The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNT...The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).展开更多
The risk of infection following consumption of foodborne pathogens contaminated foods became a significant concern for human health and imposes great economic losses to food industry.Herein,Ag nanoparticles were integ...The risk of infection following consumption of foodborne pathogens contaminated foods became a significant concern for human health and imposes great economic losses to food industry.Herein,Ag nanoparticles were integrated to Cu-based metal-organic framework(Cu-MOF)for antibacterial activity.The crystal structure,morphology and composition of the prepared composite Ag@Cu-MOF were confirmed by powder X-ray diffraction,thermogravimetric analysis,scanning electron microscope,transmission electron microscope,Fourier transform infrared spectroscopy,and X-ray photoelectron spectroscopy.Antibacterial assays revealed that Ag@Cu-MOF exhibited increased inhibitory activity against Escherichia coli O157:H7 in comparison to Cu-MOF.Ag@Cu-MOF treated bacterial cells displayed distinct morphological changes,a decreased ratio of live/dead cells,as well as a reduction of intracellular ATP.Antibiofilm studies demonstrated that Ag@CuMOF could dramatically inhibit biofilm formation and disrupt preformed biofilms by interfering the metabolic activity and decreasing the expression of biofilm-associated genes.Food contamination model illustrated that Ag@Cu-MOF significantly prevented the growth of E.coli O157:H7 in packed pork.This study sheds light on the potential of Ag@Cu-MOF as a promising antimicrobial material for preserving pork.展开更多
Energy conversion and environmental pollution present significant challenges that necessitate the development of materials with optimal characteristics for effective applications in solar energy-driven photocatalysis....Energy conversion and environmental pollution present significant challenges that necessitate the development of materials with optimal characteristics for effective applications in solar energy-driven photocatalysis.Metal-organic frameworks(MOFs)serve as excellent platforms for the development of various MOF-derived materials,which have garnered extensive attention due to their unique structural features,high crystallinity,large surface areas,diverse morphologies,adjustable dimensions,tunable textural characteristics,and inherent catalytic activity.However,the sluggish charge kinetics and poor stability of MOFs and MOF-derived photocatalysts restrict their photocatalytic activity,thereby limiting their applications in the field of photocatalysis.Consequently,substantial research efforts have been directed toward maximizing the advantages of these intriguing materials while addressing their shortcomings.This review provides a comprehensive summary and analysis of various synthesis strategies of MOFs and their derivatives.Effective modification strategies to enhance the performance of these novel materials are also summarized.This review systematically explores the current advancements in the application of MOFs and their derivatives for photocatalytic water splitting,photocatalytic CO_(2)reduction,and environmental water pollution treatment.Finally,it discusses the challenges and future prospects of MOFs and MOF-derived materials in photocatalytic applications.Researchers should systematically optimize synthetic strategies and functionalize MOFs and their derivatives to enhance their application in energy conversion and environmental pollution control,thereby underscoring their extensive potential.Future research will increasingly concentrate on the intelligent design and functionalization of MOFs to attain superior catalytic performance and tackle the urgent energy and environmental challenges confronting the world.展开更多
Fluorinated gases(F-gases)play a vital role in the chemical industry and in the fields of air conditioning,refrigeration,health care,and organic synthesis.However,the direct emission of waste gases containing F-gases ...Fluorinated gases(F-gases)play a vital role in the chemical industry and in the fields of air conditioning,refrigeration,health care,and organic synthesis.However,the direct emission of waste gases containing F-gases into the atmosphere contributes to greenhouse effects and generates toxic substances.Developing porous materials for the energy-efficient capture,separation,and recovery of F-gases is highly desired.Recently,as a highly designable porous adsorbents,metal–organic frameworks(MOFs)exhibit excellent selective sorption performance toward F-gases,especially for the recognition and separation of different F-gases with highly similar properties,showing their great potential in F-gases control and recovery.In this review,we discuss the capture and separation of F-gases and their azeotropic,near-azeotropic,and isomeric mixtures in various application scenarios by MOFs,specifically classify and analyze molecular interaction between F-gases and MOFs,and interpret the mechanisms underlying their high performance regarding both adsorption capacity and selectivity,providing a repertoire for future materials design.Challenges faced in the transformation research roadmap of MOFs adsorbent separation technologies toward F-gases are also discussed,and areas for future research endeavors are highlighted.展开更多
Due to the significant impact of carbon dioxide on global ecology,more efforts have been put into the exploration on CO_(2)capture and utilization.Porous organic framework materials,as a kind of materials with high po...Due to the significant impact of carbon dioxide on global ecology,more efforts have been put into the exploration on CO_(2)capture and utilization.Porous organic framework materials,as a kind of materials with high porosity and designable structure,have been considered as effective host materials for adsorbing carbon dioxide or separating it from other gases.This review gives a deep insight into the applications of metal-organic frameworks,covalent-organic frameworks,and other porous frameworks on CO_(2)capture,focusing on the enhanced capture performances originated from their high surface area with abundant porous structure,functional groups with specific heteroatoms modification,or other building unit interactions.Besides,the main challenges associated with porous frameworks for CO_(2)capture and proposed strategies to address these obstacles,including the structural design strategy or the capture mechanism exploration,have been demonstrated and emphasized.This review can contribute to further investigation on porous frameworks for gas capture and separation with enhanced performance and efficiency.展开更多
