Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have e...Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have exploded in popularity in the field of biomaterials as excellent protective materials with the advantages of conformational flexibility,thermal and chemical stability,and functional controllability.With these superior properties,the applications of ZIF-based materials in combination with various therapies for cancer treatment have grown rapidly in recent years,showing remarkable achievements and great potential.This review elucidates the recent advancements in the use of ZIFs as drug delivery agents for cancer therapy.The structures,synthesis methods,properties,and various modifiers of ZIFs used in oncotherapy are presented.Recent advances in the application of ZIF-based nanoparticles as single or combination tumor treatments are reviewed.Furthermore,the future prospects,potential limitations,and challenges of the application of ZIF-based nanomaterials in cancer treatment are discussed.We except to fully explore the potential of ZIF-based materials to present a clear outline for their application as an effective cancer treatment to help them achieve early clinical application.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
The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively red...The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.展开更多
The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the divers...The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the diverse oxidation states and structural tunability of cerium-based metal-organic frameworks(Ce-MOFs),this study employed a competitive coordination strategy utilizing a single carboxylate functional group ligand to construct a series of MOF-808-X(X=-NH_(2),-OH,-Br,and-NO_(2))featuring rich solid-state FLPs for hydrogenation of unsaturated olefins.The-X functional group serves as a microenvironment,enhancing hydrogenation activity by modulating the electronic properties and acid-base characteristics of the FLP sites.The unique redox properties of elemental cerium facilitate the exposure of unsaturated Ce sites(Ce-CUS,Lewis acid(LA))and adjacent Ce-OH(Lewis base(LB))sites within the MOFs,generating abundant solid-state FLP(Ce-CUS/Ce-OH)sites.Experimental results demonstrate that Ce-CUS and Ce-OH interact with theσandσ^(*)orbitals of H-H,and this"push-pull"synergy promotes heterolytic cleavage of the H-H bond.The lone pair electrons of the electron-donating functional group are transmitted through the molecular backbone to the LB site,thereby increasing its strength and reducing the activation energy required for H_(2)heterolytic cleavage.Notably,at 100℃and 2 MPa H_(2),MOF-808-NH_(2)achieves complete conversion of styrene and dicyclopentadiene,significantly outperforming MOF-808.Based on in-situ analysis and density functional theory calculations,a plausible reaction mechanism is proposed.This research enriches the theoretical framework for unsaturated olefin hydrogenation catalysts and contributes to the development of efficient catalytic systems.展开更多
Photocatalytic water splitting for hydrogen evolution reaction(HER)has emerged as one of the most promising approaches for solar energy utilization.Porous easily functionalized metal-organic framework(MOF)represents a...Photocatalytic water splitting for hydrogen evolution reaction(HER)has emerged as one of the most promising approaches for solar energy utilization.Porous easily functionalized metal-organic framework(MOF)represents a rising crystalline material for photocatalytic application.Yet,most MOFs still face challenges like chemical instability in solution media,no photosensitization,and ambiguous active sites.Herein,thiol-dense Hf-or Zr-based porous frameworks(Hf-,Zr-TBAPy-8SH)were prepared as platforms for facile construction of HER active sites by anchoring transition metal(TM)ions as well as forming heterojunction with nanoscale semiconductor(CdS).The highest HER rate of 8.15mmol g^(-1) h^(-1) by Co(Ⅱ)-loaded Hf-based composite highlight(1)[S^(-)-Co]motifs as competent HER site,(2)match heterojunction outweighing traditional photosensitizer-mediated HER,(3)regulating electron density of metal-oxo cluster as a way to harness HER activity.This study firstly demonstrates synergy of Hf-oxo clusters,thiol functionalities and heterojunction as an easy yet controllable strategy to form integrated photocatalyst.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
