CN103951684B - Mixed ligand zeolitic imidazolate framework material, preparation method and the application in carbon dioxide selectivity absorption - Google Patents
Mixed ligand zeolitic imidazolate framework material, preparation method and the application in carbon dioxide selectivity absorption Download PDFInfo
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- imidazolate framework
- benzoglyoxaline
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Abstract
Mixed ligand zeolitic imidazolate framework material, preparation method and the application in carbon dioxide selectivity absorption, belong to the preparing technical field of zeolitic imidazolate framework material.Its structural formula is Zn
4(2-mbIm)
3(bIm)
54H
2o, wherein 2-mbIm is 2 tolimidazole ions, and bIm is benzoglyoxaline ion, H
2o represents object water molecules; Crystalline structure is rhombic system, belong to Pnma i.e. No. 62 spacers, the benzoglyoxaline of the low cost that the present invention selects raw material sources to be easy to get and 2-tolimidazole, utilize hydro-thermal reaction synthetic method, go to synthesize a kind of novel zeolitic imidazolate framework material, this material has excellent thermostability and chemical stability, there is good carbon dioxide selectivity adsorptive power, to carbon dioxide selectivity absorption and separation, there is the performance that potential application prospect has the absorption of better carbon dioxide selectivity.
Description
Technical field
The invention belongs to the preparing technical field of zeolitic imidazolate framework material, be specifically related to a kind of carbon dioxide selectivity that is applied to and adsorb, store the preparation method with the mixture body zeolitic imidazolate framework material be separated.
Background technology
Metal-organic framework structured material (Metal-Organic Frameworks) is the porous organo-metallic skeleton crystal structure materials that a metal ion species and organic ligand self assembling process formed, had periodic network structure.And zeolite imidazole class framework material (ZIFs) is the metal-organic framework materials grown up in recent years, compared to the metal-organic framework materials of other kinds, their feature is thermostability and chemical stability, larger porosity and the selective adsorption to carbonic acid gas of their excellences, thus be much better than inorganic zeolite molecular sieve as its absorption property of carbon dioxide absorber, thus become a kind of material of potential carbon dioxide adsorption separation.
Zeolitic imidazolate framework material generally contains and Zn
2+, Cd
2+and Co
2+a kind of glyoxaline ligand of ion coordination or multiple glyoxaline ligand, form the skeleton of zeolitic imidazolate framework material.The suitable selection of metal or glyoxaline compound makes it likely for required Application Areas to optimize a kind of material of skeleton duct or hole wall.Such as, the selection of glyoxaline compound can have impact to pore size, and in addition, the selection of metal also has a certain impact to absorption property.The zeolitic imidazolate framework material zeolitic imidazolate framework material that is considered to be formed than single part in addition containing mixing glyoxaline ligand has and adsorbs better carbon dioxide selectivity.
In more than the 100 kind of ZIFs material reported, 16 kinds of ZIFs materials are only had to be made up of mixing glyoxaline ligand.And Yaghi group reports (reference: A.Phan, C.J.Doonan, F.J.Uribe-Romo, C.B.Knobler, M.O'keeffe, O.M.Yaghi, Acc.Chem.Res.43 (2010), 58-67; W.Morris, B.Leung, H.Furukawa, O.K.Yaghi, N.He, H.Hayashi, Y.Houndonougbo, M.Asta, B.B.Laird, O.M.Yaghi, J.Am.Chem.Soc.132 (2010) 11006-11008) ZIFs of a series of mixing glyoxaline ligand, wherein ZIF-70 to ZIF-78, along with the molecular volume of glyoxaline ligand participating in coordination is increasing, the aperture of the ZIFs obtained from
(ZIF-70) be reduced to
, and it is more and more stronger to the selective adsorption of carbonic acid gas (ZIF-78).
