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
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
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
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
Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated fo...Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.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
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
This study presents a predictive model for condensed-phase heats of formation of metal-containing energetic complexes(MCECs)and energetic metal-organic frameworks(EMOFs),leveraging a dataset of 148 compounds.Using ele...This study presents a predictive model for condensed-phase heats of formation of metal-containing energetic complexes(MCECs)and energetic metal-organic frameworks(EMOFs),leveraging a dataset of 148 compounds.Using elemental composition,triazole rings,and metal presence,the model achieves high accuracy(R^(2)>0.94,mean absolute error(MAE)≈390 kJ/mol)for screening high-energy materials.It outperforms prior methods,particularly for polycyclic systems,offering a practical tool for safer design and risk assessment in defense and industrial applications.展开更多
The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic ...The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.展开更多
Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to it...Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to its unique composition and bonding mode,which has advantages such as large specific surface area,high porosity,adjustable structure,and designable composition.Herein,MOF-derived MAMs are highlighted based on morphology and structure.The synthesis strategies of MOF-derived MAMs of different dimensions are discussed.On this basis,the structure-activity relationships can be deeply explored through the precise control of material structure and property by atomic engineering.Finally,perspectives are given for the existing problems of MOF-derived MAMs,which will open a new horizon and promote the development of MAMs.展开更多
Metal-organic frameworks(MOFs)represent a class of multifunctional hybrid materials distinguished by their tunable structural architectures,adjustable pore dimensions,and tailorable surface chemical functionalities,wh...Metal-organic frameworks(MOFs)represent a class of multifunctional hybrid materials distinguished by their tunable structural architectures,adjustable pore dimensions,and tailorable surface chemical functionalities,which underpin their broad applicability across diverse domains.Within the cosmetics industry,MOFs exhibit significant application potential owing to their high thermal and chemical stability,substantial loading capacity,low biological toxicity,favorable luminescent characteristics,and robust catalytic activity,leading to their increasing deployment in various cosmetic-related applications.This article systematically outlines the structural features and functional properties of MOFs,emphasizing their suitability for integration into cosmetic systems.Furthermore,it provides a comprehensive review of recent advances in the utilization of MOFs in cosmetics,encompassing the detection of organic contaminants and metal ions,ultraviolet protection,encapsulation,and controlled release of volatile active ingredients,as well as targeted delivery of dermatological therapeutic agents.The structure-property-application relationships of MOFs are critically examined.Building upon the foundation of existing research,this study offers a comprehensive outlook on the future development of MOFs in the field of cosmetics.It presents several strategic perspectives,including an in-depth analysis of current application studies,the expansion of MOFs applications into additional cosmetic domains,the integration of multifunctional MOFs systems,the development of MOFs-based composite materials,and the scale-up of synthesis processes from laboratory-scale research to industrial production.It is expected that the present piece of paper can contribute valuable guidance for further exploration and practical implementation in this emerging field of cosmetics.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
A cobalt-based metal-organic framework[Co_(3)(L)_(2)(1,4-bib)_(4)]·4H_(2)O(Co-MOF)was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid(H_(3)L)and 1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib)as ligands.The...A cobalt-based metal-organic framework[Co_(3)(L)_(2)(1,4-bib)_(4)]·4H_(2)O(Co-MOF)was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid(H_(3)L)and 1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib)as ligands.Then,an electrochemical sensor modified with Co-MOF on a glassy carbon electrode(Co-MOF@GCE)was constructed for detecting Cd^(2+)and Pb^(2+)in aqueous solutions.The sensor exhibited a linear range of 1.0-16.0µmol·L^(-1)with a detection limit(LOD)of 4.609 nmol·L^(-1)for Cd^(2+),and 0.5-10.0µmol·L^(-1)with an LOD of 1.307 nmol·L^(-1)for Pb^(2+).Simultaneous detection of both ions within 0.5-7.0µmol·L^(-1)achieved LOD values of 0.47 nmol·L^(-1)(Cd^(2+))and 0.008 nmol·L^(-1)(Pb^(2+)),respectively.Analysis of real water samples(tap water,mineral water,and river water)yielded recoveries of 95%-105%,validating practical applicability.Density functional theory(DFT)calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency.CCDC:2160744.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
