This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordinatio...This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordination and covalent bonding adapted from metal-organic frameworks(MOFs)and covalent organic frameworks(COFs),respectively.With an emphasis on the MCOF and CMOF structures,this review surveys their building blocks and topologies.Specifically,the frameworks are classified based on the dimensions of their components(building blocks),namely,discrete building blocks and one-dimensional infinite building blocks.For the first category,the materials are further divided into collections of two-and three-dimensional networks based on their topologies.For the second category,the recently emerging MCOFs with woven structures are covered.Finally,the state-of-the-art in MCOF and CMOF chemistry has been laid out for promising avenues in future developments.展开更多
The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous st...The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.展开更多
Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal...Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal-organic frameworks(MOFs)with tunable Lewis-base passivation sites have been constructed(Cd-Httb and Cd-Httb-BDC,Httb=5-(4-(1H-1,2,4-triazole-1-yl)benzyl)-1h-tetrazole,BDC=1,4-dicarboxybenzene)to eliminate deep-level defects and simultaneously as nanostructured heterogeneous nucleation seed to assist the growth of large-grained perovskite films.Compared with the control and Cd-Httb,Cd-Httb-BDC designed with mix-ligands strategy exhibited the enhanced inducted effect on the crystallization and nucleation of high-quality perovskite films during annealing process.Consequently,the resultant Cd-Httb-BDC-modified device achieved higher power conversion efficiency(PCE)(22.18%)than the control(20.89%)and Cd-Httb(21.56%).Meanwhile,the unencapsulated Cd-Httb-BDC-modified device still maintained 90%of initial PCE after 1500 h in ambient conditions and exhibited enhanced thermal stability(85℃ in N_(2) atmosphere).This work presented a successful example of mixligands strategy on construction of high-quality MOF-assisted perovskite films for high-efficient and stable PSCs.展开更多
As more and more pollutants threaten human health, it is necessary and essential to develop sensitive, accurate and rapid methods and sensory materials to detect harmful substance. Metal-organic frameworks (MOFs) are ...As more and more pollutants threaten human health, it is necessary and essential to develop sensitive, accurate and rapid methods and sensory materials to detect harmful substance. Metal-organic frameworks (MOFs) are inorganic-organic hybrids assembled from inorganic metal ions or clusters and suitable organic ligands. Zinc-based MOFs (Zn-MOFs) have emerged as one of the most promising sensory material of MOFs for practical applications, and attracted significant attention due to structural diversity and incomparable stability properties. However, there are few reviews on systemic summary of synthesis design, mechanism and application of Zn-MOFs. In this review, we summarize the synthesis design methods, structure types and luminescence mechanism of Zn-MOFs sensor recognition in the past ten years and their applications in metal cations, anions, organic compounds and other analytes. Finally, we present a short conclusion, and look forward to the future development direction of Zn-MOFs.展开更多
Direct electrochemical reduction of CO2 into valuable chemicals and fuel is one of the most promising approaches to address the current energy crisis and lower CO2 emission.Recently,numerous metal-organic framework(MO...Direct electrochemical reduction of CO2 into valuable chemicals and fuel is one of the most promising approaches to address the current energy crisis and lower CO2 emission.Recently,numerous metal-organic framework(MOF)and their derived materials have extensively been developed as electrocatalysts for CO2 reduction owing to their unique structure including porosity,large specific surface area,and tunable chemical structures.In this review,the recent progress of MOF-based electrocatalysts for CO2 reduction was summarized and discussed.Detailed discussions mainly focus on the synthesis and mechanism of pristine MOFs and MOF-derived materials for electrocatalytic CO2 reduction.These examples are expected to provide clues to rational design and synthesis of stable and high-performance MOFs-based electrocatalysts for CO2 reduction.展开更多
It is critical to synthesize high-efficiency electrocatalysts to boost the performance of water splitting to meet the requirements of industrial applications. Metal-organic frameworks(MOFs) can function as ideal molec...It is critical to synthesize high-efficiency electrocatalysts to boost the performance of water splitting to meet the requirements of industrial applications. Metal-organic frameworks(MOFs) can function as ideal molecular platforms for the design of highly reactive transition metal phosphides(TMPs), a kind of candidates for high-efficiently electrocatalytic water splitting. The intrinsic activity of the electrocatalysts can be greatly improved via modulating the electronic structure of the catalytic center through the MOF precursors/templates. Moreover, the carbon layer converted in-situ by the organic ligands can not only protect the TMPs from being degraded in the harsh electrochemical environments, but also avoid agglomeration of the catalysts, thereby promoting their activities and stabilities. Furthermore,heteroatom-containing ligands can incorporate N, S or P, etc. atoms into the carbon matrixes after conversion, regulating the coordination microenvironments of the active centers as well as their electronic structures. In this review, we first summarized the latest developments in MOF-derived TMPs by the unique advantages in metal, organic ligand, and morphology regulations for electrocatalytic water splitting. Secondly, we concluded the critical scientific issues currently facing for designing state-of-the-art TMP-based electrocatalysts. Finally, we presented an outlook on this research area, encompassing electrocatalyst construction, catalytic mechanism research, etc.展开更多
Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic framew...Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic frameworks(MOFs,UiO-66-NH_(2))and superacid ZrO_(2)(S-ZrO_(2))fillers are proposed,and the samples were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),thermo-gravimetric analyzer(TGA)and some other electrochemical measurements.The-NH_(2) groups of UiO-66-NH_(2) combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)chains by hydrogen bonds,leading to a high electrochemical stability window of 5 V.Owing to the incorporation of UiO-66-NH_(2) and S-ZrO_(2) in PVDF-HFP polymer,the open metal sites of MOFs and acid surfaces of S-ZrO_(2) can immobilize anions by strong Lewis acid-base interaction,which enhances the effect of immobilization anions,achieving a high Li-ion transference number(t_(+))of 0.72,and acquiring a high ionic conductivity of 1.05×10^(-4) S·cm^(-1) at 60℃.The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm^(-2) without the shortcircuit occurring.Besides,the solid composite Li/LiFePO_(4)(LFP)cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g^(-1) at 0.2 C.The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.展开更多
Transition metal phthalocyanines (TMPc) and relevant derivatives can act as pervasive molecules for their electronic, magnetic, and optical applications. Numerous researches based on TMPc are carried out, attempting t...Transition metal phthalocyanines (TMPc) and relevant derivatives can act as pervasive molecules for their electronic, magnetic, and optical applications. Numerous researches based on TMPc are carried out, attempting to synthesize novel two-dimensional (2D) metal-organic frameworks. Recently, some 2D poly-TMPc frameworks including FePc [J. Am. Chem. Soc. 133, 1203 (2011)], CoPc [Chem. Commun. 51, 2836 (2015)], and Ni-NiPc [J. Mater. Chem. A 6, 1188 (2018)] frameworks have been successfully synthesized experimentally. Meanwhile, potential applications in catalysis, gas storage, and spintronics were predicted by theoretical studies. Here, we propose a new kind of 2D poly-TMPc frameworks with kagome lattice (denoted as kag-TMPc) and systematically investigate their electronic and magnetic properties by employing first-principles calculations. We have demonstrated that the 2D kag-MnPc framework displays quite stable ferromagnetic ordering with Curie temperature about 125 K as indicated by Monte Carlo simulations based on Heisenberg model and prefers out-of-plane easy-magnetization axis. The 2D kag-CrPc framework is an ideal candidate for S=2 kagome antiferromagnet with RT3 magnetic order. Particularly, the investigations on optical absorption suggest that when the TMPc molecules are self-assembled into 2D kag- TMPc frameworks, their absorption wave bands are broadened, especially in visible region.展开更多
Introduction of multiple pore size regimes into metalorganic frameworks(MOFs)to form hierarchical porous structures can lead to improved performance of the material in various applications.In many cases,where interact...Introduction of multiple pore size regimes into metalorganic frameworks(MOFs)to form hierarchical porous structures can lead to improved performance of the material in various applications.In many cases,where interactions with bulky molecules are involved,enlarging the pore size of typically microporous MOF adsorbents or MOF catalysts is crucial for enhancing both mass transfer and molecular accessibility.In this review,we examine the range of synthetic strategies which have been reported thus far to prepare hierarchical MOFs or MOF composites with added macroporosity.These fabrication techniques can be either pre-or post-synthetic and include using hard or soft structural template agents,defect formation,routes involving supercritical CO2,and 3D printing.We also discuss potential applications and some of the challenges involved with current techniques,which must be addressed if any of these approaches are to be taken forward for industrial applications.展开更多
Metal-organic frameworks(MOFs)with high porosity and variable structure have attracted extensive attention in the field of electrochemistry,but their poor conductivity and stability have limited their development.Mate...Metal-organic frameworks(MOFs)with high porosity and variable structure have attracted extensive attention in the field of electrochemistry,but their poor conductivity and stability have limited their development.Materials derived from MOFs can maintain the structural diversity and porosity characteristics of MOFs while improving their electrical conductivity and stability.Metal phosphides play an important role in electrochemistry because they possess rich active sites,unique physicochemical properties,and a porous structure.Published results show that MOF-derived metal-phosphides materials have great promise in the field of electrochemistry due to their controllable structure,high specific surface area,high stability and excellent electrical conductivity.MOF-derived metal-phosphides with significant electrochemical properties can be obtained by simply,economical and scalable synthetic methods.This work reviews the application of MOF-derived metal phosphides in electrochemistry.Specifically,the synthesis methodology and morphological characterization of MOFs derived metal-phosphides and their application in electrochemistry are described.Based on recent scientific advances,we discuss the challenges and opportunities for future research on MOF-derived metal-phosphides materials.展开更多