The Fushan Depression is one of the petroliferous depressions in the Beibuwan Basin,South China Sea.Previous studies have preliminarily explored the origin and source of crude oils in some areas of this depression.Nev...The Fushan Depression is one of the petroliferous depressions in the Beibuwan Basin,South China Sea.Previous studies have preliminarily explored the origin and source of crude oils in some areas of this depression.Nevertheless,no systematic investigations on the classification and origin of oils and hy-drocarbon migration processes have been made for the entire petroleum system in this depression,which has significantly hindered the hydrocarbon exploration in the region.A total of 32 mudstone and 58 oil samples from the Fushan Depression were analyzed to definite the detailed oil-source correlation within the sequence and sedimentary framework.The organic matter of third member of Paleogene Liushagang Formation(Els(3))source rocks,both deltaic and lacustrine mudstone,are algal-dominated with high abundance of C_(23)tricyclic terpane and C_(30)4-methylsteranes.The deltaic source rocks occur-ring in the first member(Els_(1))and second member(Els_(2))of the Paleogene Liushagang Formation are characterized by high abundance of C_(19+20)tricyclic terpane and oleanane,reflecting a more terrestrial plants contribution.While lacustrine source rocks of Els_(1)and Els_(2)display the reduced input of terrige-nous organic matter with relatively low abundance of C 19+20 tricyclic terpane and oleanane.Three types of oils were identified by their biomarker compositions in this study.Most of the oils discovered in the Huachang and Bailian Els_(1)reservoir belong to group A and were derived from lacustrine source rocks of Els_(1)and Els_(2).Group B oils are found within the Els_(1)and Els_(2)reservoirs,showing a close relation to the deltaic source rocks of Els_(1)and Els_(2),respectively.Group C oils,occurring in the Els3 reservoirs,have a good affinity with the Els3 source rocks.The spatial distribution and accumulation of different groups of oils are mainly controlled by the sedimentary facies and specific structural conditions.The Els_(2)reservoir in the Yong'an area belonging to Group B oil,are adjacent to the source kitchen and could be considered as the favorable exploration area in the future.展开更多
Lanthanide metal-organic frameworks(Ln-MOFs)have received extensive attention in the development of photoluminescent(PL)materials due to their stable structures and unique line-like emission spectroscopic properties.H...Lanthanide metal-organic frameworks(Ln-MOFs)have received extensive attention in the development of photoluminescent(PL)materials due to their stable structures and unique line-like emission spectroscopic properties.However,in order to prepare Ln-MOFs with high PL quantum yield(PLQY),further improving the sensitization efficiency of the“antenna effect”is essential.Herein,remarkably enhanced PL in[Tb_(2)(BDC)_(3)(DMF)_(2)(H_(2)O)_(2)]_n MOF is successfully achieved via high-pressure engineering at room temperature.Notably,the PL intensity continues to increase as the pressure increases,reaching its peak at 12.0 GPa,which is 4.4 times that of the initial state.Detailed experimental and theoretical calculations have demonstrated that pressure engineering significantly narrows the bandgap of[Tb_(2)(BDC)_(3)(DMF)_(2)(H_(2)O)_(2)]_n,optimizing both singlet and triplet energy levels.Ultimately,higher antenna effect sensitization efficiency is achieved by promoting intersystem crossing and energy transfer processes.Our work provides a promising strategy for the development of high PLQY Ln-MOFs.展开更多
The capture of CO_(2)from CO_(2)/H_(2)gas mixtures in syngas is a crucial issue for hydrogen production from steam methane reforming in industry,as the presence of CO_(2)directly affects the purity of H_(2).A combinat...The capture of CO_(2)from CO_(2)/H_(2)gas mixtures in syngas is a crucial issue for hydrogen production from steam methane reforming in industry,as the presence of CO_(2)directly affects the purity of H_(2).A combination of a high-throughput screening method and grand canonical Monte Carlo simulation was utilized to evaluate and screen 1725 metal–organic frameworks(MOFs)in detail as a means of determining their adsorption performance for CO_(2)/H_(2)gas mixtures.The adsorption and separation performance of double-linker MOFs was comprehensively evaluated using eight evaluation indicators,namely,the largest cavity diameter,accessible surface area,pore occupied accessible volume,porosity,adsorption selectivity,working capacity,adsorbent performance score and percent regeneration.Six optimal performance frameworks were screened to further study their single-component adsorption and binary competitive adsorption of CO_(2)/H_(2)respectively.The CO_(2)adsorption selectivity at different CO_(2)/H_(2)feed ratios was also evaluated,which indicated their excellent adsorption and separation performance.The microscopic adsorption mechanisms for CO_(2)and H_(2)at the molecular level were investigated by analyzing the radial distribution function and density distribution.This study may provide directional guidance and reference for subsequent experiments on the adsorption and separation of CO_(2)/H_(2).展开更多
