Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixtur...Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixture and linker exchange of activated single-linker MOFs. Functionality proportion was impacted by the thermodynamics during the one-pot MOF construction, resulting in preference of BDC over BDC-NH2 in the MTV-MOF, in agreement with the quantum mechanics calculations. The functionality difference also affects the thermodynamics in the linker exchange process, as indicated by the more effective linker exchange in BDC-NH2-based IRMOF-3 than in BDC-based MOF-5. Furthermore,the thermal decomposition temperatures and chemical integrity upon ambient air exposure of these MOFs with variate functionalities were investigated, and it reveals that higher proportion of BDC in the MTV-MOF crystals contribute to both higher thermal and higher chemical stabilities.展开更多
The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative p...The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.展开更多
Photocatalytic carbon dioxide reduction reaction(CO_(2)RR)is a carbon-neutral strategy to address global energy use and its impact on climate.Metal oxide and metal chalcogenide catalysts are the most investigated cata...Photocatalytic carbon dioxide reduction reaction(CO_(2)RR)is a carbon-neutral strategy to address global energy use and its impact on climate.Metal oxide and metal chalcogenide catalysts are the most investigated catalysts for photocatalytic CO_(2)RR.Unfortunately,low CO_(2)adsorption ability and limited active sites of metal oxide and metal chalcogenide catalysts for CO_(2)RR make them less competitive compared to their industrial counterparts.Inspired by applications of porphyrin-based metal-organic framework(MOF)catalysts for hydrogen evolution and photodynamic therapy,the investigations of these porphyrin-based MOFs,including pristine and composite porphyrin-based MOFs in photocatalytic CO_(2)RR,have attracted significant attention in the last five years due to their excellent CO_(2)adsorption capacities,high porosity,high stability,exceptional optoelectronic properties,and multi-functionality.However,due to the difference in photocatalytic CO_(2)RR,several critical issues need to be addressed to achieve the rational design of advanced porphyrin-based MOF photocatalysts to improve activity,selectivity,and stability for CO_(2)RR.Here,we review recent developments in the field of porphyrin-based MOF CO_(2)RR photocatalysts,along with critical issues,challenges,and perspectives concerning porphyrin-based MOF catalysts for photocatalytic CO_(2)RR.展开更多
Lead-halide perovskite solar cells(PSCs)have rapidly achieved certified efficiencies>27%,rivaling silicon photovoltaics.However,their commercialization is hindered by intrinsic material challenges:poor operational ...Lead-halide perovskite solar cells(PSCs)have rapidly achieved certified efficiencies>27%,rivaling silicon photovoltaics.However,their commercialization is hindered by intrinsic material challenges:poor operational stability under moisture,heat,and light;toxic lead leakage from degraded films.Metal-organic frameworks(MOFs),with their unique framework structure,large specific surface area,high heavy metal capturing capacity,and tunable conductivity,offer promising solutions to these issues.Recent studies have integrated MOFs into PSCs architectures to enhance performance and durability.This comprehensive review begins with an in-depth discussion of the structure,optical properties,electrical characteristics,and stability of MOFs,as well as their theoretical compatibility with perovskites.Subsequently,it provides a detailed analysis of how MOFs enhance charge carrier transport,promote perovskite crystallinity,improve device stability,and suppress lead leakage in PSCs.In summary,this review examines the research progress and potential of integrating MOFs with perovskites to address the critical PSCs challenges of efficiency,instability,and toxicity.展开更多
Metal-organic frameworks(MOFs)with high porosity,specific surface area,and unique topologies are highly regarded for their applications in photocatalysis,medical treatment,and environmental pollutant degradation.Howev...Metal-organic frameworks(MOFs)with high porosity,specific surface area,and unique topologies are highly regarded for their applications in photocatalysis,medical treatment,and environmental pollutant degradation.However,due to the limitations of the tumor microenvironment(TME),traditional MOFs have limited efficacy in this environment.This paper designs multi-metal oxide-based heterostructure POMOFs nanoreactors with a nesting doll-like structure.This new structure not only exhibits therapeutic effects in TME but also utilizes ultrasound(US)to enhance the release of reactive oxygen species(ROS)for CDT&SDT co-therapy,becoming an effective sound sensitizer for destroying tumor cells.In summary,our study proposes an idea for constructing multi-metal oxide-based heterostructure MOFs nanoreactors material with a nesting doll-like structure to enhance ROS release and synergistically treat tumor diseases.展开更多
The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by ca...The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.展开更多
