CN106866988A - A kind of layer column type metal-organic framework material as well as preparation method and application thereof - Google Patents
A kind of layer column type metal-organic framework material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of layer column type metal-organic framework material as well as preparation method and application thereof.Its composition be represented by the chemical formula for：C51H22N8O14Zn2.The material has good chemical stability and heat endurance, and have studied it to common energy gas CH4, greenhouse gases CO2And N2Absorption property.The preparation method that the present invention is provided is simple and easy to apply, to CO2/N2And CO2/CH4The good separating effect of gas, is a kind of more satisfactory gas separation material.
Description
Technical field
The present invention relates to metal-organic framework material synthesis technical field, and in particular to one kind based on 3,7- dihydroxy naphthlenes-
2,6- dicarboxylate metals organic framework materials are used as the application in terms of gas-selectively separation.
Background technology
Metal organic frame (MOFs) is a class to be assembled by coordinate bond with organic ligand by metal ion or cluster and is formed
The periodicity frame material of high-sequential, with good designability and Scalability, unique light, electricity, magnetic and absorption etc.
Physicochemical properties, thus get more and more people's extensive concerning.Referring to：Nandasiri,M.I.；Jambovane,S.R.；
McGrail,B.P.；Schaef,H.T.；Nune,S.K.Coord.Chem.Rev.2016,311,38-52；Nandi,S.；
Luna,P.D.；Thomas,D.D.；Rother,J.；Liu,M.；Buchanan,W.；Hawari,A.I.；Woo,T.K.；
Vaidhyanathan,R.Sci.Adv.2015,1,1-9.Due to the change of global climate, greenhouse gases CO2A large amount of discharges
As urgent problem, used as a kind of new porous material, MOFs has high porosity, uniform aperture, Gao Bibiao
The characteristic such as area, aperture are adjustable is to CO2Be selectively adsorbing and separating with good effect.With traditional activated carbon, molecular sieve
Compared Deng porous material, MOFs materials can be entered by the reasonable design and the selection of metal center/metal cluster to organic ligand
Row controlled syntheses, so as to regulate and control the separating effect to gas with various.It is main at present to pass through open metallic site, introduce polarity
Functional group and suitable pore size is controlled to strengthen interaction of the framework to some specific gas.Referring to：Millward,
A.R.；Yaghi,O.M.J.Am.Chem.Soc.2005,127,17998-17999.Vaidhyanathan,R.；Iremonger,
S.S.；Shimizu,G.K.；Boyd,P.G.；Alavi,S.；Woo,T.K.Science.2010,330,650-653.Du,L.；
Lu,Z.；Zheng,K.；Wang,J.；Zheng,X.；Pan,Y.；You,X.；Bai,J.J.Am.Chem.Soc.2013,135,
562-565；Chen,Q.；Chang,Z.；Song,W.C.；Song,H.；Song,H.B.；Hu,T.L.；Bu,
X.H.Angew.Chem.Int.Ed.2013,52,11550.
The content of the invention
It is an object of the invention to layer column type metal-organic framework material to the performance study in terms of the adsorbing separation of gas,
A kind of metal-organic framework material is provided, while there is provided a kind of preparation method of the metal-organic framework material.The compound
Three-dimensional structure with rhombus and BODY WITH SQUARE APERTURE, its structure has of a relatively high chemical stability and heat endurance, to CO2/N2
And CO2/CH4The separating effect of gas is a kind of more satisfactory gas separation material preferably, is had very in material science
Good application prospect.
Technical scheme：
A kind of layer column type metal-organic framework material, chemical formula is C51H22N8O14Zn2, with 3,7- dihydroxy naphthlene -2,6- bis-
Carboxylic acid is main part, and 4,4'- bipyridyls are assistant ligand, and using solvent-thermal method, solvent is methyl alcohol and DMF
Mixed solution, the three-dimensional layer pole structure of synthesis.In this compound, zinc ion is pentacoordinate configuration, same three 3,7- dihydroxy naphthlenes-
Nitrogen-atoms coordination in carboxyl oxygen atom and two difference 4,4'- bipyridine ligands in 2,6- dicarboxylates.The chemical combination
Constitute the secondary construction unit of two cores, further shape in thing with two zinc ions respectively from three carboxyls on different main parts
Into plane, then three-dimensional layer pole structure is connected and composed as pillar by 4,4'- bipyridyls.The three-dimensional structure is on a, b, c-axis direction
There are one-dimensional channels, and dimethylamine ion and hydrone are filled with duct, dimethylamine ion is in the compound
Play a part of balancing charge.After solvent molecule in removal duct, PLATON program calculated results show that porosity is
26.7%.Its topological structure is pcu type topological structures.The metal-organic framework material crystal belongs to rhombic system, Pcca spaces
Group, cell parameter is respectively： α=β=γ
=90 °；The decomposition temperature of co-ordinating backbone is 280 DEG C.
