(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under...(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.展开更多
The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively red...The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.展开更多
Preparing multifunctional coatings with both anti-corrosion and anti-biofouling properties is crucial.Copper has been in the spotlight as an effective biocide,especially in the recent past concerning its impact on cau...Preparing multifunctional coatings with both anti-corrosion and anti-biofouling properties is crucial.Copper has been in the spotlight as an effective biocide,especially in the recent past concerning its impact on causing environmental hazards.Reducing the amount used and increasing its efficiency have become the focus of researchers.The hybridization of titanium dioxide nanoparticles(NPs)with copper metal-organic frameworks(MOFs)can significantly improve antimicrobial performance due to its photocatalytic properties.Composites(TiO_(2)-Cu-BTC)of titanium dioxide nanoparticles and copper 1,3,5-benzenetricarboxylate acid(Cu-BTC),obtained by three up-sampling methods,namely hydrothermal,mechanical stirring,and in-situ growth,were doped into epoxy resin(TiO_(2)-Cu-BTC/EP)to enhance its anticorrosion and antifouling properties.The loaded forms were determined by field emission scanning electron microscopy and confirmed using Fourier infrared spectroscopy and X-ray diffraction spectroscopy.The lethality of the composite coating against Escherichia coli(E.coli)increased by 12%after 3 h of exposure to light,and the impedance value increased by 1×1010Ω.The efficiency of the coating was greatly improved.展开更多
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
Recent advancements have led to the synthesis of various new metal-containing explosives,particularly energetic metal-organic frameworks(EMOFs),which feature high-energy ligands within well-ordered crystalline structu...Recent advancements have led to the synthesis of various new metal-containing explosives,particularly energetic metal-organic frameworks(EMOFs),which feature high-energy ligands within well-ordered crystalline structures.These explosives exhibit significant advantages over traditional compounds,including higher density,greater heats of detonation,improved mechanical hardness,and excellent thermal stability.To effectively evaluate their detonation performance,it is crucial to have a reliable method for predicting detonation heat,velocity,and pressure.This study leverages experimental data and outputs from the leading commercial computer code to identify suitable decomposition pathways for different metal oxides,facilitating straightforward calculations for the detonation performance of alkali metal salts,and metal coordination compounds,along with EMOFs.The new model enhances predictive reliability for detonation velocities,aligning more closely with experimental results,as evi-denced by a root mean square error(RMSE)of 0.68 km/s compared to 1.12 km/s for existing methods.Furthermore,it accommodates a broader range of compounds,including those containing Sr,Cd,and Ag,and provides predictions for EMOFs that are more consistent with computer code outputs than previous predictive models.展开更多
Strontium-90,a highly radioactive isotope,accumulates within the food chain and skeletal structure,posing significant risks to human health.There is a critical need for a sensitive detection strategy for Strontium-90 ...Strontium-90,a highly radioactive isotope,accumulates within the food chain and skeletal structure,posing significant risks to human health.There is a critical need for a sensitive detection strategy for Strontium-90 in complex environmental samples.Here,solid-state nanochannels,modified with metal-organic frameworks(MOF)and specific aptamers,were engineered for highly sensitive detection of strontium ion(Sr^(2+)).The synergistic effect between the reduced effective diameter of the nanochannels due to MOF and the specific binding of Sr^(2+) by aptamers amplifies the difference in ionic current signals,enhancing detection sensitivity significantly.The MOF-modified nanochannels exhibit highly sensitive detection of Sr^(2+),with a limit of detection(LOD)being 0.03 nmol·L^(-1),whereas the LOD for anodized aluminum oxide(AAO)without the modified MOF nanosheets is only 1000 nmol·L^(-1).These findings indicate that the LOD of Sr^(2+) detected by the MOF-modified nanochannels is approximately 33,000 times higher than that by the nanochannels without MOF modification.Additionally,the highly reliable detection of Sr^(2+) in various water samples was achieved,with a recovery rate ranging from 94.00%to 118.70%.This study provides valuable insights into the rapidly advancing field of advanced nanochannel-based sensors and their diverse applications for analyzing complex samples,including environmental contaminant detection,food analysis,medical diagnostics,and more.展开更多