Lithium-sulfur batteries(Li–S batteries) are promising candidates for the next generation high-energy rechargeable Li batteries due to their high theoretical specific capacity(1672 m Ahg-1) and energy density(2500 Wh...Lithium-sulfur batteries(Li–S batteries) are promising candidates for the next generation high-energy rechargeable Li batteries due to their high theoretical specific capacity(1672 m Ahg-1) and energy density(2500 Wh kg-1). The commercialization of Li–S batteries is impeded by several key challenges at cathode side, e.g. the insulating nature of sulfur and discharged products(Li2S 2 and Li2S), the solubility of long-chain polysulfides and volume variation of sulfur cathode upon cycling. Recently, the carbonbased derivatives from metal-organic frameworks(MOFs) has emerged talent in their utilization as cathode hosts for Li–S batteries. They are not only highly conductive and porous to enable the acceleration of Li +/e-transfer and accommodation of volumetric expansion of sulfur cathode during cycling, but also enriched by controllable chemical active sites to enable the adsorption of polysulfides and promotion of their conversion reaction kinetics. In this review, based on the types of MOFs(e.g. ZIF-8, ZIF-67, Prussian blue, Al-MOF, MOF-5, Cu-MOF, Ni-MOF), the synthetic methods, formation process and morphology, structural superiority of MOFs-derived carbon frameworks along with their electrochemical performance as cathode host in Li–S batteries are summarized and discussed.展开更多
In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature.Mixture comp...In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature.Mixture composed of CO2 and H2 was selected as the model system to separate.The results show that CO2 selectivity in catenated MOFs with multi-porous frameworks is much higher than their non-catenated counterparts.The simulations also show that the electrostatic interactions are very important for the selectivity,and the contributions of different electrostatic interactions are different,depending on pore size,pressure and mixture composition.In fact,changing the electrostatic interactions can even qualitatively change the adsorption behavior.A general conclusion is that the electrostatic interactions between adsorbate molecules and the framework atoms play a dominant role at low pressures,and these interactions in catenated MOFs have much more pronounced effects than those in their non-catenated counterparts,while the electrostatic interactions between adsorbate molecules become evident with increasing pressure,and eventually dominant.展开更多
Metal–organic frameworks (MOFs) as photocatalysts and photocatalyst supports combine several advantages of homogeneous and heterogeneous catalyses, including stability, post-reaction separation, catalyst reusability,...Metal–organic frameworks (MOFs) as photocatalysts and photocatalyst supports combine several advantages of homogeneous and heterogeneous catalyses, including stability, post-reaction separation, catalyst reusability,and tunability, and they have been intensively studied for photocatalytic applications. There are several reviews that focus mainly or even entirely on experimental work. The present review is intended to complement those reviews by focusing on computational work that can provide a further understanding of the photocatalytic properties of MOF photocatalysts. We first present a summary of computational methods, including density functional theory, combined quantum mechanical and molecular mechanical methods, and force fields for MOFs. Then, computational investigations on MOF-based photocatalysis are briefly discussed. The discussions focus on the electronic structure, photoexcitation, charge mobility, and photoredox catalysis of MOFs, especially the widely studied Ui O-66-based MOFs.展开更多
The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,q...The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.展开更多
Catalytic properties of the metal-organic framework Cr-MIL-101 in solvent-free cycloaddition of CO2 to epoxides to produce cyclic carbon- ates using tetrabutylammonium bromide as co-catalyst have been explored under m...Catalytic properties of the metal-organic framework Cr-MIL-101 in solvent-free cycloaddition of CO2 to epoxides to produce cyclic carbon- ates using tetrabutylammonium bromide as co-catalyst have been explored under mild reaction conditions (8 bar CO2, 25 ~C). Styrene and propylene carbonates were formed with high yields (95% and 82%, respectively). Catalytic performance of Cr-MIL-101 was compared with other MOFs: Fe-MIL-101, Zn-MOF-5 and HKUST-1, The catalytic properties of different quaternary ammonium bromides, Cr-MIL-101 as well as PW12/Cr-MIL-101 composite material have been assessed in oxidative carboxylation of styrene in the presence of both tert-butyl hydroperoxide and H202 as oxidants at 8-100bar CO2 and 25-80 ~C with selectivity to styrene carbonate up to 44% at 57% substrate conversion.展开更多
Three new metal-organic frameworks [Cd(L)(obba)]·H)2O(1),[Co(L)(obba)]·MeCN(2) and [Cd_2(L)_2(ip)_2]·6H_2O·DMF(3)(H_2obba = 4,4?-oxybisbenzoic acid,H2 ip = m-phthalic acid) ha...Three new metal-organic frameworks [Cd(L)(obba)]·H)2O(1),[Co(L)(obba)]·MeCN(2) and [Cd_2(L)_2(ip)_2]·6H_2O·DMF(3)(H_2obba = 4,4?-oxybisbenzoic acid,H2 ip = m-phthalic acid) have been successfully synthesized based on the controllable self-assembly of 9-ethyl-3,6-diimidazolyl-carbazole(L),varied carboxylates and different metal ions under solvothermal conditions,which were characterized by single-crystal X-ray diffraction,elemental analysis,IR spectroscopy and thermogravimetry. Furthermore,luminescence and magnetic susceptibility of compound 2 are also investigated in detail. Single-crystal X-ray diffraction and topology analysis reveal that complexes 1~3 exhibit similar two-dimensional(2D) networks.展开更多