Zinc-ion batteries(ZIBs)are inexpensive and safe,but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications.In this study,1,3,5-triformylphloroglycerol(Tp)and various diamine monomer...Zinc-ion batteries(ZIBs)are inexpensive and safe,but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications.In this study,1,3,5-triformylphloroglycerol(Tp)and various diamine monomers(p-phenylenediamine(Pa),benzidine(BD),and 4,4"-diamino-p-terphenyl(DATP))were used to synthesize a series of two-dimensional covalent-organic frameworks(COFs).The resulting COFs were named TpPa,TpBD,and TpDATP,respectively,and they showed uniform zincophilic sites,different pore sizes,and high Young's moduli on the Zn anode.Among them,TpPa and TpBD showed lower surface work functions and higher ion transfer numbers,which were conducive to uniform galvanizing/stripping zinc and inhibited dendrite growth.Theoretical calculations showed that TpPa and TpBD had wider negative potential region and greater adsorption capacity for Zn2+than TpDATP,providing more electron donor sites to coordinate with Zn^(2+).Symmetric cells protected by TpPa and TpBD stably cycled for more than 2300 h,whereas TpDATP@Zn and the bare zinc symmetric cells failed after around 150 and200 h.The full cells containing TpPa and TpBD modification layers also showed excellent cycling capacity at 1 A/g.This study provides comprehensive insights into the construction of highly reversible Zn anodes via COF modification layers for advanced rechargeable ZIBs.展开更多
Organophosphorus pesticides(OPPs)in foods pose a serious threat to human health,motivating the development of novel analytical methods for their rapid detection and quantification.A magnetic covalent organic framework...Organophosphorus pesticides(OPPs)in foods pose a serious threat to human health,motivating the development of novel analytical methods for their rapid detection and quantification.A magnetic covalent organic framework(M-COF)adsorbent for the magnetic solid-phase extraction(MSPE)of OPPs from foods was reported.M-COF was synthesized by the Schiff base condensation reaction of 1,3,5-tris(4-aminophenyl)benzene and 4,4-biphenyldicarboxaldehyde on the surface of amino-functionalized magnetic nanoparticles.Density functional theory(DFT)calculations showed that adsorption of OPPs onto the surface of M-COF involved hydrophobic effects,van der Waals interactions,π-πinteractions,halogen-N bonding,and hydrogen bonding.Combined with gas chromatography-mass spectrometry(GC-MS)technology,the MSPE method features low limits of detection for OPPs(0.002-0.015μg/L),good reproducibility(1.45%-6.14%),wide linear detection range(0.01-1μg/L,R≥0.9935),and satisfactory recoveries(87.3%-110.4%).The method was successfully applied for the trace analysis of OPPs in spiked fruit juices.展开更多
The hydrogen-bonded organic frameworks(HOFs)as a new type of porous framework materials have been widely studied in various areas.However,the lack of appropriate active sites,low intrinsic conductivity,and poor stabil...The hydrogen-bonded organic frameworks(HOFs)as a new type of porous framework materials have been widely studied in various areas.However,the lack of appropriate active sites,low intrinsic conductivity,and poor stability limited their performance in the field of electrocatalysis.Herein,we designed two 2D metal hydrogen-bonded organic frameworks(2D–M–HOF,M=Cu^(2+)or Ni^(2+))with coordination compounds based on 2,3,6,7,14,15-hexahydroxyl cyclotricatechylene and transition metal ions(Cu^(2+)and Ni^(2+)),respectively.The crystal structure of 2D–Cu–HOF is determined by continuous rotation electron diffraction,indicating an undulated 2D hydrogen-bond network with interlayeredπ-πstacking.The flexible structure of 2D–M–HOF leads to the formation of self-adaption interlayered sites,resulting in superior activity and selectivity in the electrocatalytic conversion of CO_(2) to C_(2) products,achieving a total Faradaic efficiency exceeding 80%due to the high-efficiency C–C coupling.The experimental results and density functional calculations verify that the undulated 2D–M–HOF enables the energetically favorable formation of*OCCHO intermediate.This work provides a promising strategy for designing HOF catalysts in electrocatalysis and related processes.展开更多
Drone swarm systems,equipped with photoelectric imaging and intelligent target perception,are essential for reconnaissance and strike missions in complex and high-risk environments.They excel in information sharing,an...Drone swarm systems,equipped with photoelectric imaging and intelligent target perception,are essential for reconnaissance and strike missions in complex and high-risk environments.They excel in information sharing,anti-jamming capabilities,and combat performance,making them critical for future warfare.However,varied perspectives in collaborative combat scenarios pose challenges to object detection,hindering traditional detection algorithms and reducing accuracy.Limited angle-prior data and sparse samples further complicate detection.This paper presents the Multi-View Collaborative Detection System,which tackles the challenges of multi-view object detection in collaborative combat scenarios.The system is designed to enhance multi-view image generation and detection algorithms,thereby improving the accuracy and efficiency of object detection across varying perspectives.First,an observation model for three-dimensional targets through line-of-sight angle transformation is constructed,and a multi-view image generation algorithm based on the Pix2Pix network is designed.For object detection,YOLOX is utilized,and a deep feature extraction network,BA-RepCSPDarknet,is developed to address challenges related to small target scale and feature extraction challenges.Additionally,a feature fusion network NS-PAFPN is developed to mitigate the issue of deep feature map information loss in UAV images.A visual attention module(BAM)is employed to manage appearance differences under varying angles,while a feature mapping module(DFM)prevents fine-grained feature loss.These advancements lead to the development of BA-YOLOX,a multi-view object detection network model suitable for drone platforms,enhancing accuracy and effectively targeting small objects.展开更多