The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalyt...The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalytic active center.Therefore,the electronic conductivity is a vital parameter for oxygen reduction reaction(ORR).Covalent triazine frameworks(CTFs)have shown great potential application as electrocatalysts in ORR with a merit of the diverse building blocks.However,the intrinsic low conductivity and high impedance of CTFs could be significant setbacks in electrocatalytic application.Herein,CTFs were constructed by introducing F and N co-modification for efficient 2e^(-)ORR.Compared with the pristine CTF,the co-presence of F,N could increase the conductivity obviously by 1000-fold.As a result,F-N-CTF exhibits enhanced catalytic performance of H_(2)O_(2)generation and selectivity towards reaction pathways.This work reveals the importance of conductivity optimization for CTFs and provides guidance for designing high conductivity non-metallic organic semiconductor catalysts for 2e^(-)ORR.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
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
Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined acti...Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined active sites and high loadings under precise control has become a hotly debated topic in scientific research.Metal-organic frameworks(MOFs),with their exceptional properties such as ultrahigh specific surface areas,precisely controllable structural de-signs,and highly flexible functional cus-tomization capabilities,are regarded as one of the ideal matrices for supporting and sta-bilizing SACs.This review provides an in-sightful overview of the diverse preparation strategies for MOFs-derived SACs.It comprehen-sively analyzes the unique advantages and challenges of each method in achieving efficient synthesis of SACs,emphasizing the crucial role of optimized processes in unlocking the antici-pated performance of SACs.Furthermore,this review delves into a series of advanced charac-terization techniques,including aberration-corrected scanning transmission electron mi-croscopy(AC-STEM),electron energy loss spectroscopy(EELS),X-ray absorption spec-troscopy(XAS),and infrared absorption spectroscopy(IRAS),offering valuable insights into the atomic-scale fine structures and properties of SACs,significantly advancing the under-standing of SAC mechanisms.Moreover,this review focuses on exploring the potential appli-cations of MOFs-derived SACs in electrocatalysis frontier fields.This comprehensive exami-nation lays a solid theoretical foundation and provides a directional guidance for the rational design and controllable synthesis of high-performance MOFs-derived SACs.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
Baicalin,a major flavonoid compound found in Scutellariae radix,is the first SARS-CoV-23CLpro virus inhibitor.Therefore,developing an accurate and reliable strategy to detect baicalin in biological systems is vital.He...Baicalin,a major flavonoid compound found in Scutellariae radix,is the first SARS-CoV-23CLpro virus inhibitor.Therefore,developing an accurate and reliable strategy to detect baicalin in biological systems is vital.Herein,we report the first indolyl-lanthanide metal-organic framework(MOF)materials and their application as baicalin sensors.The results of this study indicate that the new crystal structure has good stability and luminous performance.The detection limits of baicalin in serum and urine are 0.05 and 0.04μmol/L,respectively,suggesting high sensitivity and selectivity.Various background substances present in practical samples,such as anions,cations,and amino acids,do not interfere with the photoluminescence analytical signal of Eu^(3+).We identified that the quenching of the Eu-MOF is due to the inner filter effect,absorption energy competition,and photoinduced electron transfer among the baicalin,ligand,and MOF through powder X-ray diffraction analysis,Fourier transform infrared spectroscopy,luminescence lifetimes,ultraviolet studies,and computational analysis.Thus,we designed a convenient,sensitive,and facile detection method using the Eu-MOF and demonstrate that Eu^(3+)-based materials are promising sensors for baicalin detection in actual serum and urine.Additionally,the prepared Eu-MOF@polyvinyl alcohol composite matrix membrane test film has considerable practical application value for the portable detection of baicalin.展开更多
