CN102250130B - 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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- CN102250130B CN102250130B CN201110131882.1A CN201110131882A CN102250130B CN 102250130 B CN102250130 B CN 102250130B CN 201110131882 A CN201110131882 A CN 201110131882A CN 102250130 B CN102250130 B CN 102250130B
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- organic framework
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000013336 microporous metal-organic framework Substances 0.000 title abstract 5
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 5
- 125000000168 pyrrolyl group Chemical group 0.000 claims abstract description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000013384 organic framework Substances 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 150000002531 isophthalic acids Chemical class 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000003446 ligand Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- -1 p-carboxyl phenyl Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000373 single-crystal X-ray diffraction data Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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 m-phthalic acid derivative and its preparation method and application.
Background technology
Nearly 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 chemical sensor and receiving much concern.
And in the process of these structures of establishment, organic ligand is being played the part of very important role.Carboxylic-acid coordination polymer material is because of the stability of its structure, and diversity and the application aspect gas adsorption have caused people's extensive concern, especially aspect Chu Qing, demonstrates its unique advantage.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 metal center being fixed to aspect different directions, thereby has produced numerous multidimensional network structures with novel magnetic and point photosensitiveness, sizes duct or hole.What tool was significant is the MOF-5 series that Yaghi group is used terephthalic acid to construct.The class MOF-5 structure of terephthaldehyde's acid construct that in addition, organic group phenyl ring is modified is also reported out in succession.Similar with it, 1,3-phthalic acid is the important and conventional Carboxylic acid ligand of another one.This part can be by constructing rung formula secondary building unit or further building polyhedron cage structure by the hexagonal hole road structure of one-dimensional inorganic chain formation.The m-phthalic acid of modifying due to phenyl ring more easily obtains than terephthalic acid, and 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.In the time that the using value of micropore metal organic coordination polymer is discussed, must consider whether these structures stand test in elasticity and thermostability.In fact, thermostability is a great problem that these ligand polymer face not.As long as continuous heating, even at medium temperature, the guest molecule in skeleton structure is also difficult to retain.And the loss of guest molecule can make the stability of original structure greatly reduce, just reduce their using value simultaneously.By contrast, in the time of initial formation, do not contain and just there is higher stability without the ligand polymer (GFMMOFs) of guest molecule.In addition, generally the duct yardstick of GFMMOFs can be less than 7, and this size is just in time applicable to some micro-molecular gas of selective adsorption, is also applicable to hydrogen storage simultaneously.For example [Cu (hfipbb)] (H
2hfipbb)
0.5[H
2hfipbb is two (p-carboxyl phenyl) HFC-236fa of 2,2-] be exactly ligand polymer so, it has shown interesting character aspect atmosphere storage, and more valuable is its crystalline structure still remains intact when continuous heating at 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 is wherein pybdc of Zn (pybdc)
2-for the 5-(1-pyrrolidyl)-1 of de-proton, 3-phthalic acid.
Framework material crystallization of the present invention is in trigonal system, and spacer is
r-3m.In single crystal structure, Metal Zn
2+in tetrahedron center, be 4 coordinations, each metallic zinc center, under the bridge chain effect of carboxylate radical, is assembled into one-dimensional inorganic chain structure, pybdc along c-axis direction
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 bond distance's scope of typical four-coordination metallic zinc ion.Part pybdc
2-in five yuan of pyrrole rings and phenyl ring and hydroxy-acid group be almost totally one plane.Five yuan of pyrrole rings do not form significantly " boat form " conformation simultaneously.In crystalline structure, each metallic zinc center, under the bridge chain effect of carboxylate radical, is assembled into one-dimensional inorganic chain structure along c-axis direction.Structural analysis discovery, these have chirality without chain, 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, the achirality three-dimensional framework structure of symmetry centered by being built into.Analyze and find, this three-dimensional framework structure exists one-dimensional tunnel structure along c-axis direction, and the methylene group of five yuan of pyrrole rings stretches in the middle of duct, and duct window size is about 4.By calculating, specific surface is 866.33
2/ unit cell (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 requiring according to Zn (pybdc), by 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 temperature 1 ~ 5 hour, suspension liquid is transferred to in teflon-lined stainless steel cauldron, 100 ~ 150 ℃ of crystallization 8 ~ 100 hours, obtain brown transparent needle-like crystal, after filtration, washing, the dry metal target-organic framework material that obtains.
Micropore metal-organic framework material of the present invention is characterized in that having in described material structure a certain size duct, can be used for the safety storing of the solvent that hydrogen or molecular size are suitable.