Composite solid-state electrolytes(CSEs)are promising candidates for solid-state sodium batteries.However,achieving high ionic conductivity while maintaining adequate mechanical strength presents a significant challen...Composite solid-state electrolytes(CSEs)are promising candidates for solid-state sodium batteries.However,achieving high ionic conductivity while maintaining adequate mechanical strength presents a significant challenge.For roll-to-roll manufacturing,researchers have sought to incorporate an inert framework,such as polyethylene(PE)separators,as substrates for ultra-thin CSEs membranes.Nevertheless,these inert substrates result in poor ionic conductivity and uneven sodium ion(Na^(+))flux,promoting sodium dendrite growth.Here,we propose a flexible and ion-conducting framework based on polymer-reinforced-ceramic(PRC)electrospun fibers.This design features a poly(vinylidene fluoride)(PVDF)-based polymer electrolyte as a flexible core and an Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)-based ceramic electrolyte as a rigid shell.A continuous Na^(+)conduction pathway is created in the PRC fiber by taking advantage of the superior Na^(+)-conduction behavior along the interface between NZSP nanoparticles and PVDF polymer.A tape-casted ultra-thin composite electrolyte membrane(thickness:17.8μm)based on the PRC three-dimensional(3D)framework exhibits sufficient ionic conductivity(6.6×10^(-4)S cm^(-1),60℃)and enables a stable Na plating/stripping in symmetric Na/Na cells and a long-term cycling of solidstate Na-metal batteries.The suppressed sodium dendrite can be attributed to the Na_(3)P-rich SEIs derived from the NZSP shells in the PRC frameworks.This work provides a novel strategy for designing ionconducting frameworks for ultra-thin CSEs membranes and promotes potential applications in highperformance solid-state sodium metal batteries.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
Carbon peaking and carbon neutralization trigger a technical revolution in energy&environment related fields.Development of new technologies for green energy production and storage,industrial energy saving and eff...Carbon peaking and carbon neutralization trigger a technical revolution in energy&environment related fields.Development of new technologies for green energy production and storage,industrial energy saving and efficiency reinforcement,carbon capture,and pollutant gas treatment is in highly imperious demand.The emerging porous framework materials such as metal–organic frameworks(MOFs),covalent organic frameworks(COFs)and hydrogen-bonded organic frameworks(HOFs),owing to the permanent porosity,tremendous specific surface area,designable structure and customizable functionality,have shown great potential in major energy-consuming industrial processes,including sustainable energy gas catalytic conversion,energy-efficient industrial gas separation and storage.Herein,this manuscript presents a systematic review of porous framework materials for global and comprehensive energy&environment related applications,from a macroscopic and application perspective.展开更多
Free-standing covalent organic framework(COFs)nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li^(+) in lithium-ion batteries,while simultaneously exposing affluent active sites in superca...Free-standing covalent organic framework(COFs)nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li^(+) in lithium-ion batteries,while simultaneously exposing affluent active sites in supercapacitors.The development of these nanofilms offers a promising solution to address the persistent challenge of imbalanced charge storage kinetics between battery-type anode and capacitor-type cathode in lithium-ion capacitors(LICs).Herein,for the first time,custom-made COFBTMB-TP and COFTAPB-BPY nanofilms are synthesized as the anode and cathode,respectively,for an all-COF nanofilm-structured LIC.The COFBTMB-TP nanofilm with strong electronegative–CF3 groups enables tuning the partial electron cloud density for Li^(+) migration to ensure the rapid anode kinetic process.The thickness-regulated cathodic COFTAPB-BPY nanofilm can fit the anodic COF nanofilm in the capacity.Due to the aligned 1D channel,2D aromatic skeleton and accessible active sites of COF nanofilms,the whole COFTAPB-BPY//COFBTMB-TP LIC demonstrates a high energy density of 318 mWh cm^(−3) at a high-power density of 6 W cm^(−3),excellent rate capability,good cycle stability with the capacity retention rate of 77%after 5000-cycle.The COFTAPB-BPY//COFBTMB-TP LIC represents a new benchmark for currently reported film-type LICs and even film-type supercapacitors.After being comprehensively explored via ex situ XPS,7Li solid-state NMR analyses,and DFT calculation,it is found that the COFBTMB-TP nanofilm facilitates the reversible conversion of semi-ionic to ionic C–F bonds during lithium storage.COFBTMB-TP exhibits a strong interaction with Li^(+) due to the C–F,C=O,and C–N bonds,facilitating Li^(+) desolation and absorption from the electrolyte.This work addresses the challenge of imbalanced charge storage kinetics and capacity between the anode and cathode and also pave the way for future miniaturized and wearable LIC devices.展开更多
Metal-organic framework(MOF)and covalent organic framework(COF)are a huge group of advanced porous materials exhibiting attractive and tunable microstructural features,such as large surface area,tunable pore size,and ...Metal-organic framework(MOF)and covalent organic framework(COF)are a huge group of advanced porous materials exhibiting attractive and tunable microstructural features,such as large surface area,tunable pore size,and functional surfaces,which have significant values in various application areas.The emerging 3D printing technology further provides MOF and COFs(M/COFs)with higher designability of their macrostructure and demonstrates large achievements in their performance by shaping them into advanced 3D monoliths.However,the currently available 3D printing M/COFs strategy faces a major challenge of severe destruction of M/COFs’microstructural features,both during and after 3D printing.It is envisioned that preserving the microstructure of M/COFs in the 3D-printed monolith will bring a great improvement to the related applications.In this overview,the 3D-printed M/COFs are categorized into M/COF-mixed monoliths and M/COF-covered monoliths.Their differences in the properties,applications,and current research states are discussed.The up-to-date advancements in paste/scaffold composition and printing/covering methods to preserve the superior M/COF microstructure during 3D printing are further discussed for the two types of 3D-printed M/COF.Throughout the analysis of the current states of 3D-printed M/COFs,the expected future research direction to achieve a highly preserved microstructure in the 3D monolith is proposed.展开更多
基金the financial support from the National Natural Science Foundation of China(No.22178307)China Southern Power Grid(Grant Nos.0470002022030103HX00002-01).
文摘The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).