In this paper,we exploit our prior successful synthesis of MOF-199 single crystals using the reaction-diffusion framework(RDF),to synthesize multivariate metal-organic frameworks(MTV-MOFs)version with enhanced propert...In this paper,we exploit our prior successful synthesis of MOF-199 single crystals using the reaction-diffusion framework(RDF),to synthesize multivariate metal-organic frameworks(MTV-MOFs)version with enhanced properties.The MTV-MOFs are synthesized by creating defects within the MOF-199 crystal structure by integrating organic linkers entailing different functional groups.Accordingly,5-aminoisophthalic acid(NH_(2)-BDC)and 5-hydroxyisophthalic acid(OH-BDC)are separately mixed with 1,3,5-benzenetricarboxylic acid(BTC)in three different starting ratios of X-BDC:BTC(1:3,1:1)and(3:1).The effects of this linker on the morphology of the synthesized MTV-MOFs,their thermal stability,and their surface area are investigated.The extent of the incorporation of the linkers in the framework is elucidated via^(1)H-NMR spectroscopy and it is shown that the incorporation varies as a function of the location along the tubular reactor,a characteristic of RDF.The enhanced properties of the synthesized MTV-MOFs are further demonstrated by measuring its adsorptive capability for methylene blue(MB)and rhodamine B(Rh B)in aqueous solution,and compared with that of the as-synthesized MOF-199.The kinetic and thermodynamic studies reveal that MTV-MOFs with the ratio of X-BDC:BTC(1:1)exhibit the best uptakes of MB(263 mg/g)for X=OH and Rh B(156 mg/g)for X=NH_(2).The adsorbents are also easily regenerated for three consecutive cycles without losing their efficiency.We finally demonstrate that MTV-MOFs can be designed to tune the dye removal selectivity and enhance the removal capacity of both MB and RhB in a binary aqueous solution of these dyes.展开更多
In this study,a nickel-based MOF{(NH_(2)(CH_(3))_(2))_(2)[Ni_(3)(O)(L)3(NH(CH_(3))_(2))_(3)]}_(n)(Ni_(3)-MOF),with pore sizes of approximately 1.6 nm×1.6 nm,was synthesized by reacting 4,4′-biphenyldicarboxylic ...In this study,a nickel-based MOF{(NH_(2)(CH_(3))_(2))_(2)[Ni_(3)(O)(L)3(NH(CH_(3))_(2))_(3)]}_(n)(Ni_(3)-MOF),with pore sizes of approximately 1.6 nm×1.6 nm,was synthesized by reacting 4,4′-biphenyldicarboxylic acid(H_(2)L)with Ni(NO_(3))_(2)·6H_(2)O in an N,N-dimethylformamide(DMF)solution.The nanoscale adsorbent Ni_(3)-MOF-N with a particle diameter of approximately 200 nm was prepared using Ni_(3)-MOF.It exhibited a maximum equilibrium tetracycline(TC)adsorption capacity of 358.2 mg·g^(-1)at its isoelectric point(pH=6.50),outperforming most reported MOF-based adsorbents.This exceptional performance is likely attributed to the well-matched pore size of Ni_(3)-MOF-N(1.6 nm×1.6 nm)and the molecular dimensions of TC(0.8 nm×1.2 nm),combined with the presence of partial Ni(Ⅱ)sites on the surface of Ni_(3)-MOF-N.These features collectively facilitate effective TC adsorption through a combination of pore filling,electrostatic attraction,hydrogen bonding,surface complexation,andπ-πinteractions.Recycling experiments demonstrated that Ni_(3)-MOF-N possesses excellent structural stability and consistent adsorption performance.CCDC:2481791,Ni_(3)-MOF.展开更多
A metal-organic framework{[Zn(L)_(0.5)(1,2,4,5-tpb)_(0.5)]·DMF·3H_(2)O}_(n)(1)was synthesized by solvothermal reaction,where H4L=5,5'-(ethane-1,2-diyl)diisophthalic acid,and 1,2,4,5-tpb=1,2,4,5-tetra(pyr...A metal-organic framework{[Zn(L)_(0.5)(1,2,4,5-tpb)_(0.5)]·DMF·3H_(2)O}_(n)(1)was synthesized by solvothermal reaction,where H4L=5,5'-(ethane-1,2-diyl)diisophthalic acid,and 1,2,4,5-tpb=1,2,4,5-tetra(pyridin-4-yl)benzene.The analysis of the single crystal structure indicates that L^(4-)and 1,2,4,5-tpb are connected with Zn(Ⅱ)to form a 2D layered structure,and the layers are linked by 1,2,4,5-tpb to form a 3D structure.1 can be used as a highly selective fluorescent probe for the detection of 2,4-dinitrophenylhydrazine(DNP)and tetracycline(TET),and the detection limits were 0.013 and 0.31μmol·L^(-1),respectively.1 was applied successfully to the determination of TET content in the Yanhe River water sample.CCDC:2466221.展开更多
Aqueous zinc-ion batteries(AZIBs)have emerged as a promising complement to lithium-ion batteries due to their inherent safety benefits.However,the cycle life of AZIBs is severely limited by the poor stability of zinc ...Aqueous zinc-ion batteries(AZIBs)have emerged as a promising complement to lithium-ion batteries due to their inherent safety benefits.However,the cycle life of AZIBs is severely limited by the poor stability of zinc anodes,manifested in uncontrolled dendritic growth and persistent side reactions,which hinder wider application.Herein,we report an ion-selective separator(UIO-66-4F/GF)achieved by in situ growth of a fluorine-functionalized metal-organic framework(UIO-66-4F)onto commercial glass fiber(GF).The synergistic mechanism,involving electrostatic repulsion between-F groups and SO_(4)^(2-)anions along with strong interactions between-F and Zn^(2+)cations,effectively restrict SO_(4)^(2-)migration,suppresses 2D Zn^(2+)diffusion across electrode interfaces,and enhances[Zn(H_(2)O)_(6)]^(2+)desolvation.Furthermore,the-F groups enable precise regulation of interfacial electric fields and Zn^(2+)concentration gradients,thereby homogenizing ion flux to realize dendrite-free Zn deposition.The UIO-66-4F separator achieves stable Zn||Zn cell operation for 1500 h at 1 mA cm^(-2)via oriented deposition and sustains long-term cycling over 1000 h at 1 mA cm^(-2),and delivers a Zn||Cu cell with 99.4%Coulombic efficiency.Moreover,the Zn|UIO-66-4F/GF|NH_(4)V_(4)O_(10) full cell represents an ultrastable cycling stability with a high capacity retention of 90%after 500 cycles at a current density of 1 A g^(-1).展开更多
