CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organ...CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.展开更多
Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystall...Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.展开更多
The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Coval...The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Covalent organic frameworks(COFs) are ideal adsorbents for gold recovery owing to their large surface area,good stability,easily functionalized ability,periodic structures,and definitive nanopores.Herein,a cyano-functionalized COF(COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold.The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance,which possesses fast adsorption kinetics,high cycling stability,and adsorption capacity up to 663.67 mg/g.Excitingly,COF-CN showed extremely high selectivity for gold ions,even in the presence of various competing cations and anions.The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE.The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.展开更多
Composite solid-state electrolytes incorporating metal-organic frameworks(MOFs)demonstrate tremendous potential for ameliorating Li^(+)conduction in lithium metal batteries.However,their practical application is hinde...Composite solid-state electrolytes incorporating metal-organic frameworks(MOFs)demonstrate tremendous potential for ameliorating Li^(+)conduction in lithium metal batteries.However,their practical application is hindered by low ionic co nductivity and unstable Li^(+)transport at the electrode interfaces.To overcome these challenges,a previously unreported family of indium based MOFs(In-BDC-F_(x),x=0,4,6)with tunable fluorine content was synthesized and integrated into PVDF-HFP matrices to construct highperformance quasi-solid-state electrolytes.By systematically modulating linker fluorination,a bifunctional enhancement mechanism is revealed:fluorinated indium centers simultaneously suppress polymer crystallinity and establish preferential Li^(+)conduction pathways.Remarkably,In-BDC-F_(6) manifests exceptional synergistic interactions between-CF_(3) functionalities and indium coordination sites,amplifying Lewis acidity to facilitate LiTFSI dissociation and TFSI-immobilization,culminating in homogeneous LiF-enriched solid electrolyte interphases.The optimized electrolyte demonstrates compelling electrochemical performance:ionic conductivity of 9.68×10^(-4) S cm^(-1),Li^(+)transference number of 0.70,and electrochemical stability window of 4.96 V.Li‖Li symmetric cell demonstrated a critical current density of 3.5 mA cm^(-2) and stable plating/stripping for over 1000 h at 0.2 mA cm^(-2),while LiFePO_(4)‖Li cells retain96.66%capacity after 1300 cycles at 10C,underscoring the transformative potential of fluorinated MOF architectures in fast-charging solid-state batteries.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
Gas sensors are valuable tools for human applications,and extensive research has been conducted in this field.However,practical implementation has yet to be fully realized.In response,efforts have been made to explore...Gas sensors are valuable tools for human applications,and extensive research has been conducted in this field.However,practical implementation has yet to be fully realized.In response,efforts have been made to explore metal-organic frameworks(MOFs),a novel class of porous materials,as potential solutions.MOFs exhibit exceptional porosity and highly tunable chemical compositions and structures,giving rise to a wide range of unique physical and chemical properties.Significant progress has been achieved in developing MOF-based gas sensors,improving sensing performance for various gases.This review aims to provide a comprehensive understanding of MOF-based gas sensors,even for readers unfamiliar with MOFs and gas sensors.It covers the working principles of these sensors,fundamental concepts of MOFs,strategies for tuning MOF properties,fabrication techniques for MOF films,and recent studies on MOF and MOF-derivative gas sensors.Finally,current challenges,overlooked aspects,and future directions for fully exploiting the potential of MOFs in gas sensor development are discussed.展开更多
As a class of crystalline porous materials,metal-organic frameworks(MOFs)have shown unique advantages in the fields of catalysis,gas storage and separation,but their inherent microporous structure(pore diameter<2 n...As a class of crystalline porous materials,metal-organic frameworks(MOFs)have shown unique advantages in the fields of catalysis,gas storage and separation,but their inherent microporous structure(pore diameter<2 nm)severely limits their application in scenarios such as macromolecular mass transfer and so on.In order to overcome this re-striction,mesoporous MOFs(meso-MOFs)with a larger aperture(2-50 nm)have attracted much attention due to their potential applications in biological macromolecular catalysis,energy storage and other fields.To date,how to accurately regulate its mesopore topology and pore ordering still faces important technical challenges.展开更多
(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under...(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.展开更多
