CN102030767B - Supramolecular metal-organic framework (MOF) compound material - Google Patents
Supramolecular metal-organic framework (MOF) compound material Download PDFInfo
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- CN102030767B CN102030767B CN2009101796169A CN200910179616A CN102030767B CN 102030767 B CN102030767 B CN 102030767B CN 2009101796169 A CN2009101796169 A CN 2009101796169A CN 200910179616 A CN200910179616 A CN 200910179616A CN 102030767 B CN102030767 B CN 102030767B
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Abstract
The invention relates to a novel supramolecular metal-organic framework (MOF) compound and a synthesis method thereof, and belongs to the technical fields of an inorganic material, coordination chemistry and supramolecular science. The structural formula of the compound is [Cu2(THFTCA)(phen)(H2O)3.EtOH.3H2O]n. The synthesis method comprises the following steps: at room temperature, dissolving sodium hydroxide and 2,3.4,5-tetrahydrofuroic acid in water, dissolving 1,10-phenanthroline monohydrate and cupric salt in ethanol and water respectively, and then sequentially mixing the three types of solutions; heating to 80 DEG C, reacting for 1 hour and then filtering to obtain solid, and washing the obtained solid with mixed liquid of ethanol and water; naturally airing to obtain the solid product of the supramolecular MOF compound; and treating the obtained compound at the temperature of 105 DEG C for 5 hours, and removing guest molecules from the framework to obtain the solid product of an MOF microporous material. The obtained MOF microporous material has good application prospect in gas adsorption and storage as well as sensitive materials of water and ethanol sensors.
Description
Technical field
The present invention relates to a kind of novel supramolecule metallic organic framework compound-material, belong to inorganic materials, coordination chemistry and supramolecule science and technology field, a kind of supramolecule metallic organic framework compound as the small molecules sorbing material particularly is provided.
Background technology
Field, forward position as chemistry; Supramolecular chemistry receives people's attention day by day; Nobel chemistry Prize in 1987 is authorized three scientist (C.J.Pedersen of the U.S. that are engaged in supramolecular chemistry research; The J.M.Lehn professor of D.J.Cram professor and France) after, obtained unprecedented development especially.Generate the molecular chemistry of molecule corresponding to being connect with chemical bond by atom and atom, supramolecular chemistry then is that molecule and molecule connect with Intermolecular Forces and the molecule aggregates that forms, is called for short supramolecule.With the supramolecular chemistry is the supramolecule material on basis; Be a kind of modern type material that is in the development phase, it generally is meant the bonding action (like interaction of hydrogen bond, pi-pi accumulation interaction, interionic interaction and hydrophobic interaction etc.) that utilizes intermolecular non covalent bond and the material for preparing.Compare with traditional material, the supramolecule material has many new rerum naturas, has showed tempting research and development prospect.The research of all kinds super molecular compound at present concentrates on mainly that it is synthetic, structural characterization, character exploration aspect, strengthens that the research of this class formation is had significance for the molecular engineering that realizes the hyperspace assembling.Be based on the subject crossing point in fields such as chemistry, physics, material, information; The exploitation super molecular compound will produce great scientific meaning and practical value in the application of aspects such as molecular magnetic materials, optical material, molecular recognition material, atmosphere storage and catalytic material.
One of challenge that field of porous materials is outstanding is design and the synthetic material that special construction and high-specific surface area are arranged.In many practical applications, like storage of catalyzer, separation and gas etc., such material all is very important.Along with supramolecule coordination chemistry and organometallics design and assembly CHEMICAL DEVELOPMENT, novel porous metal-organic framework compound begins to occur.The porous metal-organic framework compound is called metal organic coordination polymer again, and it is built into through covalent linkage or ionic linkage self-assembly by metals ion and organic ligand, is the crystalline state polycrystalline material with regular pore canal or opening structure.Hole in this type material has different shape and size, be the porous material of zeolite and molecular sieve and so on observed less than.They have following characteristic: 1) stronger bonding action is that skeleton structure provides rigidity and stability; 2) organic ligand that connects central metal or metal cluster can be adjusted through the organic synthesis process; 3) pore structure of skeleton formation can be controlled through adjustment metal center or organic ligand.Owing to had the easy design control of organic materials and the advantages such as stability of inorganic materials concurrently; And have big specific surface area and be easy to design the control punch structure, so its gas and small molecules absorption with separate, there is special advantages aspects such as selective adsorption sensitive material, catalyzer.
