CN103951684A - Mixed ligand zeolitic imidazole framework, preparation method and application to carbon dioxide selective adsorption - Google Patents
Mixed ligand zeolitic imidazole framework, preparation method and application to carbon dioxide selective adsorption Download PDFInfo
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Abstract
The invention relates to a mixed ligand zeolitic imidazole framework, a preparation method and application to carbon dioxide selective adsorption, and belongs to the technical field of preparation of zeolitic imidazole frameworks. The structural formula of the mixed ligand zeolitic imidazole framework is Zn4(2-mbIm)3(bIm)5.4H2O, wherein 2-mbIm is 2-methylbenzimidazole ion, bIm is benzimidazole ion, H2O represents guest water molecule. The crystal structure is an orthorhombic system and belongs to Pnma, that is, space group No. 62. Benzimidazole and 2-methylbenzimidazole which are low in cost and easily available in raw materials are employed, and a hydro-thermal reaction synthetic method is utilized, so that the novel zeolitic imidazole framework is synthesized. The material has excellent thermal stability and chemical stability, has good carbon dioxide selective adsorption capability, has potential application prospect on carbon dioxide selective adsorption and separation, and has relatively good carbon dioxide selective adsorption performance.
Description
Technical field
The invention belongs to the preparing technical field of zeolitic imidazolate framework material, be specifically related to be a kind ofly applied to carbon dioxide selectivity absorption, store the preparation method with the separated body zeolitic imidazolate framework material that is mixed.
Background technology
Metal-organic framework structured material (Metal-Organic Frameworks) is a metal ion species and organic ligand self assembling process porous organo-metallic skeleton crystalline structure material that form, that have periodic network structure.And zeolite imidazoles framework material (ZIFs) is the metal-organic framework materials growing up in recent years, metal-organic framework materials than other kinds, they are characterised in that the thermostability of their excellences and chemical stability, larger porosity and the selective adsorption to carbonic acid gas, thereby as its absorption property of carbon dioxide absorber, be much better than inorganic zeolite molecular sieve, thereby become a kind of material of potential carbonic acid gas fractionation by adsorption.
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, the skeleton of formation zeolitic imidazolate framework material.The suitable selection of metal or glyoxaline compound makes it likely for required Application Areas, optimize a kind of material of skeleton duct or hole wall.For example, 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.Containing in addition the zeolitic imidazolate framework material that the zeolitic imidazolate framework material that mixes glyoxaline ligand is considered to form than single part has better carbon dioxide selectivity absorption.
In more than the 100 kind of ZIFs material of having reported, only have 16 kinds of ZIFs materials to form by mixing glyoxaline ligand.And Yaghi group has been reported (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 is to ZIF-78, and along with participating in, the molecular volume of glyoxaline ligand of coordination is increasing, the aperture of the ZIFs obtaining from
(ZIF-70) be reduced to
, and its selective adsorption to carbonic acid gas is more and more stronger (ZIF-78).
Therefore, it is part that the present invention selects benzoglyoxaline cheaply and the 2-tolimidazole that two kinds of raw material sources are easy to get, take zinc nitrate as source metal, utilize hydro-thermal reaction synthetic method, remove 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, carbon dioxide selectivity absorption and separation are had to the performance that potential application prospect has better carbon dioxide selectivity absorption.
Summary of the invention
The present invention selects two kinds of benzoglyoxaline and 2-tolimidazoles that molecular volume is larger, utilize hydro-thermal reaction synthetic method, remove 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, carbon dioxide selectivity absorption and separation are had to the performance that potential application prospect has better carbon dioxide selectivity absorption.
One of 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, bIm (bIm=benzimidazol) is benzoglyoxaline ion, H
2o represents object water molecules; Crystalline structure is rhombic system, belongs to Pnma (No. 62) spacer, and unit cell parameters is
unit cell volume is
z=4, D
c=1.402Mg/m
3, this skeleton is 3 D stereo skeleton, has GIS topology molecular sieve structure, contains 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.The nitrogen-atoms that Zn1 atom and two come from bIm part is that N2A and N7A and two nitrogen-atoms that come from 2-mbIm part are N1A and N5 coordination; The nitrogen-atoms that Zn2 and three come from bIm part is that N3, N6 and N8 and a nitrogen-atoms that comes from 2-mbIm part are N4 coordination, and two kinds of Zn atoms represent to be [4 with Shi Laifuli symbol
6.8
4].
Said structure can also be described with the secondary structure unit of tetra-atomic ring or octatomic ring, and this secondary structure unit is coupled together and is parallel to (100) face and forms three-dimensional structure by [100] direction, 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 being just synthesized.