Photocatalytic CO_(2)cycloaddition reaction presents a promising CO_(2)conversion strategy to establish carbon neutrality.Among emerging catalysts,metal‑organic frameworks(MOFs)have been regarded as paradigmshifting p...Photocatalytic CO_(2)cycloaddition reaction presents a promising CO_(2)conversion strategy to establish carbon neutrality.Among emerging catalysts,metal‑organic frameworks(MOFs)have been regarded as paradigmshifting photocatalysts for their atomic precision in active site engineering,controllable porosity,and exceptional photochemical stability under ambient conditions.However,inherent limitations persist in conventional MOFs,including restricted solar spectrum utilization,inefficient charge carrier separation,and inadequate epoxide activation ability.Recent breakthroughs address these challenges through multiple strategies:ligand engineering,dopant incorporation,and composite construction.This review systematically maps the evolutionary trajectory of MOF‑based photocatalysts,providing mechanistic insights into structure‑activity relationships and providing insights and directions for the design of high‑performance MOF‑based photocatalysts.展开更多
Sludge,the massive by-product of the sewage system,became a major challenge for the wastewater treatment industry.Yet,conventional methods often face challenges like low efficiency,high energy consumption,and environm...Sludge,the massive by-product of the sewage system,became a major challenge for the wastewater treatment industry.Yet,conventional methods often face challenges like low efficiency,high energy consumption,and environmental pollution.Especially,the improper treatment and disposal of toxic sludge generated from different industrial processes or specific wastewater treatment operations exerted significant pressure and threat to hydrosphere,pedosphere,atmosphere and even biosphere.展开更多
Ultramicroporous materials(pore dimension<7Å,as defined by IUPAC)have emerged as an intriguing class of porous substances with exceptional potential in molecular separation.Current benchmark materials includin...Ultramicroporous materials(pore dimension<7Å,as defined by IUPAC)have emerged as an intriguing class of porous substances with exceptional potential in molecular separation.Current benchmark materials including zeolites face inherent limitations in achieving hyperfine control of pore metrics,which hinder their ability to discriminate and separate molecules of very close dimensions and properties.Metal-organic frameworks,constructed by deliberate connections of metal nodes and organic linkers,have offered a great solution in addressing these challenges due to their atomic precision that allows angstrom-level engineering of pore width[1-3].展开更多
Stimuli-responsive two-dimensional (2D) covalent organic frameworks (COFs) with precise structures and permanent porosity have been employed as platforms for sensors. The slight change of backbones inside frameworks l...Stimuli-responsive two-dimensional (2D) covalent organic frameworks (COFs) with precise structures and permanent porosity have been employed as platforms for sensors. The slight change of backbones inside frameworks leads to different electronic states by external stimuli, such as solvent, pH, and water. Herein, we introduced an alkynyl-based building block (ETBA) with high planarity to synthesize two imine-based alkynyl-COFs (ETBA-TAPE-COF and ETBA-PYTA-COF) with high yield, good crystallinity, and chemical stability. Due to the presence of acetylene bonds, ETBA-TAPE-COF does not adopt the completely overlapping AA stacking mode. Slight interlayer displacement occurs along the parallel direction relative to the acetylene linkages, which facilitates lower configurational energy. Additionally, the introduction of pyrene group contributes to high π-electron mobility of ETBA-PYTA-COF. The interactions between electron-withdrawing group (ETBA) and electron-donating group (PYTA) during the processes of protonation and intramolecular charge transfer (ICT) endow ETBA-PYTA-COF with excellent acidochromic and solvatochromic properties, respectively. Based on this, a fluorescence sensor is successfully established, which can be used for rapid response to trace amounts of water in organic solvents. In contrast, ETBA-TAPE-COF does not exhibit these photophysical properties due to its higher HOMO–LUMO gap compared to ETBA-PYTA-COF. This work proposes a new strategy for designing and preparing COFs with unique photophysical properties without introducing additional functional groups.展开更多
Metal organic frameworks(MOFs)have emerged as promising candidates for atmospheric water harvesting due to their high porosity and tunable functionality.Among diverse MOFs,MOF-303 has demonstrated excellent water adso...Metal organic frameworks(MOFs)have emerged as promising candidates for atmospheric water harvesting due to their high porosity and tunable functionality.Among diverse MOFs,MOF-303 has demonstrated excellent water adsorption capacity,rapid desorption kinetics and structural stability.Nevertheless,its practical application is still limited by the time-consuming synthesis process and difficultiesin morphological control.To overcome these challenges,a surfactant-mediated microwaveassisted strategy was proposed.Compared to conventional heating methods,microwave irradiation reduced the reaction duration from 24 h to 1 h with a 13%increase in product yield(from 76%to 89%).However,the accelerated nucleation under microwave irradiation resulted in smaller crystal dimensions(from 50 nm±10 nm to 35 nm±10 nm),therefore inducing severe particle agglomeration.To mitigate this morphological drawback,systematic investigations were conducted to evaluate the effects of surfactants’species on crystal growth.Among