Therefore, the low cost that the present invention selects two kinds of raw material sources to be easy to get benzoglyoxaline and 2-tolimidazole be part, take zinc nitrate as source metal, utilize hydro-thermal reaction synthetic method, go to synthesize a kind of novel zeolitic imidazolate framework material, this material has excellent thermostability and chemical stability, has good carbon dioxide selectivity adsorptive power, has to carbon dioxide selectivity absorption and separation the performance that potential application prospect has the absorption of better carbon dioxide selectivity.
Summary of the invention
The benzoglyoxaline that the present invention selects two kinds of molecular volumes larger and 2-tolimidazole, utilize hydro-thermal reaction synthetic method, go to synthesize a kind of novel zeolitic imidazolate framework material, this material has excellent thermostability and chemical stability, there is good carbon dioxide selectivity adsorptive power, to carbon dioxide selectivity absorption and separation, there is the performance that potential application prospect has the absorption of better carbon dioxide selectivity.
An object of the present invention is to provide a kind of novel mixed ligand zeolitic imidazolate framework material, and its structural formula is Zn
4(2-mbIm)
3(bIm)
54H
2o, wherein 2-mbIm (2-mbIm=2-methylbenzimidazole) is 2 tolimidazole ions, and bIm (bIm=benzimidazol) is benzoglyoxaline ion, H
2o represents object water molecules; Crystalline structure is rhombic system, and belong to Pnma (namely No. 62) spacer, unit cell parameters is
unit cell volume is
z=4, D
c=1.402Mg/m
3, this skeleton is three-dimensional skeleton, has GIS topology molecular sieve structure, containing two kinds of Zn in the list of coordination units of its crystal
2+ion, as shown in Figure 1, i.e. Zn1 and Zn2.Zn1 atom and two come from nitrogen-atoms and N1A and the N5 coordination that the nitrogen-atoms of bIm part and N2A and N7A and two come from 2-mbIm part; Zn2 and three comes from nitrogen-atoms and the N4 coordination that the nitrogen-atoms of bIm part and N3, N6 and N8 and come from 2-mbIm part, and two kinds of Zn atoms represent with Shi Laifuli symbol and are [4
6.8
4].
Said structure can also describe with the secondary structure unit of tetra-atomic ring or octatomic ring, this secondary structure unit is coupled together by [100] direction and is parallel to (100) face and forms three-dimensional structure, and this structure is exactly GIS topology molecular sieve structure completely.Therefore, because have GIS topological framework, this structure contains
the cage of radius, has one in [100] direction
one-dimensional channels.And water molecules just exists in the basket structure skeleton of the material be just synthesized.
Two of object of the present invention is to provide a kind of method preparing above-mentioned mixed ligand zeolitic imidazolate framework material, the method with benzoglyoxaline and 2-tolimidazole for part, take zinc as metal center, obtain novel mixed ligand zeolitic imidazolate framework material by solvent thermal reaction, and utilize the formed body of this material to measure its character of sign and carbon dioxide selectivity adsorption property.
A kind of method preparing mixed ligand zeolitic imidazolate framework material of the present invention, its step is as follows:
(1) stir after the DMF solution of zinc nitrate hexahydrate, benzoglyoxaline and 2-tolimidazole being mixed, wherein, zinc nitrate and glyoxaline ligand (benzoglyoxaline and 2-tolimidazole) and mol ratio be 1:2, in glyoxaline ligand, the mol ratio of 2-tolimidazole and benzoglyoxaline is 3:5;
(2) above-mentioned mixing solutions is transferred in reactor, react 48 ~ 144 hours under 140 ~ 180 DEG C of conditions;
(3) reactor is naturally cooled to room temperature, obtain transparent partially yellow crystal, after DMF washing, filtration, drying, obtain thick product;
(4) above-mentioned thick product anhydrous methanol is exchanged 3 ~ 5 times, each 2 ~ 4 hours; Exchange is centrifugal afterwards obtains solid;
(5) by solid 120 ~ 200 DEG C, activation treatment 3 ~ 24 hours under vacuum condition, thus obtain the formed body that activates, i.e. mixed ligand zeolitic imidazolate framework material.