基金funded by the Key Research and Development Projects of Shaanxi Province(2023-YBNY-178)Shaanxi Fundamental Science Research Project for Chemistry&Biology(22JHQ029)+1 种基金China Postdoctoral Science Foundation(2019M653766)National Natural Science Foundation of China(21901212)。
文摘The risk of infection following consumption of foodborne pathogens contaminated foods became a significant concern for human health and imposes great economic losses to food industry.Herein,Ag nanoparticles were integrated to Cu-based metal-organic framework(Cu-MOF)for antibacterial activity.The crystal structure,morphology and composition of the prepared composite Ag@Cu-MOF were confirmed by powder X-ray diffraction,thermogravimetric analysis,scanning electron microscope,transmission electron microscope,Fourier transform infrared spectroscopy,and X-ray photoelectron spectroscopy.Antibacterial assays revealed that Ag@Cu-MOF exhibited increased inhibitory activity against Escherichia coli O157:H7 in comparison to Cu-MOF.Ag@Cu-MOF treated bacterial cells displayed distinct morphological changes,a decreased ratio of live/dead cells,as well as a reduction of intracellular ATP.Antibiofilm studies demonstrated that Ag@CuMOF could dramatically inhibit biofilm formation and disrupt preformed biofilms by interfering the metabolic activity and decreasing the expression of biofilm-associated genes.Food contamination model illustrated that Ag@Cu-MOF significantly prevented the growth of E.coli O157:H7 in packed pork.This study sheds light on the potential of Ag@Cu-MOF as a promising antimicrobial material for preserving pork.
基金The financial support for this study by the Technology Project of Qingdao(22-3-7-cspz-9-nsh)the National Key Research and Development Program(2021YFB3500102)。
文摘Energy conversion and environmental pollution present significant challenges that necessitate the development of materials with optimal characteristics for effective applications in solar energy-driven photocatalysis.Metal-organic frameworks(MOFs)serve as excellent platforms for the development of various MOF-derived materials,which have garnered extensive attention due to their unique structural features,high crystallinity,large surface areas,diverse morphologies,adjustable dimensions,tunable textural characteristics,and inherent catalytic activity.However,the sluggish charge kinetics and poor stability of MOFs and MOF-derived photocatalysts restrict their photocatalytic activity,thereby limiting their applications in the field of photocatalysis.Consequently,substantial research efforts have been directed toward maximizing the advantages of these intriguing materials while addressing their shortcomings.This review provides a comprehensive summary and analysis of various synthesis strategies of MOFs and their derivatives.Effective modification strategies to enhance the performance of these novel materials are also summarized.This review systematically explores the current advancements in the application of MOFs and their derivatives for photocatalytic water splitting,photocatalytic CO_(2)reduction,and environmental water pollution treatment.Finally,it discusses the challenges and future prospects of MOFs and MOF-derived materials in photocatalytic applications.Researchers should systematically optimize synthetic strategies and functionalize MOFs and their derivatives to enhance their application in energy conversion and environmental pollution control,thereby underscoring their extensive potential.Future research will increasingly concentrate on the intelligent design and functionalization of MOFs to attain superior catalytic performance and tackle the urgent energy and environmental challenges confronting the world.
基金funded by the National Key Research and Development Program of China(2022YFE0110500)National Natural Science Foundation of China(22376161,52373154,52103181)+1 种基金the Fundamental Research Funds for the Central Universities of Chinathe Interdisciplinary Project in Environmental Science and Engineering of Tongji University(2023-3-YB-02)。
文摘Fluorinated gases(F-gases)play a vital role in the chemical industry and in the fields of air conditioning,refrigeration,health care,and organic synthesis.However,the direct emission of waste gases containing F-gases into the atmosphere contributes to greenhouse effects and generates toxic substances.Developing porous materials for the energy-efficient capture,separation,and recovery of F-gases is highly desired.Recently,as a highly designable porous adsorbents,metal–organic frameworks(MOFs)exhibit excellent selective sorption performance toward F-gases,especially for the recognition and separation of different F-gases with highly similar properties,showing their great potential in F-gases control and recovery.In this review,we discuss the capture and separation of F-gases and their azeotropic,near-azeotropic,and isomeric mixtures in various application scenarios by MOFs,specifically classify and analyze molecular interaction between F-gases and MOFs,and interpret the mechanisms underlying their high performance regarding both adsorption capacity and selectivity,providing a repertoire for future materials design.Challenges faced in the transformation research roadmap of MOFs adsorbent separation technologies toward F-gases are also discussed,and areas for future research endeavors are highlighted.
基金the Natural Science Foundation of Shanghai(23ZR1422600)the Innovative research team of high-level local university in Shanghai for their financial support.
文摘Due to the significant impact of carbon dioxide on global ecology,more efforts have been put into the exploration on CO_(2)capture and utilization.Porous organic framework materials,as a kind of materials with high porosity and designable structure,have been considered as effective host materials for adsorbing carbon dioxide or separating it from other gases.This review gives a deep insight into the applications of metal-organic frameworks,covalent-organic frameworks,and other porous frameworks on CO_(2)capture,focusing on the enhanced capture performances originated from their high surface area with abundant porous structure,functional groups with specific heteroatoms modification,or other building unit interactions.Besides,the main challenges associated with porous frameworks for CO_(2)capture and proposed strategies to address these obstacles,including the structural design strategy or the capture mechanism exploration,have been demonstrated and emphasized.This review can contribute to further investigation on porous frameworks for gas capture and separation with enhanced performance and efficiency.
基金funded by the South Oil Exploration and Development Company of PetroChina(2021-HNYJ-010).