The equilibrium, kinetics and thermodynamics of the adsorption of methylene blue( MB) from aqueous solution onto copper coordination polymer with dithiooxamide( H2dtoaCu),one of the metal-organic frameworks( MOFs),wer...The equilibrium, kinetics and thermodynamics of the adsorption of methylene blue( MB) from aqueous solution onto copper coordination polymer with dithiooxamide( H2dtoaCu),one of the metal-organic frameworks( MOFs),were investigated in a batch adsorption system as a function of initial pH, adsorbent concentration, contact time, initial dye concentration, and temperature. The Langmuir, Freundlich, and DubininRadushkevich( D-R) isotherm models were used for modeling the adsorption equilibrium. It was found that Langmuir model yielded a much better fit than the Freundlich model under different temperatures. The maximum monolayer adsorption capacities of MB were 192. 98,229. 86,and 297. 38 mg /g at 298,308,and 318 K,respectively. The calculated mean adsorption energy( 8. 26-11. 04 kJ /mol) using D-R model indicated that the adsorption process might take place by chemical adsorption mechanism.Otherwise,the kinetic studies revealed that the adsorption process could be well explained by pseudo-second-order rate kinetics and intraparticle diffusion was not the rate-limiting step.Thermodynamic studies indicated that this system was feasible,spontaneous,and endothermic process. Based on these studies,H2dtoaCu can be considered as a potential adsorbent for the removal of MB from aqueous solution.展开更多
Two metal-organic frameworks [(Zn0.5L)·(H2O)]n (1) and [(Ni0.5L)?(H2O)]n (2) constructed by the 3-formyl-4-(pyridin-4-yl) benzoic acid ligand (HL) were synthesized and characterized by single-cry...Two metal-organic frameworks [(Zn0.5L)·(H2O)]n (1) and [(Ni0.5L)?(H2O)]n (2) constructed by the 3-formyl-4-(pyridin-4-yl) benzoic acid ligand (HL) were synthesized and characterized by single-crystal X-ray diffraction. 1 crystallizes in orthorhombic space group Pnna with a = 16.6152(8), b = 12.6825(6), c = 15.3908(8) A, V = 3243.2(3) ?3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F(000) = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ(I). 2 is isostructural to 1, which also crystallizes in orthorhombic space group Pnna with a = 16.6152(8), b = 12.6825(6), c = 15.3908(8) ?, V = 3243.2(3) ?3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F(000) = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ(I). Additionally, thermogravimetric analysis, FT-IR spectroscopy and powder X-ray diffraction were discussed.展开更多
Two new complexes,[Zn(L1)2(SCN)2]·H2O(1,L1 = 3,5-dimethyl-4-p-tolyl-4H1,2,4-triazole and [Cd3(L2)6(SCN)6](2,L2 = 3,5-dimethyl-4-phenyl-4H-1,2,4-triazole),have been hydrothermally prepared and character...Two new complexes,[Zn(L1)2(SCN)2]·H2O(1,L1 = 3,5-dimethyl-4-p-tolyl-4H1,2,4-triazole and [Cd3(L2)6(SCN)6](2,L2 = 3,5-dimethyl-4-phenyl-4H-1,2,4-triazole),have been hydrothermally prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and PXRD.Complex 1 crystallizes in monoclinic,space group P21 /n with a = 11.246(13),b = 9.640(11),c = 26.13(3),β = 100.97(3),V = 1108.5(3) 3,Z = 4,C24 H28 N8 OS2 Zn,Mr = 572.02,Dc = 1.366 g/cm3,μ = 1.065 mm-1,S = 0.992,F(000) = 1184,the final R = 0.0602 and wR = 0.1700 for 2925 observed reflections(I 2σ(I)).Complex 2 crystallizes in triclinic,space group P1 with a = 11.6669(3),b = 12.0957(2),c = 14.3674(3),α = 105.380(3),β = 91.020(2),γ = 92.4100(10)o,V = 1952.30(7)3,Z = 1,C66H66N24S6Cd3,Mr = 1725.08,Dc = 1.467 g/cm3,μ = 1.025 mm-1,S = 1.037,F(000) = 870,the final R = 0.0336 and wR = 0.0946 for 7819 observed reflections(I 2σ(I)).In the title complexes,complex 1 is a mononuclear molecule where the centre Zn(II) coordinates to two 3,4,5-substituted 1,2,4-triazole ligands(L1) and two terminal SCN-anions in a tetrahedral environment while six-coordinated centre Cd(II) atoms with octahedral geometry in complex 2 are bridged by virtue of substituted 1,2,4-triazole(L2) in N1,N2-bridging mode and μ2-N,N-SCN-anions into a trinuclear molecule.展开更多
The cyanide groups of letrozole(1-[bis(4-cyanophenyl)methyl]-1,2,4-triazole) were hydrolyzed into the carboxylic groups under alkaline conditions. Then the hydrolysis product(1-[bis(4-carboxylphenyl)methyl]-1,2,4-tria...The cyanide groups of letrozole(1-[bis(4-cyanophenyl)methyl]-1,2,4-triazole) were hydrolyzed into the carboxylic groups under alkaline conditions. Then the hydrolysis product(1-[bis(4-carboxylphenyl)methyl]-1,2,4-triazole, H2ltzda) reacted with Co(NO3)2·6H2O in the presence of different bipyridl-typed ligands under hydrothermal conditions. As a result, two new Co(Ⅱ) MOFs were obtained, formulated as [Co2(ltzda)2(bpp)2]n(1) and {[Co2(ltzda)2(bpy)]·4H2O}n(2)(bpp = 1,3-di(4-pyridyl)propane, bpy = 4,4’-bipyridine). Two MOFs have been characterized by single-crystal X-ray diffraction, thermogravimetric analysis and magnetic measure. 1 displays a 2D metal-organic framework containing wave layers and 2 shows a pillared-layer structure existing in a 2-fold interpenetrated mode.展开更多
基金financially supported by the National Natural Science Foundation of China(No.22176135)the Fundamental Research Funds for the Central Universities in China(No.YJ201976)。
文摘This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordination and covalent bonding adapted from metal-organic frameworks(MOFs)and covalent organic frameworks(COFs),respectively.With an emphasis on the MCOF and CMOF structures,this review surveys their building blocks and topologies.Specifically,the frameworks are classified based on the dimensions of their components(building blocks),namely,discrete building blocks and one-dimensional infinite building blocks.For the first category,the materials are further divided into collections of two-and three-dimensional networks based on their topologies.For the second category,the recently emerging MCOFs with woven structures are covered.Finally,the state-of-the-art in MCOF and CMOF chemistry has been laid out for promising avenues in future developments.