Iron-porphyrin metal-organic frameworks(MOFs)have emerged as a remarkable class of semiconductors with adjustable photoelectrical properties and peroxidase-mimicking activities,yet their full potential remains largely...Iron-porphyrin metal-organic frameworks(MOFs)have emerged as a remarkable class of semiconductors with adjustable photoelectrical properties and peroxidase-mimicking activities,yet their full potential remains largely unexplored.The organic photoelectrochemical transistor(OPECT)has been proven to be a prominent platform for diverse applications.Herein,iron-porphyrin MOFs,as bifunctional photo-gating module and horseradish peroxidase-mimicking nanozyme,is explored for novel OPECT bioanalysis.Exemplified by alpha-fetoprotein(AFP)-dependent sandwich immunorecognition and therein glucose oxidase(GOx)-generated H_(2)O_(2)to etch CdS quantum dots on the surface of iron-porphyrin MOFs,this OPECT bioanalysis achieved high-performance AFP detection with a low detection limit of 24 fg/mL.This work featured a bifunctional iron-porphyrin MOFs gated OPECT,which is envisioned to inspire more interest in developing the diverse MOFs-nanozymes toward novel optoelectronics and beyond.展开更多
Themetal-organic frameworks(MOFs)MIL-100 andNH2-MIL-125 have hierarchical structure pores with high adsorption capacities and have therefore been suggested for drug delivery,gas storage,catalysis and chemical sensing....Themetal-organic frameworks(MOFs)MIL-100 andNH2-MIL-125 have hierarchical structure pores with high adsorption capacities and have therefore been suggested for drug delivery,gas storage,catalysis and chemical sensing.The widespread applications of these MOFs raise concerns about the possible release into the environment and subsequent human exposure.Yet,the available knowledge of the toxicity of these MOFs is rather scarce despite the encouraging applications.Here,we investigated the hematopoietic effects in different organs induced by MIL-100 and NH_(2)-MIL-125 in mice after intratracheal instillation.The hematopoietic cells in the bonemarrow(BM),lungs,and spleen were analyzed through flow cytometry method.Compared to NH2-MIL-125,MIL-100 triggered changes in more types of hematopoietic cells in the BM and spleen,but comparable changes in the lungs.In the BM and lungs,both the twoMOFs suppressedmyelopoiesis on day 1,but promotedmyelopoiesis on day 7.In the spleen,by contrast,continuous suppressedmyelopoiesis were found on day 1 and day 7.Moreover,changes in megakaryocyte progenitors(MkPs)were only detected in the lungs.These results unveil the potential disruption of hematopoietic homeostasis during inhalation of the two MOFs,which provided in vivo biological effect data for further evaluation of the biosafety of MOFs for future medical applications.展开更多
Preparing multifunctional coatings with both anti-corrosion and anti-biofouling properties is crucial.Copper has been in the spotlight as an effective biocide,especially in the recent past concerning its impact on cau...Preparing multifunctional coatings with both anti-corrosion and anti-biofouling properties is crucial.Copper has been in the spotlight as an effective biocide,especially in the recent past concerning its impact on causing environmental hazards.Reducing the amount used and increasing its efficiency have become the focus of researchers.The hybridization of titanium dioxide nanoparticles(NPs)with copper metal-organic frameworks(MOFs)can significantly improve antimicrobial performance due to its photocatalytic properties.Composites(TiO_(2)-Cu-BTC)of titanium dioxide nanoparticles and copper 1,3,5-benzenetricarboxylate acid(Cu-BTC),obtained by three up-sampling methods,namely hydrothermal,mechanical stirring,and in-situ growth,were doped into epoxy resin(TiO_(2)-Cu-BTC/EP)to enhance its anticorrosion and antifouling properties.The loaded forms were determined by field emission scanning electron microscopy and confirmed using Fourier infrared spectroscopy and X-ray diffraction spectroscopy.The lethality of the composite coating against Escherichia coli(E.coli)increased by 12%after 3 h of exposure to light,and the impedance value increased by 1×1010Ω.The efficiency of the coating was greatly improved.展开更多
Metal-Organic Frameworks(MOFs)have emerged as promising materials for gas adsorption and separation due to their exceptional surface area,tunable porosity,and versatility in functionalization.This paper explores the m...Metal-Organic Frameworks(MOFs)have emerged as promising materials for gas adsorption and separation due to their exceptional surface area,tunable porosity,and versatility in functionalization.This paper explores the mechanisms of gas adsorption in MOFs,including physical adsorption,chemisorption,and synergistic effects,which contribute to their efficiency in capturing and separating gases.The applications of MOFs in key areas such as carbon dioxide capture,hydrogen storage,natural gas separation,and air purification are discussed,highlighting their potential to address pressing environmental and energy challenges.Additionally,the use of MOFs in selective gas separation,membranes,and adsorption-based technologies like Pressure Swing Adsorption(PSA)and Vacuum Swing Adsorption(VSA)is explored,emphasizing their advantages over traditional materials.Despite challenges related to scalability,stability,and cost,MOFs hold great promise for advancing gas separation technologies in the near future,offering more efficient,sustainable,and environmentally friendly solutions.展开更多