The reaction of Mg^(2+)and 5-{1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl}terephthalic acid(H_(2)L)leads to two metal-organic frameworks,[Mg(L)(DMF)_(2)(H_(2)O)_(2)]_(2)·5DMF·2H_(2)O(1)with a 1D structure and...The reaction of Mg^(2+)and 5-{1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl}terephthalic acid(H_(2)L)leads to two metal-organic frameworks,[Mg(L)(DMF)_(2)(H_(2)O)_(2)]_(2)·5DMF·2H_(2)O(1)with a 1D structure and[Mg_(2)(L)_(2)(DMSO)_(3)(H_(2)O)](2)with a 2D(4,4)-net structure.Interestingly,the two compounds exhibit distinct luminescent responses to external mechanical stimuli.1 exhibited exceptional resistance mechanical chromic luminescence(RMCL),which can be attributed to the predominant hydrogen bonds and the presence of high-boiling-point solvent molecules within its structure.2 had a reversible MCL property,which can be attributed to the dominantπ-πweak interactions,coupled with the reversible destruction/restoration of its crystallinity under grinding/fumigation.CCDC:2410963,1;2410964,2.展开更多
Constructing hierarchical nanostructures with highly exposed surfaces is a promising strategy for developing advanced cathode materials in aqueous batteries.Herein,we employed a competitive coordination strategy to op...Constructing hierarchical nanostructures with highly exposed surfaces is a promising strategy for developing advanced cathode materials in aqueous batteries.Herein,we employed a competitive coordination strategy to optimize the characteristics of nickel metal-organic framework(Ni-MOF).Specifically,the acetate ions were employed as precise regulators,exerting a distinct influence on the morphology of the Ni-MOF and leading to a structural transition from a block structure to a two-dimensional(2D)layered structure.The optimized Ni-MOF exhibits a unique superstructure composed of hierarchical 2D layers assembled into flower-like architectures.This distinctive superstructure increases the electrochemically active surface area of Ni-MOF(N-2)and provides abundant pathways for electron/ion transfer,thereby facilitating efficient electrochemical reactions.Remarkably,the assembled aqueous alkaline N-2//Zn battery demonstrated enhanced specific capacity(0.446 mAh·cm^(-2)at 1 mA·cm^(-2))and excellent maximum energy/power density(0.789 mWh·cm^(-2)/17.262 mW·cm^(-2)).This work not only offers valuable insights into regulating MOF morphology,but also makes a contribution toward enhancing the application potential of MOFs in aqueous batteries.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
The effi ciency of photocatalytic ammonia(NH_(3))synthesis is severely limited by the extremely diffi cult activation of N_(2) owing to its high N≡N triple bond energy.To address this challenge,we propose an N-doping...The effi ciency of photocatalytic ammonia(NH_(3))synthesis is severely limited by the extremely diffi cult activation of N_(2) owing to its high N≡N triple bond energy.To address this challenge,we propose an N-doping strategy to facilitate the N_(2) activation.Our strategy involves optimizing the electronic structure of the metal active sites by modulating the coordination element.First,we introduce fi ve diff erent N-coordination ligands with distinct steric hindrances and N electron densities(2-methyl-imidazole(MI),isoindolin-1-one(II),1,2-benzisothiazolin-3-one(BIT),benzo[d]isoxazol-3-ol(BIX),and terephthalamide(TA))into an amino-functionalized metal-organic framework(MOF),NH_(2)-MIL-68(NM),to construct the N-coordination via the partial replacement of the O-coordination in the metal clusters.Electrochemical impedance spectroscopy and photocur-rent analysis demonstrate that N-doping enhances electron transfer and carrier separation.Moreover,incorporating ligands with moderate sizes and steric hindrances(II,BIT,and BIX)more eff ectively boosts the carrier separation efficiency than incorporating small(MI)or large(TA)ligands.Furthermore,the N-doped MOF modifi ed with BIT(in which N exhibits a moderate electron density)exhibits the strongest carrier separation capability.Concurrently,the X-ray photoelectron spec-troscopy,density functional theory,and N_(2) temperature-programmed desorption results confi rm that the established low-electronegativity N-coordination elevates the electron density of the metal active sites,which consequently enhances the N_(2) activation process.The systematic optimization of the N-coordinating ligand species and doping concentrations allows the optimal NM-0.5BIT to achieve a NH 3 production rate of 175.5μmol/(g·h).The proposed N-doping strategy off ers several insights into the activation of inert molecules and the development of organic framework photocatalysts.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