the selected surfactants,poly(sodium-p-styrene sulfonate)(PSS)was identifiedas an effective morphology-directing agent,achieving uniform crystal sizes with improved monodispersity through preferential adsorption on specificcrystallographic planes of the MOF.Subsequent optimization of synthetic conditions,including temperature(120-160℃),reaction time(15 min^(-1) h),and surfactant concentration,yielded MOF-303 with a yield of 96.37%,with particle uniformity of(35 nm±10 nm)and predominantly blocky crystal morphology.Water adsorption measurements confirmedthat the surfactant-modifiedMOF-303 retained comparable performance to the surfactant-free counterpart,with a maximum capacity(water/MOF)of 0.214 g·g^(-1) at 35%RH.This study establishes a scalable and tunable synthetic protocol for MOF-303,providing critical insights into microwave-accelerated crystal engineering.展开更多
Metal-organic frameworks(MOFs),assembled periodically by coordinating inorganic metal ions and organic motifs,have arisen widespread curiosity and intensive investigation owing to their tailorable electronic propertie...Metal-organic frameworks(MOFs),assembled periodically by coordinating inorganic metal ions and organic motifs,have arisen widespread curiosity and intensive investigation owing to their tailorable electronic properties and well-defined topological structure.However,the majority of MOFs are intrinsically dielectric or insulative[1]and typically form as 3D bulk or powder crystals,making them incompatible with complementary metal-oxide semiconductor(CMOS)techniques.In recent years,layer-stacked two-dimensional conjugated MOFs(2D c-MOFs),composed of planar conjugated ligands and linkages[2],have demonstrated high in-plane π conjugation and weak out-of-plane van der Waals interactions,due to their long-range electron delocalization over metal ions and ligands[3].As a result,highly tunable band gaps from semiconductor to conductor,modulable porosity from micropore to macropore and versatile processability into conductive 2D thin films with controllable lateral thickness and domain size are presented,rendering charming potential for applications in(opto-)electronics compared with classic 2D metal oxide,chalcogenide and crystalline polymer materials.To improve interfacial charge-transport and precisely tune the charge extraction and band alignment of 2D c-MOFs in(opto-)electronic devices[4],developing highly efficient synthetic methods of 2D c-MOFs is of utmost importance.展开更多
Covalent organic frameworks(COFs)are two-(2D)or threedimensional(3D)crystalline,porous networks generated by reversible polymerization of organic building blocks[1,2].The structures and functionalities of COFs are pre...Covalent organic frameworks(COFs)are two-(2D)or threedimensional(3D)crystalline,porous networks generated by reversible polymerization of organic building blocks[1,2].The structures and functionalities of COFs are precisely controlled via appropriately selected organic building blocks.This design imparts unique properties to COFs,including exceptional structural stability,tunable pore structure,and surface chemical activity,making them promising for gas separation,catalysis,optoelectronics,and sensing applications.Since Yaghi et al.'s seminal report on COFs in 2005[2],these frameworks have swiftly emerged as a hotspot in the field of materials.Originally,the focus was on fabricating rigid frameworks with static structures and optoelectronic properties.However,the inherently static nature of these frameworks hinders their responsiveness to external stimuli,potentially constraining their functionality in specific applications.Hence,an increasing number of researchers are now directing their attention toward the development of dynamic COFs capable of modifying their structures in response to external stimuli[3].Specifically,dynamic 2D COFs exhibiting enhanced structural responsiveness are of particular interest due to their capability to integrate switchable geometries and porosities with semiconductor building blocks,as well as electron conjugation across COF layers and π-stacked columns,which may enable stimuli-responsive electronic and spin properties[4].展开更多
Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a sustainable route to convert water and oxygen into H_(2)O_(2)using solar energy.However,achieving long-term stability in photocatalysts remains a critica...Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a sustainable route to convert water and oxygen into H_(2)O_(2)using solar energy.However,achieving long-term stability in photocatalysts remains a critical challenge due to mismatched kinetics between oxygen reduction(ORR)and water oxidation(WOR),which leads to hole accumulation and oxidative degradation.Here,we report a redox-mediated strategy to address this bottleneck by designing a hydroquinone-embedded covalent organic framework(Tz-QH-COF)that enables reversible hole buffering and kinetic balance.The hydroquinone(QH)units act as dynamic hole reservoirs,capturing excess holes during ORR and converting to benzoquinone(Q),which is regenerated to QH via WOR,thereby preventing oxidative decomposition.This reversible QH/Q cycle,directly visualized through in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy,ensures unmatched stability,achieving continuous H_(2)O_(2) production for 528 h(22 d)with an accumulated yield of 18.6 mmol L^(–1)—the highest reported duration for organic photocatalysts.Density functional theory calculations reveal that the QH units exhibit a strong oxygen adsorption energy and favorable two-electron ORR/WOR pathways with low energy barriers.The synergy between experimental and theoretical insights elucidates a redox-mediated charge-balance mechanism,advancing the design of robust photocatalysts for solar-driven H_(2)O_(2) synthesis.展开更多
