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
Aluminum-based metal-organic frameworks(Al-MOFs)feature low density,high stability,and non-toxicity,making them highly promising for adsorption-related applications.In this study,we report the construction of a novel ...Aluminum-based metal-organic frameworks(Al-MOFs)feature low density,high stability,and non-toxicity,making them highly promising for adsorption-related applications.In this study,we report the construction of a novel nia-type Al-MOF based on 6-connected trinuclear Al3 clusters,HIAM-341,employing an isophthalate-derived hexatopic linker.It exhibits a robust structure with a BET surface area of 1094 m^(2)·g^(–1),with a pore size of 4.7A.HIAM-341 demonstrates size-sieving separation of hexane isomers,with adsorption capacities of 164 and 54 mg·g^(-1) for n-hexane and 3-methylpentane at 303 K and 1 bar,respectively,while excluding 2,2-dimethylbutane.Multicomponent breakthrough experiments further confirm its separation capability,and the underlying selective molecular exclusion mechanism has been uncovered by DFT calculations.Our research provides new insights into the rational design of robust Al-MOFs with tailored pore structures by employing organic linkers with high coordination density for targeted separations.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
Atomically dispersed Cu-based single-metal-site catalysts(Cu-N-C)have emerged as a frontier for electrocatalytic oxygen reduction reactions(ORR)because they can effectively optimize the D-band center of the Cu active ...Atomically dispersed Cu-based single-metal-site catalysts(Cu-N-C)have emerged as a frontier for electrocatalytic oxygen reduction reactions(ORR)because they can effectively optimize the D-band center of the Cu active site and provide appropriate adsorption/desorption energy for oxygen-containing intermediates.Metal-organic frameworks(MOFs)show excellent prospects in many fields because of their structural regularity and designability,but their direct use for electrocatalysis has been rarely reported due to the low intrinsic conductivity.Here,a MOF material(Cu-TCNQ)with highly regular single-atom copper active centers was successfully prepared using a solution chemical reaction method.Subsequently,Cu-TCNQ and graphene oxide(GO)were directly self-assembled to form a Cu-TCNQ/GO composite,which improved the conductivity of the catalyst while maintained the atomically precise controllability.The resistivity of the Cu-TCNQ/GO decreased by three orders of magnitude(1663.6-2.7 W/cm)compared with pure Cu-TCNQ.The half-wave potential was as high as 0.92 V in 0.1 mol/L KOH,even better than that of commercial 20%Pt/C.In alkaline polymer electrolyte fuel cells(APEFCs),the open-circuit voltage and power density of Cu-TCNQ/GO electrode reached 0.95 V and 320 m W/cm^(2),respectively,which suggests that Cu-TCNQ/GO has a good potential for application as a cathode ORR catalyst.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
Selective oxidation of olefin to epoxides is an important reaction in industry,however,developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O_(2)atmosphere at room temperature ...Selective oxidation of olefin to epoxides is an important reaction in industry,however,developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O_(2)atmosphere at room temperature is challenging but highly desired.In this work,two novel 2D cobalt metal-organic complexes,namely[Co(L)(5-HIP)]·2H_(2)O(Co-MOC-1)and[Co(L)(BTEC)_(0.5)]·H_(2)O(Co-MOC-2)(L=(E)-4,4-(ethene-1,2-diyl))bis(N-(pyridin-3-yl)benzamide;5-H_(2)HIP=5-hydroxyisophthalic acid;H4BTEC=pyromellitic acid)were designed and synthesized through hydrothermal method,which exhibited different metal coordination modes(4-coordinate and 5-coordinate,respectively)and 2D layer structures directed by different carboxylates co-ligands.Two Co-MOCs can serve as heterogeneous catalysts for the selective oxidation of olefins to epoxides at room temperature using O_(2)as oxidant.Furthermore,a higher catalysis activity of Co-MOC-1 than Co-MOC-2(96.7%vs.90.2%yield of 1,2-epoxycyclooctane)was observed,which may be attributed to the coordination unsaturated Co centers,the less coordination number and larger interlayer spacing of Co-MOC-1.展开更多