A thickness-controllable method for preparing metal-organic framework hollow nanofiowers on magnetic cores(Fe_(3)O_(4)@MOFs HFs)was demonstrated for the first time.The petal of magnetic core with hollow nanofiower str...A thickness-controllable method for preparing metal-organic framework hollow nanofiowers on magnetic cores(Fe_(3)O_(4)@MOFs HFs)was demonstrated for the first time.The petal of magnetic core with hollow nanofiower structure served as medium for assembling Ui O-66-NH_(2)shell with different thickness.To further improve its performance,Zr^(4+)was immobilized on the surface of Fe_(3)O_(4)@Ui O-66-NH_(2).Compared with conventional Fe_(3)O_(4)@Ui O-66-NH_(2)-Zr^(4+)nanospheres,the Fe_(3)O_(4)@Ui O-66-NH2-Zr4+HFs showed increased enrichment performance for phosphopeptides.The Fe_(3)O_(4)@Ui O-66-NH2-Zr4+HFs served as an attractive restricted-access adsorption material exhibited good selectivity(m_(β-casein):m_(BSA)=1:1000),high sensitivity(1.0 fmol)and excellent size-exclusion effect(m)((β-casein digests):m_(BSA)=1:200).Furthermore,the Fe_(3)O_(4)@Ui O-66-NH_(2)-Zr^(4+)HFs was successfully applied to the specific capture of ultratrace phosphopeptide from complex biological samples,revealing the great potential for the identification and analysis of trace phosphopeptides in clinical analysis.This work can be easily extended to the fabrication of diverse mag-MOF HFs with multifunctional and easy to post-modify properties,and open up a new avenue for the design and construction of new MOFs material.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
In order to protect the environment and economize energy,a nitrogen-fixing photocatalyst,VMCeact,is investigated in this work.This catalyst is prepared from a natural mineral,vermiculite,and modified by Ce-based metal...In order to protect the environment and economize energy,a nitrogen-fixing photocatalyst,VMCeact,is investigated in this work.This catalyst is prepared from a natural mineral,vermiculite,and modified by Ce-based metal-organic framework,Ce-UiO-66.Vermiculite was treated with formic acid;thus,Ce-UiO-66 particles grew in-situ on vermiculite;then,Ce-UiO-66 particles were activated by ultraviolet irradiation.The vermiculite absorbed visible light with a narrow band gap,and transferred photogenerated electrons to the active sites on Ce-UiO-66.Moreover,the lamella structure of vermiculite protected Ce-UiO-66 during photocatalytic process.Therefore,with only 45.92 wt%of Ce-UiO-66,the nitrogen fixation performance of VMCeact was 2.29 times that of pure activated Ce-UiO-66 particles under 455nm light irradiation(apparent quantum efficiency of 4.49%),and retained at least 96.05%performance after 7×24 h of photocatalytic reaction.This cost-reduced,efficient and stable photocatalyst has the opportunity to facilitate environmentally friendly ammonia production.展开更多
In recent years,stimulus-responsive metal-organic cages(MOCs)have attracted significant attention due to their dynamic structures and properties,which greatly enhance the structural diversity and functional adaptabili...In recent years,stimulus-responsive metal-organic cages(MOCs)have attracted significant attention due to their dynamic structures and properties,which greatly enhance the structural diversity and functional adaptability of these supramolecular assemblies.Among various external stimuli,light stands out as a straightforward and efficient means of modulating MOCs through the incorporation of photoresponsive units,such as azobenzene,thereby enabling precise photoresponsive behavior.Substantial progress has been made in the development of azobenzene-containing MOCs,underscoring their research significance and broad application potential across multiple fields.Given these advancements,it is timely to provide a comprehensive summary of the latest progress in azophenyl-based MOCs.This review will highlight key developments and explore their functional applications.展开更多
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 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supported by the National Natural Science Foundation of China (Nos.22064020,22364022,and 22174125)the Applied Basic Research Foundation of Yunnan Province (Nos.202101AT070101 and 202201AT070029)。
文摘Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.
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This study presents a predictive model for condensed-phase heats of formation of metal-containing energetic complexes(MCECs)and energetic metal-organic frameworks(EMOFs),leveraging a dataset of 148 compounds.Using elemental composition,triazole rings,and metal presence,the model achieves high accuracy(R^(2)>0.94,mean absolute error(MAE)≈390 kJ/mol)for screening high-energy materials.It outperforms prior methods,particularly for polycyclic systems,offering a practical tool for safer design and risk assessment in defense and industrial applications.
基金supported by the Natural Science Research Project of the Anhui Educational Committee,China(No.2022AH050827)the Open Research Fund Program of Anhui Province Key Laboratory of Specialty Polymers,Anhui University of Science and Technology,China(No.AHKLSP23-12)the Joint National-Local Engineering Research Center for Safe and Precise Coal Mining Fund,China(No.EC2022020)。
文摘The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.