The effect of the information delay, which was caused by thc naturc of the distance sensors and wireless communication systems, on the string stability of platoon of automated vehicles was studied. The longitudinal ve...The effect of the information delay, which was caused by thc naturc of the distance sensors and wireless communication systems, on the string stability of platoon of automated vehicles was studied. The longitudinal vehicle dynamics model was built by taking the information delay into consideration, and three typical information frameworks, i.e., leader-predecessor framework （LPF）, multiple-predecessors framework （MPF） and predecessor-successor framework （PSF）, were defined and their related spacing error dynamics models in frequency domain were proposed. The string stability of platoon of automated vehicles was analyzed for the LPF, MPF and PSF, respectively. Meanwhile, the related sufficient string stable conditions were also obtained. The results demonstrate that the string stability can be guaranteed tbr the LPF and PSF with considering the information delay, but the ranges of the control gains of the control laws are smaller than those without considering the information delay. For the MPF, the ＂weak＂ string stability, which can be guaranteed without considering the information delay, cannot be obtained with considering the information delay. The comparative simulations further demonstrate that the LPF shows better string stability, but the PSF shows better string scalable performance.展开更多
The realization of real-time thermal feedback for monitoring photothermal therapy(PTT)under near-infrared(NIR)light irradiation is of great interest and challenge for antitumor therapy.Herein,by assembling highly effi...The realization of real-time thermal feedback for monitoring photothermal therapy(PTT)under near-infrared(NIR)light irradiation is of great interest and challenge for antitumor therapy.Herein,by assembling highly efficient photothermal conversion gold nanorods and a temperature-responsive probe((E)-4-(4-(diethylamino)styryl)-1-methylpyridin-1-ium,PyS)within MOF-199,an intelligent nanoplatform(AMPP)was fabricated for simultaneous chemodynamic therapy and NIR light-induced temperature-feedback PTT.The fluorescence intensity and temperature of the PyS probe are linearly related due to the restriction of the rotation of the characteristic monomethine bridge.Moreover,the copper ions resulting from the degradation of MOF-199 in an acidic microenvironment can convert H_(2)O_(2)into•OH,resulting in tumor ablation through a Fenton-like reaction,and this process can be accelerated by increasing the temperature.This study establishes a feasible platform for fabricating highly sensitive temperature sensors for efficient temperature-feedback PTT.展开更多
Photocatalytic CO_(2)cycloaddition reaction presents a promising CO_(2)conversion strategy to establish carbon neutrality.Among emerging catalysts,metal‑organic frameworks(MOFs)have been regarded as paradigmshifting p...Photocatalytic CO_(2)cycloaddition reaction presents a promising CO_(2)conversion strategy to establish carbon neutrality.Among emerging catalysts,metal‑organic frameworks(MOFs)have been regarded as paradigmshifting photocatalysts for their atomic precision in active site engineering,controllable porosity,and exceptional photochemical stability under ambient conditions.However,inherent limitations persist in conventional MOFs,including restricted solar spectrum utilization,inefficient charge carrier separation,and inadequate epoxide activation ability.Recent breakthroughs address these challenges through multiple strategies:ligand engineering,dopant incorporation,and composite construction.This review systematically maps the evolutionary trajectory of MOF‑based photocatalysts,providing mechanistic insights into structure‑activity relationships and providing insights and directions for the design of high‑performance MOF‑based photocatalysts.展开更多
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
Metal-organic frameworks(MOFs)are import-ant as possible energy storage materials.Nitrogen-doped iron-cobalt MOFs were synthesized by a one-pot solvo-thermal method using CoCl_(3)·6H_(2)O and FeCl_(3)·6H_(2)...Metal-organic frameworks(MOFs)are import-ant as possible energy storage materials.Nitrogen-doped iron-cobalt MOFs were synthesized by a one-pot solvo-thermal method using CoCl_(3)·6H_(2)O and FeCl_(3)·6H_(2)O dis-solved in N,N-dimethylformamide,and were converted into Fe-Co embedded in N-doped porous carbon polyhedra by pyrolysis in a nitrogen atmosphere.During pyrolysis,the or-ganic ligands transformed into N-doped porous carbon which improved their structural stability and also their electrical contact with other materials.The Fe and Co are tightly bound together because of their encapsulation by the carbon nitride and are well dispersed in the carbon matrix,and improve the material’s conductivity and stability and provide additional capacity.When used as the anode for lithium-ion batteries,the material gives an initial capacity of up to 2230.7 mAh g^(-1)and a reversible capa-city of 1146.3 mAh g^(-1)is retained after 500 cycles at a current density of 0.5 A g^(-1),making it an excellent candidate for this purpose.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
Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then...Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).展开更多
AgVO_(3)/ZIF-8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO_(3)and ZIF-8.X-ray diffraction(XRD),scanning electron microscopy(SEM),high-power transmission electron microscopy(...AgVO_(3)/ZIF-8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO_(3)and ZIF-8.X-ray diffraction(XRD),scanning electron microscopy(SEM),high-power transmission electron microscopy(HRTEM),X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectroscopy(UV-Vis DRS),photoluminescence(PL)spectroscopy,electron spin resonance(ESR)spectroscopy,transient photocurrent and electrochemical impedance spectroscopy(EIS)were used to characterize binary composites.Tetracycline(TC)was used as a substrate to study the performance efficiency of the degradation of photocatalysts under light conditions,and the degradation effect of TC was also evaluated under different mass concentrations and ionic contents.In addition,we further investigated the photocatalytic mechanism of the binary composite material AgVO_(3)/ZIF-8 and identified the key active components responsible for the catalytic degradation of this new photocatalyst.The experimental results show that the degradation efficiency of 10%-AZ,prepared with a molar ratio of 10%AgVO_(3)and ZIF-8 to TC,was 75.0%.This indicates that the photocatalytic activity can be maintained even under a certain ionic content,making it a suitable photocatalyst for optimal use.In addition,the photocatalytic mechanism of binary composites was further studied by the active species trapping experiment.展开更多
Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nano...Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.展开更多
The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation ...The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation and oxygen evolution competition,sluggish kinetics,low Faradaic efficiency,and limited nitrate yields.In this work,a novel two-dimensional(2D)layered MOF Mn-BCPPy(H_(2)BCPPy=3,5-di(4'-carboxyphenyl)pyridine)has been successfully synthesized.The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites(OMSs)and Lewis base sites(LBSs).The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which NO_(3)^(-)exhibited relatively high activity with a yield of 99.75μg/(h·mg)and a Faraday efficiency(FE)of 32.09%.Furthermore,it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics(NFs).Therefore,this work explores the application of MOF materials in the field of electrocatalytic NOR,which reveals that manganese-based MOFs have great potential prospects.展开更多
In pursuit of more efficient and stable electrochemical energy storage materials,composite materials consisting of metal oxides and graphene oxide have garnered significant attention due to their unique structures and...In pursuit of more efficient and stable electrochemical energy storage materials,composite materials consisting of metal oxides and graphene oxide have garnered significant attention due to their unique structures and exceptional properties.Graphene oxide(GO),a two-dimensional material with an extremely high specific surface area and excellent conductivity,offers new possibilities for enhancing the electrochemical performance of metal oxides.In this work,we synthesized met-al-organic framework(MOF)and GO composites by regulating the amount of GO,and successfully prepared composites of metal oxides supported by nitrogen-doped carbon frameworks and GO through a simple one-step calcination process.Based on the electrochemical tests,the optimal amount of GO was determined.This research will provide new insights into and directions for designing and synthesizing metal oxide and graphene oxide composite materials with an ideal electro-chemical performance.展开更多
Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1....Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.展开更多
Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imida...Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.展开更多
文摘(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.
文摘The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.