Although nanodrugs based on antiangiogenic and oxidative stress have received widespread attention in oncotherapy,low delivery efficiency and drug payload have greatly hindered their further applications.The self-targ...Although nanodrugs based on antiangiogenic and oxidative stress have received widespread attention in oncotherapy,low delivery efficiency and drug payload have greatly hindered their further applications.The self-targeting carrier-free metal-organic nanodrugs are constructed via the dynamic ligand-driven self-assembly of anti-angiogenesis pseudolaric acid B(PAB),Fenton-like agent copper ion,and the chemo-drug pemetrexed(PEM)to enhance anti-angiogenic-oxidative stress oncotherapy.After intravenous injection,it is found that such nanodrugs can be efficiently accumulated in tumor site and internalized into tumor cells by folate receptors-mediated self-targeting.After that,nanodrugs are disassembled to achieve the burst release of drugs under stimuli of acidic lysosome and endogenous glutathione(GSH).Interestingly,the released Cu[II]can efficiently decompose the endogenous hydrogen peroxide(H2O2)into hydroxyl radicals(·OH)and significantly weaken reactive oxygen species(ROS)elimination by downregulating endogenous GSH to self-amplify intracellular oxidative stress.Meanwhile,the released PAB can obviously inhibit the secretion of vascular endothelial growth factor(VEGF),block the formation of new blood vessels,and regulate the conformation of VEGF receptor 2(VEGFR2)to inhibit the angiogenesis signaling pathway.After two weeks of treatment,PEM-Cu[II]-PAB(PCP)nanodrugs achieved a 95%tumor inhibition rate and 100%survival rate in tumor-bearing mice.Taken together,our study can expect to provide a promising method for targeted oncotherapy based on the synergistic therapy of antiangiogenic or oxidative stress.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
Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of C...Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.展开更多
Metal-organic frameworks(MOFs)attract broad interests in mercury(Hg)ion adsorption field,while unreasonable distribution of active groups commonly restricts their utilization efficiency.In this work,we constructed a n...Metal-organic frameworks(MOFs)attract broad interests in mercury(Hg)ion adsorption field,while unreasonable distribution of active groups commonly restricts their utilization efficiency.In this work,we constructed a new MOF(TYUST-6)with dense thiol-rich traps in the 1D pore wall.This accessible channel and rational distribution of thiols allow the smooth diffusion of Hg ions and thereby result in a high Langmuir adsorption capacity of 1347.6 mg/g,almost reaching the theoretical maximum(1444.3 mg/g).Adsorption equilibrium needs 10 and 30 min at the initial concentrations of 10 and 100 mg/L,respectively.Common co-existing ions and solution pH show almost negligible interferences on the adsorption,and adsorbent regeneration can be well achieved.Combining experimental characterizations and theoretical calculations,the thiol groups in the pore wall are proved to be the dominant interaction sites.Thus,this work reports a novel high-capacity adsorbent for Hg^(2+),and proposes a feasible guideline for designing effective adsorbents.展开更多
Baicalin,a major flavonoid compound found in Scutellariae radix,is the first SARS-CoV-23CLpro virus inhibitor.Therefore,developing an accurate and reliable strategy to detect baicalin in biological systems is vital.He...Baicalin,a major flavonoid compound found in Scutellariae radix,is the first SARS-CoV-23CLpro virus inhibitor.Therefore,developing an accurate and reliable strategy to detect baicalin in biological systems is vital.Herein,we report the first indolyl-lanthanide metal-organic framework(MOF)materials and their application as baicalin sensors.The results of this study indicate that the new crystal structure has good stability and luminous performance.The detection limits of baicalin in serum and urine are 0.05 and 0.04μmol/L,respectively,suggesting high sensitivity and selectivity.Various background substances present in practical samples,such as anions,cations,and amino acids,do not interfere with the photoluminescence analytical signal of Eu^(3+).We identified that the quenching of the Eu-MOF is due to the inner filter effect,absorption energy competition,and photoinduced electron transfer among the baicalin,ligand,and MOF through powder X-ray diffraction analysis,Fourier transform infrared spectroscopy,luminescence lifetimes,ultraviolet studies,and computational analysis.Thus,we designed a convenient,sensitive,and facile detection method using the Eu-MOF and demonstrate that Eu^(3+)-based materials are promising sensors for baicalin detection in actual serum and urine.Additionally,the prepared Eu-MOF@polyvinyl alcohol composite matrix membrane test film has considerable practical application value for the portable detection of baicalin.展开更多