文摘The Fushan Depression is one of the petroliferous depressions in the Beibuwan Basin,South China Sea.Previous studies have preliminarily explored the origin and source of crude oils in some areas of this depression.Nevertheless,no systematic investigations on the classification and origin of oils and hy-drocarbon migration processes have been made for the entire petroleum system in this depression,which has significantly hindered the hydrocarbon exploration in the region.A total of 32 mudstone and 58 oil samples from the Fushan Depression were analyzed to definite the detailed oil-source correlation within the sequence and sedimentary framework.The organic matter of third member of Paleogene Liushagang Formation(Els(3))source rocks,both deltaic and lacustrine mudstone,are algal-dominated with high abundance of C_(23)tricyclic terpane and C_(30)4-methylsteranes.The deltaic source rocks occur-ring in the first member(Els_(1))and second member(Els_(2))of the Paleogene Liushagang Formation are characterized by high abundance of C_(19+20)tricyclic terpane and oleanane,reflecting a more terrestrial plants contribution.While lacustrine source rocks of Els_(1)and Els_(2)display the reduced input of terrige-nous organic matter with relatively low abundance of C 19+20 tricyclic terpane and oleanane.Three types of oils were identified by their biomarker compositions in this study.Most of the oils discovered in the Huachang and Bailian Els_(1)reservoir belong to group A and were derived from lacustrine source rocks of Els_(1)and Els_(2).Group B oils are found within the Els_(1)and Els_(2)reservoirs,showing a close relation to the deltaic source rocks of Els_(1)and Els_(2),respectively.Group C oils,occurring in the Els3 reservoirs,have a good affinity with the Els3 source rocks.The spatial distribution and accumulation of different groups of oils are mainly controlled by the sedimentary facies and specific structural conditions.The Els_(2)reservoir in the Yong'an area belonging to Group B oil,are adjacent to the source kitchen and could be considered as the favorable exploration area in the future.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12304261 and 12274177)the China Postdoctoral Science Foundation(Grant No.2024M751076)。
文摘Lanthanide metal-organic frameworks(Ln-MOFs)have received extensive attention in the development of photoluminescent(PL)materials due to their stable structures and unique line-like emission spectroscopic properties.However,in order to prepare Ln-MOFs with high PL quantum yield(PLQY),further improving the sensitization efficiency of the“antenna effect”is essential.Herein,remarkably enhanced PL in[Tb_(2)(BDC)_(3)(DMF)_(2)(H_(2)O)_(2)]_n MOF is successfully achieved via high-pressure engineering at room temperature.Notably,the PL intensity continues to increase as the pressure increases,reaching its peak at 12.0 GPa,which is 4.4 times that of the initial state.Detailed experimental and theoretical calculations have demonstrated that pressure engineering significantly narrows the bandgap of[Tb_(2)(BDC)_(3)(DMF)_(2)(H_(2)O)_(2)]_n,optimizing both singlet and triplet energy levels.Ultimately,higher antenna effect sensitization efficiency is achieved by promoting intersystem crossing and energy transfer processes.Our work provides a promising strategy for the development of high PLQY Ln-MOFs.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11304079,11404094,and 11504088)Science and Technology Research Project of Henan Science and Technology Department(Grant No.182102410076)。
文摘The capture of CO_(2)from CO_(2)/H_(2)gas mixtures in syngas is a crucial issue for hydrogen production from steam methane reforming in industry,as the presence of CO_(2)directly affects the purity of H_(2).A combination of a high-throughput screening method and grand canonical Monte Carlo simulation was utilized to evaluate and screen 1725 metal–organic frameworks(MOFs)in detail as a means of determining their adsorption performance for CO_(2)/H_(2)gas mixtures.The adsorption and separation performance of double-linker MOFs was comprehensively evaluated using eight evaluation indicators,namely,the largest cavity diameter,accessible surface area,pore occupied accessible volume,porosity,adsorption selectivity,working capacity,adsorbent performance score and percent regeneration.Six optimal performance frameworks were screened to further study their single-component adsorption and binary competitive adsorption of CO_(2)/H_(2)respectively.The CO_(2)adsorption selectivity at different CO_(2)/H_(2)feed ratios was also evaluated,which indicated their excellent adsorption and separation performance.The microscopic adsorption mechanisms for CO_(2)and H_(2)at the molecular level were investigated by analyzing the radial distribution function and density distribution.This study may provide directional guidance and reference for subsequent experiments on the adsorption and separation of CO_(2)/H_(2).
基金financially supported by the National Natural Science Foundation of China(62464010)Spring City Plan-Special Program for Young Talents(K202005007)+3 种基金Yunnan Talents Support Plan for Yong Talents(XDYC-QNRC-2022-0482)Yunnan Local Colleges Applied Basic Research Projects(202101BA070001-138)Key Laboratory of Artificial Microstructures in Yunnan Higher EducationFrontier Research Team of Kunming University 2023。
文摘Zinc-ion batteries(ZIBs)are inexpensive and safe,but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications.In this study,1,3,5-triformylphloroglycerol(Tp)and various diamine monomers(p-phenylenediamine(Pa),benzidine(BD),and 4,4"-diamino-p-terphenyl(DATP))were used to synthesize a series of two-dimensional covalent-organic frameworks(COFs).The resulting COFs were named TpPa,TpBD,and TpDATP,respectively,and they showed uniform zincophilic sites,different pore sizes,and high Young's moduli on the Zn anode.Among them,TpPa and TpBD showed lower surface work functions and higher ion transfer numbers,which were conducive to uniform galvanizing/stripping zinc and inhibited dendrite growth.Theoretical calculations showed that TpPa and TpBD had wider negative potential region and greater adsorption capacity for Zn2+than TpDATP,providing more electron donor sites to coordinate with Zn^(2+).Symmetric cells protected by TpPa and TpBD stably cycled for more than 2300 h,whereas TpDATP@Zn and the bare zinc symmetric cells failed after around 150 and200 h.The full cells containing TpPa and TpBD modification layers also showed excellent cycling capacity at 1 A/g.This study provides comprehensive insights into the construction of highly reversible Zn anodes via COF modification layers for advanced rechargeable ZIBs.