基金Project(52073311) supported by the National Natural Science Foundation of ChinaProject(2023A0505010011) supported by the Guangdong-Hong Kong-Macao Joint Innovation Field Research Foundation,ChinaProject(2021A1515012281) supported by the Guangdong Basic and Applied Basic Research Foundation,China。
文摘Preparing multifunctional coatings with both anti-corrosion and anti-biofouling properties is crucial.Copper has been in the spotlight as an effective biocide,especially in the recent past concerning its impact on causing environmental hazards.Reducing the amount used and increasing its efficiency have become the focus of researchers.The hybridization of titanium dioxide nanoparticles(NPs)with copper metal-organic frameworks(MOFs)can significantly improve antimicrobial performance due to its photocatalytic properties.Composites(TiO_(2)-Cu-BTC)of titanium dioxide nanoparticles and copper 1,3,5-benzenetricarboxylate acid(Cu-BTC),obtained by three up-sampling methods,namely hydrothermal,mechanical stirring,and in-situ growth,were doped into epoxy resin(TiO_(2)-Cu-BTC/EP)to enhance its anticorrosion and antifouling properties.The loaded forms were determined by field emission scanning electron microscopy and confirmed using Fourier infrared spectroscopy and X-ray diffraction spectroscopy.The lethality of the composite coating against Escherichia coli(E.coli)increased by 12%after 3 h of exposure to light,and the impedance value increased by 1×1010Ω.The efficiency of the coating was greatly improved.
文摘The reaction of Mg^(2+)and 5-{1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl}terephthalic acid(H_(2)L)leads to two metal-organic frameworks,[Mg(L)(DMF)_(2)(H_(2)O)_(2)]_(2)·5DMF·2H_(2)O(1)with a 1D structure and[Mg_(2)(L)_(2)(DMSO)_(3)(H_(2)O)](2)with a 2D(4,4)-net structure.Interestingly,the two compounds exhibit distinct luminescent responses to external mechanical stimuli.1 exhibited exceptional resistance mechanical chromic luminescence(RMCL),which can be attributed to the predominant hydrogen bonds and the presence of high-boiling-point solvent molecules within its structure.2 had a reversible MCL property,which can be attributed to the dominantπ-πweak interactions,coupled with the reversible destruction/restoration of its crystallinity under grinding/fumigation.CCDC:2410963,1;2410964,2.
基金the research committee at Malek Ashtar University of Technology (MUT) for their invaluable support of this project
文摘Recent advancements have led to the synthesis of various new metal-containing explosives,particularly energetic metal-organic frameworks(EMOFs),which feature high-energy ligands within well-ordered crystalline structures.These explosives exhibit significant advantages over traditional compounds,including higher density,greater heats of detonation,improved mechanical hardness,and excellent thermal stability.To effectively evaluate their detonation performance,it is crucial to have a reliable method for predicting detonation heat,velocity,and pressure.This study leverages experimental data and outputs from the leading commercial computer code to identify suitable decomposition pathways for different metal oxides,facilitating straightforward calculations for the detonation performance of alkali metal salts,and metal coordination compounds,along with EMOFs.The new model enhances predictive reliability for detonation velocities,aligning more closely with experimental results,as evi-denced by a root mean square error(RMSE)of 0.68 km/s compared to 1.12 km/s for existing methods.Furthermore,it accommodates a broader range of compounds,including those containing Sr,Cd,and Ag,and provides predictions for EMOFs that are more consistent with computer code outputs than previous predictive models.