Summary of the invention
The compound method that the purpose of this invention is to provide a kind of supramolecule metallic organic framework compound, and as the performance of porous compounds material to gas adsorption, and possibly have good application prospects aspect small molecules absorption and the molecule sensitive sensing material.
The porous metal-organic framework compound of report is all constructed through the covalent linkage self-assembly by metals ion and organic ligand and is formed before this, has the crystalline state polycrystalline material of rigid backbone duct or opening structure.Its reason that forms skeleton duct or opening structure is that direct coordination becomes key and forms the rigid support power to skeleton metals ion with organic ligand on the three-dimensional.
Supramolecule metallic organic framework compound of the present invention; Then be metals ion and organic ligand at first coordination assembling form the inflexible molecular layer, interact by intensive supramolecule pi-pi accumulation between the molecular layer then and support rigidity and more stable three-dimensional open-framework.Method in view of the above, the synthetic of porous metal-organic framework compound will have the more design space of horn of plenty, the ability that its duct or opening structure also will have certain elasticity and hold guest molecule widely.
The technical scheme that the present invention adopts is:
Under the room temperature fully 2,3,4 of deprotonation, the 5-THF tetracarboxylic acid aqueous solution, 1, the ethanolic soln of the adjacent luxuriant and rich with fragrance sound of vomiting quinoline of 10-and the aqueous solution of cupric salt, three kinds of solution make supramolecule metallic organic framework compound successively to adding reaction through self-assembly.Specific operation process is:
1) under the room temperature with 2-10mmol sodium hydroxide and 2,3,4,5-THF tetracarboxylic acid is dissolved in the 10-40ml water fully, both mol ratios are 4: 1;
2) under the room temperature with 1, the adjacent luxuriant and rich with fragrance sound of vomiting of 10-quinoline is dissolved in the 4-20ml ethanol fully, cupric salt is dissolved in the 5-20ml water fully, cupric salt and 2,3,4,5-THF tetracarboxylic acid, 1, the adjacent luxuriant and rich with fragrance mol ratio of vomiting quinoline of 10-all is 2: 1;
3) under the room temperature with 1, the ethanolic soln of the adjacent luxuriant and rich with fragrance sound of vomiting of 10-quinoline joins above-mentioned 1) solution in, stir, become colourless uniform solution;
4) under the room temperature aqueous solution of cupric salt is added drop-wise to above-mentioned 3) solution in, fully stir simultaneously, separate out a large amount of flockss gradually;
5) with above-mentioned 4) turbid solution that forms is heated to 1 hour after-filtration of 80 ℃ of reactions, and filter cake washs with the mixed solution of second alcohol and water; Naturally the blue solid product after drying is this supramolecule metallic organic framework compound; Productive rate is 96%.
With the solid that obtains, carried out ultimate analysis, infrared and monocrystalline X-ray test respectively, analytical results shows that the solid that obtains is cupric supramolecule metallic organic framework compound.
The structural formula of institute of the present invention synthetic compound is [Cu
2(THFTCA) (phen) (H
2O)
3EtOH3H
2O]
n, belong to oblique system, P2
1/ n (No.14) spacer, unit cell parameters a=8.8276 (18), b=23.476 (5),
β=91.01 (3) °,
Z=4, D
c=1.774g/cm
3, the compound color is blue; Be by nine tooth ligands 2,3,4,5-THF tetracarboxylic acid (THFTCA
4-), aromaticity end group ligand 1,10-adjacent luxuriant and rich with fragrance sound of vomiting quinoline (phen) and Cu
2+The three-dimensional supramolecule metallic organic framework compound that ion is built into is being filled guest molecule H in the skeleton duct
2O and CH
3CH
2OH; Wherein there are two kinds of copper atoms, are in the hexa-coordinate pentacoordinate environment tapered of octahedral build respectively with the four directions; And the bridge joint effect through this poly carboxylic acid part of THFTCA; Two kinds of copper atoms are joined into the laminated metal-organic polymer molecule for two dimension; 1 of bidentate chelating, 10-phen has stoped the further polymerization between hydroxy-acid group and the atoms metal as a kind of part that hangs; When molecular layer is piled up along structure cell b direction of principal axis, receive its intensive pi-pi accumulation function influence between the interior phen part of layer separately between layer and the layer, finally formed the firm organic porous skeleton of three-dimensional supramolecule metal; Four of THFTCA complete deprotonations of carboxyl in the skeleton, thus reach charge balance with two bivalent cupric ions; A comparison outstanding feature is on this compound structure, along a direction of principal axis one dimension prismatic supramolecule channel pore array is arranged, and the aperture is about 0.5 * 1.0nm, and a large amount of object water moleculess and ethanol molecule then are stored in this main body duct.