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
In recent years,reducing carbon emissions to achieve carbon neutrality has become an urgent issue for environmental protection and sustainable development.Converting CO_(2) into valuable chemical products through elec...In recent years,reducing carbon emissions to achieve carbon neutrality has become an urgent issue for environmental protection and sustainable development.Converting CO_(2) into valuable chemical products through electrocatalysis powered by renewable electricity exhibits great potential.However,the electroreduction of CO_(2) heavily relies on efficient catalysts to overcome the required energy barrier due to the high stability of CO_(2).p-block metal-based MOFs and MOF-derived catalysts have been proven to be efficient catalysts for electrochemical CO_(2) reduction reaction(CO_(2)RR)due to their unique electronic structure and clear active sites.However,factors such as conductivity and stability limit the practical application of p-block metal-based MOFs and MOF-derived catalysts.In this review,we summarize the latest progress of MOFs and MOF-derived catalysts based on typical p-block metals in the field of CO_(2)RR.Then the modification strategies for MOFs-based catalysts and the related catalytic mechanism are briefly introduced.Furthermore,we offer the challenges and prospects of p-block metal-based MOFs and MOF-derived catalysts in the hope of providing guidance for potential applications.展开更多
Controlled synthesis of two-dimensional covalent organic frameworks(2D COFs),including stoichiometric and sub-stoichiometric variations,is a topic of growing interest due to its potential in gas separation application...Controlled synthesis of two-dimensional covalent organic frameworks(2D COFs),including stoichiometric and sub-stoichiometric variations,is a topic of growing interest due to its potential in gas separation applications.In this study,we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of[4+4]type COFs.These included a stoichiometric[4+4]type COF and two sub-stoichiometric[4+2]type COFs,featuring unreacted amino or formyl groups.The resulting COFs exhibit different gas adsorption and separation properties.Specifically,sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C_(2)H_(2),C_(2)H_(4),and CO_(2)to stoichiometric COF-DAPy.In contrast,sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C_(2)H_(2)/C_(2)H_(4)and C_(2)H_(2)/CO_(2)separation,with the C_(2)H_(2)/C_(2)H_(4)selectivity being the highest among reported COFs,attributed to increased pore polarity resulting from the presence of formyl groups.This study not only offers an additional example of substoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials,particularly in the field of gas adsorption and separation.展开更多
The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-ri...The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.展开更多
基金National Natural Science Foundation of China(52073278)the“Medical Science+X”Cross-innovation Team of the Norman Bethune Health Science of Jilin University(2022JBGS10)+2 种基金the Jilin Province Science and Technology Development Program(20190201044JC20230101045JC)the Education Department of Jilin Province(JJKH20231205KJ).
文摘Biological nanotechnologies based on functional nanoplatforms have synergistically catalyzed the emergence of cancer therapies.As a subtype of metal-organic frameworks(MOFs),zeolitic imidazolate frameworks(ZIFs)have exploded in popularity in the field of biomaterials as excellent protective materials with the advantages of conformational flexibility,thermal and chemical stability,and functional controllability.With these superior properties,the applications of ZIF-based materials in combination with various therapies for cancer treatment have grown rapidly in recent years,showing remarkable achievements and great potential.This review elucidates the recent advancements in the use of ZIFs as drug delivery agents for cancer therapy.The structures,synthesis methods,properties,and various modifiers of ZIFs used in oncotherapy are presented.Recent advances in the application of ZIF-based nanoparticles as single or combination tumor treatments are reviewed.Furthermore,the future prospects,potential limitations,and challenges of the application of ZIF-based nanomaterials in cancer treatment are discussed.We except to fully explore the potential of ZIF-based materials to present a clear outline for their application as an effective cancer treatment to help them achieve early clinical application.
