Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully construct...Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.展开更多
Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fund...Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.展开更多
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
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
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
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
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
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
Cancer is one of the most complex diseases and the second leading cause of mortality worldwide.Due to its poor prognosis and challenges in diagnosis,eradicating cancer remains highly difficult.The limitations associat...Cancer is one of the most complex diseases and the second leading cause of mortality worldwide.Due to its poor prognosis and challenges in diagnosis,eradicating cancer remains highly difficult.The limitations associated with conventional therapies have led to the emergence of copious therapeutic strategies such as chemotherapy,phototherapy,starvation therapy,radiotherapy and immunotherapy;however,limited therapeutic efficacy,poor tumor cell selectivity and substantial adverse effects remain significant concern.Attributed to the expeditious advancement of nanotechnology,the amalgamation of nanomaterials with therapeutic approaches provides an opportunity to address the shortcomings of conventional chemotherapy.Metal-organic frameworks(MOFs),which consist of bridging ligands and ions/clusters connected by coordination bonds,have been widely used in cancer therapy to address the limitations of currently therapeutic interventions,such as poor efficacy,low stability and severe side effects.This potential arises from their tuneable porosities,high specific surface area-to-volume ratio,tailorable diameters,tractable morphologies,variegated compositions,biocompatibility and facile functionalization.We summarized the role of MOF-based nanoplatforms along with mechanistic insights into emerging avenues-such as cuproptosis,ferroptosis,cell-penetrating and biomimetic MOFs,and tumor microenvironment-responsive MOFs-alongside recent advancements in mono-and multifunctional cancer therapeutics.Theragnostic and imaging functionalities,as well as regulatory considerations and future prospects of MOF-based nanoplatforms utilized in cancer treatment,are also discussed.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
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
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
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
文摘Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.
基金supported by National Natural Science Foundation of China(32494793).
文摘Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.
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.
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.
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.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funding support by the Department of Pharmaceuticals(DoP),Ministry of Chemicals and Fertilizers,Govt.of India to“Pharmaceutical Innovation and Translational Research Lab”(PITRL),National Institute of Pharmaceutical Education and Research(NIPER),Hyderabad,INDIA.
文摘Cancer is one of the most complex diseases and the second leading cause of mortality worldwide.Due to its poor prognosis and challenges in diagnosis,eradicating cancer remains highly difficult.The limitations associated with conventional therapies have led to the emergence of copious therapeutic strategies such as chemotherapy,phototherapy,starvation therapy,radiotherapy and immunotherapy;however,limited therapeutic efficacy,poor tumor cell selectivity and substantial adverse effects remain significant concern.Attributed to the expeditious advancement of nanotechnology,the amalgamation of nanomaterials with therapeutic approaches provides an opportunity to address the shortcomings of conventional chemotherapy.Metal-organic frameworks(MOFs),which consist of bridging ligands and ions/clusters connected by coordination bonds,have been widely used in cancer therapy to address the limitations of currently therapeutic interventions,such as poor efficacy,low stability and severe side effects.This potential arises from their tuneable porosities,high specific surface area-to-volume ratio,tailorable diameters,tractable morphologies,variegated compositions,biocompatibility and facile functionalization.We summarized the role of MOF-based nanoplatforms along with mechanistic insights into emerging avenues-such as cuproptosis,ferroptosis,cell-penetrating and biomimetic MOFs,and tumor microenvironment-responsive MOFs-alongside recent advancements in mono-and multifunctional cancer therapeutics.Theragnostic and imaging functionalities,as well as regulatory considerations and future prospects of MOF-based nanoplatforms utilized in cancer treatment,are also discussed.
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 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.
