CN102250130A - Microporous metal-organic framework material as well as preparation method and application thereof - Google Patents
Microporous metal-organic framework material as well as preparation method and application thereof Download PDFInfo
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- CN102250130A CN102250130A CN2011101318821A CN201110131882A CN102250130A CN 102250130 A CN102250130 A CN 102250130A CN 2011101318821 A CN2011101318821 A CN 2011101318821A CN 201110131882 A CN201110131882 A CN 201110131882A CN 102250130 A CN102250130 A CN 102250130A
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Abstract
The invention belongs to the technical field of a microporous metal-organic framework material and particularly relates to a microporous metal-organic framework material based on isophthalic acid derivatives as well as a preparation method and an application thereof. The chemical formula of the microporous metal-organic framework material provided by the invention has a chemical formula of Zn(pybdc), wherein pybdc<2-> is deprotonated 5-(1-pyrrolidyl)-1,3-phthalic acid and n represents an infinite link of the structural unit. The metal-organic framework material provided by the invention is crystallized in a trigonal system and the space group is R-3m; the metal Zn<2+> is located in the center of a tetrahedron and is tetrachordinate. The microporous metal-organic framework material provided by the invention has a one-dimensional porous channel structure along the direction of axis c and a methylene group of a pentary pyrrole ring stretches into the porous channel; the window of the porous channel is about 4 angstroms and the porosity is 18.6%. The structure of the material provided by the invention has the porous channel, so that the material can be used for safely storing gas or solvent molecules.
Description
Technical field
The invention belongs to micropore metal-organic framework material technical field, be specifically related to a kind of micropore metal-organic framework material based on the m-phthalic acid derivative and its production and application.
Background technology
Over past ten years, micropore metal-organic framework material (MOFs) always with its abundant topological framework with in atmosphere storage or separate, application aspect ion-exchange, catalysis and even the chemical sensor and receiving much concern.
And in the process of setting up these structures, organic ligand is being played the part of very important role.The carboxylic-acid coordination polymer material is because of its stability of structure, and diversity and the application aspect gas adsorption have caused people's extensive concern, especially demonstrates its special advantages aspect Chu Qing.The carboxyl plane of poly carboxylic acid ylidene ligands and the interplanar interfacial angle of phenyl ring have diversity, this feature makes them show significant advantage aspect the different directions in that metal center is fixed to, thereby has produced numerous multidimensional network structures that have novel magnetic and divide photosensitiveness, multiple size duct or hole.What tool was significant is the MOF-5 series that Yaghi group uses terephthalic acid to construct.In addition, the class MOF-5 structure of terephthaldehyde's acid construct of organic group phenyl ring modification is also reported in succession.Similar with it, 1, the 3-phthalic acid is an another one carboxylic acid part important and commonly used.This part can be by constructing rung formula secondary building unit or further making up the polyhedron cage structure by the hexagonal hole road structure of one-dimensional inorganic chain formation.Because the m-phthalic acid that phenyl ring is modified obtains than terephthalic acid is easier, how interesting structure is synthesized out based on this type of part.For example based on the 5-tertiary butyl-1, the ligand polymer Ni of 3-phthalic acid (5-bbdc)
8(5-bbdc) 6 (μ
3-OH)
4And Zn (5-bbdc), based on 4 '-tertiary butyl-3, the M of 5-biphenyl dicarboxylic acid (bbpdc)
2(H
2O)
2(bbpdc)
2(M is Zn to 3DMF
2+, Cu
2+, Co
2+).
MOFs has plenty of dense packing, has plenty of vesicular structure.The using value of porous MOFs, particularly selective adsorption separating property are the focus and emphasis of scientists study.When the using value of micropore metal organic coordination polymer is discussed, must consider whether these structures stand test on elasticity and thermostability.In fact, thermostability is a great problem that these ligand polymer face inadequately.As long as continue heating, even under medium temperature, the guest molecule in the skeleton structure also is difficult to keep.And the stability that can make original structure of losing of guest molecule reduces greatly, has just reduced their using value simultaneously.By contrast, the ligand polymer (GFMMOFs) that does not contain no guest molecule when initial formation just has advantages of higher stability.In addition, the duct yardstick of GFMMOFs can be less than 7 generally speaking, and this size just in time is fit to some micro-molecular gas of selective adsorption, also are fit to hydrogen storage simultaneously.[Cu (hfipbb)] (H for example
2Hfipbb)
0.5[H
2Hfipbb is 2, two (right-carboxyl phenyl) HFC-236fa of 2-] be exactly ligand polymer so, it has shown interesting property aspect atmosphere storage, and more valuable is, and its crystalline structure still remains intact when continuing heating down for 330 ℃.Based on above domain background, in theory the derivative of m-phthalic acid also can with the metal ion of four-coordination.