The preparation method of the metal-organic framework material, comprises the following steps：
1) by organic ligand 3,7- dihydroxy naphthlene -2,6- dicarboxylic acids and 4,4'- bipyridyl, and zinc nitrate hexahydrate is placed in
In 10ml vials equipped with methyl alcohol and DMF mixed solvent, methyl alcohol and N, N- diformazan in the mixed solvent
The volume ratio of base formamide is 3：1, it is well mixed；
2) it is placed in 100 DEG C of baking oven after above-mentioned vial is sealed, carries out incubating solvent thermal response, is reacted 72 hours
Afterwards, you can obtain faint yellow strip crystal；
3) above-mentioned faint yellow strip crystal is washed with N,N-dimethylformamide and methyl alcohol, dry after can be prepared by this
Metal-organic framework material.
Further, 3,7- dihydroxy naphthlene -2,6- dicarboxylic acids, 4,4'- bipyridyls and zinc nitrate hexahydrate mole
Than being 1:1:1.
Further, the volume ratio of methyl alcohol and DMF is 3 in the mixed solvent：1,3,7- dihydroxy
Naphthalene -2,6- dicarboxylic acids is 0.05 mM with the amount ratio of mixed solvent：4.0 milliliters.
Metal-organic framework material of the present invention is separated for gas, and method is that the crystalline material is carried out into solvent by methyl alcohol
Exchange, after 150 DEG C of high vacuum degassings, selectivity to gas with various CH4、CO2And N2Carry out adsorbing separation.In 298K, 1bar
When to CO2Adsorbance be 51.41cm3g-1, and CO2/N2(15:And CO 85)2/CH4(50:50) adsorptive selectivity is respectively
59.33 and 9.19, and the selectivity with the enhancing change of pressure it is little, can be as a kind of efficient gas separation material.
It is an advantage of the invention that：The metal-organic framework material preparation method is simple, and raw material is easy to get, and compound has higher
Chemical stability, heat endurance and good gas separating property.The compound in gas separation process, show compared with
CO high2Adsorbance, CO2/N2And CO2/CH4The separating effect of gas preferably and the excellent feature such as can reuse,
Gas is separated and energy storage aspect has a good application prospect.
Brief description of the drawings
Fig. 1 is compound b direction planes (a) and three-dimensional layer pole structure figure (b).
Fig. 2 is the powder diagram (a) and thermal multigraph (b) of the compound.
Fig. 3 is N under compound 77K2Adsorption curve (a) and graph of pore diameter distribution (b).
Fig. 4 is all kinds of adsorption curves of the compound：(a) CO in 298K2And CH4Adsorption curve and CO2/CH4's
Selectivity curve；(b) CO in 298K2And N2Adsorption curve and CO2/N2Selectivity curve；(c) CO in 273K2With
CH4Adsorption curve and CO2/CH4Selectivity curve；(d) CO in 273K2And N2Adsorption curve and CO2/N2Choosing
Select linearity curve；
Fig. 5 is the compound to CO2(a) and CH4The absorption heating curve of (b).
Specific embodiment
Embodiment：
The preparation method of layer column type metal-organic framework material of the present invention, comprises the following steps：
1) by 3,7- dihydroxy naphthlene -2,6- dicarboxylic acids (12.4mg), 4,4'- bipyridyls (7.8mg), zinc nitrate hexahydrate
(14.9mg) is added in the vial of 10ml, adds 4mL methyl alcohol/DMF (v:V=3:1) mixing is molten
Liquid.
2) it is placed in 100 DEG C of baking oven after above-mentioned vial is sealed, carries out incubating solvent thermal response, is reacted 72 hours
Afterwards, strip light yellow crystal is obtained, yield is about 80%.
3) above-mentioned light yellow crystal is washed with N,N-dimethylformamide and methyl alcohol, dry after can be prepared by the metal and have
Machine frame frame material.
Gained metal-organic framework material chemical formula is C51H22N8O14Zn2, with 3,7- dihydroxy naphthlene -2, based on 6- dicarboxylic acids
Part, 4,4'- bipyridyls are assistant ligand, and solvent is methyl alcohol and DMF mixed solution.Match somebody with somebody from different masters
Three carboxyls on body constitute the secondary construction unit of two cores with two zinc ions respectively, further extend and form plane, then by
4,4'- bipyridyls connect and compose three-dimensional layer pole structure as pillar.As in accompanying drawing 1, structure includes rhombus and BODY WITH SQUARE APERTURE, hole
Gap rate is 26.7%；Illustrate that prepared sample purity is very high in accompanying drawing 2, the decomposition temperature of co-ordinating backbone is 280 DEG C.