Among the present invention, with metallic organic framework compound 1 roasting 5 hours under 105 ℃ of conditions, obtain blue powder, thermogravimetric and powder X-ray RD analyze and show that this powder is the supramolecule metallic organic framework poromerics [Cu that sloughs guest molecule
2(THFTCA) (phen) (H
2O)
3]
n(1a); Use is purchased ASAP2010 Chemi instrument from Micromeritics's, through Langmuir method (N
2) detect the specific surface area of metallic organic framework porous material, detected simultaneously this material in the time of 50 ℃ for H
2The absorption storage power.
Metallic organic framework compound-material of the present invention has following characteristics:
(1) [Cu
2(THFTCA) (phen) (H
2O)
3EtOH3H
2O]
nMaterial is a kind of super molecular compound with one dimension prismatic channel pore array; Its duct is made up of through the effect of intensive pi-pi accumulation molecular layer; The aperture is about 0.5 * 1.0nm; Can hold a large amount of object water moleculess, ethanol molecule and other micromolecular turnover, can the object small molecules in the main body duct be removed through heat treated, and main body framework still keep its stability.The crystalline structure iron is like Fig. 1, shown in 2 and 3.
(2) preparation technology is simple, and raw material is simple and easy to, and cost is lower, adopts the method for substep solution reaction synthetic under the room temperature, can obtain having the very product of high yield in a short period of time.
(3) has hydrophilic oxygen enrichment atom position in the pore passage structure of material, than being easier to adsorbed water molecule, ethanol molecule and the stronger molecule of other polarity; Simultaneously also have hydrophobic aromaticity ligand site, have certain oleophilicity, can adsorb the more weak molecule of polarity.
Description of drawings
Fig. 1 is the present invention [Cu
2(THFTCA) (phen) (H
2O)
3EtOH3H
2O]
n(1) the metal organic polymer molecular layer structure iron seen from the b direction of principal axis of material.
Fig. 2 is the present invention [Cu
2(THFTCA) (phen) (H
2O)
3EtOH3H
2O]
n(1) the metal organic polymer molecular layer structure iron seen from a direction of principal axis of material.
Fig. 3 is the present invention [Cu
2(THFTCA) (phen) (H
2O)
3EtOH3H
2O]
n(1) material prolongs the axial pore passage structure figure of a from what the bc face was seen, and wherein the molecule piled up of the inside that shows of ball-type is object water and ethanol molecule.
Fig. 4 is the X-ray powder diffraction figure according to the metallic organic framework compound (1) of embodiment 2.X-coordinate is represented 2 θ scales, and Intensity (counting) draws in ordinate zou.
Fig. 5 is the present invention [Cu
2(THFTCA) (phen) (H
2O)
3EtOH3H
2O]
n(1) thermogravimetric analysis of material (TGA) curve, X-coordinate is represented temperature, weight percentage is drawn in ordinate zou.
Fig. 6 is the X-ray powder diffraction figure of metallic organic framework compound (1) after treatment of different temperature according to embodiment 2.X-coordinate is represented 2 θ scales, and Intensity (counting) draws in ordinate zou.
Fig. 7 is nitrogen adsorption and the desorption curve of supramolecule metallic organic framework poromerics (1a) under 77K according to embodiment 3.X-coordinate is represented relative pressure, and adsorptive capacity is drawn in ordinate zou.
Embodiment
Embodiment 1
Synthetic supramolecule metallic organic framework compound [Cu
2(THFTCA) (phen) (H
2O)
3EtOH3H
2O]
n(1) monocrystalline: take by weighing 130mg H
4After THFTCA and 82mg NaOH are dissolved in the 10mL water, add 242mg Cu (NO
3)
23H
2O also stirs slightly and makes its dissolving, filters back covering 5mL on filtrating and contains 100mg 1, the ethanolic soln of 10-phen.Separate out the about 105mg of a large amount of strip blue colored crystals, productive rate 30% after leaving standstill a couple of days.The blue colored crystal of selecting a 0.48mm * 0.08mm * 0.04mm size is used for the x-ray crystal structure test.The molecular layer structural diagrams of this compound is in Fig. 1 and 2, and the structural diagrams of supramolecule metallic organic framework is in Fig. 3.