A novel composite material,Poly(IL-AA)@MIL-101(Cr),combining metal-organic framework,polymeric ionic liquid and acrylic acid,was synthesized for the selective and efficient adsorption of rare earths europium(Ⅲ)(Eu3+)...A novel composite material,Poly(IL-AA)@MIL-101(Cr),combining metal-organic framework,polymeric ionic liquid and acrylic acid,was synthesized for the selective and efficient adsorption of rare earths europium(Ⅲ)(Eu3+).Characterization of the materials was carried out using techniques such as X-ray diffraction(XRD),Fourier transform infrared(FTIR),scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDS),thermogravimetric analysis(TGA)and Brunauer-Emmett-Teller(BET).The results demonstrate successful incorporation of the polymeric ionic liquid onto the material surface while preserving the crystal structure and mo rphology of MIL-101(Cr).Adsorption experiments were conducted to explore parameters including equilibrium pH,initial Eu3+concentration,and duration,with comprehensive analyses of adsorption kinetics,isotherms,and mechanisms.Findings reveal that Poly(IL1-AA)@MIL-101(Cr),Poly(IL3-AA)@MIL-101(Cr),and Poly(IL5-AA)@MIL-101(Cr)achieve adsorption equilibrium for Eu3+at approximately 9 h with an equilibrium pH of 6.2.The adso rption of Eu^(3+)predominantly follows a pseudo-second-order kinetic model and Langmuir isotherm adsorption model.Moreover,the prepared composite material exhibits superior adsorption selectivity for Eu^(3+)over other metal ions in the mixture(K^(+),Mg^(2+),Ni^(2+),Co^(2+),Zn^(2+),La^(3+),and Nd^(3+)).Even after five adsorption-desorption cycles,the composite material maintains satis factory adsorption performance.展开更多
The facets effect on the catalytic properties of inorganic compounds and metal-organic frameworks(MOFs)has been widely demonstrated,but the intrinsic facets effect free of interference of capping agents has not been d...The facets effect on the catalytic properties of inorganic compounds and metal-organic frameworks(MOFs)has been widely demonstrated,but the intrinsic facets effect free of interference of capping agents has not been discussed.Here we give a proof-of-concept illustration on the intrinsic facets effect by employing the popularly investigated NH2-MIL-125(Ti)MOFs with{001},{111}and{100}facets controllably exposed as model photocatalysts,which were synthesized via a simple supersaturation strategy free of any capping agents.Compared to conventional synthetic routes with capping agents employed,the NH2-MIL-125(Ti)MOFs obtained in this work exhibit remarkably different physical and chemical properties such as surface wettability,charge separation as well as trend of facets effect on photocatalytic water splitting performance.The main reason has been unraveled to originate from unavoidable residue/influence of capping agents during the conventional facets-controlled synthetic routes leading to changed local surface structural environment as well as distinct charge separation property.Our results demonstrate the importance and feasibility of facets-controllable synthesis free of capping agents in getting insight into the intrinsic facets effect of MOFs-related materials.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
Metal-organic frameworks(MOFs)have emerged as promising materials owing to their high surface areas,tunable pore sizes,and diverse functionalities.However,their practical deployment is frequently hindered by intrinsic...Metal-organic frameworks(MOFs)have emerged as promising materials owing to their high surface areas,tunable pore sizes,and diverse functionalities.However,their practical deployment is frequently hindered by intrinsic microporosity and structural fragility.In this review,we systematically analyze recent advancements in MOF etching techniques,which strategically modify framework architectures to enhance mass transport,expose active sites,and improve stability.The discussion encompasses a range of methods―including acid,base,ion,solvent,steam,selective,in-situ,pyrolysis,and physical etching―with emphasis on the underlying mechanisms that govern the formation of hierarchical pore structures,defect engineering,and heterojunction formation.Notably,etching approaches facilitate precise control over crystal morphology and surface chemistry,thereby optimizing MOF performance in catalysis,electrocatalysis,photocatalysis,adsorption,energy storage,sensing,and biomedical applications.We also outline challenges such as etchant toxicity,over-etching risks,and scalability,while highlighting emerging strategies and computational simulations to refine the etching process.Ultimately,this review underscores the transformative impact of etching on MOF properties,paving the way for the design of next-generation multifunctional materials that address critical issues in environmental remediation,energy conversion,and beyond.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
基金supported by the "Top-Notch Students Training in Basic Disciplines" undergraduate program of Ministry of Education of China
文摘Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixture and linker exchange of activated single-linker MOFs. Functionality proportion was impacted by the thermodynamics during the one-pot MOF construction, resulting in preference of BDC over BDC-NH2 in the MTV-MOF, in agreement with the quantum mechanics calculations. The functionality difference also affects the thermodynamics in the linker exchange process, as indicated by the more effective linker exchange in BDC-NH2-based IRMOF-3 than in BDC-based MOF-5. Furthermore,the thermal decomposition temperatures and chemical integrity upon ambient air exposure of these MOFs with variate functionalities were investigated, and it reveals that higher proportion of BDC in the MTV-MOF crystals contribute to both higher thermal and higher chemical stabilities.