Natural enzymes are able to precisely bind substrates and catalyze activities because of their distinct framework structures.To mimic this ability,chemists are designing framework structures that resemble real enzymes...Natural enzymes are able to precisely bind substrates and catalyze activities because of their distinct framework structures.To mimic this ability,chemists are designing framework structures that resemble real enzymes.The use of metal-organic frameworks(MOFs)to mimic natural enzymes has advanced recently;this paper reviews these developments.This research specifically focuses on how the catalytically active center of natural enzymes can be exactly replicated by carefully controlling the composition and structure of MOFs.By identifying and attaching to substrates,MOFs can accelerate changes in a manner akin to that of real enzymes.The role of MOFs in simulating catalytic processes,enzyme activity,and potential uses in brain chemistry are also investigated in this work.It also discusses the most recent MOF applications in detecting and treating chemical abnormalities of the brain.The report finishes with a discussion of future research areas and potential applications,providing useful insights for researchers in the subject.展开更多
The arbitrary discharge of tetracycline(TC)residuals has seriously influenced the ecosystem and human health.Laccase(Lac)-based biodegradation technology is considered a more effective way to remove TC due to its high...The arbitrary discharge of tetracycline(TC)residuals has seriously influenced the ecosystem and human health.Laccase(Lac)-based biodegradation technology is considered a more effective way to remove TC due to its high catalytic efficiency and less by-product.Nevertheless,free Lac suffers from poor stability,easy inactivation and difficult recovery,restricting its application.Immobilization of Lac is considered an efficient strategy for addressing these obstacles.In this study,a magnetic metal-organic framework of Fe_(3)O_(4)@SiO_(2)@UiO-66-NH_(2)(MMOF)was prepared and used as a carrier to immobilize Lac(Lac@MMOF)for TC degradation.Benefiting from the multiple binding sites,adsorption,and protection effect of MMOF,Lac@MMOF displayed a wider pH application range(2–7)and better thermal(15–85℃),repeatability,and storage stability than free Lac.Furthermore,owing to the synergism of MOF adsorption and Lac biocatalysis,the removal rate of Lac@MMOF for TC could be up to 98%at pH=7 within 1 hr,which was 1.29 and 1.24 times that of free Lac and MMOF,respectively.More importantly,Lac@MMOF could easily be separated from aqueous solution under a magnetic field and maintained good removal performance(80%)after five cycles.The degradation products were identified by applying LC-MS/MS,and possible degradation mechanisms and pathways were proposed.Finally,the antibacterial activity of intermediate products was evaluated using Escherichia coli,which revealed that the toxicity of TC was reduced effectively by the degradation of Lac@MMOF.Overall,Lac@MMOF is a green alternative for residual antibiotic removal in water.展开更多
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the National Natural Science Foundation of China(22478251)Shenzhen Polytechnic University Research Fund(Nos.6024310024K,6022312041K)the Post-doctoral Later-stage Foundation Project of Shenzhen Poly-technic(Project No.6021271010K)for financial support.
文摘Aluminum-based metal-organic frameworks(Al-MOFs)feature low density,high stability,and non-toxicity,making them highly promising for adsorption-related applications.In this study,we report the construction of a novel nia-type Al-MOF based on 6-connected trinuclear Al3 clusters,HIAM-341,employing an isophthalate-derived hexatopic linker.It exhibits a robust structure with a BET surface area of 1094 m^(2)·g^(–1),with a pore size of 4.7A.HIAM-341 demonstrates size-sieving separation of hexane isomers,with adsorption capacities of 164 and 54 mg·g^(-1) for n-hexane and 3-methylpentane at 303 K and 1 bar,respectively,while excluding 2,2-dimethylbutane.Multicomponent breakthrough experiments further confirm its separation capability,and the underlying selective molecular exclusion mechanism has been uncovered by DFT calculations.Our research provides new insights into the rational design of robust Al-MOFs with tailored pore structures by employing organic linkers with high coordination density for targeted separations.