To the sign of obtained metal-organic framework material：
Crystal structure determination
The monocrystalline of suitable size is chosen under the microscope, with the Mo-K through graphite monochromator monochromatization on single crystal diffractometer
Alpha ray, temperature is 113K, withMode collects diffraction data.All diffraction datas carry out absorption school using SADABS programs
Just.Cell parameter is determined with least square method.Data convert and structure elucidation are completed using SAINT and SHELXTL programs respectively.
First determine whole non-hydrogen atom coordinates with difference function method and least square method, and the hydrogen of main body framework is obtained with theoretical hydrogenation method
Atom site, then carries out refine with least square method to crystal structure.Crystallography point diffraction Data Collection and structure refinement
Partial parameters see the table below 1.
Table 1：The crystal parameter table of the metal organic frame
R1=Σ | | Fo|-|Fc||/Σ|Fo|；wR2=[Σ [w (Fo 2-Fc 2)2]/Σw(Fo 2)2]1/2.
3) gas absorption Separate Efficiency Study
Before gas absorption test is carried out, sample is carried out into exchange of solvent 3 days with absolute methanol first, first is changed daily
Alcohol 3 times, then in 150 DEG C, high vacuum (10-5Torr degassing is activated for 4 hours under).
Secondly, the sample for 278.8mg being chosen after activation carries out N under 77K2Absorption test.In accompanying drawing 3, the absorption is bent
Line has I type adsorption curve features, and pore size is aboutShow that the compound has microcellular structure, with its crystal structure
It is consistent.Meanwhile, test result shows that BET the and Langmuir specific surface areas of the compound are respectively 264.0 and 346.6m2g-1。
The compound is then tested in 273K and 298K to CO2、CH4And N2Absorption property.Can be with accompanying drawing 4
Find out that the compound is to CO in 298K, 1bar2Adsorbance reaches 51.41cm3g-1, and corresponding CH4And N2Adsorbance only have
19.39 and 5.11cm3g-1.Obtained to double-component system CO based on Ideal adsorption solution theory (IAST) and adsorpting data fitting2/
CH4(50:And CO 50)2/N2(15:85) selectivity is respectively 9.19 and 59.33.In addition, for study subject framework and CO2
Between interaction, we are calculated using Clausisus-Clapeyron equations and have fitted the compound to CO2And CH4
Absorption heating curve.Show in accompanying drawing 5, the compound is to CO2And CH4Initial adsorption heat be respectively 30.91 and 21.21kJ
mol-1, it was demonstrated that CO2There is stronger interaction between framework.Gas absorption experiment is automatically compared by ASAP 2020M
Surface meter is tested, and acquired results in the accompanying drawings, use Origin Software on Drawing.
It should be noted that the above-mentioned description to embodiment is understood that for ease of those skilled in the art
It is of the invention with application, therefore, the invention is not restricted to embodiment here, those skilled in the art's announcement of the invention is right
The conspicuously improved and modification made in the present invention all should be within protection scope of the present invention.
Claims (8)
1. a kind of layer column type metal-organic framework material, it is characterised in that：Chemical formula is C51H22N8O14Zn2, with 3,7- dihydroxy naphthlene -2,
6- dicarboxylic acids is main part, and 4,4'- bipyridyls are assistant ligand, and solvent is methyl alcohol and DMF mixed solution, is come
Three carboxyls from different main parts constitute the secondary construction unit of two cores with two zinc ions respectively, further extend and form flat
Face, then connect and compose three-dimensional layer pole structure as pillar by 4,4'- bipyridyls；The metal-organic framework material crystal belongs to orthorhombic
System, Pcca space groups, cell parameter is respectively：α
=β=γ=90 °；The decomposition temperature of co-ordinating backbone is 280 DEG C.
2. according to claim 1 layer of column type metal-organic framework material, it is characterised in that：The frame material has rhombus
And BODY WITH SQUARE APERTURE, porosity is 26.7%；The decomposition temperature of co-ordinating backbone is 280 DEG C.