Three of object of the present invention is to provide above-mentioned novel mixed ligand zeolitic imidazolate framework material for adsorbent for its storage, controlled release, separation, chemical reaction or the purposes as carrier object.Described adsorbent is carbonic acid gas, nitrogen and oxygen.Particularly, novel mixed ligand zeolitic imidazolate framework material of the present invention is applied in carbon dioxide selectivity absorption.
Accompanying drawing explanation
Fig. 1: the coordination environment figure of Zn atom in the zeolitic imidazolate framework material of embodiment 1;
Fig. 2: the crystalline structure figure of embodiment 1; Wherein (a) is that [001] direction is with ZnN
4tetrahedron is the 3D crystalline structure figure of manifestation; Cage cavity in b GIS topological framework that () is embodiment 1 and structure, wherein skeletal atom is Zn, and namely spheroid represents cage cavity.
Fig. 3: curve (a) is the powder X-ray RD diffraction curve of simulation, the powder X-ray RD diffraction curve that curve (b) is embodiment 1;
Fig. 4: the thermogravimetric analysis spectrogram of embodiment 1;
Fig. 5: the original position intensification powder X-ray RD diffraction spectrogram of embodiment 1;
Fig. 6: the powder X-ray RD diffraction spectrogram of the chemical stability test after product of embodiment 1;
Fig. 7: gray line is the powder X-ray RD diffraction curve of the formed body after activation, black line is the powder X-ray RD diffraction curve of simulation;
Fig. 8: the thermogravimetric analysis spectrogram of formed body;
Fig. 9: the carbon dioxide adsorption curve of formed body under 195K condition;
Figure 10: the gas adsorption curve of formed body under 273K condition;
Figure 11: the carbon dioxide adsorption enthalpy curve of formed body.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1:
The Zn of preparation GIS topological framework
4(2-mbIm)
3(bIm)
54H
2the molecular sieve imidazate framework material of O
Make the DMF solution of 0.1M zinc nitrate
The zinc nitrate hexahydrate getting 14.874g is dissolved in the DMF of 500mL completely, the DMF solution of the zinc nitrate namely preparing 0.1M that stirs;
Make the DMF solution of 0.1M benzoglyoxaline
The benzoglyoxaline getting 5.9g is dissolved in the DMF of 500mL completely, the DMF solution of the benzoglyoxaline namely preparing 0.1M that stirs;
Make the DMF solution of the 2-tolimidazole of 0.1M
The 2-tolimidazole getting 6.6g is dissolved in the DMF of 500mL completely, the DMF solution of the benzoglyoxaline namely preparing 0.1M that stirs;
The 2-tolimidazole getting the 0.1M of the DMF solution of the 0.1M zinc nitrate of 4mL, the 0.1M benzoglyoxaline of 5mL and 3mL respectively joins in the beaker of 25mL and stirs, and obtains mixing solutions.Gained mixing solutions is joined in the reactor of 20mL, then puts in 180 DEG C of baking ovens and react 72 hours.After the time, take out reactor, naturally cool to room temperature, obtain light yellow clear crystal, and rinse several times with DMF, filtration drying afterwards, namely obtains thick product.The large single crystal got wherein carries out single crystal X-ray diffraction structural analysis, and its structural unit, as Fig. 1, can find out in structure the coordination Zn ion having two kinds of environment.And the structure obtained as Fig. 2, can find out that it has one-dimensional channels and caged cavity from structure iron.Its simulation powder XRD pattern spectrum and thick product XRD are as Fig. 3, the framework material X-ray diffraction pattern (XRD) of embodiment 1 has first reflection peak near 2 θ=6.2 °, and from figure, contrasts visible analogue spectrums and product spectrogram is identical.