Two of object of the present invention is to provide a kind of method of preparing above-mentioned mixed ligand zeolitic imidazolate framework material, it is part that the method be take benzoglyoxaline and 2-tolimidazole, take zinc as metal center, by solvent thermal reaction, obtain novel mixed ligand zeolitic imidazolate framework material, and utilize the formed body of this material to measure its character of sign and carbon dioxide selectivity adsorption property.
A kind of method of preparing mixed ligand zeolitic imidazolate framework material of the present invention, its step is as follows:
(1) will after the DMF solution mixing of zinc nitrate hexahydrate, benzoglyoxaline and 2-tolimidazole, stir, 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, under 140～180 ℃ of conditions, reacted 48～144 hours;
(3) reactor is naturally cooled to room temperature, obtain transparent partially yellow crystal, DMF obtains thick product after washing, filter, being dried;
(4) by anhydrous methanol exchange 3～5 times for above-mentioned thick product, each 2～4 hours; The centrifugal solid that obtains after exchange;
(5) by solid activation treatment 3～24 hours under 120～200 ℃, vacuum condition, thereby obtain the formed body of activation, i.e. mixed ligand zeolitic imidazolate framework material.
Three of object of the present invention be to provide above-mentioned novel mixed ligand zeolitic imidazolate framework material for adsorbent for its storage, controlled release, separation, chemical reaction or as the purposes of 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
The coordination environment figure of Zn atom in the zeolitic imidazolate framework material of Fig. 1: embodiment 1;
The crystalline structure figure of Fig. 2: embodiment 1; Wherein (a) is that [001] direction is with ZnN
4tetrahedron is the 3D crystalline structure figure of manifestation; (b) be the GIS topological framework of embodiment 1 and the cage cavity in structure, wherein skeletal atom is Zn, and spheroid represents cage cavity.
Fig. 3: curve (a) is the powder X-ray RD diffraction curve of simulation, and curve (b) is the powder X-ray RD diffraction curve of embodiment 1;
The thermogravimetric analysis spectrogram of Fig. 4: embodiment 1;
The original position intensification powder X-ray RD diffraction spectrogram of Fig. 5: embodiment 1;
The powder X-ray RD diffraction spectrogram of the chemical stability test after product of Fig. 6: embodiment 1;
Fig. 7: gray line is the powder X-ray RD diffraction curve of the formed body after activating, and black line is the powder X-ray RD diffraction curve of simulation;
Fig. 8: the thermogravimetric analysis spectrogram of formed body;
Fig. 9: the carbonic acid gas adsorption curve of formed body under 195K condition;
Figure 10: the gas adsorption curve of formed body under 273K condition;
Figure 11: the carbonic acid gas 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 of getting 14.874g is dissolved in the DMF of 500mL completely, the DMF solution of the zinc nitrate that prepares 0.1M of stirring;
Make the DMF solution of 0.1M benzoglyoxaline
The benzoglyoxaline of getting 5.9g is dissolved in the DMF of 500mL completely, the DMF solution of the benzoglyoxaline that prepares 0.1M of stirring;
Make the DMF solution of the 2-tolimidazole of 0.1M
The 2-tolimidazole of getting 6.6g is dissolved in the DMF of 500mL completely, the DMF solution of the benzoglyoxaline that prepares 0.1M of stirring;
The 2-tolimidazole of getting respectively the 0.1M of the DMF solution of the 0.1M zinc nitrate of 4mL, the 0.1M benzoglyoxaline of 5mL and 3mL joins in the beaker of 25mL and stirs, and obtains mixing solutions.Gained mixing solutions is joined in the reactor of 20mL, then put in 180 ℃ of baking ovens and react 72 hours.After the time, take out reactor, naturally cool to room temperature, obtain light yellow transparent crystals, and rinse several times with DMF, filtration drying, obtains thick product afterwards.A large single crystal of getting wherein carries out the analysis of Single Crystal X-ray diffraction structure, and its structural unit, as Fig. 1, can be found out and in structure, have the coordination of two kinds of environment Zn ion.And obtain the structure as Fig. 2, from structure iron, can find out that it has one-dimensional channels and cage shape cavity.Its simulation powder X-ray RD diffracting spectrum and thick product XRD be as Fig. 3, and the framework material X-ray diffraction pattern (XRD) of embodiment 1 has near first reflection peak 2 θ=6.2 °, and contrast visible simulation spectrogram and product spectrogram coincide from figure.
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.From scheming visible thick product weightlessness between 150-300 ℃, be 5.7%, this weightlessness is just in time that object water molecules departs from the weightlessness that duct evaporation causes, and thick product is a platform between 300-500 ℃, illustrate between this temperature and there is no weightlessness, product may not cave at this temperature range skeleton.Until just start weightlessness after 500 ℃, this explanation skeleton has started to cave in to have decomposed.The original position intensification powder X-ray RD diffracting spectrum of thick product is as Fig. 5, therefrom further confirmed product until 500 degrees Celsius still keep skeleton stable, to 550 ℃ of skeletons, just cave in completely.