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The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.
文摘The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the diverse oxidation states and structural tunability of cerium-based metal-organic frameworks(Ce-MOFs),this study employed a competitive coordination strategy utilizing a single carboxylate functional group ligand to construct a series of MOF-808-X(X=-NH_(2),-OH,-Br,and-NO_(2))featuring rich solid-state FLPs for hydrogenation of unsaturated olefins.The-X functional group serves as a microenvironment,enhancing hydrogenation activity by modulating the electronic properties and acid-base characteristics of the FLP sites.The unique redox properties of elemental cerium facilitate the exposure of unsaturated Ce sites(Ce-CUS,Lewis acid(LA))and adjacent Ce-OH(Lewis base(LB))sites within the MOFs,generating abundant solid-state FLP(Ce-CUS/Ce-OH)sites.Experimental results demonstrate that Ce-CUS and Ce-OH interact with theσandσ^(*)orbitals of H-H,and this"push-pull"synergy promotes heterolytic cleavage of the H-H bond.The lone pair electrons of the electron-donating functional group are transmitted through the molecular backbone to the LB site,thereby increasing its strength and reducing the activation energy required for H_(2)heterolytic cleavage.Notably,at 100℃and 2 MPa H_(2),MOF-808-NH_(2)achieves complete conversion of styrene and dicyclopentadiene,significantly outperforming MOF-808.Based on in-situ analysis and density functional theory calculations,a plausible reaction mechanism is proposed.This research enriches the theoretical framework for unsaturated olefin hydrogenation catalysts and contributes to the development of efficient catalytic systems.
基金supported by the National Natural Science Foundation of China(Nos.22371054,22301045)the Foundation of Basic and Applied Basic Research of Guangdong Province(Nos.2020B1515120024,2024A1515012801)Science and Technology Planning Project of Guangdong Province(Nos.2021A0505030066,2023A0505050164).
文摘Photocatalytic water splitting for hydrogen evolution reaction(HER)has emerged as one of the most promising approaches for solar energy utilization.Porous easily functionalized metal-organic framework(MOF)represents a rising crystalline material for photocatalytic application.Yet,most MOFs still face challenges like chemical instability in solution media,no photosensitization,and ambiguous active sites.Herein,thiol-dense Hf-or Zr-based porous frameworks(Hf-,Zr-TBAPy-8SH)were prepared as platforms for facile construction of HER active sites by anchoring transition metal(TM)ions as well as forming heterojunction with nanoscale semiconductor(CdS).The highest HER rate of 8.15mmol g^(-1) h^(-1) by Co(Ⅱ)-loaded Hf-based composite highlight(1)[S^(-)-Co]motifs as competent HER site,(2)match heterojunction outweighing traditional photosensitizer-mediated HER,(3)regulating electron density of metal-oxo cluster as a way to harness HER activity.This study firstly demonstrates synergy of Hf-oxo clusters,thiol functionalities and heterojunction as an easy yet controllable strategy to form integrated photocatalyst.