Embodiment 2
High yield is synthesized metallic organic framework compound [Cu
2(THFTCA) (phen) (H
2O)
3EtOH3H
2O]
n(1) polycrystal powder: take by weighing 390mg H
4After THFTCA and 82mg NaOH are dissolved in the 25mL water, take by weighing 300mg phen and be dissolved in the 12ml ethanol, after stirring is fully dissolved, the adduction thorough mixing; Take by weighing 726mg Cu (NO
3)
23H
2O is dissolved in the 15ml water; The aqueous solution with mantoquita is added drop-wise in the mixing solutions of above-mentioned organic ligand then, fully stirs simultaneously, separates out a large amount of flockss gradually; The turbid solution that forms is heated to 1 hour after-filtration of 80 ℃ of reactions, and filter cake is with the mixed solution washing of second alcohol and water; Naturally obtain the blue solid product after drying.Confirm that through powder X-ray RD the solid that obtains is title product (being shown in Fig. 4), productive rate is 96%.Further powder X-ray RD (the being shown in Fig. 6) analysis after thermogravimetric (being shown in Fig. 5) and the treatment of different temperature confirms that the skeleton structure of this material still keeps stable after sloughing guest molecule; And the supramolecule skeleton does not cave in before 210 ℃, has good skeleton stability.
Embodiment 3
With metallic organic framework compound 1 roasting 5 hours under 105 ℃ of conditions, obtain blue powder, thermogravimetric and powder X-ray RD analyze and show that this powder is the supramolecule metallic organic framework poromerics [Cu that sloughs guest molecule
2(THFTCA) (phen) (H
2O)
3]
n(1a); Use N
2Detect (being shown in Fig. 7), framework material has absorption property preferably, and specific surface area is 28.1914m
2/ g's; H
2Absorption detects, and has the hydrogen-storage amount of 6.91213ml/g when showing 50 ℃.
Claims (5)
1. supramolecule metallic organic framework compound, it is characterized in that: the structural formula of compound is [Cu
2(THFTCA) (phen) (H
2O)
3EtOH3H
2O]
n, belong to oblique system, P2
1/ n (No.14) spacer, unit cell parameters
β=91.01 (3) °,
Z=4, D
c=1.774g/cm
3, the compound color is blue; Be by nine tooth ligands 2,3,4,5-THF tetramethyl acid group (THFTCA
4-), aromaticity end group ligand 1,10-phenanthroline (phen) and Cu
2+The three-dimensional supramolecule metallic organic framework compound that ion is built into is being filled guest molecule H in the skeleton duct
2O and CH
3CH
2OH; Wherein there are two kinds of copper atoms, are in the hexa-coordinate pentacoordinate environment tapered of octahedral build respectively with the four directions; And the bridge joint effect through this poly carboxylic acid part of THFTCA; Two kinds of copper atoms are joined into the laminated metal-organic polymer molecule for two dimension; 1 of bidentate chelating, 10-phen has stoped the further polymerization between hydroxy-acid group and the atoms metal as a kind of part that hangs; When molecular layer is piled up along structure cell b direction of principal axis, receive its intensive pi-pi accumulation function influence between the interior phen part of layer separately between layer and the layer, finally formed the firm organic porous skeleton of three-dimensional supramolecule metal; Four of THFTCA complete deprotonations of carboxyl in the skeleton, thus reach charge balance with two bivalent cupric ions; A comparison outstanding feature is on this compound structure, along a direction of principal axis one dimension prismatic supramolecule channel pore array is arranged, and the aperture is 0.5 * 1.0nm, and a large amount of object water moleculess and ethanol molecule then are stored in this main body duct.
2. the preparation method of the said supramolecule metallic organic framework of claim 1 compound-material is characterized in that: it adopts the preparation of substep solution reaction method, and specific operation process does,
1) under the room temperature with the sodium hydroxide and 2,3,4 of 2-10mmol, 5-THF tetracarboxylic acid is dissolved in the 10-40ml water fully, both mol ratios are 4: 1;
2) under the room temperature with 1, the 10-phenanthroline is dissolved in the 4-20ml ethanol fully, cupric salt is dissolved in the 5-20ml water fully, cupric salt and 2,3,4,5-THF tetracarboxylic acid, 1, the mol ratio of 10-phenanthroline all is 2: 1;
3) under the room temperature with 1, the ethanolic soln of 10-phenanthroline joins above-mentioned 1) solution in, stir, become colourless uniform solution;
4) under the room temperature aqueous solution of cupric salt is added drop-wise to above-mentioned 3) solution in, fully stir simultaneously, separate out a large amount of flockss gradually;
5) with above-mentioned 4) turbid solution that forms is heated to 1 hour after-filtration of 80 ℃ of reactions, the mixed solution washing of second alcohol and water; Naturally the blue solid product after drying is this supramolecule metallic organic framework compound.