As global atmospheric carbon dioxide concentrations continue to rise,the utilization of environmentally friendly alternative fuels becomes increasingly crucial[1].Methane,with its high hydrogen-to-carbon(H/C)ratio,emi...As global atmospheric carbon dioxide concentrations continue to rise,the utilization of environmentally friendly alternative fuels becomes increasingly crucial[1].Methane,with its high hydrogen-to-carbon(H/C)ratio,emits less CO_(2) than petroleum upon combustion,making it an efficient and clean energy source[2].Efficient methane storage is therefore a critical challenge and goal.Adsorbed natural gas(ANG)has recently been widely reported as a promising methane adsorption method,which utilizes porous materials to adsorb methane at high pressure and desorb it at relatively low pressure,offering superior working capacity performance over conventional compressed natural gas systems[3].Covalent organic frameworks(COFs),porous crystalline materials with permanent porosity and highly ordered structures constructed via strong covalent bonds,show good potential as methane adsorbents due to their permanent porosity[4].However,achieving high specific surface area and appropriate pore size in COFs for enhanced methane adsorption capacity remains a challenge.展开更多
Porous materials are excellent adsorbents for the removal of organic dyes from sewage and play a significant role in environmental restoration.Herein,two ferrocene(Fc)-based covalent organic frameworks(Fc-COFs),namely...Porous materials are excellent adsorbents for the removal of organic dyes from sewage and play a significant role in environmental restoration.Herein,two ferrocene(Fc)-based covalent organic frameworks(Fc-COFs),namely FcTF-COF and FcBD-COF,are successfully synthesized for the first time through a solvothermal method,and the obtained Fc-COFs powders are used to adsorb Congo red(CR)from water.The results show that both FcTF-COF and FcBD-COF have superb adsorption performance towards CR with ultrahigh adsorption capability of 1672.2 mg g−1 and 1983.7 mg g−1 at pH=4.0,respectively,outperforming the majority of the reported solid porous adsorbents.The maximum adsorption of both Fc-COFs agrees with the Sips adsorption isothermal model,indicating that their adsorption was dominated by heterogeneous adsorption.The Coulombic interactions,hydrogen bonding,π-πinteractions and ion-dipolar interactions should all contribute to their ultrahigh CR adsorption capability and high-pH resistance performance regardless of the pH in the range of 4-9.In addition,after five cycles,both COFs still remain their exceptional high CR adsorption capabilities.This study offers a prospective organic porous adsorbent with promising applications for organic dye removal in sewage processing.展开更多
Hydrogen-bonded organic frameworks(HOFs)represent an innovative category of crystalline porous materials,formed through the self-assembly of organic building blocks via intermolecular hydrogen bonds,along with supplem...Hydrogen-bonded organic frameworks(HOFs)represent an innovative category of crystalline porous materials,formed through the self-assembly of organic building blocks via intermolecular hydrogen bonds,along with supplementary interactions such asπ-πstacking and van der Waals forces.The relatively weak nature of hydrogen bonding endows HOFs with remarkable structural flexibility and a wide range of functional potential.Among them,luminescent HOFs(LHOFs)not only preserve the inherent luminescent properties of their organic fluorophore components but also exhibit key features characteristic of HOF materials,including porosity,recyclability,solution processability,and exceptional biocompatibility.This review outlines the design principles of LHOFs and explores their most recent applications,such as in sensing,bioimaging,and white-light emission.Lastly,we discuss current challenges and provide an outlook on future research directions in this field.展开更多
Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis...Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel,and also requires a large amount of poisonous solvents,which is generally not available for scaling-up production and commercial application.In recent years,great efforts have been made to explore simple,green,and efficient approaches for COFs synthesis.In this comprehensive review,we summarized the advances in emergent strategies by highlighting their distinct features.Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.展开更多
文摘CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.
基金supported by the National Key R&D Program of China(No.2023YFA1507204)National Natural Science Foundation ofChina(Nos.22475074,22171139,22225109,22302055)+4 种基金Natural Science Foundation of Guangdong Province(No.2023B1515020076)Key Scientific Research Project Plan of Colleges and Universities of Henan Province(No.24B150004)The Double Thousand Talents Plan of Jiangxi Province(No.jxsq2023102003)Project supported by the Guangdong Provincial Key Laboratory of Carbon Dioxide Resource Utilization(No.2024B121201001)Project supportedby the Major Research plan of the National Natural Science Foundation of China(No.92461310).