基金supported by the National Natural Science Foundation of China(No.52304329)the Yunnan Fundamental Research Projects(No.202201BE070001-003),Guo Lin would like to acknowledge Xing Dian talent support program of Yunnan Province.
文摘The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.
基金financially supported by the National Natural Science Foundation of China(No.22305009)the Science and Technology Development Fund,Macao SAR(File no.FDCT-0125/2022/A and FDCT-0006/2023/RIB1)Hong Kong Research Grant Council(RGC)General Research Fund(GRF)City U 11305419,11306920,CityU 11308721,CityU 11316522,and SIRG7020022。
文摘Photocatalytic carbon dioxide reduction reaction(CO_(2)RR)is a carbon-neutral strategy to address global energy use and its impact on climate.Metal oxide and metal chalcogenide catalysts are the most investigated catalysts for photocatalytic CO_(2)RR.Unfortunately,low CO_(2)adsorption ability and limited active sites of metal oxide and metal chalcogenide catalysts for CO_(2)RR make them less competitive compared to their industrial counterparts.Inspired by applications of porphyrin-based metal-organic framework(MOF)catalysts for hydrogen evolution and photodynamic therapy,the investigations of these porphyrin-based MOFs,including pristine and composite porphyrin-based MOFs in photocatalytic CO_(2)RR,have attracted significant attention in the last five years due to their excellent CO_(2)adsorption capacities,high porosity,high stability,exceptional optoelectronic properties,and multi-functionality.However,due to the difference in photocatalytic CO_(2)RR,several critical issues need to be addressed to achieve the rational design of advanced porphyrin-based MOF photocatalysts to improve activity,selectivity,and stability for CO_(2)RR.Here,we review recent developments in the field of porphyrin-based MOF CO_(2)RR photocatalysts,along with critical issues,challenges,and perspectives concerning porphyrin-based MOF catalysts for photocatalytic CO_(2)RR.
基金financially supported by the National Natural Science foundation of China(grants nos.52272176)。
文摘Lead-halide perovskite solar cells(PSCs)have rapidly achieved certified efficiencies>27%,rivaling silicon photovoltaics.However,their commercialization is hindered by intrinsic material challenges:poor operational stability under moisture,heat,and light;toxic lead leakage from degraded films.Metal-organic frameworks(MOFs),with their unique framework structure,large specific surface area,high heavy metal capturing capacity,and tunable conductivity,offer promising solutions to these issues.Recent studies have integrated MOFs into PSCs architectures to enhance performance and durability.This comprehensive review begins with an in-depth discussion of the structure,optical properties,electrical characteristics,and stability of MOFs,as well as their theoretical compatibility with perovskites.Subsequently,it provides a detailed analysis of how MOFs enhance charge carrier transport,promote perovskite crystallinity,improve device stability,and suppress lead leakage in PSCs.In summary,this review examines the research progress and potential of integrating MOFs with perovskites to address the critical PSCs challenges of efficiency,instability,and toxicity.
基金funded by the National Natural Science Foundation of China(Nos.52372264,32271609and 52473109)+2 种基金The Natural Science Foundation of Heilongjiang Province of China(No.LH2023B002)The Fundamental Research Funds for the Central Universities(No.2572023CT12)Undergraduate Training Programs for Innovations by NEFU(No.202310225565)。
文摘Metal-organic frameworks(MOFs)with high porosity,specific surface area,and unique topologies are highly regarded for their applications in photocatalysis,medical treatment,and environmental pollutant degradation.However,due to the limitations of the tumor microenvironment(TME),traditional MOFs have limited efficacy in this environment.This paper designs multi-metal oxide-based heterostructure POMOFs nanoreactors with a nesting doll-like structure.This new structure not only exhibits therapeutic effects in TME but also utilizes ultrasound(US)to enhance the release of reactive oxygen species(ROS)for CDT&SDT co-therapy,becoming an effective sound sensitizer for destroying tumor cells.In summary,our study proposes an idea for constructing multi-metal oxide-based heterostructure MOFs nanoreactors material with a nesting doll-like structure to enhance ROS release and synergistically treat tumor diseases.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2023-00217581)supported by the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(RS-2024-00406724)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(RS-2025-25430676)。
文摘The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.