基金supported by the National Natural Science Foundation of China(No.22090050,No.22090052,No.22176180)National Basic Research Program of China(No.2021YFA1200400)+1 种基金the Natural Science Foundation of Hubei Province(No.2024AFA001)Shenzhen Science and Technology Program(No.JCYJ20220530162406014)。
文摘Strontium-90,a highly radioactive isotope,accumulates within the food chain and skeletal structure,posing significant risks to human health.There is a critical need for a sensitive detection strategy for Strontium-90 in complex environmental samples.Here,solid-state nanochannels,modified with metal-organic frameworks(MOF)and specific aptamers,were engineered for highly sensitive detection of strontium ion(Sr^(2+)).The synergistic effect between the reduced effective diameter of the nanochannels due to MOF and the specific binding of Sr^(2+) by aptamers amplifies the difference in ionic current signals,enhancing detection sensitivity significantly.The MOF-modified nanochannels exhibit highly sensitive detection of Sr^(2+),with a limit of detection(LOD)being 0.03 nmol·L^(-1),whereas the LOD for anodized aluminum oxide(AAO)without the modified MOF nanosheets is only 1000 nmol·L^(-1).These findings indicate that the LOD of Sr^(2+) detected by the MOF-modified nanochannels is approximately 33,000 times higher than that by the nanochannels without MOF modification.Additionally,the highly reliable detection of Sr^(2+) in various water samples was achieved,with a recovery rate ranging from 94.00%to 118.70%.This study provides valuable insights into the rapidly advancing field of advanced nanochannel-based sensors and their diverse applications for analyzing complex samples,including environmental contaminant detection,food analysis,medical diagnostics,and more.
基金Project(20070006011) supported by the Doctoral Foundation of Ministry of Education of China
文摘The effect of the information delay, which was caused by thc naturc of the distance sensors and wireless communication systems, on the string stability of platoon of automated vehicles was studied. The longitudinal vehicle dynamics model was built by taking the information delay into consideration, and three typical information frameworks, i.e., leader-predecessor framework （LPF）, multiple-predecessors framework （MPF） and predecessor-successor framework （PSF）, were defined and their related spacing error dynamics models in frequency domain were proposed. The string stability of platoon of automated vehicles was analyzed for the LPF, MPF and PSF, respectively. Meanwhile, the related sufficient string stable conditions were also obtained. The results demonstrate that the string stability can be guaranteed tbr the LPF and PSF with considering the information delay, but the ranges of the control gains of the control laws are smaller than those without considering the information delay. For the MPF, the ＂weak＂ string stability, which can be guaranteed without considering the information delay, cannot be obtained with considering the information delay. The comparative simulations further demonstrate that the LPF shows better string stability, but the PSF shows better string scalable performance.
基金supported by the National Natural Science Foundation of China(22171001,22305001,51972001,52372073)the Natural Science Foundation of Anhui Province of China(2108085MB49).
文摘The realization of real-time thermal feedback for monitoring photothermal therapy(PTT)under near-infrared(NIR)light irradiation is of great interest and challenge for antitumor therapy.Herein,by assembling highly efficient photothermal conversion gold nanorods and a temperature-responsive probe((E)-4-(4-(diethylamino)styryl)-1-methylpyridin-1-ium,PyS)within MOF-199,an intelligent nanoplatform(AMPP)was fabricated for simultaneous chemodynamic therapy and NIR light-induced temperature-feedback PTT.The fluorescence intensity and temperature of the PyS probe are linearly related due to the restriction of the rotation of the characteristic monomethine bridge.Moreover,the copper ions resulting from the degradation of MOF-199 in an acidic microenvironment can convert H_(2)O_(2)into•OH,resulting in tumor ablation through a Fenton-like reaction,and this process can be accelerated by increasing the temperature.This study establishes a feasible platform for fabricating highly sensitive temperature sensors for efficient temperature-feedback PTT.
文摘Photocatalytic CO_(2)cycloaddition reaction presents a promising CO_(2)conversion strategy to establish carbon neutrality.Among emerging catalysts,metal‑organic frameworks(MOFs)have been regarded as paradigmshifting photocatalysts for their atomic precision in active site engineering,controllable porosity,and exceptional photochemical stability under ambient conditions.However,inherent limitations persist in conventional MOFs,including restricted solar spectrum utilization,inefficient charge carrier separation,and inadequate epoxide activation ability.Recent breakthroughs address these challenges through multiple strategies:ligand engineering,dopant incorporation,and composite construction.This review systematically maps the evolutionary trajectory of MOF‑based photocatalysts,providing mechanistic insights into structure‑activity relationships and providing insights and directions for the design of high‑performance MOF‑based photocatalysts.