基金financially supported by the Scientific Research Startup Funds from Tsinghua Shenzhen International Graduate School。
文摘The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.
基金supported by the National Natural Science Foundation of China(22072034,22001050,and 21873025)the China Postdoctoral Science Foundation(2020T130147,2020M681084,and 2022M710949)+1 种基金the Postdoctoral Foundation of Heilongjiang Province(LBH-Z19059)the Natural Science Foundation of Heilongjiang Youth Fund(YQ2021B002).
文摘Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal-organic frameworks(MOFs)with tunable Lewis-base passivation sites have been constructed(Cd-Httb and Cd-Httb-BDC,Httb=5-(4-(1H-1,2,4-triazole-1-yl)benzyl)-1h-tetrazole,BDC=1,4-dicarboxybenzene)to eliminate deep-level defects and simultaneously as nanostructured heterogeneous nucleation seed to assist the growth of large-grained perovskite films.Compared with the control and Cd-Httb,Cd-Httb-BDC designed with mix-ligands strategy exhibited the enhanced inducted effect on the crystallization and nucleation of high-quality perovskite films during annealing process.Consequently,the resultant Cd-Httb-BDC-modified device achieved higher power conversion efficiency(PCE)(22.18%)than the control(20.89%)and Cd-Httb(21.56%).Meanwhile,the unencapsulated Cd-Httb-BDC-modified device still maintained 90%of initial PCE after 1500 h in ambient conditions and exhibited enhanced thermal stability(85℃ in N_(2) atmosphere).This work presented a successful example of mixligands strategy on construction of high-quality MOF-assisted perovskite films for high-efficient and stable PSCs.
文摘As more and more pollutants threaten human health, it is necessary and essential to develop sensitive, accurate and rapid methods and sensory materials to detect harmful substance. Metal-organic frameworks (MOFs) are inorganic-organic hybrids assembled from inorganic metal ions or clusters and suitable organic ligands. Zinc-based MOFs (Zn-MOFs) have emerged as one of the most promising sensory material of MOFs for practical applications, and attracted significant attention due to structural diversity and incomparable stability properties. However, there are few reviews on systemic summary of synthesis design, mechanism and application of Zn-MOFs. In this review, we summarize the synthesis design methods, structure types and luminescence mechanism of Zn-MOFs sensor recognition in the past ten years and their applications in metal cations, anions, organic compounds and other analytes. Finally, we present a short conclusion, and look forward to the future development direction of Zn-MOFs.
基金supported by the National Natural Science Foundation of China (51772291, 21673238, 21773242)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000)
文摘Direct electrochemical reduction of CO2 into valuable chemicals and fuel is one of the most promising approaches to address the current energy crisis and lower CO2 emission.Recently,numerous metal-organic framework(MOF)and their derived materials have extensively been developed as electrocatalysts for CO2 reduction owing to their unique structure including porosity,large specific surface area,and tunable chemical structures.In this review,the recent progress of MOF-based electrocatalysts for CO2 reduction was summarized and discussed.Detailed discussions mainly focus on the synthesis and mechanism of pristine MOFs and MOF-derived materials for electrocatalytic CO2 reduction.These examples are expected to provide clues to rational design and synthesis of stable and high-performance MOFs-based electrocatalysts for CO2 reduction.
基金supported by the National Natural Science Foundation of China (21901088, 21901089, 22161021, 21971091)the Natural Science Foundation of Jiangxi Province(20192ACB20013)+1 种基金support of Jiangxi Province (jxsq2018106041)the “Young Elite Scientists Sponsorship Program” by CAST。
文摘It is critical to synthesize high-efficiency electrocatalysts to boost the performance of water splitting to meet the requirements of industrial applications. Metal-organic frameworks(MOFs) can function as ideal molecular platforms for the design of highly reactive transition metal phosphides(TMPs), a kind of candidates for high-efficiently electrocatalytic water splitting. The intrinsic activity of the electrocatalysts can be greatly improved via modulating the electronic structure of the catalytic center through the MOF precursors/templates. Moreover, the carbon layer converted in-situ by the organic ligands can not only protect the TMPs from being degraded in the harsh electrochemical environments, but also avoid agglomeration of the catalysts, thereby promoting their activities and stabilities. Furthermore,heteroatom-containing ligands can incorporate N, S or P, etc. atoms into the carbon matrixes after conversion, regulating the coordination microenvironments of the active centers as well as their electronic structures. In this review, we first summarized the latest developments in MOF-derived TMPs by the unique advantages in metal, organic ligand, and morphology regulations for electrocatalytic water splitting. Secondly, we concluded the critical scientific issues currently facing for designing state-of-the-art TMP-based electrocatalysts. Finally, we presented an outlook on this research area, encompassing electrocatalyst construction, catalytic mechanism research, etc.
基金financially supported by National Natural Science Foundation of China(No.21701083)Zhenjiang Key Laboratory of Marine Power Equipment Performance(SS2018006)+1 种基金The Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.SJCX19_0612)Project of Jiangsu University(High-Tech Ship)Collaborative Innovation Center(2019,1174871801-11).