文摘Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.
基金financially supported by the National Natural Science Foundation of China (No.51972302)。
文摘The recovery of gold from waste electronic and electric equipment(WEEE) has gained great attention with the increased number of WEEE,because it can largely alleviate the pressure on the environment and resources.Covalent organic frameworks(COFs) are ideal adsorbents for gold recovery owing to their large surface area,good stability,easily functionalized ability,periodic structures,and definitive nanopores.Herein,a cyano-functionalized COF(COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold.The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance,which possesses fast adsorption kinetics,high cycling stability,and adsorption capacity up to 663.67 mg/g.Excitingly,COF-CN showed extremely high selectivity for gold ions,even in the presence of various competing cations and anions.The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE.The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
基金the support of the Shenzhen Science and Technology Program(no.JCYJ20220818100405012)National Natural Science Foundation of China(NSFC,no.62374080)Shenzhen Key Laboratory of Intelligent Manufacturing for Continuous Carbon Fiber Reinforced Composites(no.ZDSYS20220527171404011)。
文摘Composite solid-state electrolytes incorporating metal-organic frameworks(MOFs)demonstrate tremendous potential for ameliorating Li^(+)conduction in lithium metal batteries.However,their practical application is hindered by low ionic co nductivity and unstable Li^(+)transport at the electrode interfaces.To overcome these challenges,a previously unreported family of indium based MOFs(In-BDC-F_(x),x=0,4,6)with tunable fluorine content was synthesized and integrated into PVDF-HFP matrices to construct highperformance quasi-solid-state electrolytes.By systematically modulating linker fluorination,a bifunctional enhancement mechanism is revealed:fluorinated indium centers simultaneously suppress polymer crystallinity and establish preferential Li^(+)conduction pathways.Remarkably,In-BDC-F_(6) manifests exceptional synergistic interactions between-CF_(3) functionalities and indium coordination sites,amplifying Lewis acidity to facilitate LiTFSI dissociation and TFSI-immobilization,culminating in homogeneous LiF-enriched solid electrolyte interphases.The optimized electrolyte demonstrates compelling electrochemical performance:ionic conductivity of 9.68×10^(-4) S cm^(-1),Li^(+)transference number of 0.70,and electrochemical stability window of 4.96 V.Li‖Li symmetric cell demonstrated a critical current density of 3.5 mA cm^(-2) and stable plating/stripping for over 1000 h at 0.2 mA cm^(-2),while LiFePO_(4)‖Li cells retain96.66%capacity after 1300 cycles at 10C,underscoring the transformative potential of fluorinated MOF architectures in fast-charging solid-state batteries.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(RS-2024-00333650)supported by basic science research program through the National Research Foundation of Korea funded by the Ministry of Education(NRF-2019R1A6A1A11055660)+1 种基金supported by the Technology Innovation Program(“20013621”,Center for Super Critical Material Industrial Technology)funded By the Ministry of Trade,Industry&Energy(MOTIE,Korea)supported by Strategic Networking&Development Program funded by the Ministry of Science and ICT through the National Research Foundation of Korea(RS-2023-00268523)。
文摘Gas sensors are valuable tools for human applications,and extensive research has been conducted in this field.However,practical implementation has yet to be fully realized.In response,efforts have been made to explore metal-organic frameworks(MOFs),a novel class of porous materials,as potential solutions.MOFs exhibit exceptional porosity and highly tunable chemical compositions and structures,giving rise to a wide range of unique physical and chemical properties.Significant progress has been achieved in developing MOF-based gas sensors,improving sensing performance for various gases.This review aims to provide a comprehensive understanding of MOF-based gas sensors,even for readers unfamiliar with MOFs and gas sensors.It covers the working principles of these sensors,fundamental concepts of MOFs,strategies for tuning MOF properties,fabrication techniques for MOF films,and recent studies on MOF and MOF-derivative gas sensors.Finally,current challenges,overlooked aspects,and future directions for fully exploiting the potential of MOFs in gas sensor development are discussed.
基金support from the National Natural Science Foundation of China(22088101,21733003,22365021,22305132)the Inner Mongolia Autonomous Region“Grassland Talents”Project(2024098)+3 种基金the Inner Mongolia Natural Science Foundation Youth Fund(2023QN02014)The Local Talent Project of Inner Mongolia(12000-15042222)the Basic Research Expenses Supported under 45 Years Old of Inner Mongolia(10000-23112101/036)the“Young Academic Talents”Program of Inner Mongolia University 23600-5233706.