3. a kind of preparation method of metal-organic framework material as claimed in claim 1, it is characterised in that comprise the following steps：
1) by organic ligand 3,7- dihydroxy naphthlene -2,6- dicarboxylic acids and 4,4'- bipyridyl, and zinc nitrate hexahydrate is placed in and is equipped with
In the 10ml vials of methyl alcohol and DMF mixed solvent, methyl alcohol and N, N- dimethyl methyl in the mixed solvent
The volume ratio of acid amides is 3：1, it is well mixed；
2) it is placed in 100 DEG C of baking oven after above-mentioned vial is sealed, carries out incubating solvent thermal response, after reacting 72 hours, i.e.,
Can obtain faint yellow strip crystal；
3) above-mentioned faint yellow strip crystal is washed with N,N-dimethylformamide and methyl alcohol, dry after can be prepared by the metal
Organic framework materials.
4. the preparation method of metal-organic framework material according to claim 3, it is characterised in that：The 3,7- dihydroxy
The mol ratio of naphthalene -2,6- dicarboxylic acids, 4,4'- bipyridyls and zinc nitrate hexahydrate is 1:1:1.
5. the preparation method of metal-organic framework material according to claim 3, it is characterised in that：First in the mixed solvent
The volume ratio of alcohol and N,N-dimethylformamide is 3：1,3,7- dihydroxy naphthlene -2,6- dicarboxylic acids is with the amount ratio of mixed solvent
0.05 mM：4.0 milliliters.
6. a kind of purposes of metal-organic framework material as claimed in claim 1, it is characterised in that：For gas with various absorption
Separate.
7. the purposes of metal-organic framework material according to claim 6, it is characterised in that：Application process is by the crystal
Material carries out exchange of solvent by methyl alcohol, and after 150 DEG C of high vacuum degassings, selective carries out adsorbing separation to gas with various.
8. the purposes of the metal-organic framework material according to claim 6 or 7, it is characterised in that：For to gas with various
CH4、CO2And N2Absorption.
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Cited By (7)
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|---|---|---|---|---|
| CN107602592A (en) * | 2017-10-25 | 2018-01-19 | 青岛大学 | One kind separation CO2Metal-organic framework material and preparation method thereof |
| CN108299475A (en) * | 2018-02-06 | 2018-07-20 | 云南农业大学 | 3-dimensional metal based on 5- chlorothiophene -2- carboxylic acids and 4,4 '-bipyridyls-organic backbone crystalline material and preparation method |
| CN109336809A (en) * | 2018-11-15 | 2019-02-15 | 安徽师范大学 | The stable metal-organic framework material and its preparation method and application of performance |
| CN109351334A (en) * | 2018-09-12 | 2019-02-19 | 内蒙古大学 | A kind of methylene blue adsorption number material and its preparation method and application that water is stable |
| CN109517184A (en) * | 2017-09-19 | 2019-03-26 | 南开大学 | A kind of metal-organic framework material, preparation method and application |
| CN110270314A (en) * | 2019-06-28 | 2019-09-24 | 盐城工学院 | One kind efficiently separating CO in flue gas2Naphthalimide Zn-MOF preparation method |
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| WO2015127033A1 (en) * | 2014-02-19 | 2015-08-27 | The Regents Of The University Of California | Acid, solvent, and thermal resistant metal-organic frameworks |
| CN104628790A (en) * | 2015-01-26 | 2015-05-20 | 郑州轻工业学院 | Microporous cobalt metal-organic framework material with selective adsorption function and preparation method thereof |
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| CN109517184A (en) * | 2017-09-19 | 2019-03-26 | 南开大学 | A kind of metal-organic framework material, preparation method and application |
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| CN107602592A (en) * | 2017-10-25 | 2018-01-19 | 青岛大学 | One kind separation CO2Metal-organic framework material and preparation method thereof |
| CN108299475A (en) * | 2018-02-06 | 2018-07-20 | 云南农业大学 | 3-dimensional metal based on 5- chlorothiophene -2- carboxylic acids and 4,4 '-bipyridyls-organic backbone crystalline material and preparation method |
| CN109351334A (en) * | 2018-09-12 | 2019-02-19 | 内蒙古大学 | A kind of methylene blue adsorption number material and its preparation method and application that water is stable |
| CN109336809A (en) * | 2018-11-15 | 2019-02-15 | 安徽师范大学 | The stable metal-organic framework material and its preparation method and application of performance |
| CN110270314A (en) * | 2019-06-28 | 2019-09-24 | 盐城工学院 | One kind efficiently separating CO in flue gas2Naphthalimide Zn-MOF preparation method |
| CN110270314B (en) * | 2019-06-28 | 2022-07-19 | 盐城工学院 | Effectively separate CO in flue gas2Preparation method of naphthalimide Zn-MOF |
| WO2021233065A1 (en) * | 2020-05-18 | 2021-11-25 | 上海科技大学 | Metal-organic framework material |
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