文摘Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic frameworks(MOFs,UiO-66-NH_(2))and superacid ZrO_(2)(S-ZrO_(2))fillers are proposed,and the samples were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),thermo-gravimetric analyzer(TGA)and some other electrochemical measurements.The-NH_(2) groups of UiO-66-NH_(2) combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)chains by hydrogen bonds,leading to a high electrochemical stability window of 5 V.Owing to the incorporation of UiO-66-NH_(2) and S-ZrO_(2) in PVDF-HFP polymer,the open metal sites of MOFs and acid surfaces of S-ZrO_(2) can immobilize anions by strong Lewis acid-base interaction,which enhances the effect of immobilization anions,achieving a high Li-ion transference number(t_(+))of 0.72,and acquiring a high ionic conductivity of 1.05×10^(-4) S·cm^(-1) at 60℃.The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm^(-2) without the shortcircuit occurring.Besides,the solid composite Li/LiFePO_(4)(LFP)cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g^(-1) at 0.2 C.The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.
基金the National Key Research Development Program of China (No.2016YFA0200604 and No.2017YFA0204904)the National Natural Science Foundation of China (No.21473174)+1 种基金the Fundamental Research Funds for the Central Universities (No.WK2340000074 and No.WK2060190084)The computational resources of Super-computing Center of University of Science and Technology of China, Supercomputing Center of Chinese Academy of Sciences, Tianjing, and Shanghai Supercomputer Centers are also acknowledged.
文摘Transition metal phthalocyanines (TMPc) and relevant derivatives can act as pervasive molecules for their electronic, magnetic, and optical applications. Numerous researches based on TMPc are carried out, attempting to synthesize novel two-dimensional (2D) metal-organic frameworks. Recently, some 2D poly-TMPc frameworks including FePc [J. Am. Chem. Soc. 133, 1203 (2011)], CoPc [Chem. Commun. 51, 2836 (2015)], and Ni-NiPc [J. Mater. Chem. A 6, 1188 (2018)] frameworks have been successfully synthesized experimentally. Meanwhile, potential applications in catalysis, gas storage, and spintronics were predicted by theoretical studies. Here, we propose a new kind of 2D poly-TMPc frameworks with kagome lattice (denoted as kag-TMPc) and systematically investigate their electronic and magnetic properties by employing first-principles calculations. We have demonstrated that the 2D kag-MnPc framework displays quite stable ferromagnetic ordering with Curie temperature about 125 K as indicated by Monte Carlo simulations based on Heisenberg model and prefers out-of-plane easy-magnetization axis. The 2D kag-CrPc framework is an ideal candidate for S=2 kagome antiferromagnet with RT3 magnetic order. Particularly, the investigations on optical absorption suggest that when the TMPc molecules are self-assembled into 2D kag- TMPc frameworks, their absorption wave bands are broadened, especially in visible region.
基金financially supported by the Vietnamese Ministry of Education and Training and the UK Engineering and Physical Sciences Research Council (EP/R01650X/1 and EP/L016028/1)
文摘Introduction of multiple pore size regimes into metalorganic frameworks(MOFs)to form hierarchical porous structures can lead to improved performance of the material in various applications.In many cases,where interactions with bulky molecules are involved,enlarging the pore size of typically microporous MOF adsorbents or MOF catalysts is crucial for enhancing both mass transfer and molecular accessibility.In this review,we examine the range of synthetic strategies which have been reported thus far to prepare hierarchical MOFs or MOF composites with added macroporosity.These fabrication techniques can be either pre-or post-synthetic and include using hard or soft structural template agents,defect formation,routes involving supercritical CO2,and 3D printing.We also discuss potential applications and some of the challenges involved with current techniques,which must be addressed if any of these approaches are to be taken forward for industrial applications.
基金supported by the National Natural Science Foundation of China(U1904215)Natural Science Foundation of Jiangsu Province(BK20200044)Changjiang scholars program of the Ministry of Education(Q2018270)。
文摘Metal-organic frameworks(MOFs)with high porosity and variable structure have attracted extensive attention in the field of electrochemistry,but their poor conductivity and stability have limited their development.Materials derived from MOFs can maintain the structural diversity and porosity characteristics of MOFs while improving their electrical conductivity and stability.Metal phosphides play an important role in electrochemistry because they possess rich active sites,unique physicochemical properties,and a porous structure.Published results show that MOF-derived metal-phosphides materials have great promise in the field of electrochemistry due to their controllable structure,high specific surface area,high stability and excellent electrical conductivity.MOF-derived metal-phosphides with significant electrochemical properties can be obtained by simply,economical and scalable synthetic methods.This work reviews the application of MOF-derived metal phosphides in electrochemistry.Specifically,the synthesis methodology and morphological characterization of MOFs derived metal-phosphides and their application in electrochemistry are described.Based on recent scientific advances,we discuss the challenges and opportunities for future research on MOF-derived metal-phosphides materials.