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the financial support by the National Natural Science Foundation of China(Nos.22205124,52172206)Natural Science Foundation of Shandong province(Nos.ZR2021QB070,ZR2023QB110)+2 种基金Basic Research Projects for the Pilot Project of Integrating Science and Education and Industry of Qilu University of Technology(Shandong Academy of Sciences)(Nos.2023PY024,2023PX108)Special Fund for Taishan Scholars Projectthe Development Plan of Youth Innovation Team in Colleges and Universities of Shandong Province。
文摘The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalytic active center.Therefore,the electronic conductivity is a vital parameter for oxygen reduction reaction(ORR).Covalent triazine frameworks(CTFs)have shown great potential application as electrocatalysts in ORR with a merit of the diverse building blocks.However,the intrinsic low conductivity and high impedance of CTFs could be significant setbacks in electrocatalytic application.Herein,CTFs were constructed by introducing F and N co-modification for efficient 2e^(-)ORR.Compared with the pristine CTF,the co-presence of F,N could increase the conductivity obviously by 1000-fold.As a result,F-N-CTF exhibits enhanced catalytic performance of H_(2)O_(2)generation and selectivity towards reaction pathways.This work reveals the importance of conductivity optimization for CTFs and provides guidance for designing high conductivity non-metallic organic semiconductor catalysts for 2e^(-)ORR.
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supported by Henan Province Key Research and Development and Promotion of Science and Technology Project(No.25A150001)the National Natural Science Foundation of China(Nos.22409171,22125303,92361302,and 92061203).
文摘Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined active sites and high loadings under precise control has become a hotly debated topic in scientific research.Metal-organic frameworks(MOFs),with their exceptional properties such as ultrahigh specific surface areas,precisely controllable structural de-signs,and highly flexible functional cus-tomization capabilities,are regarded as one of the ideal matrices for supporting and sta-bilizing SACs.This review provides an in-sightful overview of the diverse preparation strategies for MOFs-derived SACs.It comprehen-sively analyzes the unique advantages and challenges of each method in achieving efficient synthesis of SACs,emphasizing the crucial role of optimized processes in unlocking the antici-pated performance of SACs.Furthermore,this review delves into a series of advanced charac-terization techniques,including aberration-corrected scanning transmission electron mi-croscopy(AC-STEM),electron energy loss spectroscopy(EELS),X-ray absorption spec-troscopy(XAS),and infrared absorption spectroscopy(IRAS),offering valuable insights into the atomic-scale fine structures and properties of SACs,significantly advancing the under-standing of SAC mechanisms.Moreover,this review focuses on exploring the potential appli-cations of MOFs-derived SACs in electrocatalysis frontier fields.This comprehensive exami-nation lays a solid theoretical foundation and provides a directional guidance for the rational design and controllable synthesis of high-performance MOFs-derived SACs.
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.
基金Project supported by Jilin Province Science and Technology Development Plan Project(20210201061GX)。
文摘Baicalin,a major flavonoid compound found in Scutellariae radix,is the first SARS-CoV-23CLpro virus inhibitor.Therefore,developing an accurate and reliable strategy to detect baicalin in biological systems is vital.Herein,we report the first indolyl-lanthanide metal-organic framework(MOF)materials and their application as baicalin sensors.The results of this study indicate that the new crystal structure has good stability and luminous performance.The detection limits of baicalin in serum and urine are 0.05 and 0.04μmol/L,respectively,suggesting high sensitivity and selectivity.Various background substances present in practical samples,such as anions,cations,and amino acids,do not interfere with the photoluminescence analytical signal of Eu^(3+).We identified that the quenching of the Eu-MOF is due to the inner filter effect,absorption energy competition,and photoinduced electron transfer among the baicalin,ligand,and MOF through powder X-ray diffraction analysis,Fourier transform infrared spectroscopy,luminescence lifetimes,ultraviolet studies,and computational analysis.Thus,we designed a convenient,sensitive,and facile detection method using the Eu-MOF and demonstrate that Eu^(3+)-based materials are promising sensors for baicalin detection in actual serum and urine.Additionally,the prepared Eu-MOF@polyvinyl alcohol composite matrix membrane test film has considerable practical application value for the portable detection of baicalin.
基金financially supported by the National Natural Science Foundation of China(Nos.22034003,22374066)the Fundamental Research Funds for the Central Universities(No.2022300285)+1 种基金the Excellent Research Program of Nanjing University(No.ZYJH004)State Key Laboratory of Analytical Chemistry for Life Science(No.5431ZZXM2203).