3. according to the preparation method of the said metallic organic framework compound-material of claim 2, it is characterized in that: said cupric salt is cupric nitrate, copper sulfate or cupric chloride.
4. according to the preparation method of the said metallic organic framework compound-material of claim 2, it is characterized in that: be used to dissolve 1 said step 2), the amount of ethanol of 10-phenanthroline is slightly less than 1) the half the consumption of middle solvent for use water.
5. micropore powdered material, this material is processed through bakingout process by the said metallic organic framework compound-material of claim 1; Concrete heat treating method is 105 ℃ of roasting temperatures 5 hours; Prepared micropore powder has 28.1914m
2The specific surface area of/g is through Langmuir method N
2Detect; And has the hydrogen-storage amount of 6.91213ml/g 50 ℃ the time.
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| US9192913B2 (en) * | 2011-09-05 | 2015-11-24 | Kuraray Co., Ltd. | Adsorbent |
| CN102936239B (en) * | 2012-11-16 | 2014-05-14 | 山东师范大学 | Organic ligand, metal organic frames based on Cu (I) ions, synthetic method for organic ligand and metal organic frames based on Cu (I) ions and application |
| JP6698325B2 (en) * | 2014-12-08 | 2020-05-27 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Supramolecular metal-organic structure material and method for producing the same |
| US10676488B2 (en) | 2014-12-08 | 2020-06-09 | Samsung Electronics Co., Ltd. | Multifunctional supramolecular hybrids encompassing hierarchical self-ordering of metal-organic framework nanoparticles and method of preparing same |
| CN104587966A (en) * | 2014-12-15 | 2015-05-06 | 北京思达安新材料科技有限公司 | MOF (metal-organic framework) hierarchical porous material IPD-mesoMOF-9 and preparation method |
| CN104697940A (en) * | 2015-03-31 | 2015-06-10 | 中国人民解放军国防科学技术大学 | Naked-eye detection sensor and preparation method and application thereof |
| CN106824277B (en) * | 2015-12-04 | 2019-06-18 | 中国科学院大连化学物理研究所 | Cerium Base Metal-organic framework material catalyzing hydrolysis organic compound phosphatide key method |
| CN106010504B (en) * | 2016-05-05 | 2018-02-27 | 中国计量大学 | A kind of green fluorescent material based on rare earth metal organic framework |
| CN105860961B (en) * | 2016-05-05 | 2018-02-27 | 中国计量大学 | A kind of infrared lumious material of rare earth metal organic framework |
| CN110280233B (en) * | 2019-06-10 | 2020-09-01 | 中南大学 | Catalyst for amine reduction methylation and preparation and application thereof |
| EP3772529B1 (en) * | 2019-08-05 | 2023-04-19 | Sanko Tekstil Isletmeleri San. Ve Tic. A.S. | Ph-sensitive dyes for textile materials, a process for their preparation and uses thereof |
| CN110961081B (en) * | 2019-10-17 | 2020-11-20 | 广东省测试分析研究所（中国广州分析测试中心） | Preparation method and application of porous metal-organic complex material |
| CN113861434B (en) * | 2021-09-14 | 2022-10-21 | 南开大学 | Novel magnesium-based MOF material and solution processing method of MOF material |
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Non-Patent Citations (4)
| Title |
|---|
| Jacqueline M.Knaust et al..Linking triangles:synthesis and structure of [Cu3(phen)4(PPh3)](BF4)3.X and [Cu5(phen)7](BF4)5.4(NO2C6H5)(phen=4,7-phenanthroline and X=Et2O or 2THF).《Polyhedron》.2003,第22卷 * |
| JacquelineM.Knaustetal..Linkingtriangles:synthesisandstructureof[Cu3(phen)4(PPh3)](BF4)3.Xand[Cu5(phen)7](BF4)5.4(NO2C6H5)(phen=4 7-phenanthroline and X=Et2O or 2THF).《Polyhedron》.2003 |
| 侯红卫 等.三维超分子体系[Cu(C5H4NCOO)2(H2O)2].H2O的晶体结构及合成机理.《郑州大学学报（理学版）》.2004,第36卷(第2期), * |
| 王崇臣.一种配合物的合成、晶体结构以及热性能研究.《北京建筑工程学院学报》.2006,第22卷(第4期), * |
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