The thick product of respectively getting 200mg is put into the tetrafluoroethylene reactor of 3 25mL, in reactor, add 15mL water respectively, the aqueous sodium hydroxide solution of the 8mol/L concentration of 15mL benzene and 15mL, afterwards these 3 reactors are sealed in the baking oven of putting into 100 ℃ and heated 7 days, after finishing, naturally cool to room temperature, after filtering drying, carrying out respectively powder X-ray RD diffraction characterizes, result is as Fig. 6, visible its characteristic peak of spectrogram contrast by the product X RD spectrogram after processing under each condition and thick product and the XRD spectra of simulation and the XRD spectra of thick product fit like a glove, this explanation crude product so all can keep the stability of its structure under exacting terms.
Embodiment 3: the formed body that obtains activation
The thick product that embodiment 1 is obtained takes out 200mg, puts into 25mL beaker, adds 15mL anhydrous methanol, soaks, and exchange, outwelled upper solution after 2 hours.Repetitive operation 3 times.Afterwards the thick product after exchange is vacuumized and is heated to 140 ℃ and carries out activation treatment 5 hours, the powder X-ray RD diffraction spectrogram of the formed body after its activation is as Fig. 7, from spectrogram, can find out, the characteristic peak of the XRD spectra of the formed body XRD spectra after activation and thick product fits like a glove, and the formed body skeleton structure after known activation remains unchanged.Thermogravimetric spectrogram is as Fig. 8, and it is a platform from 50 ℃ to 500 ℃, there is no weightlessness, therefrom can find out that the formed body structure after activation is constant, and duct object water molecules is processed clean, 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 carbonic acid gas adsorption curve of 195K and measure, as Fig. 9, utilize BET algorithm can show that its BET specific surface is 210m
2/ g.Carry out respectively afterwards the absorption test of carbonic acid gas, methane, oxygen and nitrogen at 273K temperature, and the absorption of the carbonic acid gas at 293K temperature test, 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 calculate the carbonic acid gas adsorption enthalpy of formed body, as Figure 11, its adsorption enthalpy is 25.3kJ/mol.。
To sum up, the present invention utilizes solvent process for thermosynthesizing, select two kinds of glyoxaline ligands to synthesize a kind of novel molecular sieve imidazate framework material, this material thermostability high (being greater than 500 ℃), chemical stability is excellent (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 separated a kind of material.
Claims (3)
1. a novel 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 ions, bIm is benzoglyoxaline ion, H
2o represents object water molecules; Crystalline structure is rhombic system, Pnma62 spacer, and unit cell parameters is
unit cell volume is
z=4, D
c=1.402Mg/m
3, this skeleton is 3 D stereo skeleton, has GIS topology molecular sieve structure, contains two kinds of Zn in the list of coordination units of its crystal
2+ion, i.e. Zn1 and Zn2; The nitrogen-atoms that Zn1 atom and two come from bIm part is that N2A and N7A and two nitrogen-atoms that come from 2-mbIm part are N1A and N5 coordination; The nitrogen-atoms that Zn2 and three come from bIm part is that N3, N6 and N8 and a nitrogen-atoms that comes from 2-mbIm part are N4 coordination, and two kinds of Zn atoms represent to be [4 with Shi Laifuli symbol
6.8
4].
2. a method of preparing mixed ligand zeolitic imidazolate framework material claimed in claim 1, its step is as follows:
(1) will after the DMF solution mixing of zinc nitrate hexahydrate, benzoglyoxaline and 2-tolimidazole, stir, wherein, zinc nitrate hexahydrate and benzoglyoxaline and 2-tolimidazole and mol ratio be 1:2, the mol ratio of 2-tolimidazole and benzoglyoxaline is 3:5;
(2) above-mentioned mixing solutions is transferred in reactor, under 140～180 ℃ of conditions, reacted 48～144 hours;
(3) reactor is naturally cooled to room temperature, after gained crystal DMF is washed, filters, is dried, obtain thick product;
(4) by anhydrous methanol exchange 3～5 times for above-mentioned thick product, each 2～4 hours; The centrifugal solid that obtains after exchange;
(5) by gained solid activation treatment 3～24 hours under 120～200 ℃, vacuum condition, thereby obtain the formed body of activation, i.e. mixed ligand zeolitic imidazolate framework material.
3. the application of mixed ligand zeolitic imidazolate framework material claimed in claim 1 in carbon dioxide selectivity absorption.
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| CN108473325A (en) * | 2015-11-27 | 2018-08-31 | 加利福尼亚大学董事会 | Zeolite imidazole ester frame |
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