文摘Iron-porphyrin metal-organic frameworks(MOFs)have emerged as a remarkable class of semiconductors with adjustable photoelectrical properties and peroxidase-mimicking activities,yet their full potential remains largely unexplored.The organic photoelectrochemical transistor(OPECT)has been proven to be a prominent platform for diverse applications.Herein,iron-porphyrin MOFs,as bifunctional photo-gating module and horseradish peroxidase-mimicking nanozyme,is explored for novel OPECT bioanalysis.Exemplified by alpha-fetoprotein(AFP)-dependent sandwich immunorecognition and therein glucose oxidase(GOx)-generated H_(2)O_(2)to etch CdS quantum dots on the surface of iron-porphyrin MOFs,this OPECT bioanalysis achieved high-performance AFP detection with a low detection limit of 24 fg/mL.This work featured a bifunctional iron-porphyrin MOFs gated OPECT,which is envisioned to inspire more interest in developing the diverse MOFs-nanozymes toward novel optoelectronics and beyond.
基金supported by the National Natural Science Foundation of China(Nos.22193053,42377386,and 22325606)the National Key Research and Development Programof China(No.2023YFA0915101)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0750000).
文摘Themetal-organic frameworks(MOFs)MIL-100 andNH2-MIL-125 have hierarchical structure pores with high adsorption capacities and have therefore been suggested for drug delivery,gas storage,catalysis and chemical sensing.The widespread applications of these MOFs raise concerns about the possible release into the environment and subsequent human exposure.Yet,the available knowledge of the toxicity of these MOFs is rather scarce despite the encouraging applications.Here,we investigated the hematopoietic effects in different organs induced by MIL-100 and NH_(2)-MIL-125 in mice after intratracheal instillation.The hematopoietic cells in the bonemarrow(BM),lungs,and spleen were analyzed through flow cytometry method.Compared to NH2-MIL-125,MIL-100 triggered changes in more types of hematopoietic cells in the BM and spleen,but comparable changes in the lungs.In the BM and lungs,both the twoMOFs suppressedmyelopoiesis on day 1,but promotedmyelopoiesis on day 7.In the spleen,by contrast,continuous suppressedmyelopoiesis were found on day 1 and day 7.Moreover,changes in megakaryocyte progenitors(MkPs)were only detected in the lungs.These results unveil the potential disruption of hematopoietic homeostasis during inhalation of the two MOFs,which provided in vivo biological effect data for further evaluation of the biosafety of MOFs for future medical applications.
基金Project(52073311) supported by the National Natural Science Foundation of ChinaProject(2023A0505010011) supported by the Guangdong-Hong Kong-Macao Joint Innovation Field Research Foundation,ChinaProject(2021A1515012281) supported by the Guangdong Basic and Applied Basic Research Foundation,China。
文摘Preparing multifunctional coatings with both anti-corrosion and anti-biofouling properties is crucial.Copper has been in the spotlight as an effective biocide,especially in the recent past concerning its impact on causing environmental hazards.Reducing the amount used and increasing its efficiency have become the focus of researchers.The hybridization of titanium dioxide nanoparticles(NPs)with copper metal-organic frameworks(MOFs)can significantly improve antimicrobial performance due to its photocatalytic properties.Composites(TiO_(2)-Cu-BTC)of titanium dioxide nanoparticles and copper 1,3,5-benzenetricarboxylate acid(Cu-BTC),obtained by three up-sampling methods,namely hydrothermal,mechanical stirring,and in-situ growth,were doped into epoxy resin(TiO_(2)-Cu-BTC/EP)to enhance its anticorrosion and antifouling properties.The loaded forms were determined by field emission scanning electron microscopy and confirmed using Fourier infrared spectroscopy and X-ray diffraction spectroscopy.The lethality of the composite coating against Escherichia coli(E.coli)increased by 12%after 3 h of exposure to light,and the impedance value increased by 1×1010Ω.The efficiency of the coating was greatly improved.