基金supported by the National Natural Science Foundation of China(Nos.52373280,52177014 and 52273257).
文摘Exploring efficient microwave absorbing materials(MAMs)has gradually become a hot topic in recent years because it is crucial in both civil and military fields.Metal-organic framework(MOF)has great potential due to its unique composition and bonding mode,which has advantages such as large specific surface area,high porosity,adjustable structure,and designable composition.Herein,MOF-derived MAMs are highlighted based on morphology and structure.The synthesis strategies of MOF-derived MAMs of different dimensions are discussed.On this basis,the structure-activity relationships can be deeply explored through the precise control of material structure and property by atomic engineering.Finally,perspectives are given for the existing problems of MOF-derived MAMs,which will open a new horizon and promote the development of MAMs.
文摘Metal-organic frameworks(MOFs)represent a class of multifunctional hybrid materials distinguished by their tunable structural architectures,adjustable pore dimensions,and tailorable surface chemical functionalities,which underpin their broad applicability across diverse domains.Within the cosmetics industry,MOFs exhibit significant application potential owing to their high thermal and chemical stability,substantial loading capacity,low biological toxicity,favorable luminescent characteristics,and robust catalytic activity,leading to their increasing deployment in various cosmetic-related applications.This article systematically outlines the structural features and functional properties of MOFs,emphasizing their suitability for integration into cosmetic systems.Furthermore,it provides a comprehensive review of recent advances in the utilization of MOFs in cosmetics,encompassing the detection of organic contaminants and metal ions,ultraviolet protection,encapsulation,and controlled release of volatile active ingredients,as well as targeted delivery of dermatological therapeutic agents.The structure-property-application relationships of MOFs are critically examined.Building upon the foundation of existing research,this study offers a comprehensive outlook on the future development of MOFs in the field of cosmetics.It presents several strategic perspectives,including an in-depth analysis of current application studies,the expansion of MOFs applications into additional cosmetic domains,the integration of multifunctional MOFs systems,the development of MOFs-based composite materials,and the scale-up of synthesis processes from laboratory-scale research to industrial production.It is expected that the present piece of paper can contribute valuable guidance for further exploration and practical implementation in this emerging field of cosmetics.
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.
文摘A cobalt-based metal-organic framework[Co_(3)(L)_(2)(1,4-bib)_(4)]·4H_(2)O(Co-MOF)was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid(H_(3)L)and 1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib)as ligands.Then,an electrochemical sensor modified with Co-MOF on a glassy carbon electrode(Co-MOF@GCE)was constructed for detecting Cd^(2+)and Pb^(2+)in aqueous solutions.The sensor exhibited a linear range of 1.0-16.0µmol·L^(-1)with a detection limit(LOD)of 4.609 nmol·L^(-1)for Cd^(2+),and 0.5-10.0µmol·L^(-1)with an LOD of 1.307 nmol·L^(-1)for Pb^(2+).Simultaneous detection of both ions within 0.5-7.0µmol·L^(-1)achieved LOD values of 0.47 nmol·L^(-1)(Cd^(2+))and 0.008 nmol·L^(-1)(Pb^(2+)),respectively.Analysis of real water samples(tap water,mineral water,and river water)yielded recoveries of 95%-105%,validating practical applicability.Density functional theory(DFT)calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency.CCDC:2160744.
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.
基金sponsored by the National Natural Science Foundation of China (Nos. 22106038, 22204171 and 22076038)the Henan Provincial Science and Technology Research Project (No. 232102310112)+2 种基金the China Postdoctoral Science Foundation (No. 2022M713299)Natural Science Foundation of Henan Province, China (No. 202300410044)Henan key scientific research programs to Universities and Colleges (No. 22ZX003)。
文摘A thickness-controllable method for preparing metal-organic framework hollow nanofiowers on magnetic cores(Fe_(3)O_(4)@MOFs HFs)was demonstrated for the first time.The petal of magnetic core with hollow nanofiower structure served as medium for assembling Ui O-66-NH_(2)shell with different thickness.To further improve its performance,Zr^(4+)was immobilized on the surface of Fe_(3)O_(4)@Ui O-66-NH_(2).Compared with conventional Fe_(3)O_(4)@Ui O-66-NH_(2)-Zr^(4+)nanospheres,the Fe_(3)O_(4)@Ui O-66-NH2-Zr4+HFs showed increased enrichment performance for phosphopeptides.The Fe_(3)O_(4)@Ui O-66-NH2-Zr4+HFs served as an attractive restricted-access adsorption material exhibited good selectivity(m_(β-casein):m_(BSA)=1:1000),high sensitivity(1.0 fmol)and excellent size-exclusion effect(m)((β-casein digests):m_(BSA)=1:200).Furthermore,the Fe_(3)O_(4)@Ui O-66-NH_(2)-Zr^(4+)HFs was successfully applied to the specific capture of ultratrace phosphopeptide from complex biological samples,revealing the great potential for the identification and analysis of trace phosphopeptides in clinical analysis.This work can be easily extended to the fabrication of diverse mag-MOF HFs with multifunctional and easy to post-modify properties,and open up a new avenue for the design and construction of new MOFs material.