基金supported by National Key R&D Program of China(2016YFB0901600)the National Natural Science Foundation of China(51772313 , U1830113 and 51802334)
文摘Lithium-sulfur batteries(Li–S batteries) are promising candidates for the next generation high-energy rechargeable Li batteries due to their high theoretical specific capacity(1672 m Ahg-1) and energy density(2500 Wh kg-1). The commercialization of Li–S batteries is impeded by several key challenges at cathode side, e.g. the insulating nature of sulfur and discharged products(Li2S 2 and Li2S), the solubility of long-chain polysulfides and volume variation of sulfur cathode upon cycling. Recently, the carbonbased derivatives from metal-organic frameworks(MOFs) has emerged talent in their utilization as cathode hosts for Li–S batteries. They are not only highly conductive and porous to enable the acceleration of Li +/e-transfer and accommodation of volumetric expansion of sulfur cathode during cycling, but also enriched by controllable chemical active sites to enable the adsorption of polysulfides and promotion of their conversion reaction kinetics. In this review, based on the types of MOFs(e.g. ZIF-8, ZIF-67, Prussian blue, Al-MOF, MOF-5, Cu-MOF, Ni-MOF), the synthetic methods, formation process and morphology, structural superiority of MOFs-derived carbon frameworks along with their electrochemical performance as cathode host in Li–S batteries are summarized and discussed.
基金Supported by the National Natural Science Foundation of China (20725622, 20706002, and 20876006), Beijing Nova Program (2008B15) and the Dutch STW/CW Separation Technology Program (700.56.655-DPC.6243).
文摘In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature.Mixture composed of CO2 and H2 was selected as the model system to separate.The results show that CO2 selectivity in catenated MOFs with multi-porous frameworks is much higher than their non-catenated counterparts.The simulations also show that the electrostatic interactions are very important for the selectivity,and the contributions of different electrostatic interactions are different,depending on pore size,pressure and mixture composition.In fact,changing the electrostatic interactions can even qualitatively change the adsorption behavior.A general conclusion is that the electrostatic interactions between adsorbate molecules and the framework atoms play a dominant role at low pressures,and these interactions in catenated MOFs have much more pronounced effects than those in their non-catenated counterparts,while the electrostatic interactions between adsorbate molecules become evident with increasing pressure,and eventually dominant.
基金supported as part of the Nanoporous Materials Genome Center by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Award No. DE-FG0217ER16362
文摘Metal–organic frameworks (MOFs) as photocatalysts and photocatalyst supports combine several advantages of homogeneous and heterogeneous catalyses, including stability, post-reaction separation, catalyst reusability,and tunability, and they have been intensively studied for photocatalytic applications. There are several reviews that focus mainly or even entirely on experimental work. The present review is intended to complement those reviews by focusing on computational work that can provide a further understanding of the photocatalytic properties of MOF photocatalysts. We first present a summary of computational methods, including density functional theory, combined quantum mechanical and molecular mechanical methods, and force fields for MOFs. Then, computational investigations on MOF-based photocatalysis are briefly discussed. The discussions focus on the electronic structure, photoexcitation, charge mobility, and photoredox catalysis of MOFs, especially the widely studied Ui O-66-based MOFs.
基金supported by the Program for New Century Excellent Talents in University (NCET-04-0270)National Basic Research Program of China (2011CB201301)
文摘The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.
基金the Russian Foundation for Basic Research(RFBR grant12-03-31537)
文摘Catalytic properties of the metal-organic framework Cr-MIL-101 in solvent-free cycloaddition of CO2 to epoxides to produce cyclic carbon- ates using tetrabutylammonium bromide as co-catalyst have been explored under mild reaction conditions (8 bar CO2, 25 ~C). Styrene and propylene carbonates were formed with high yields (95% and 82%, respectively). Catalytic performance of Cr-MIL-101 was compared with other MOFs: Fe-MIL-101, Zn-MOF-5 and HKUST-1, The catalytic properties of different quaternary ammonium bromides, Cr-MIL-101 as well as PW12/Cr-MIL-101 composite material have been assessed in oxidative carboxylation of styrene in the presence of both tert-butyl hydroperoxide and H202 as oxidants at 8-100bar CO2 and 25-80 ~C with selectivity to styrene carbonate up to 44% at 57% substrate conversion.
基金supported by the National Natural Science Foundation of China(21102117)Key Laboratory of Chemical Synthesis and Pollution Control of Sichuan Province(CSPC2014-4-1)
文摘Three new metal-organic frameworks [Cd(L)(obba)]·H)2O(1),[Co(L)(obba)]·MeCN(2) and [Cd_2(L)_2(ip)_2]·6H_2O·DMF(3)(H_2obba = 4,4?-oxybisbenzoic acid,H2 ip = m-phthalic acid) have been successfully synthesized based on the controllable self-assembly of 9-ethyl-3,6-diimidazolyl-carbazole(L),varied carboxylates and different metal ions under solvothermal conditions,which were characterized by single-crystal X-ray diffraction,elemental analysis,IR spectroscopy and thermogravimetry. Furthermore,luminescence and magnetic susceptibility of compound 2 are also investigated in detail. Single-crystal X-ray diffraction and topology analysis reveal that complexes 1~3 exhibit similar two-dimensional(2D) networks.