Summary of the invention
The object of the present invention is to provide a kind of micropore metal-organic framework material.
Another object of the present invention has been to provide the preparation method of above-mentioned micropore metal-organic framework material.
A further object of the invention is to provide the application of above-mentioned micropore metal-organic framework material.
Micropore metal-organic framework material provided by the invention, chemical formula are wherein pybdc of Zn (pybdc)
2-Be the 5-(1-pyrrolidyl)-1 that takes off proton, 3-phthalic acid.
Framework material crystallization of the present invention is in trigonal system, and spacer is
R-3mIn single crystal structure, Metal Zn
2+Being in the tetrahedron center, is 4 coordinations, and each metallic zinc center is under the bridge chain effect of carboxylate radical, along the assembling becoming of c direction of principal axis one-dimensional inorganic chain structure, pybdc
2-Be 4 coordinations.The bond distance of Zn (1)-O (1) and Zn (1)-O (2) is respectively 1.942 and 1.925, belongs to typical four-coordination metallic zinc ionic bond distance scope.Part pybdc
2-In five yuan of pyrrole rings and phenyl ring and hydroxy-acid group almost be totally one plane.Five yuan of pyrrole rings do not form significantly " boat form " conformation simultaneously.In the crystalline structure, each metallic zinc center becomes the one-dimensional inorganic chain structure along the assembling of c direction of principal axis under the bridge chain effect of carboxylate radical.Structural analysis finds that these no chains have chirality, are respectively left hand helix and right-handed helix, and their pitch is about 8.3.The inorganic chain of these left hand helixs and right-handed helix is through part pybdc
2-The alternate links effect of middle phenyl ring, constructing becomes centrosymmetric achirality three-dimensional framework structure.Analyze and find that this three-dimensional framework structure exists one-dimensional tunnel structure along the c direction of principal axis, the methylene group of five yuan of pyrrole rings stretches in the middle of the duct, and the duct window size is about 4.By calculating, specific surface is 866.33
2/ unit cell (the probe atomic radius is 1.4), porosity is 18.6 %.
The synthetic method of micropore metal-organic framework material of the present invention is as follows: express the mol ratio that requires according to Zn (pybdc), with 5-(1-pyrrolidyl)-1,3-phthalic acid and zinc acetate are dissolved in the solution of 4 ~ 10 mL deionized waters and 1 ~ 5 mL dehydrated alcohol, stirring at room 1 ~ 5 hour, suspension liquid is transferred to has in the teflon-lined stainless steel cauldron, 100 ~ 150 ℃ of crystallization 8 ~ 100 hours, obtain brown transparent needle-like crystal, after filtration, washing, drying obtain metal target-organic framework material.
Micropore metal-organic framework material of the present invention is characterized in that having in the described material structure a certain size duct, can be used for the safety storing of the suitable solvent of hydrogen or molecular size.
Description of drawings
Fig. 1 is the structure iron of micropore metal-organic framework material of the present invention.Wherein, a is the local coordination structure; B is the one-dimensional inorganic chain of this material along the C axle; C is a tomograph.
Fig. 2 is the x-ray diffractogram of powder and simulation X-ray diffractogram of micropore metal-organic framework material of the present invention.
Fig. 3 is the thermogravimetric curve figure of micropore metal-organic framework material of the present invention.
The H of Fig. 4 micropore metal-organic framework material of the present invention under 77K
2With the CO under the 273K
2The adsorption isotherm line chart.
Embodiment
Further explain the present invention below in conjunction with embodiment, but embodiment does not do any type of restriction to the present invention.
Embodiment 1 consists of the preparation of Zn (pybdc) micropore metal-organic framework material.
Take by weighing Zn (AcO)
22H
2O 0.025 g (0.1 mmol), H
2Pybdc 0.02 g (0.1 mmol), be dissolved in the solution of 8 mL deionized waters and 2 ml dehydrated alcohols, stirring at room 2 hours, suspension liquid is transferred to 15 ml to be had in the teflon-lined stainless steel cauldron, 140 ° of crystallization 72 hours, be cooled to room temperature, have brown transparent needle-like crystal Zn (pybdc) to separate out, filtration, washing, the dry 25mg that gets.Productive rate 55.5%.The X-ray diffractogram of product and monocrystalline simulation X-ray diffractogram are seen Fig. 2.
Embodiment 2 consists of the structural characterization of Zn (pybdc) micropore metal-organic framework material.