文摘The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the diverse oxidation states and structural tunability of cerium-based metal-organic frameworks(Ce-MOFs),this study employed a competitive coordination strategy utilizing a single carboxylate functional group ligand to construct a series of MOF-808-X(X=-NH_(2),-OH,-Br,and-NO_(2))featuring rich solid-state FLPs for hydrogenation of unsaturated olefins.The-X functional group serves as a microenvironment,enhancing hydrogenation activity by modulating the electronic properties and acid-base characteristics of the FLP sites.The unique redox properties of elemental cerium facilitate the exposure of unsaturated Ce sites(Ce-CUS,Lewis acid(LA))and adjacent Ce-OH(Lewis base(LB))sites within the MOFs,generating abundant solid-state FLP(Ce-CUS/Ce-OH)sites.Experimental results demonstrate that Ce-CUS and Ce-OH interact with theσandσ^(*)orbitals of H-H,and this"push-pull"synergy promotes heterolytic cleavage of the H-H bond.The lone pair electrons of the electron-donating functional group are transmitted through the molecular backbone to the LB site,thereby increasing its strength and reducing the activation energy required for H_(2)heterolytic cleavage.Notably,at 100℃and 2 MPa H_(2),MOF-808-NH_(2)achieves complete conversion of styrene and dicyclopentadiene,significantly outperforming MOF-808.Based on in-situ analysis and density functional theory calculations,a plausible reaction mechanism is proposed.This research enriches the theoretical framework for unsaturated olefin hydrogenation catalysts and contributes to the development of efficient catalytic systems.
基金supported by the National Natural Science Foundation of China(Nos.21978251,22102141 and U1904215)Natural Science Foundation of Jiangsu Province(No.BK20200044).
文摘In order to protect the environment and economize energy,a nitrogen-fixing photocatalyst,VMCeact,is investigated in this work.This catalyst is prepared from a natural mineral,vermiculite,and modified by Ce-based metal-organic framework,Ce-UiO-66.Vermiculite was treated with formic acid;thus,Ce-UiO-66 particles grew in-situ on vermiculite;then,Ce-UiO-66 particles were activated by ultraviolet irradiation.The vermiculite absorbed visible light with a narrow band gap,and transferred photogenerated electrons to the active sites on Ce-UiO-66.Moreover,the lamella structure of vermiculite protected Ce-UiO-66 during photocatalytic process.Therefore,with only 45.92 wt%of Ce-UiO-66,the nitrogen fixation performance of VMCeact was 2.29 times that of pure activated Ce-UiO-66 particles under 455nm light irradiation(apparent quantum efficiency of 4.49%),and retained at least 96.05%performance after 7×24 h of photocatalytic reaction.This cost-reduced,efficient and stable photocatalyst has the opportunity to facilitate environmentally friendly ammonia production.
基金supported by the National Nature Science Foundation of China(No.22401096)the Fundamental Research Funds for the Central Universities(East China Normal University)。
文摘In recent years,stimulus-responsive metal-organic cages(MOCs)have attracted significant attention due to their dynamic structures and properties,which greatly enhance the structural diversity and functional adaptability of these supramolecular assemblies.Among various external stimuli,light stands out as a straightforward and efficient means of modulating MOCs through the incorporation of photoresponsive units,such as azobenzene,thereby enabling precise photoresponsive behavior.Substantial progress has been made in the development of azobenzene-containing MOCs,underscoring their research significance and broad application potential across multiple fields.Given these advancements,it is timely to provide a comprehensive summary of the latest progress in azophenyl-based MOCs.This review will highlight key developments and explore their functional applications.