文摘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Metal-organic frameworks(MOFs)are import-ant as possible energy storage materials.Nitrogen-doped iron-cobalt MOFs were synthesized by a one-pot solvo-thermal method using CoCl_(3)·6H_(2)O and FeCl_(3)·6H_(2)O dis-solved in N,N-dimethylformamide,and were converted into Fe-Co embedded in N-doped porous carbon polyhedra by pyrolysis in a nitrogen atmosphere.During pyrolysis,the or-ganic ligands transformed into N-doped porous carbon which improved their structural stability and also their electrical contact with other materials.The Fe and Co are tightly bound together because of their encapsulation by the carbon nitride and are well dispersed in the carbon matrix,and improve the material’s conductivity and stability and provide additional capacity.When used as the anode for lithium-ion batteries,the material gives an initial capacity of up to 2230.7 mAh g^(-1)and a reversible capa-city of 1146.3 mAh g^(-1)is retained after 500 cycles at a current density of 0.5 A g^(-1),making it an excellent candidate for this purpose.
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.
文摘Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).
文摘AgVO_(3)/ZIF-8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO_(3)and ZIF-8.X-ray diffraction(XRD),scanning electron microscopy(SEM),high-power transmission electron microscopy(HRTEM),X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectroscopy(UV-Vis DRS),photoluminescence(PL)spectroscopy,electron spin resonance(ESR)spectroscopy,transient photocurrent and electrochemical impedance spectroscopy(EIS)were used to characterize binary composites.Tetracycline(TC)was used as a substrate to study the performance efficiency of the degradation of photocatalysts under light conditions,and the degradation effect of TC was also evaluated under different mass concentrations and ionic contents.In addition,we further investigated the photocatalytic mechanism of the binary composite material AgVO_(3)/ZIF-8 and identified the key active components responsible for the catalytic degradation of this new photocatalyst.The experimental results show that the degradation efficiency of 10%-AZ,prepared with a molar ratio of 10%AgVO_(3)and ZIF-8 to TC,was 75.0%.This indicates that the photocatalytic activity can be maintained even under a certain ionic content,making it a suitable photocatalyst for optimal use.In addition,the photocatalytic mechanism of binary composites was further studied by the active species trapping experiment.
文摘Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.
基金supported by Natural Science Foundation of Shandong Province(ZR2021MB075)Fundamental Research Funds for the Central Universities,Ocean University of China(202461021).
文摘The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation and oxygen evolution competition,sluggish kinetics,low Faradaic efficiency,and limited nitrate yields.In this work,a novel two-dimensional(2D)layered MOF Mn-BCPPy(H_(2)BCPPy=3,5-di(4'-carboxyphenyl)pyridine)has been successfully synthesized.The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites(OMSs)and Lewis base sites(LBSs).The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which NO_(3)^(-)exhibited relatively high activity with a yield of 99.75μg/(h·mg)and a Faraday efficiency(FE)of 32.09%.Furthermore,it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics(NFs).Therefore,this work explores the application of MOF materials in the field of electrocatalytic NOR,which reveals that manganese-based MOFs have great potential prospects.
基金supported by the National Natural Science Foundation of China(51971157)Shenzhen Science and Technology Program(JCYJ20210324115412035,JCYJ202103-24123202008,JCYJ20210324122803009 and ZDS-YS20210813095534001)Guangdong Foundation for Basic and Applied Basic Research Program(2021A1515110880).
文摘In pursuit of more efficient and stable electrochemical energy storage materials,composite materials consisting of metal oxides and graphene oxide have garnered significant attention due to their unique structures and exceptional properties.Graphene oxide(GO),a two-dimensional material with an extremely high specific surface area and excellent conductivity,offers new possibilities for enhancing the electrochemical performance of metal oxides.In this work,we synthesized met-al-organic framework(MOF)and GO composites by regulating the amount of GO,and successfully prepared composites of metal oxides supported by nitrogen-doped carbon frameworks and GO through a simple one-step calcination process.Based on the electrochemical tests,the optimal amount of GO was determined.This research will provide new insights into and directions for designing and synthesizing metal oxide and graphene oxide composite materials with an ideal electro-chemical performance.
文摘Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.
文摘Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.