Accompanying drawing explanation
Fig. 1 is the structure iron of micropore metal-organic framework material of the present invention.Wherein, a is local coordination structure; B is the one-dimensional inorganic chain of this material along C axle; C is 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 273K
2adsorption 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 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 temperature 2 hours, suspension liquid is transferred to 15 ml with in 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 to obtain.Productive rate 55.5%.The X-ray diffractogram of product and monocrystalline simulation X-ray diffractogram are shown in Fig. 2.
Embodiment 2 consists of the structural characterization of Zn (pybdc) micropore metal-organic framework material.
Single Crystal X-ray diffraction 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 Orientation Matrices are obtained by least-squares refinement, crystalline structure is resolved by direct method or Patterson method, obtain original texture, all non-hydrogen atom coordinates are obtained through least square correction and poor fourier method again, hydrogen atom on organic group adopts theoretical hydrogenation to obtain, and hydrogen atom waterborne is determined by difference fourier methods.And revise through complete matrix minimum [84] square law, all non-hydrogen atoms all adopt anisotropy thermal parameter to carry out refine.Utilize revised accurate atomic coordinate, calculated bond distance and the bond angle of chemical bond between each atom.Detailed axonometry data are in table 1.Structure is shown in 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 is shown in Fig. 3.
The gas adsorption character of embodiment 4 embodiment 1 gained micropore metal-organic framework materials characterizes.
We adopt the sample of Zn (pybdc) to carry out the CO under hydrogen adsorption and the 273 K conditions under 77 K conditions
2absorption research.Under 77K, the adsorptive capacity of hydrogen on Zn (pybdc) sample presents quick increase in low pressure area, then linear increase the along with the increase of pressure, and in the time of 800 mmHg pressure, adsorptive capacity reaches 17 cm
3/ g.And under 273K condition, CO
2adsorptive capacity on Zn (pybdc) sample presents linear increasing in whole pressure range.Its adsorption isotherm line chart is shown in Fig. 4.
Claims (4)
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-for the 5-(1-pyrrolidyl)-1 of de-proton, 3-phthalic acid.
2. according to micropore metal-organic framework material claimed in claim 1, it is characterized in that: the crystallization of this material is in trigonal system, and spacer is
r-3m; In single crystal structure, Metal Zn
2+in tetrahedron center, be 4 coordinations, each metallic zinc center, under the bridge chain effect of carboxylate radical, is assembled into one-dimensional inorganic chain structure, pybdc along c-axis direction
2-be 4 coordinations.
3. according to micropore metal-organic framework material claimed in claim 2, it is characterized in that described material three-dimensional skeleton structure, exist one-dimensional tunnel structure along c-axis direction, the methylene group of five yuan of pyrrole rings stretches in the middle of duct, duct window size is 4, and specific surface is 866.33
2/ unit cell, porosity is 18.6 %.
4. the preparation method of micropore metal-organic framework material described in claim 1 or 2 or 3, it is characterized in that comprising the steps: to express according to Zn (pybdc) mol ratio requiring, by 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 temperature 1 ~ 5 hour, suspension liquid is transferred to in teflon-lined stainless steel cauldron, 100 ~ 150 ℃ of crystallization 8 ~ 100 hours, obtain brown transparent needle-like crystal, after filtration, washing, dry micropore metal-the organic framework material that obtains.
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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 |
| 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 |
| CN102851020B (en) * | 2012-09-19 | 2014-12-03 | 复旦大学 | Magnetic-chromatic synchronously-responsive self-assembled microporous material and preparation method thereof |
| CN102886249B (en) * | 2012-10-15 | 2014-10-29 | 复旦大学 | Self-assembled microporous material capable of selectively absorbing and separating methanol molecules 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 |
| CN105080495B (en) * | 2015-09-16 | 2017-08-25 | 北京工业大学 | A kind of Zr metal-organic framework materials, preparation method and applications |
| 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 |
| 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 |
| CN107629076B (en) * | 2017-09-13 | 2019-06-18 | 华南理工大学 | A kind of ordered big hole metal organic frame monocrystalline and preparation method thereof |
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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 |
| CN101379068A (en) * | 2006-02-10 | 2009-03-04 | 巴斯夫欧洲公司 | Process for preparing porous organic framework materials |
| CN101531672A (en) * | 2008-03-12 | 2009-09-16 | 安徽大学 | Metal-organic framework material with nano pores and preparation method and application thereof |
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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 |
| CN101379068A (en) * | 2006-02-10 | 2009-03-04 | 巴斯夫欧洲公司 | Process for preparing porous organic framework materials |
| CN101531672A (en) * | 2008-03-12 | 2009-09-16 | 安徽大学 | Metal-organic framework material with nano pores and preparation method and application thereof |
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