The monocrystalline X ray diffracting data is to measure on the SMART of Bruker company APEX CCD single crystal diffractometer, adopts Mo/Ka ray (λ=0.71073) and ω scan mode to collect diffraction data.Unit cell parameters and directed matrix are obtained by least-squares refinement, crystalline structure is resolved by direct method or Patterson method, obtain original texture, all non-hydrogen atom coordinates have been obtained through least square correction and difference fourier method again, hydrogen atom on the organic group adopts theoretical hydrogenation to obtain, and hydrogen atom waterborne is then determined by the difference fourier methods.And revise through complete matrix minimum [84] square law, all non-hydrogen atoms all adopt the anisotropy thermal parameter to carry out refine.Utilize revised accurate atomic coordinate, calculated the bond distance and the bond angle of chemical bond between each atom.Detailed axonometry data see Table 1.Structure is seen Fig. 1.
Table 1
| Compond | Zn(pybdc) |
| empirical formula | C 14H 12ZnO 4N 2 |
| formula weight | 337.64 |
| crystal system | trigonal |
| space group | R-3m (No.166) |
| a [?] | 28.868(7) |
| b [?] | 28.868(7) |
| c [?] | 8.261(3) |
| α [°] | 90.00 |
| β[°] | 90.00 |
| γ[°] | 120.00 |
| V [? 3] | 5962(3) |
| Z | 18 |
| ρ calcd. (g/cm3) | 1.286 |
| μ (mm -1) | 1.945 |
| F(000) | 2340 |
| GOF | 1.033 |
| R 1, wR 2[I>2σ(I)] | 0.0431,0.1171 |
| R 1, wR 2 (all data) | 0.0562,0.1233 |
| largest diff. peak/ hole [e/? 3 ] | 0.799,-0.300 |
The thermostability of embodiment 3 embodiment 1 gained micropore metal-organic framework material Zn (pybdc) characterizes.
The thermostability of micropore metal-organic framework material Zn (pybdc) is analyzed by thermogravimetric, and thermogravimetric curve figure sees Fig. 3.
The gas adsorption character of embodiment 4 embodiment 1 gained micropore metal-organic framework material characterizes.
We adopt the sample of Zn (pybdc) to carry out hydrogen adsorption under the 77 K conditions and the CO under the 273 K conditions
2Absorption research.Under the 77K, the adsorptive capacity of hydrogen on Zn (pybdc) sample presents quick increase at low pressure area, the linear increase along with the increase of pressure then, and adsorptive capacity reaches 17 cm when 800 mmHg pressure
3/ g.And under the 273K condition, CO
2Adsorptive capacity on Zn (pybdc) sample presents linear increasing in whole pressure range.Its adsorption isotherm line chart is seen Fig. 4.
Claims (5)
1. micropore metal-organic framework material, the chemical formula that it is characterized in that this micropore metal-organic framework material is Zn (pybdc), wherein pybdc
2-Be the 5-(1-pyrrolidyl)-1 that takes off proton, 3-phthalic acid.
2. according to the described micropore metal-organic framework material of claim 1, it is characterized in that: the crystallization of this material is in trigonal system, and spacer is
R-3mIn single crystal structure, Metal Zn
2+Being in the tetrahedron center, is 4 coordinations, and each metallic zinc center is under the bridge chain effect of carboxylate radical, along the assembling becoming of c direction of principal axis one-dimensional inorganic chain structure, pybdc
2-Be 4 coordinations.
3. according to the described micropore metal-organic framework material of claim 2, it is characterized in that described material three-dimensional skeleton structure, exist one-dimensional tunnel structure along the c direction of principal axis, the methylene group of five yuan of pyrrole rings stretches in the middle of the duct, the duct window size is 4, and specific surface is 866.33
2/ unit cell, porosity are 18.6 %.
4. the preparation method of claim 1 or 2 or 3 described micropore metal-organic framework materials, it is characterized in that comprising the steps: to express the mol ratio that requires according to Zn (pybdc), with 5-(1-pyrrolidyl)-1,3-phthalic acid and zinc acetate are dissolved in the solution of 4 ~ 10 mL deionized waters and 1 ~ 5 mL dehydrated alcohol, stirring at room 1 ~ 5 hour, suspension liquid is transferred to has in the teflon-lined stainless steel cauldron, 100 ~ 150 ℃ of crystallization 8 ~ 100 hours, obtain brown transparent needle-like crystal, after filtration, washing, drying obtains micropore metal-organic framework material.
As claim 1 or 2 or 3 described micropore metal-organic framework materials according to the application in the safety storing of the suitable solvent of hydrogen or molecular size of the size in its duct.