基金supported by Key Research and Development Project of Shandong Province(2021ZDSYS12)National Natural Science Foundation of China(22076086,21777089)+3 种基金Taishan Scholar Program of Shandong Province(ts20190948)Shandong Province Science and Technology Small and Medium Enterprises Innovation Ability Enhancement Project(2023TSGC0689,2023TSGC0055)Natural Science Foundation of Shandong Province(ZR2021MB086,ZR2023QB035)Jinan City University and Institute Innovation Team Project(2021GXRC061,20228045,202333027)。
文摘Organophosphorus pesticides(OPPs)in foods pose a serious threat to human health,motivating the development of novel analytical methods for their rapid detection and quantification.A magnetic covalent organic framework(M-COF)adsorbent for the magnetic solid-phase extraction(MSPE)of OPPs from foods was reported.M-COF was synthesized by the Schiff base condensation reaction of 1,3,5-tris(4-aminophenyl)benzene and 4,4-biphenyldicarboxaldehyde on the surface of amino-functionalized magnetic nanoparticles.Density functional theory(DFT)calculations showed that adsorption of OPPs onto the surface of M-COF involved hydrophobic effects,van der Waals interactions,π-πinteractions,halogen-N bonding,and hydrogen bonding.Combined with gas chromatography-mass spectrometry(GC-MS)technology,the MSPE method features low limits of detection for OPPs(0.002-0.015μg/L),good reproducibility(1.45%-6.14%),wide linear detection range(0.01-1μg/L,R≥0.9935),and satisfactory recoveries(87.3%-110.4%).The method was successfully applied for the trace analysis of OPPs in spiked fruit juices.
基金financially supported by the National Natural Science Foundation of China(nos.21971012,61933002,21601015,21625102,21674012,and 81601549)the National Key Research and Development Program of China(2020YFB1506300)Beijing Institute of Technology Research Fund Program for Young Scholars。
文摘The hydrogen-bonded organic frameworks(HOFs)as a new type of porous framework materials have been widely studied in various areas.However,the lack of appropriate active sites,low intrinsic conductivity,and poor stability limited their performance in the field of electrocatalysis.Herein,we designed two 2D metal hydrogen-bonded organic frameworks(2D–M–HOF,M=Cu^(2+)or Ni^(2+))with coordination compounds based on 2,3,6,7,14,15-hexahydroxyl cyclotricatechylene and transition metal ions(Cu^(2+)and Ni^(2+)),respectively.The crystal structure of 2D–Cu–HOF is determined by continuous rotation electron diffraction,indicating an undulated 2D hydrogen-bond network with interlayeredπ-πstacking.The flexible structure of 2D–M–HOF leads to the formation of self-adaption interlayered sites,resulting in superior activity and selectivity in the electrocatalytic conversion of CO_(2) to C_(2) products,achieving a total Faradaic efficiency exceeding 80%due to the high-efficiency C–C coupling.The experimental results and density functional calculations verify that the undulated 2D–M–HOF enables the energetically favorable formation of*OCCHO intermediate.This work provides a promising strategy for designing HOF catalysts in electrocatalysis and related processes.
基金supported by the Natural Science Foundation of China,Grant No.62103052.
文摘Drone swarm systems,equipped with photoelectric imaging and intelligent target perception,are essential for reconnaissance and strike missions in complex and high-risk environments.They excel in information sharing,anti-jamming capabilities,and combat performance,making them critical for future warfare.However,varied perspectives in collaborative combat scenarios pose challenges to object detection,hindering traditional detection algorithms and reducing accuracy.Limited angle-prior data and sparse samples further complicate detection.This paper presents the Multi-View Collaborative Detection System,which tackles the challenges of multi-view object detection in collaborative combat scenarios.The system is designed to enhance multi-view image generation and detection algorithms,thereby improving the accuracy and efficiency of object detection across varying perspectives.First,an observation model for three-dimensional targets through line-of-sight angle transformation is constructed,and a multi-view image generation algorithm based on the Pix2Pix network is designed.For object detection,YOLOX is utilized,and a deep feature extraction network,BA-RepCSPDarknet,is developed to address challenges related to small target scale and feature extraction challenges.Additionally,a feature fusion network NS-PAFPN is developed to mitigate the issue of deep feature map information loss in UAV images.A visual attention module(BAM)is employed to manage appearance differences under varying angles,while a feature mapping module(DFM)prevents fine-grained feature loss.These advancements lead to the development of BA-YOLOX,a multi-view object detection network model suitable for drone platforms,enhancing accuracy and effectively targeting small objects.