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 Key Research and Development Program of China(No.2022YFB3807500)the National Natural Science Foundation of China(No.22220102003)+1 种基金the Beijing Natural Science Foundation(No.JL23003)“Double-First-Class”construction projects(Nos.XK180301 and XK1804-02)。
文摘Atomically dispersed Cu-based single-metal-site catalysts(Cu-N-C)have emerged as a frontier for electrocatalytic oxygen reduction reactions(ORR)because they can effectively optimize the D-band center of the Cu active site and provide appropriate adsorption/desorption energy for oxygen-containing intermediates.Metal-organic frameworks(MOFs)show excellent prospects in many fields because of their structural regularity and designability,but their direct use for electrocatalysis has been rarely reported due to the low intrinsic conductivity.Here,a MOF material(Cu-TCNQ)with highly regular single-atom copper active centers was successfully prepared using a solution chemical reaction method.Subsequently,Cu-TCNQ and graphene oxide(GO)were directly self-assembled to form a Cu-TCNQ/GO composite,which improved the conductivity of the catalyst while maintained the atomically precise controllability.The resistivity of the Cu-TCNQ/GO decreased by three orders of magnitude(1663.6-2.7 W/cm)compared with pure Cu-TCNQ.The half-wave potential was as high as 0.92 V in 0.1 mol/L KOH,even better than that of commercial 20%Pt/C.In alkaline polymer electrolyte fuel cells(APEFCs),the open-circuit voltage and power density of Cu-TCNQ/GO electrode reached 0.95 V and 320 m W/cm^(2),respectively,which suggests that Cu-TCNQ/GO has a good potential for application as a cathode ORR catalyst.
基金supported by Henan Province Key Research and Development and Promotion of Science and Technology Project(No.25A150001)the National Natural Science Foundation of China(Nos.22409171,22125303,92361302,and 92061203).
文摘Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined active sites and high loadings under precise control has become a hotly debated topic in scientific research.Metal-organic frameworks(MOFs),with their exceptional properties such as ultrahigh specific surface areas,precisely controllable structural de-signs,and highly flexible functional cus-tomization capabilities,are regarded as one of the ideal matrices for supporting and sta-bilizing SACs.This review provides an in-sightful overview of the diverse preparation strategies for MOFs-derived SACs.It comprehen-sively analyzes the unique advantages and challenges of each method in achieving efficient synthesis of SACs,emphasizing the crucial role of optimized processes in unlocking the antici-pated performance of SACs.Furthermore,this review delves into a series of advanced charac-terization techniques,including aberration-corrected scanning transmission electron mi-croscopy(AC-STEM),electron energy loss spectroscopy(EELS),X-ray absorption spec-troscopy(XAS),and infrared absorption spectroscopy(IRAS),offering valuable insights into the atomic-scale fine structures and properties of SACs,significantly advancing the under-standing of SAC mechanisms.Moreover,this review focuses on exploring the potential appli-cations of MOFs-derived SACs in electrocatalysis frontier fields.This comprehensive exami-nation lays a solid theoretical foundation and provides a directional guidance for the rational design and controllable synthesis of high-performance MOFs-derived SACs.