Embodiment 2: the thick product that embodiment 1 obtains carries out thermal stability analysis and Chemical Stability
The thermogravimetric analysis that thick product carries out is as Fig. 4.5.7% from the visible thick product weightlessness between 150-300 DEG C of figure, this weightlessness is just in time that the weightlessness caused is evaporated in object water molecules disengaging duct, and thick product is a platform between 300-500 DEG C, illustrate do not have weightlessness between this temperature, namely product may not cave at this temperature range skeleton.Until 500 DEG C just start weightlessness, this illustrates that skeleton has started to cave in have decomposed.The original position intensification powder XRD pattern spectrum of thick product, as Fig. 5, therefrom further demonstrate that product until 500 degrees Celsius still keep skeleton stable, just caves in completely to 550 DEG C of skeletons.
The thick product respectively getting 200mg puts into the tetrafluoroethylene reactor of 3 25mL, 15mL water is added respectively in reactor, the aqueous sodium hydroxide solution of the 8mol/L concentration of 15mL benzene and 15mL, afterwards these 3 reactors are closed in the baking oven putting into 100 DEG C and heat 7 days, room temperature is naturally cooled to after terminating, carry out powder X-ray RD diffraction after filtering drying respectively to characterize, result is as Fig. 6, fitted like a glove by the XRD spectra of the product X RD spectrogram after process under each condition and spectrogram contrast its characteristic peak visible of thick product and the XRD spectra of simulation and thick product, this illustrates that crude product all can keep the stability of its structure under exacting terms like this.
Embodiment 3: the formed body obtaining activation
Thick product embodiment 1 obtained takes out 200mg, puts into 25mL beaker, adds 15mL anhydrous methanol, soaks, and exchanges, outwells upper solution after 2 hours.Repetitive operation 3 times.Afterwards the thick product after exchanging is vacuumized and be heated to 140 DEG C and carry out activation treatment 5 hours, the powder X-ray RD diffraction spectrogram of the formed body after its activation is as Fig. 7, as can be seen from spectrogram, the characteristic peak of the formed body XRD spectra after activation and the XRD spectra of thick product fits like a glove, and the formed body skeleton structure namely after known activation remains unchanged.Thermogravimetric spectrogram is as Fig. 8, and it is a platform from 50 DEG C to 500 DEG C, does not namely have weightlessness, and therefrom can find out that the formed body structure after activation is constant, duct object water molecules is totally processed, is convenient to carry out next step gas adsorption character research.
Embodiment 4: the gas adsorption character research of formed body
Get the formed body of 150mg, carry out the carbon dioxide adsorption curve determination of 195K, as Fig. 9, its BET specific surface is 210m to utilize BET algorithm to draw
2/ g.Carry out the absorption test of carbonic acid gas, methane, oxygen and the nitrogen at 273K temperature afterwards respectively, and the carbon dioxide adsorption test at 293K temperature, obtain the curve of Figure 10, through can be calculated CO
2/ CH
4, CO
2/ O
2and CO
2/ N
2selectivity be respectively 5.6:1,28:1 and 65:1, this result is all higher than the carbon dioxide selectivity of some other kind ZIFs (ZIF-68, ZIF-69, ZIF-70, ZIF-78, ZIF-79, ZIF-81, ZIF-82, ZIF-95, ZIF-100), also the carbon dioxide adsorption enthalpy of formed body is calculated, as Figure 11, its adsorption enthalpy is 25.3kJ/mol.。
To sum up, the present invention utilizes solvent process for thermosynthesizing, a kind of novel molecular sieve imidazate framework material of having selected two kinds of glyoxaline ligands to synthesize, this material thermostability high (being greater than 500 DEG C), chemical stability excellence is (even in the concentrated base sodium hydroxide solution of 8mol/L, can keep stable), to CO
2there is good absorption property, its CO
2/ CH
4, CO
2/ O
2and CO
2/ N
2deng in mixed gas to CO
2selective adsorption excellent performance, becomes potential CO
2selective adsorption and a kind of material be separated.