文摘As a class of crystalline porous materials,metal-organic frameworks(MOFs)have shown unique advantages in the fields of catalysis,gas storage and separation,but their inherent microporous structure(pore diameter<2 nm)severely limits their application in scenarios such as macromolecular mass transfer and so on.In order to overcome this re-striction,mesoporous MOFs(meso-MOFs)with a larger aperture(2-50 nm)have attracted much attention due to their potential applications in biological macromolecular catalysis,energy storage and other fields.To date,how to accurately regulate its mesopore topology and pore ordering still faces important technical challenges.
文摘(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.
文摘Photocatalytic CO_(2)cycloaddition reaction presents a promising CO_(2)conversion strategy to establish carbon neutrality.Among emerging catalysts,metal‑organic frameworks(MOFs)have been regarded as paradigmshifting photocatalysts for their atomic precision in active site engineering,controllable porosity,and exceptional photochemical stability under ambient conditions.However,inherent limitations persist in conventional MOFs,including restricted solar spectrum utilization,inefficient charge carrier separation,and inadequate epoxide activation ability.Recent breakthroughs address these challenges through multiple strategies:ligand engineering,dopant incorporation,and composite construction.This review systematically maps the evolutionary trajectory of MOF‑based photocatalysts,providing mechanistic insights into structure‑activity relationships and providing insights and directions for the design of high‑performance MOF‑based photocatalysts.
基金supported by National Natural Science Foundation of China(Nos.52370025,22176012)BUCEA Post Graduate Innovation Project(No.PG2024086)。
文摘Sludge,the massive by-product of the sewage system,became a major challenge for the wastewater treatment industry.Yet,conventional methods often face challenges like low efficiency,high energy consumption,and environmental pollution.Especially,the improper treatment and disposal of toxic sludge generated from different industrial processes or specific wastewater treatment operations exerted significant pressure and threat to hydrosphere,pedosphere,atmosphere and even biosphere.
基金support from the National Key R&D Program of China(2023YFA1507601)the National Natural Science Foundation of China(52373213,22301176)the Shanghai Pujiang Program(23PJ1405000).
文摘Ultramicroporous materials(pore dimension<7Å,as defined by IUPAC)have emerged as an intriguing class of porous substances with exceptional potential in molecular separation.Current benchmark materials including zeolites face inherent limitations in achieving hyperfine control of pore metrics,which hinder their ability to discriminate and separate molecules of very close dimensions and properties.Metal-organic frameworks,constructed by deliberate connections of metal nodes and organic linkers,have offered a great solution in addressing these challenges due to their atomic precision that allows angstrom-level engineering of pore width[1-3].
基金supported by the National Natural Science Foundation of China(22172055)the Science Fund for Distinguished Young Scholars of Guangdong Province(2023B1515040026)+1 种基金the Key Area Research and Development Program of Guangdong Province(2023B0101200008)the Natural Science Foundation of Guangdong Province(2022A1515011892).
文摘Stimuli-responsive two-dimensional (2D) covalent organic frameworks (COFs) with precise structures and permanent porosity have been employed as platforms for sensors. The slight change of backbones inside frameworks leads to different electronic states by external stimuli, such as solvent, pH, and water. Herein, we introduced an alkynyl-based building block (ETBA) with high planarity to synthesize two imine-based alkynyl-COFs (ETBA-TAPE-COF and ETBA-PYTA-COF) with high yield, good crystallinity, and chemical stability. Due to the presence of acetylene bonds, ETBA-TAPE-COF does not adopt the completely overlapping AA stacking mode. Slight interlayer displacement occurs along the parallel direction relative to the acetylene linkages, which facilitates lower configurational energy. Additionally, the introduction of pyrene group contributes to high π-electron mobility of ETBA-PYTA-COF. The interactions between electron-withdrawing group (ETBA) and electron-donating group (PYTA) during the processes of protonation and intramolecular charge transfer (ICT) endow ETBA-PYTA-COF with excellent acidochromic and solvatochromic properties, respectively. Based on this, a fluorescence sensor is successfully established, which can be used for rapid response to trace amounts of water in organic solvents. In contrast, ETBA-TAPE-COF does not exhibit these photophysical properties due to its higher HOMO–LUMO gap compared to ETBA-PYTA-COF. This work proposes a new strategy for designing and preparing COFs with unique photophysical properties without introducing additional functional groups.