基金financially supported by the National Natural Science Foundation of China(Nos.22271021,21971024,22201021)the Doctoral Scientific Research Foundation of Liaoning Province(No.2022-BS-302)。
文摘Selective oxidation of olefin to epoxides is an important reaction in industry,however,developing heterogeneous catalysts to achieve the effective catalysis for this reaction under O_(2)atmosphere at room temperature is challenging but highly desired.In this work,two novel 2D cobalt metal-organic complexes,namely[Co(L)(5-HIP)]·2H_(2)O(Co-MOC-1)and[Co(L)(BTEC)_(0.5)]·H_(2)O(Co-MOC-2)(L=(E)-4,4-(ethene-1,2-diyl))bis(N-(pyridin-3-yl)benzamide;5-H_(2)HIP=5-hydroxyisophthalic acid;H4BTEC=pyromellitic acid)were designed and synthesized through hydrothermal method,which exhibited different metal coordination modes(4-coordinate and 5-coordinate,respectively)and 2D layer structures directed by different carboxylates co-ligands.Two Co-MOCs can serve as heterogeneous catalysts for the selective oxidation of olefins to epoxides at room temperature using O_(2)as oxidant.Furthermore,a higher catalysis activity of Co-MOC-1 than Co-MOC-2(96.7%vs.90.2%yield of 1,2-epoxycyclooctane)was observed,which may be attributed to the coordination unsaturated Co centers,the less coordination number and larger interlayer spacing of Co-MOC-1.
基金supported by the Key Research and Development Program in the Xinjiang Uygur Autonomous Region(No.2023B02030-1)the National Natural Science Foundation of China(No.82560364).
文摘Although nanodrugs based on antiangiogenic and oxidative stress have received widespread attention in oncotherapy,low delivery efficiency and drug payload have greatly hindered their further applications.The self-targeting carrier-free metal-organic nanodrugs are constructed via the dynamic ligand-driven self-assembly of anti-angiogenesis pseudolaric acid B(PAB),Fenton-like agent copper ion,and the chemo-drug pemetrexed(PEM)to enhance anti-angiogenic-oxidative stress oncotherapy.After intravenous injection,it is found that such nanodrugs can be efficiently accumulated in tumor site and internalized into tumor cells by folate receptors-mediated self-targeting.After that,nanodrugs are disassembled to achieve the burst release of drugs under stimuli of acidic lysosome and endogenous glutathione(GSH).Interestingly,the released Cu[II]can efficiently decompose the endogenous hydrogen peroxide(H2O2)into hydroxyl radicals(·OH)and significantly weaken reactive oxygen species(ROS)elimination by downregulating endogenous GSH to self-amplify intracellular oxidative stress.Meanwhile,the released PAB can obviously inhibit the secretion of vascular endothelial growth factor(VEGF),block the formation of new blood vessels,and regulate the conformation of VEGF receptor 2(VEGFR2)to inhibit the angiogenesis signaling pathway.After two weeks of treatment,PEM-Cu[II]-PAB(PCP)nanodrugs achieved a 95%tumor inhibition rate and 100%survival rate in tumor-bearing mice.Taken together,our study can expect to provide a promising method for targeted oncotherapy based on the synergistic therapy of antiangiogenic or oxidative stress.
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the financial support from National Natural Science Foundation of China (No. 21503097)Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX23_3905)。
文摘Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.
基金supported by the National Natural Science Foundation of China(No.22208230)Fundamental Research Program of Shanxi Province(No.202103021223281)。
文摘Metal-organic frameworks(MOFs)attract broad interests in mercury(Hg)ion adsorption field,while unreasonable distribution of active groups commonly restricts their utilization efficiency.In this work,we constructed a new MOF(TYUST-6)with dense thiol-rich traps in the 1D pore wall.This accessible channel and rational distribution of thiols allow the smooth diffusion of Hg ions and thereby result in a high Langmuir adsorption capacity of 1347.6 mg/g,almost reaching the theoretical maximum(1444.3 mg/g).Adsorption equilibrium needs 10 and 30 min at the initial concentrations of 10 and 100 mg/L,respectively.Common co-existing ions and solution pH show almost negligible interferences on the adsorption,and adsorbent regeneration can be well achieved.Combining experimental characterizations and theoretical calculations,the thiol groups in the pore wall are proved to be the dominant interaction sites.Thus,this work reports a novel high-capacity adsorbent for Hg^(2+),and proposes a feasible guideline for designing effective adsorbents.