基金supported by the National Key R&D Program of China(2023YFB2503900)the National Natural Science Foundation of China(12474171 and 52372203)。
文摘Composite solid-state electrolytes(CSEs)are promising candidates for solid-state sodium batteries.However,achieving high ionic conductivity while maintaining adequate mechanical strength presents a significant challenge.For roll-to-roll manufacturing,researchers have sought to incorporate an inert framework,such as polyethylene(PE)separators,as substrates for ultra-thin CSEs membranes.Nevertheless,these inert substrates result in poor ionic conductivity and uneven sodium ion(Na^(+))flux,promoting sodium dendrite growth.Here,we propose a flexible and ion-conducting framework based on polymer-reinforced-ceramic(PRC)electrospun fibers.This design features a poly(vinylidene fluoride)(PVDF)-based polymer electrolyte as a flexible core and an Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)-based ceramic electrolyte as a rigid shell.A continuous Na^(+)conduction pathway is created in the PRC fiber by taking advantage of the superior Na^(+)-conduction behavior along the interface between NZSP nanoparticles and PVDF polymer.A tape-casted ultra-thin composite electrolyte membrane(thickness:17.8μm)based on the PRC three-dimensional(3D)framework exhibits sufficient ionic conductivity(6.6×10^(-4)S cm^(-1),60℃)and enables a stable Na plating/stripping in symmetric Na/Na cells and a long-term cycling of solidstate Na-metal batteries.The suppressed sodium dendrite can be attributed to the Na_(3)P-rich SEIs derived from the NZSP shells in the PRC frameworks.This work provides a novel strategy for designing ionconducting frameworks for ultra-thin CSEs membranes and promotes potential applications in highperformance solid-state sodium metal batteries.
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the financial support from the National Natural Science Foundation of China(22090062,21922810,21825802,22138003,22108083,and 21725603)the Guangdong Pearl River Talents Program(2021QN02C8)+3 种基金the Science and Technology Program of Guangzhou(202201010118)Zhejiang Provincial Natural Science Foundation of China(LR20B060001)National Science Fund for Excellent Young Scholars(22122811)China Postdoctoral Science Foundation(2022M710123)。
文摘Carbon peaking and carbon neutralization trigger a technical revolution in energy&environment related fields.Development of new technologies for green energy production and storage,industrial energy saving and efficiency reinforcement,carbon capture,and pollutant gas treatment is in highly imperious demand.The emerging porous framework materials such as metal–organic frameworks(MOFs),covalent organic frameworks(COFs)and hydrogen-bonded organic frameworks(HOFs),owing to the permanent porosity,tremendous specific surface area,designable structure and customizable functionality,have shown great potential in major energy-consuming industrial processes,including sustainable energy gas catalytic conversion,energy-efficient industrial gas separation and storage.Herein,this manuscript presents a systematic review of porous framework materials for global and comprehensive energy&environment related applications,from a macroscopic and application perspective.
基金We are grateful to National Natural Science Foundation of China(Grant No.22375056,52272163)the Key R&D Program of Hebei(Grant No.216Z1201G)+1 种基金Natural Science Foundation of Hebei Province(Grant No.E2022208066,B2021208014)Key R&D Program of Hebei Technological Innovation Center of Chiral Medicine(Grant No.ZXJJ20220105).
文摘Free-standing covalent organic framework(COFs)nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li^(+) in lithium-ion batteries,while simultaneously exposing affluent active sites in supercapacitors.The development of these nanofilms offers a promising solution to address the persistent challenge of imbalanced charge storage kinetics between battery-type anode and capacitor-type cathode in lithium-ion capacitors(LICs).Herein,for the first time,custom-made COFBTMB-TP and COFTAPB-BPY nanofilms are synthesized as the anode and cathode,respectively,for an all-COF nanofilm-structured LIC.The COFBTMB-TP nanofilm with strong electronegative–CF3 groups enables tuning the partial electron cloud density for Li^(+) migration to ensure the rapid anode kinetic process.The thickness-regulated cathodic COFTAPB-BPY nanofilm can fit the anodic COF nanofilm in the capacity.Due to the aligned 1D channel,2D aromatic skeleton and accessible active sites of COF nanofilms,the whole COFTAPB-BPY//COFBTMB-TP LIC demonstrates a high energy density of 318 mWh cm^(−3) at a high-power density of 6 W cm^(−3),excellent rate capability,good cycle stability with the capacity retention rate of 77%after 5000-cycle.The COFTAPB-BPY//COFBTMB-TP LIC represents a new benchmark for currently reported film-type LICs and even film-type supercapacitors.After being comprehensively explored via ex situ XPS,7Li solid-state NMR analyses,and DFT calculation,it is found that the COFBTMB-TP nanofilm facilitates the reversible conversion of semi-ionic to ionic C–F bonds during lithium storage.COFBTMB-TP exhibits a strong interaction with Li^(+) due to the C–F,C=O,and C–N bonds,facilitating Li^(+) desolation and absorption from the electrolyte.This work addresses the challenge of imbalanced charge storage kinetics and capacity between the anode and cathode and also pave the way for future miniaturized and wearable LIC devices.
基金the support by National Research Foundation of Singapore(NRF,Project:NRF-CRP262021RS-0002),for research conducted at the National University of Singapore(NUS)。
文摘Metal-organic framework(MOF)and covalent organic framework(COF)are a huge group of advanced porous materials exhibiting attractive and tunable microstructural features,such as large surface area,tunable pore size,and functional surfaces,which have significant values in various application areas.The emerging 3D printing technology further provides MOF and COFs(M/COFs)with higher designability of their macrostructure and demonstrates large achievements in their performance by shaping them into advanced 3D monoliths.However,the currently available 3D printing M/COFs strategy faces a major challenge of severe destruction of M/COFs’microstructural features,both during and after 3D printing.It is envisioned that preserving the microstructure of M/COFs in the 3D-printed monolith will bring a great improvement to the related applications.In this overview,the 3D-printed M/COFs are categorized into M/COF-mixed monoliths and M/COF-covered monoliths.Their differences in the properties,applications,and current research states are discussed.The up-to-date advancements in paste/scaffold composition and printing/covering methods to preserve the superior M/COF microstructure during 3D printing are further discussed for the two types of 3D-printed M/COF.Throughout the analysis of the current states of 3D-printed M/COFs,the expected future research direction to achieve a highly preserved microstructure in the 3D monolith is proposed.