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Cited By (11)
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| CN102633841A (en) * | 2012-02-27 | 2012-08-15 | 江苏科技大学 | Three-dimensional porous coordination polymer, preparation method for same and application thereof |
| CN102851020A (en) * | 2012-09-19 | 2013-01-02 | 复旦大学 | Magnetic-chromatic synchronously-responsive self-assembled microporous material and preparation method thereof |
| CN102886249A (en) * | 2012-10-15 | 2013-01-23 | 复旦大学 | Self-assembled microporous material capable of selectively absorbing and separating methanol molecules and preparation method thereof |
| CN103100372A (en) * | 2013-01-25 | 2013-05-15 | 浙江大学 | Metal-organic framework material for methane adsorption and storage and preparation method thereof |
| CN103509040A (en) * | 2012-06-26 | 2014-01-15 | 宁波大学 | Coordination polymer with high thermal stability and fluorescence properties and preparation method thereof |
| CN105080495A (en) * | 2015-09-16 | 2015-11-25 | 北京工业大学 | Metal-organic framework material of Zr and preparation method and application thereof |
| CN105669593A (en) * | 2014-11-19 | 2016-06-15 | 中国科学院大连化学物理研究所 | Barium base metal organic framework material preparation method |
| CN106008567A (en) * | 2016-07-28 | 2016-10-12 | 天津师范大学 | 4H thioether bitriazole terephthalic acid two-dimensional zinc complex monocrystal and application |
| CN106475059A (en) * | 2016-10-31 | 2017-03-08 | 华南理工大学 | A kind of to C6Isomer has ferrous metals organic framework material of high adsorptive selectivity and preparation method and application |
| CN106496580A (en) * | 2016-10-01 | 2017-03-15 | 桂林理工大学 | The zinc complex that is constructed with trimesic acid and 4 phenylpyridines and preparation method |
| CN107629076A (en) * | 2017-09-13 | 2018-01-26 | 华南理工大学 | A kind of ordered big hole metal organic frame monocrystalline and preparation method thereof |
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| CN101379068A (en) * | 2006-02-10 | 2009-03-04 | 巴斯夫欧洲公司 | Process for preparing porous organic framework materials |
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| CN1910191A (en) * | 2004-01-13 | 2007-02-07 | 巴斯福股份公司 | Organometallic framework material, preparation and use |
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|---|---|---|---|---|
| CN102633841B (en) * | 2012-02-27 | 2014-11-05 | 江苏科技大学 | Three-dimensional porous coordination polymer, preparation method for same and application thereof |
| CN102633841A (en) * | 2012-02-27 | 2012-08-15 | 江苏科技大学 | Three-dimensional porous coordination polymer, preparation method for same and application thereof |
| CN103509040A (en) * | 2012-06-26 | 2014-01-15 | 宁波大学 | Coordination polymer with high thermal stability and fluorescence properties and preparation method thereof |
| CN102851020A (en) * | 2012-09-19 | 2013-01-02 | 复旦大学 | Magnetic-chromatic synchronously-responsive self-assembled microporous material and preparation method thereof |
| CN102851020B (en) * | 2012-09-19 | 2014-12-03 | 复旦大学 | Magnetic-chromatic synchronously-responsive self-assembled microporous material and preparation method thereof |
| CN102886249A (en) * | 2012-10-15 | 2013-01-23 | 复旦大学 | Self-assembled microporous material capable of selectively absorbing and separating methanol molecules and preparation method thereof |
| CN103100372A (en) * | 2013-01-25 | 2013-05-15 | 浙江大学 | Metal-organic framework material for methane adsorption and storage and preparation method thereof |
| CN103100372B (en) * | 2013-01-25 | 2014-07-02 | 浙江大学 | Metal-organic framework material for methane adsorption and storage and preparation method thereof |
| CN105669593B (en) * | 2014-11-19 | 2018-04-06 | 中国科学院大连化学物理研究所 | A kind of preparation method of barium Base Metal organic framework material |
| CN105669593A (en) * | 2014-11-19 | 2016-06-15 | 中国科学院大连化学物理研究所 | Barium base metal organic framework material preparation method |
| CN105080495A (en) * | 2015-09-16 | 2015-11-25 | 北京工业大学 | Metal-organic framework material of Zr and preparation method and application thereof |
| CN106008567A (en) * | 2016-07-28 | 2016-10-12 | 天津师范大学 | 4H thioether bitriazole terephthalic acid two-dimensional zinc complex monocrystal and application |
| CN106496580A (en) * | 2016-10-01 | 2017-03-15 | 桂林理工大学 | The zinc complex that is constructed with trimesic acid and 4 phenylpyridines and preparation method |
| CN106475059A (en) * | 2016-10-31 | 2017-03-08 | 华南理工大学 | A kind of to C6Isomer has ferrous metals organic framework material of high adsorptive selectivity and preparation method and application |
| CN106475059B (en) * | 2016-10-31 | 2018-12-11 | 华南理工大学 | A kind of couple of C6Isomer has the ferrous metals organic framework material and the preparation method and application thereof of high adsorptive selectivity |
| CN107629076A (en) * | 2017-09-13 | 2018-01-26 | 华南理工大学 | A kind of ordered big hole metal organic frame monocrystalline and preparation method thereof |
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