基金Project supported by Jilin Province Science and Technology Development Plan Project(20210201061GX)。
文摘Baicalin,a major flavonoid compound found in Scutellariae radix,is the first SARS-CoV-23CLpro virus inhibitor.Therefore,developing an accurate and reliable strategy to detect baicalin in biological systems is vital.Herein,we report the first indolyl-lanthanide metal-organic framework(MOF)materials and their application as baicalin sensors.The results of this study indicate that the new crystal structure has good stability and luminous performance.The detection limits of baicalin in serum and urine are 0.05 and 0.04μmol/L,respectively,suggesting high sensitivity and selectivity.Various background substances present in practical samples,such as anions,cations,and amino acids,do not interfere with the photoluminescence analytical signal of Eu^(3+).We identified that the quenching of the Eu-MOF is due to the inner filter effect,absorption energy competition,and photoinduced electron transfer among the baicalin,ligand,and MOF through powder X-ray diffraction analysis,Fourier transform infrared spectroscopy,luminescence lifetimes,ultraviolet studies,and computational analysis.Thus,we designed a convenient,sensitive,and facile detection method using the Eu-MOF and demonstrate that Eu^(3+)-based materials are promising sensors for baicalin detection in actual serum and urine.Additionally,the prepared Eu-MOF@polyvinyl alcohol composite matrix membrane test film has considerable practical application value for the portable detection of baicalin.
基金financially supported by the National Natural Science Foundation,China(Nos.22074095&22374103(Y.Lin))Beijing Natural Science Foundation(No.2222005(Y.Lin))。
文摘Natural enzymes are able to precisely bind substrates and catalyze activities because of their distinct framework structures.To mimic this ability,chemists are designing framework structures that resemble real enzymes.The use of metal-organic frameworks(MOFs)to mimic natural enzymes has advanced recently;this paper reviews these developments.This research specifically focuses on how the catalytically active center of natural enzymes can be exactly replicated by carefully controlling the composition and structure of MOFs.By identifying and attaching to substrates,MOFs can accelerate changes in a manner akin to that of real enzymes.The role of MOFs in simulating catalytic processes,enzyme activity,and potential uses in brain chemistry are also investigated in this work.It also discusses the most recent MOF applications in detecting and treating chemical abnormalities of the brain.The report finishes with a discussion of future research areas and potential applications,providing useful insights for researchers in the subject.
基金supported by the National Natural Science Foundation of China(No.U20A20133)the National Key Research and Development Program of China(No.2022YFF0606703).
文摘The arbitrary discharge of tetracycline(TC)residuals has seriously influenced the ecosystem and human health.Laccase(Lac)-based biodegradation technology is considered a more effective way to remove TC due to its high catalytic efficiency and less by-product.Nevertheless,free Lac suffers from poor stability,easy inactivation and difficult recovery,restricting its application.Immobilization of Lac is considered an efficient strategy for addressing these obstacles.In this study,a magnetic metal-organic framework of Fe_(3)O_(4)@SiO_(2)@UiO-66-NH_(2)(MMOF)was prepared and used as a carrier to immobilize Lac(Lac@MMOF)for TC degradation.Benefiting from the multiple binding sites,adsorption,and protection effect of MMOF,Lac@MMOF displayed a wider pH application range(2–7)and better thermal(15–85℃),repeatability,and storage stability than free Lac.Furthermore,owing to the synergism of MOF adsorption and Lac biocatalysis,the removal rate of Lac@MMOF for TC could be up to 98%at pH=7 within 1 hr,which was 1.29 and 1.24 times that of free Lac and MMOF,respectively.More importantly,Lac@MMOF could easily be separated from aqueous solution under a magnetic field and maintained good removal performance(80%)after five cycles.The degradation products were identified by applying LC-MS/MS,and possible degradation mechanisms and pathways were proposed.Finally,the antibacterial activity of intermediate products was evaluated using Escherichia coli,which revealed that the toxicity of TC was reduced effectively by the degradation of Lac@MMOF.Overall,Lac@MMOF is a green alternative for residual antibiotic removal in water.