基金Manal Ammar and Dr.Ali Youssef for their substantial contribution and support.We thank the funding provided by the American University of Beirut Research Board and the K.Shair Central Research Science Laboratory.M.G.acknowledges the support of the Arab Fund Fellowship Program.We also acknowledge the funding provided by the Lebanese National Council for Scientific Research(Nos.103496,103487)the Masri Institute(No.103214).
文摘In this paper,we exploit our prior successful synthesis of MOF-199 single crystals using the reaction-diffusion framework(RDF),to synthesize multivariate metal-organic frameworks(MTV-MOFs)version with enhanced properties.The MTV-MOFs are synthesized by creating defects within the MOF-199 crystal structure by integrating organic linkers entailing different functional groups.Accordingly,5-aminoisophthalic acid(NH_(2)-BDC)and 5-hydroxyisophthalic acid(OH-BDC)are separately mixed with 1,3,5-benzenetricarboxylic acid(BTC)in three different starting ratios of X-BDC:BTC(1:3,1:1)and(3:1).The effects of this linker on the morphology of the synthesized MTV-MOFs,their thermal stability,and their surface area are investigated.The extent of the incorporation of the linkers in the framework is elucidated via^(1)H-NMR spectroscopy and it is shown that the incorporation varies as a function of the location along the tubular reactor,a characteristic of RDF.The enhanced properties of the synthesized MTV-MOFs are further demonstrated by measuring its adsorptive capability for methylene blue(MB)and rhodamine B(Rh B)in aqueous solution,and compared with that of the as-synthesized MOF-199.The kinetic and thermodynamic studies reveal that MTV-MOFs with the ratio of X-BDC:BTC(1:1)exhibit the best uptakes of MB(263 mg/g)for X=OH and Rh B(156 mg/g)for X=NH_(2).The adsorbents are also easily regenerated for three consecutive cycles without losing their efficiency.We finally demonstrate that MTV-MOFs can be designed to tune the dye removal selectivity and enhance the removal capacity of both MB and RhB in a binary aqueous solution of these dyes.
文摘In this study,a nickel-based MOF{(NH_(2)(CH_(3))_(2))_(2)[Ni_(3)(O)(L)3(NH(CH_(3))_(2))_(3)]}_(n)(Ni_(3)-MOF),with pore sizes of approximately 1.6 nm×1.6 nm,was synthesized by reacting 4,4′-biphenyldicarboxylic acid(H_(2)L)with Ni(NO_(3))_(2)·6H_(2)O in an N,N-dimethylformamide(DMF)solution.The nanoscale adsorbent Ni_(3)-MOF-N with a particle diameter of approximately 200 nm was prepared using Ni_(3)-MOF.It exhibited a maximum equilibrium tetracycline(TC)adsorption capacity of 358.2 mg·g^(-1)at its isoelectric point(pH=6.50),outperforming most reported MOF-based adsorbents.This exceptional performance is likely attributed to the well-matched pore size of Ni_(3)-MOF-N(1.6 nm×1.6 nm)and the molecular dimensions of TC(0.8 nm×1.2 nm),combined with the presence of partial Ni(Ⅱ)sites on the surface of Ni_(3)-MOF-N.These features collectively facilitate effective TC adsorption through a combination of pore filling,electrostatic attraction,hydrogen bonding,surface complexation,andπ-πinteractions.Recycling experiments demonstrated that Ni_(3)-MOF-N possesses excellent structural stability and consistent adsorption performance.CCDC:2481791,Ni_(3)-MOF.
文摘A metal-organic framework{[Zn(L)_(0.5)(1,2,4,5-tpb)_(0.5)]·DMF·3H_(2)O}_(n)(1)was synthesized by solvothermal reaction,where H4L=5,5'-(ethane-1,2-diyl)diisophthalic acid,and 1,2,4,5-tpb=1,2,4,5-tetra(pyridin-4-yl)benzene.The analysis of the single crystal structure indicates that L^(4-)and 1,2,4,5-tpb are connected with Zn(Ⅱ)to form a 2D layered structure,and the layers are linked by 1,2,4,5-tpb to form a 3D structure.1 can be used as a highly selective fluorescent probe for the detection of 2,4-dinitrophenylhydrazine(DNP)and tetracycline(TET),and the detection limits were 0.013 and 0.31μmol·L^(-1),respectively.1 was applied successfully to the determination of TET content in the Yanhe River water sample.CCDC:2466221.
基金supported by the Natural Science Foundation of Hunan Province(Grant No.2024JJ6100)the Scientific Research Program of Hunan Education Department(Grant No.23B0676,22B0723)the Hengyang Normal University Science Foundation Project(Grant No.2023QD22,2024HSKFJJ019).