基金National Key Technologies R&D Program of China during the 12th Five-Year Plan Period(No.2012BAD29B06,No2012BAK01B01)National Natural Science Foundation of China(No.21375021)+2 种基金Major Project of Fujian Provincial Science and Technology Program,China(No.2011N5008)Natural Science Foundation of Fujian Province of China(No.2012J05023)Program for New Century Excellent Talents in Fujian Province University,China(No.JA10011)
文摘The equilibrium, kinetics and thermodynamics of the adsorption of methylene blue( MB) from aqueous solution onto copper coordination polymer with dithiooxamide( H2dtoaCu),one of the metal-organic frameworks( MOFs),were investigated in a batch adsorption system as a function of initial pH, adsorbent concentration, contact time, initial dye concentration, and temperature. The Langmuir, Freundlich, and DubininRadushkevich( D-R) isotherm models were used for modeling the adsorption equilibrium. It was found that Langmuir model yielded a much better fit than the Freundlich model under different temperatures. The maximum monolayer adsorption capacities of MB were 192. 98,229. 86,and 297. 38 mg /g at 298,308,and 318 K,respectively. The calculated mean adsorption energy( 8. 26-11. 04 kJ /mol) using D-R model indicated that the adsorption process might take place by chemical adsorption mechanism.Otherwise,the kinetic studies revealed that the adsorption process could be well explained by pseudo-second-order rate kinetics and intraparticle diffusion was not the rate-limiting step.Thermodynamic studies indicated that this system was feasible,spontaneous,and endothermic process. Based on these studies,H2dtoaCu can be considered as a potential adsorbent for the removal of MB from aqueous solution.
基金supported by the National Natural Science Foundation of China(No.21371119,21431004,21401128,21522104,and 21620102001)the National Key Basic Research Program of China(No.2014CB932102 and 2016YFA0203400)the Shanghai“Eastern Scholar”Program
文摘Two metal-organic frameworks [(Zn0.5L)·(H2O)]n (1) and [(Ni0.5L)?(H2O)]n (2) constructed by the 3-formyl-4-(pyridin-4-yl) benzoic acid ligand (HL) were synthesized and characterized by single-crystal X-ray diffraction. 1 crystallizes in orthorhombic space group Pnna with a = 16.6152(8), b = 12.6825(6), c = 15.3908(8) A, V = 3243.2(3) ?3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F(000) = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ(I). 2 is isostructural to 1, which also crystallizes in orthorhombic space group Pnna with a = 16.6152(8), b = 12.6825(6), c = 15.3908(8) ?, V = 3243.2(3) ?3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F(000) = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ(I). Additionally, thermogravimetric analysis, FT-IR spectroscopy and powder X-ray diffraction were discussed.
基金supported by the National Natural Science Foundation of China(No.21171040)the Natural Science Foundation of Anhui Provincial Education Commission(No.KJ2011B128,2011SQRL101 and 10040606Q49)
文摘Two new complexes,[Zn(L1)2(SCN)2]·H2O(1,L1 = 3,5-dimethyl-4-p-tolyl-4H1,2,4-triazole and [Cd3(L2)6(SCN)6](2,L2 = 3,5-dimethyl-4-phenyl-4H-1,2,4-triazole),have been hydrothermally prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and PXRD.Complex 1 crystallizes in monoclinic,space group P21 /n with a = 11.246(13),b = 9.640(11),c = 26.13(3),β = 100.97(3),V = 1108.5(3) 3,Z = 4,C24 H28 N8 OS2 Zn,Mr = 572.02,Dc = 1.366 g/cm3,μ = 1.065 mm-1,S = 0.992,F(000) = 1184,the final R = 0.0602 and wR = 0.1700 for 2925 observed reflections(I 2σ(I)).Complex 2 crystallizes in triclinic,space group P1 with a = 11.6669(3),b = 12.0957(2),c = 14.3674(3),α = 105.380(3),β = 91.020(2),γ = 92.4100(10)o,V = 1952.30(7)3,Z = 1,C66H66N24S6Cd3,Mr = 1725.08,Dc = 1.467 g/cm3,μ = 1.025 mm-1,S = 1.037,F(000) = 870,the final R = 0.0336 and wR = 0.0946 for 7819 observed reflections(I 2σ(I)).In the title complexes,complex 1 is a mononuclear molecule where the centre Zn(II) coordinates to two 3,4,5-substituted 1,2,4-triazole ligands(L1) and two terminal SCN-anions in a tetrahedral environment while six-coordinated centre Cd(II) atoms with octahedral geometry in complex 2 are bridged by virtue of substituted 1,2,4-triazole(L2) in N1,N2-bridging mode and μ2-N,N-SCN-anions into a trinuclear molecule.
基金supported by the Project of Science&Technology in Henan Province(No.172102310441)the National Natural Science Foundation of China(No.21571093)
文摘The cyanide groups of letrozole(1-[bis(4-cyanophenyl)methyl]-1,2,4-triazole) were hydrolyzed into the carboxylic groups under alkaline conditions. Then the hydrolysis product(1-[bis(4-carboxylphenyl)methyl]-1,2,4-triazole, H2ltzda) reacted with Co(NO3)2·6H2O in the presence of different bipyridl-typed ligands under hydrothermal conditions. As a result, two new Co(Ⅱ) MOFs were obtained, formulated as [Co2(ltzda)2(bpp)2]n(1) and {[Co2(ltzda)2(bpy)]·4H2O}n(2)(bpp = 1,3-di(4-pyridyl)propane, bpy = 4,4’-bipyridine). Two MOFs have been characterized by single-crystal X-ray diffraction, thermogravimetric analysis and magnetic measure. 1 displays a 2D metal-organic framework containing wave layers and 2 shows a pillared-layer structure existing in a 2-fold interpenetrated mode.