基金financial support from the National Natural Science Foundation of China (22222809, 22308250)the fellowship of the China Postdoctoral Science Foundation(2022TQ0232, 2022M722365)the support from Haihe Laboratory of Sustainable Chemical Transformations
文摘Metal organic frameworks(MOFs)have emerged as promising candidates for atmospheric water harvesting due to their high porosity and tunable functionality.Among diverse MOFs,MOF-303 has demonstrated excellent water adsorption capacity,rapid desorption kinetics and structural stability.Nevertheless,its practical application is still limited by the time-consuming synthesis process and difficultiesin morphological control.To overcome these challenges,a surfactant-mediated microwaveassisted strategy was proposed.Compared to conventional heating methods,microwave irradiation reduced the reaction duration from 24 h to 1 h with a 13%increase in product yield(from 76%to 89%).However,the accelerated nucleation under microwave irradiation resulted in smaller crystal dimensions(from 50 nm±10 nm to 35 nm±10 nm),therefore inducing severe particle agglomeration.To mitigate this morphological drawback,systematic investigations were conducted to evaluate the effects of surfactants’species on crystal growth.Among the selected surfactants,poly(sodium-p-styrene sulfonate)(PSS)was identifiedas an effective morphology-directing agent,achieving uniform crystal sizes with improved monodispersity through preferential adsorption on specificcrystallographic planes of the MOF.Subsequent optimization of synthetic conditions,including temperature(120-160℃),reaction time(15 min^(-1) h),and surfactant concentration,yielded MOF-303 with a yield of 96.37%,with particle uniformity of(35 nm±10 nm)and predominantly blocky crystal morphology.Water adsorption measurements confirmedthat the surfactant-modifiedMOF-303 retained comparable performance to the surfactant-free counterpart,with a maximum capacity(water/MOF)of 0.214 g·g^(-1) at 35%RH.This study establishes a scalable and tunable synthetic protocol for MOF-303,providing critical insights into microwave-accelerated crystal engineering.
基金supported by the National Natural Science Foundation of China(Nos.22201086,22471084,92261204,21925104,and 22431005).
文摘Metal-organic frameworks(MOFs),assembled periodically by coordinating inorganic metal ions and organic motifs,have arisen widespread curiosity and intensive investigation owing to their tailorable electronic properties and well-defined topological structure.However,the majority of MOFs are intrinsically dielectric or insulative[1]and typically form as 3D bulk or powder crystals,making them incompatible with complementary metal-oxide semiconductor(CMOS)techniques.In recent years,layer-stacked two-dimensional conjugated MOFs(2D c-MOFs),composed of planar conjugated ligands and linkages[2],have demonstrated high in-plane π conjugation and weak out-of-plane van der Waals interactions,due to their long-range electron delocalization over metal ions and ligands[3].As a result,highly tunable band gaps from semiconductor to conductor,modulable porosity from micropore to macropore and versatile processability into conductive 2D thin films with controllable lateral thickness and domain size are presented,rendering charming potential for applications in(opto-)electronics compared with classic 2D metal oxide,chalcogenide and crystalline polymer materials.To improve interfacial charge-transport and precisely tune the charge extraction and band alignment of 2D c-MOFs in(opto-)electronic devices[4],developing highly efficient synthetic methods of 2D c-MOFs is of utmost importance.
基金supported by the National Natural Science Foundation of China(Nos.51902121 and 22372067)。
文摘Covalent organic frameworks(COFs)are two-(2D)or threedimensional(3D)crystalline,porous networks generated by reversible polymerization of organic building blocks[1,2].The structures and functionalities of COFs are precisely controlled via appropriately selected organic building blocks.This design imparts unique properties to COFs,including exceptional structural stability,tunable pore structure,and surface chemical activity,making them promising for gas separation,catalysis,optoelectronics,and sensing applications.Since Yaghi et al.'s seminal report on COFs in 2005[2],these frameworks have swiftly emerged as a hotspot in the field of materials.Originally,the focus was on fabricating rigid frameworks with static structures and optoelectronic properties.However,the inherently static nature of these frameworks hinders their responsiveness to external stimuli,potentially constraining their functionality in specific applications.Hence,an increasing number of researchers are now directing their attention toward the development of dynamic COFs capable of modifying their structures in response to external stimuli[3].Specifically,dynamic 2D COFs exhibiting enhanced structural responsiveness are of particular interest due to their capability to integrate switchable geometries and porosities with semiconductor building blocks,as well as electron conjugation across COF layers and π-stacked columns,which may enable stimuli-responsive electronic and spin properties[4].