文摘Aqueous zinc-ion batteries(AZIBs)have emerged as a promising complement to lithium-ion batteries due to their inherent safety benefits.However,the cycle life of AZIBs is severely limited by the poor stability of zinc anodes,manifested in uncontrolled dendritic growth and persistent side reactions,which hinder wider application.Herein,we report an ion-selective separator(UIO-66-4F/GF)achieved by in situ growth of a fluorine-functionalized metal-organic framework(UIO-66-4F)onto commercial glass fiber(GF).The synergistic mechanism,involving electrostatic repulsion between-F groups and SO_(4)^(2-)anions along with strong interactions between-F and Zn^(2+)cations,effectively restrict SO_(4)^(2-)migration,suppresses 2D Zn^(2+)diffusion across electrode interfaces,and enhances[Zn(H_(2)O)_(6)]^(2+)desolvation.Furthermore,the-F groups enable precise regulation of interfacial electric fields and Zn^(2+)concentration gradients,thereby homogenizing ion flux to realize dendrite-free Zn deposition.The UIO-66-4F separator achieves stable Zn||Zn cell operation for 1500 h at 1 mA cm^(-2)via oriented deposition and sustains long-term cycling over 1000 h at 1 mA cm^(-2),and delivers a Zn||Cu cell with 99.4%Coulombic efficiency.Moreover,the Zn|UIO-66-4F/GF|NH_(4)V_(4)O_(10) full cell represents an ultrastable cycling stability with a high capacity retention of 90%after 500 cycles at a current density of 1 A g^(-1).
文摘The reaction of Mg^(2+)and 5-{1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl}terephthalic acid(H_(2)L)leads to two metal-organic frameworks,[Mg(L)(DMF)_(2)(H_(2)O)_(2)]_(2)·5DMF·2H_(2)O(1)with a 1D structure and[Mg_(2)(L)_(2)(DMSO)_(3)(H_(2)O)](2)with a 2D(4,4)-net structure.Interestingly,the two compounds exhibit distinct luminescent responses to external mechanical stimuli.1 exhibited exceptional resistance mechanical chromic luminescence(RMCL),which can be attributed to the predominant hydrogen bonds and the presence of high-boiling-point solvent molecules within its structure.2 had a reversible MCL property,which can be attributed to the dominantπ-πweak interactions,coupled with the reversible destruction/restoration of its crystallinity under grinding/fumigation.CCDC:2410963,1;2410964,2.
基金supported by the National Natural Science Foundation of China(No.52371240)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX23_3510).
文摘Constructing hierarchical nanostructures with highly exposed surfaces is a promising strategy for developing advanced cathode materials in aqueous batteries.Herein,we employed a competitive coordination strategy to optimize the characteristics of nickel metal-organic framework(Ni-MOF).Specifically,the acetate ions were employed as precise regulators,exerting a distinct influence on the morphology of the Ni-MOF and leading to a structural transition from a block structure to a two-dimensional(2D)layered structure.The optimized Ni-MOF exhibits a unique superstructure composed of hierarchical 2D layers assembled into flower-like architectures.This distinctive superstructure increases the electrochemically active surface area of Ni-MOF(N-2)and provides abundant pathways for electron/ion transfer,thereby facilitating efficient electrochemical reactions.Remarkably,the assembled aqueous alkaline N-2//Zn battery demonstrated enhanced specific capacity(0.446 mAh·cm^(-2)at 1 mA·cm^(-2))and excellent maximum energy/power density(0.789 mWh·cm^(-2)/17.262 mW·cm^(-2)).This work not only offers valuable insights into regulating MOF morphology,but also makes a contribution toward enhancing the application potential of MOFs in aqueous batteries.
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the National Natural Science Foundation of China(Nos.21621004,22478295,and 22122809)the National Key Research and Development Program of China(Nos.2022YFC2105902 and 2024YFB4206301)+2 种基金Young Scientifi c and Technological Talents(Level One)in Tianjin(No.QN20230103)Program of Introducing Talents of Discipline to Universities(No.BP0618007)Haihe Laboratory of Sustainable Chemical Transformations.