文摘Metal-Organic Frameworks(MOFs)have emerged as promising materials for gas adsorption and separation due to their exceptional surface area,tunable porosity,and versatility in functionalization.This paper explores the mechanisms of gas adsorption in MOFs,including physical adsorption,chemisorption,and synergistic effects,which contribute to their efficiency in capturing and separating gases.The applications of MOFs in key areas such as carbon dioxide capture,hydrogen storage,natural gas separation,and air purification are discussed,highlighting their potential to address pressing environmental and energy challenges.Additionally,the use of MOFs in selective gas separation,membranes,and adsorption-based technologies like Pressure Swing Adsorption(PSA)and Vacuum Swing Adsorption(VSA)is explored,emphasizing their advantages over traditional materials.Despite challenges related to scalability,stability,and cost,MOFs hold great promise for advancing gas separation technologies in the near future,offering more efficient,sustainable,and environmentally friendly solutions.
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supported by the National Natural Science Foundation of China(Nos.22061019 and 22261021)the Jiangxi Provincial Natural Science Foundation(Nos.20224BAB203002,20232ACB203018,20232BAB203005,and 20224BAB213001)+5 种基金the Jiangxi Province Key Laboratory of Functional Crystalline Materials Chemistry(No.2024SSY05161)the Ganzhou Key Research and Development Program(No.2023PNS26963)the Youth Jinggang Scholars Program in Jiangxi Province(No.QNJG2019053)the Two Thousand Talents Program in Jiangxi Province(No.jxsq2019201068)the Doctor’s Starting Research Foundation of Jiangxi University of Science and Technology(No.205200100597)the Science and Technology Research Project of Jiangxi Provincial Department of Education(No.GJJ2200860).
文摘In recent years,reducing carbon emissions to achieve carbon neutrality has become an urgent issue for environmental protection and sustainable development.Converting CO_(2) into valuable chemical products through electrocatalysis powered by renewable electricity exhibits great potential.However,the electroreduction of CO_(2) heavily relies on efficient catalysts to overcome the required energy barrier due to the high stability of CO_(2).p-block metal-based MOFs and MOF-derived catalysts have been proven to be efficient catalysts for electrochemical CO_(2) reduction reaction(CO_(2)RR)due to their unique electronic structure and clear active sites.However,factors such as conductivity and stability limit the practical application of p-block metal-based MOFs and MOF-derived catalysts.In this review,we summarize the latest progress of MOFs and MOF-derived catalysts based on typical p-block metals in the field of CO_(2)RR.Then the modification strategies for MOFs-based catalysts and the related catalytic mechanism are briefly introduced.Furthermore,we offer the challenges and prospects of p-block metal-based MOFs and MOF-derived catalysts in the hope of providing guidance for potential applications.
基金supported by the National Key Research and Development Project of China(No.2022YFE0113800)the National Natural Science Foundation of China(No.22375179)+1 种基金the startup grant(No.2019125016829)in Zhejiang University of Technologypartially supported by the National Innovation and Entrepreneurship Training Program(No.202310337063)。
文摘Controlled synthesis of two-dimensional covalent organic frameworks(2D COFs),including stoichiometric and sub-stoichiometric variations,is a topic of growing interest due to its potential in gas separation applications.In this study,we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of[4+4]type COFs.These included a stoichiometric[4+4]type COF and two sub-stoichiometric[4+2]type COFs,featuring unreacted amino or formyl groups.The resulting COFs exhibit different gas adsorption and separation properties.Specifically,sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C_(2)H_(2),C_(2)H_(4),and CO_(2)to stoichiometric COF-DAPy.In contrast,sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C_(2)H_(2)/C_(2)H_(4)and C_(2)H_(2)/CO_(2)separation,with the C_(2)H_(2)/C_(2)H_(4)selectivity being the highest among reported COFs,attributed to increased pore polarity resulting from the presence of formyl groups.This study not only offers an additional example of substoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials,particularly in the field of gas adsorption and separation.
基金supported by the National Natural Science Foundation of China(No.51972066)the Natural Science Foundation of Guangdong Province of China(No.2024A1515012499)。
文摘The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.
