthuss mechanism,causing highly mutable ion identity and number,as well as superior dynamics due to proton transfer.This hierarchical approach provides sub-nanometer resolution insights into ion conduction,guiding intelligent membrane design and performance regulation to control ion conduction for emerging applications.
基金the funding from the SERB SUPRA[SPR/2021/000020]for funding.
摘要Advancements in nanostructures and nanomaterials have significantly impacted both academic research and industry.Notable nanomaterials include carbon materials,polymeric nanoparticles,dendrimers,metal and metal oxide nanoparticles,liposomes,zeolites,Metal-Organic Frameworks(MOFs),MXenes,molecular cages,and covalent organic frameworks(COFs).Their unique structures and properties make them suitable for diverse applications.Nano-structuration,which generates various nano-architectures with unique characteristics,influences the physical,chemical,and electrical properties of nanomaterials.This process is essential for achieving desired properties and maximizing application potential.Carbon materials,MOFs,and other nanomaterials have been classified based on their architectural dimensionality and the effects of nano-structuration on their applications.However,comprehensive studies on the synthesis and fabrication of COF nanostructures with desired architectures and dimensionalities are lacking.This review discusses the library of available nanostructures based on dimensionality,factors influencing nano-structuration,and the potential applications of nanomaterials like carbon materials,MOFs,and organic cage molecules.Additionally,it attempts to classify COFs based on architectural variation,specific synthetic strategies,and other factors influencing nano-structuration and applications.The aim is to develop novel synthetic methods for COF architectures across all dimensions,utilizing their morphological diversity for targeted applications based on their structure-property relationship,and to explore new methodologies for interconverting COF architectures through covalent and supramolecular self-assembly.
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)。
摘要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.
摘要Covalent organic frameworks(COFs)have garnered significant attention in photocatalysis owing to their exceptional light absorption capacities,tunable band structures,and high specific surface areas.However,the rapid recombination of photogenerated carriers in COFs remains a critical bottleneck limiting their practical application.In this study,a novel S-scheme heterojunction was constructed by integrating a Ni-doped zeolitic imidazolate framework-8(Ni-ZIF-8)with Py-COF,effectively addressing this challenge.Through precisely controlled synthesis,the heterojunction achieves efficient and stable material combination,which not only significantly enhances photogenerated charge separation efficiency and markedly reduces recombination rates,but also demonstrates outstanding catalytic performance(162.77 mmol·h-1·g-1)and cycling stability in hydrogen evolution reaction.This study provides new insights into the design of efficient ZIF/COF-based heterojunction catalysts.This study provides an important theoretical foundation for the design of high-performance photocatalytic materials with broad application prospects.
基金the Natural Science Foundation of ZhejiangProvince(No.LZ24B020005)the National Natural Science Foundation of China(No.22071040)for financial support.
摘要High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody(Ab1)and ferrocene(Fc),and used for electrochemical detection of AFP.Due to the small,homogeneous pore size of the COF,Ab1 with a big size was immobilized on the surface of the COF,while Fc with a small size was covalently modified both on the surface and in the pores of COF.The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers.Meanwhile,the enriched Fc molecules not only improved the conductivity of the COF,but also effectively transferred and amplified the electrochemical signal.This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL(S/N of 3:1)and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations.Furthermore,this immunosensor showed excellent selectivity,stability and reproducibility in the testing of real samples.This study presents an innovative prototype for construction of a precious metal-free,antibody-directly-immobilized,simple and stable electrochemical immunoprobe.
基金supported by the National Natural Science Foundation of China(22275107,22475115,22572031)the Taishan Scholar Project of Shandong Province(tsqn202306213)。
摘要Vinylene-linked covalent organic frameworks(COFs)are renowned for their excellent organic semiconducting properties,attributed to their in-planeπ-conjugated and robust structures.However,their synthesis remains challenging due to the complexity of reaction pathways and the limited availability of building units containing reactive methyl groups,which hinders their practical application.Herein,two vinylene-linked benzotristhiazole-based 2D COFs with high crystallinity were constructed via Aldol condensation reaction.Notably,the incorporation of fluorine atoms into the COF framework significantly enhanced its photocatalytic activity.Specifically,the fluorinated COF(BTZ-F)exhibited substantially improved performance in the selective oxidation of organic sulfides compared to its non-fluorinated counterpart(BTZ-H).A synergistic combination of experimental characterization and theoretical calculations revealed that fluorination significantly modulates the electronic structure of the framework,thereby promoting efficient charge separation and transfer.Further mechanistic investigations revealed that both electron-transfer and energy-transfer pathways are involved in the oxidation of phenyl methyl sulfide,providing deeper insights into the enhanced photocatalytic efficiency of the fluorinated framework.
基金supported by the National Key R&D Program of China(2022YFA1503104)the Natural Science Foundation of Shandong Province(ZR2025MS169)+1 种基金Funded by Basic Research Program of Jiangsu(BK20230243)Taishan Scholars Project(tspd20230601)。
摘要The conversion of nitric oxide(NO),a gaseous pollutant with an intermediate nitrogen oxidation state,into value-added ammonium nitrate(NH4NO3)via redox processes offers a sustainable alternative to conventional disposal methods,which are hampered by competing pathways that yield undesirable byproducts.Herein,we decouple the synthesis of NH4NO3into electrochemical NO oxidation(NOOR)and reduction(NORR)by employing H-terminated and Cu-metallated porphyrinic metal-organic framework catalysts(H-PMOF and Cu-PMOF,respectively),leveraging their tailored coordination environments and varied NO adsorption configurations.The H-PMOF favors O-atom adsorption via hydrogen bonding,whereas the Cu-PMOF strengthens N-atom adsorption through Cu-N interactions.They promote NOOR tand NORR to N,respectively,achieving greater Faradaic efficiencies and yield rates compared to their respective counterparts.When integrated in one electrolyzer,they enable direct synthesis of NH4NO3by generating 662.4μmol of Nand 409.5μmol of NH4+hourly.Molecular dynamics simulations reveal differences in adsorption modes,while computational results identify the ratedetermining dehydrogenation(*HNO3→*NO3for NOOR)and hydrogenation steps(*NO→~*NHO for NORR),with both catalysts exhibiting reduced energy barriers.This work presents a strategy for directing NO redox reactions through coordination engineering,paving the way for sustainable nitrogen valorization.
摘要The photogenerated carrier separation efficiency and material wettability are of critical importance for aqueous-phase photocatalytic reactions,achieving both simultaneously poses a significant challenge owing to the inherent interdependencies and trade-offs involved.In this work,a series of isoreticular benzotrithiophene-based covalent organic frameworks(COFs)were successfully synthesized by incorporating diverse hydrophobic and hydrophilic functional groups(-OH,-F,-H)onto their skeletons,thereby modulating their characteristic charge separation and transport as well as their wettability,and systematically studied their photocatalytic H2O2 production performance in O2-saturated water under visible-light irradiation.Remarkably,the synthesized hydrophilic BTT-BD-OH-COF demonstrates the highest H2O2 production rate of 6105μmol g-1 h-1 in the absence of any sacrificial agent in pure water,attributed to its extended light absorption range,improved hydrophilicity,and enhanced photo-induced charge separation and transport efficiency.Combined experimental results and the density functional theory calculations elucidate the reaction mechanism,revealing the overall H2O2 photosynthesis via both oxygen reduction reaction and water oxidation reaction dual pathways.This study demonstrates that functional-group-mediated linker engineering is a powerful approach for significantly enhancing the efficiency of COF-based photocatalysts.