文摘The effi ciency of photocatalytic ammonia(NH_(3))synthesis is severely limited by the extremely diffi cult activation of N_(2) owing to its high N≡N triple bond energy.To address this challenge,we propose an N-doping strategy to facilitate the N_(2) activation.Our strategy involves optimizing the electronic structure of the metal active sites by modulating the coordination element.First,we introduce fi ve diff erent N-coordination ligands with distinct steric hindrances and N electron densities(2-methyl-imidazole(MI),isoindolin-1-one(II),1,2-benzisothiazolin-3-one(BIT),benzo[d]isoxazol-3-ol(BIX),and terephthalamide(TA))into an amino-functionalized metal-organic framework(MOF),NH_(2)-MIL-68(NM),to construct the N-coordination via the partial replacement of the O-coordination in the metal clusters.Electrochemical impedance spectroscopy and photocur-rent analysis demonstrate that N-doping enhances electron transfer and carrier separation.Moreover,incorporating ligands with moderate sizes and steric hindrances(II,BIT,and BIX)more eff ectively boosts the carrier separation efficiency than incorporating small(MI)or large(TA)ligands.Furthermore,the N-doped MOF modifi ed with BIT(in which N exhibits a moderate electron density)exhibits the strongest carrier separation capability.Concurrently,the X-ray photoelectron spec-troscopy,density functional theory,and N_(2) temperature-programmed desorption results confi rm that the established low-electronegativity N-coordination elevates the electron density of the metal active sites,which consequently enhances the N_(2) activation process.The systematic optimization of the N-coordinating ligand species and doping concentrations allows the optimal NM-0.5BIT to achieve a NH 3 production rate of 175.5μmol/(g·h).The proposed N-doping strategy off ers several insights into the activation of inert molecules and the development of organic framework photocatalysts.
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Project supported by the State Key Laboratory of Geohazard Prevention and Geoenvironment Protection(SKLGP2020Z003)。
文摘A novel composite material,Poly(IL-AA)@MIL-101(Cr),combining metal-organic framework,polymeric ionic liquid and acrylic acid,was synthesized for the selective and efficient adsorption of rare earths europium(Ⅲ)(Eu3+).Characterization of the materials was carried out using techniques such as X-ray diffraction(XRD),Fourier transform infrared(FTIR),scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDS),thermogravimetric analysis(TGA)and Brunauer-Emmett-Teller(BET).The results demonstrate successful incorporation of the polymeric ionic liquid onto the material surface while preserving the crystal structure and mo rphology of MIL-101(Cr).Adsorption experiments were conducted to explore parameters including equilibrium pH,initial Eu3+concentration,and duration,with comprehensive analyses of adsorption kinetics,isotherms,and mechanisms.Findings reveal that Poly(IL1-AA)@MIL-101(Cr),Poly(IL3-AA)@MIL-101(Cr),and Poly(IL5-AA)@MIL-101(Cr)achieve adsorption equilibrium for Eu3+at approximately 9 h with an equilibrium pH of 6.2.The adso rption of Eu^(3+)predominantly follows a pseudo-second-order kinetic model and Langmuir isotherm adsorption model.Moreover,the prepared composite material exhibits superior adsorption selectivity for Eu^(3+)over other metal ions in the mixture(K^(+),Mg^(2+),Ni^(2+),Co^(2+),Zn^(2+),La^(3+),and Nd^(3+)).Even after five adsorption-desorption cycles,the composite material maintains satis factory adsorption performance.
文摘The facets effect on the catalytic properties of inorganic compounds and metal-organic frameworks(MOFs)has been widely demonstrated,but the intrinsic facets effect free of interference of capping agents has not been discussed.Here we give a proof-of-concept illustration on the intrinsic facets effect by employing the popularly investigated NH2-MIL-125(Ti)MOFs with{001},{111}and{100}facets controllably exposed as model photocatalysts,which were synthesized via a simple supersaturation strategy free of any capping agents.Compared to conventional synthetic routes with capping agents employed,the NH2-MIL-125(Ti)MOFs obtained in this work exhibit remarkably different physical and chemical properties such as surface wettability,charge separation as well as trend of facets effect on photocatalytic water splitting performance.The main reason has been unraveled to originate from unavoidable residue/influence of capping agents during the conventional facets-controlled synthetic routes leading to changed local surface structural environment as well as distinct charge separation property.Our results demonstrate the importance and feasibility of facets-controllable synthesis free of capping agents in getting insight into the intrinsic facets effect of MOFs-related materials.
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the financial support of the National Natural Science Foundation of China(Nos.22308296)。
文摘Metal-organic frameworks(MOFs)have emerged as promising materials owing to their high surface areas,tunable pore sizes,and diverse functionalities.However,their practical deployment is frequently hindered by intrinsic microporosity and structural fragility.In this review,we systematically analyze recent advancements in MOF etching techniques,which strategically modify framework architectures to enhance mass transport,expose active sites,and improve stability.The discussion encompasses a range of methods―including acid,base,ion,solvent,steam,selective,in-situ,pyrolysis,and physical etching―with emphasis on the underlying mechanisms that govern the formation of hierarchical pore structures,defect engineering,and heterojunction formation.Notably,etching approaches facilitate precise control over crystal morphology and surface chemistry,thereby optimizing MOF performance in catalysis,electrocatalysis,photocatalysis,adsorption,energy storage,sensing,and biomedical applications.We also outline challenges such as etchant toxicity,over-etching risks,and scalability,while highlighting emerging strategies and computational simulations to refine the etching process.Ultimately,this review underscores the transformative impact of etching on MOF properties,paving the way for the design of next-generation multifunctional materials that address critical issues in environmental remediation,energy conversion,and beyond.
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.