文摘Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a sustainable route to convert water and oxygen into H_(2)O_(2)using solar energy.However,achieving long-term stability in photocatalysts remains a critical challenge due to mismatched kinetics between oxygen reduction(ORR)and water oxidation(WOR),which leads to hole accumulation and oxidative degradation.Here,we report a redox-mediated strategy to address this bottleneck by designing a hydroquinone-embedded covalent organic framework(Tz-QH-COF)that enables reversible hole buffering and kinetic balance.The hydroquinone(QH)units act as dynamic hole reservoirs,capturing excess holes during ORR and converting to benzoquinone(Q),which is regenerated to QH via WOR,thereby preventing oxidative decomposition.This reversible QH/Q cycle,directly visualized through in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy,ensures unmatched stability,achieving continuous H_(2)O_(2) production for 528 h(22 d)with an accumulated yield of 18.6 mmol L^(–1)—the highest reported duration for organic photocatalysts.Density functional theory calculations reveal that the QH units exhibit a strong oxygen adsorption energy and favorable two-electron ORR/WOR pathways with low energy barriers.The synergy between experimental and theoretical insights elucidates a redox-mediated charge-balance mechanism,advancing the design of robust photocatalysts for solar-driven H_(2)O_(2) synthesis.
基金support by the National Natural Science Foundation of China(Nos.22201247,22471237)the startup funding from Zhejiang Universitysupported by the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2023R01007).
文摘As global atmospheric carbon dioxide concentrations continue to rise,the utilization of environmentally friendly alternative fuels becomes increasingly crucial[1].Methane,with its high hydrogen-to-carbon(H/C)ratio,emits less CO_(2) than petroleum upon combustion,making it an efficient and clean energy source[2].Efficient methane storage is therefore a critical challenge and goal.Adsorbed natural gas(ANG)has recently been widely reported as a promising methane adsorption method,which utilizes porous materials to adsorb methane at high pressure and desorb it at relatively low pressure,offering superior working capacity performance over conventional compressed natural gas systems[3].Covalent organic frameworks(COFs),porous crystalline materials with permanent porosity and highly ordered structures constructed via strong covalent bonds,show good potential as methane adsorbents due to their permanent porosity[4].However,achieving high specific surface area and appropriate pore size in COFs for enhanced methane adsorption capacity remains a challenge.
基金supported by the National Nat-ural Science Foundation of China(22465012)the Key Research and Development Project of Hainan Province,China(ZDYF2024GXJS005)the Major Science and Technology Plan of Hainan Province,China(ZDKJ202016).
文摘Porous materials are excellent adsorbents for the removal of organic dyes from sewage and play a significant role in environmental restoration.Herein,two ferrocene(Fc)-based covalent organic frameworks(Fc-COFs),namely FcTF-COF and FcBD-COF,are successfully synthesized for the first time through a solvothermal method,and the obtained Fc-COFs powders are used to adsorb Congo red(CR)from water.The results show that both FcTF-COF and FcBD-COF have superb adsorption performance towards CR with ultrahigh adsorption capability of 1672.2 mg g−1 and 1983.7 mg g−1 at pH=4.0,respectively,outperforming the majority of the reported solid porous adsorbents.The maximum adsorption of both Fc-COFs agrees with the Sips adsorption isothermal model,indicating that their adsorption was dominated by heterogeneous adsorption.The Coulombic interactions,hydrogen bonding,π-πinteractions and ion-dipolar interactions should all contribute to their ultrahigh CR adsorption capability and high-pH resistance performance regardless of the pH in the range of 4-9.In addition,after five cycles,both COFs still remain their exceptional high CR adsorption capabilities.This study offers a prospective organic porous adsorbent with promising applications for organic dye removal in sewage processing.
基金support from the National Natural Science Foundation of China(Nos.22301039,22405043 and 22401048)the Fujian Provincial Department of Science and Technology(Nos.2024J01451,2024J08047 and 2024N0059).
文摘Hydrogen-bonded organic frameworks(HOFs)represent an innovative category of crystalline porous materials,formed through the self-assembly of organic building blocks via intermolecular hydrogen bonds,along with supplementary interactions such asπ-πstacking and van der Waals forces.The relatively weak nature of hydrogen bonding endows HOFs with remarkable structural flexibility and a wide range of functional potential.Among them,luminescent HOFs(LHOFs)not only preserve the inherent luminescent properties of their organic fluorophore components but also exhibit key features characteristic of HOF materials,including porosity,recyclability,solution processability,and exceptional biocompatibility.This review outlines the design principles of LHOFs and explores their most recent applications,such as in sensing,bioimaging,and white-light emission.Lastly,we discuss current challenges and provide an outlook on future research directions in this field.
基金financially supported by the National Natural Science Foundation of China(Nos.22322801,22108010,22278124)Fundamental Research Funds for the Central Universities(No.buctrc202135)。
文摘Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel,and also requires a large amount of poisonous solvents,which is generally not available for scaling-up production and commercial application.In recent years,great efforts have been made to explore simple,green,and efficient approaches for COFs synthesis.In this comprehensive review,we summarized the advances in emergent strategies by highlighting their distinct features.Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.