Claims (2)
1. a mixed ligand zeolitic imidazolate framework material, is characterized in that: its structural formula is Zn
4(2-mbIm)
3(bIm)
54H
2o, wherein 2-mbIm is 2-tolimidazole ion, and bIm is benzoglyoxaline ion, H
2o represents object water molecules; Crystalline structure is rhombic system, and Pnma No. 62 spacers, unit cell parameters is
unit cell volume is
z=4, D
c=1.402Mg/m
3, this skeleton is three-dimensional skeleton, has GIS topology molecular sieve structure, containing two kinds of Zn in the list of coordination units of its crystal
2+ion, i.e. Zn1 and Zn2; Zn1 atom and two come from nitrogen-atoms and N1A and the N5 coordination that the nitrogen-atoms of bIm part and N2A and N7A and two come from 2-mbIm part; Zn2 and three comes from nitrogen-atoms and the N4 coordination that the nitrogen-atoms of bIm part and N3, N6 and N8 and come from 2-mbIm part, and two kinds of Zn atoms represent with Shi Laifuli symbol and are [4
6.8
4]; And this mixed ligand zeolitic imidazolate framework material is prepared by following steps,
(1) stir after the DMF solution of zinc nitrate hexahydrate, benzoglyoxaline and 2-tolimidazole being mixed, wherein, zinc nitrate hexahydrate and benzoglyoxaline and 2-tolimidazole and mol ratio be the mol ratio of 1:2,2-tolimidazole and benzoglyoxaline be 3:5;
(2) above-mentioned mixing solutions is transferred in reactor, react 48 ~ 144 hours under 140 ~ 180 DEG C of conditions;
(3) reactor is naturally cooled to room temperature, obtain thick product by after gained crystal DMF washing, filtration, drying;
(4) above-mentioned thick product anhydrous methanol is exchanged 3 ~ 5 times, each 2 ~ 4 hours; Exchange is centrifugal afterwards obtains solid;
(5) by gained solid 120 ~ 200 DEG C, activation treatment 3 ~ 24 hours under vacuum condition, thus obtain the formed body that activates, i.e. mixed ligand zeolitic imidazolate framework material.
2. the application of mixed ligand zeolitic imidazolate framework material according to claim 1 in carbon dioxide selectivity absorption.
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| EP3380437A1 (en) * | 2015-11-27 | 2018-10-03 | The Regents of The University of California | Zeolitic imidazolate frameworks |
| CN105646901A (en) * | 2016-03-28 | 2016-06-08 | 吉林大学 | Green chemical preparation method for nano zeolitic imidazolate framework material |
| CN107617417A (en) * | 2016-07-13 | 2018-01-23 | 天津师范大学 | Application of trifluoromethanesulfonic acid Ag (I) complexs that (1,6 (triazoles of 1H 1,2,4)) hexane is constructed in dyestuff is adsorbed |
| CN106311152A (en) * | 2016-08-30 | 2017-01-11 | 华南理工大学 | Mesoporous zeolite imidazate framework material as well as preparation method and application thereof |
| CN106390768B (en) * | 2016-11-14 | 2019-01-11 | 中国工程物理研究院化工材料研究所 | A kind of zeolite imidazole ester skeleton/polyamide composite film and preparation method thereof |
| US11760866B2 (en) | 2017-08-16 | 2023-09-19 | Lg Chem, Ltd. | White pigment comprising ZIF-based powder, polymer resin film and method for changing color of medium using white pigment |
| CN109529933B (en) * | 2018-12-06 | 2021-10-22 | 怀化学院 | ZIF supported catalyst and preparation method and application thereof |
| CN110394159A (en) * | 2019-08-09 | 2019-11-01 | 盐城工学院 | The method and its application of one-step method preparation ion exchange ZIF-8 adsorbent |
| CN113354829B (en) * | 2021-06-18 | 2023-01-10 | 太原理工大学 | Zeolitic imidazolate framework material CHA- [ Zn (2-mIm) x (mbIm) 2-x ]Preparation and use of |
| CN115945180A (en) * | 2023-02-28 | 2023-04-11 | 天津绿菱气体有限公司 | Adsorbent for refining hexafluoro-1, 3-butadiene and preparation method and application thereof |
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