CN108114695A - The zeolitic imidazolate framework material of solid-loaded ionic-liquid and its application in cage - Google Patents
The zeolitic imidazolate framework material of solid-loaded ionic-liquid and its application in cage Download PDFInfo
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- CN108114695A CN108114695A CN201611057553.6A CN201611057553A CN108114695A CN 108114695 A CN108114695 A CN 108114695A CN 201611057553 A CN201611057553 A CN 201611057553A CN 108114695 A CN108114695 A CN 108114695A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The zeolitic imidazolate framework material of solid-loaded ionic-liquid and its application in cage, wherein the material is the composite material that ionic liquid is formed with zeolitic imidazolate framework material.The present invention changes the cage footpath of material zeolitic imidazolate framework material and gas absorption property, it is made accurately to sieve field with broader practice prospect in gas-selectively absorption and molecule by the way that ionic liquid is introduced into the empty cage of zeolitic imidazolate framework material.
Description
Technical field
The present invention relates to a kind of zeolitic imidazolate framework materials of modification (ZIFs), are changed especially with ionic liquid
New material obtained by property and preparation method thereof.
Background technology
The isolation and purification of gas is very important process in industrial production, and gas separating method has low-temperature deep at present
Partition method, liquid absorption method, membrane separation process and absorption method etc..Wherein low-temperature deep partition method commercial Application comparative maturity, still
Energy consumption is very high, with high costs；Liquid absorption method commercial Application also comparative maturity, but its absorbent regeneration generally require it is very high
Temperature, energy consumption is very high and absorbent recycling and utilization easily have chemical contamination in the process.And gas membrane Seperation Technology and absorption
Isolation technics has the advantages that low energy consumption, pollution-free and equipment is simple, and global researchers is subject to favor extensively.In order to develop
Membrane separation technique and adsorption separation technology, the material that design, screening and synthesis are sieved with high adsorptive selectivity and molecular dimension
Material is the emphasis that we study.
Metal-organic framework materials (metal-organic frameworks, hereinafter referred to as MOFs) are a kind of new
Porous material.In MOFs families, a kind of material be connected by metallic zinc or cobalt in a manner of four-coordination with glyoxaline ligand and
Into the topological structure with similar zeolite molecular sieve is referred to as zeolitic imidazolate framework material (zeolitic
Imidazolate frameworks, hereinafter referred to as ZIFs).ZIFs materials have abundant pore passage structure, larger specific surface
Product, higher thermal stability and the characteristic modified after being easy to.Some ZIFs materials are also to some micro-molecular gas (such as H2、CO2、
CH4Deng) there is good compatibility.This has just established good base for this kind of material in the application of gas absorption and separation field
Plinth.
However, finding in our study, some the ZIFs materials of prediction with separation effect are being applied to actual mix
Expected selectivity is not achieved when closing object separation.For example, by taking ZIF-8 materials as an example, the hexa-atomic a diameter of 0.34nm of hole window, square sodium
Stone (SOD) cage footpath is 1.10nm, and theoretically, hole window can retain larger-size N2(0.364nm) and CH4(0.38nm)
And make CO2(0.33nm) is passed through, that is to say, that theoretically ZIF-8 materials can be used for CO2/CH4、CO2/N2Separation, it is and real
Border is quite different, finds ZIF-8 after forming a film for CO in research2/CH4、CO2/N2Selectivity it is very poor.According to analysis, this is because miaow
Skeleton caused by the vibration of azoles ligand is flexible and causes.Therefore, it is badly in need of effective method to solve the above problems, so as to provide more
There are separation material, separation product and the separation scheme of industry application value.
The content of the invention
One of the objects of the present invention is to provide a kind of new zeolitic imidazolate framework material, the material is immobilized in cage
The zeolitic imidazolate framework material of ionic liquid is the composite material that ionic liquid is formed with zeolitic imidazolate framework material.
Composition ionic liquid in the cage of the invention described above described in the zeolitic imidazolate framework material of solid-loaded ionic-liquid
Cation be imidazole cation.Specifically it may be selected from 1,3- methylimidazoles ion, 1- ethyl-3-methylimidazoles ion, 1-
Propyl -3- methylimidazoles ion, 1- butyl -3- methylimidazoles ions (BMIM), 1- hexyl -3- methylimidazole ions.It is wherein outstanding
Its preferred 1- butyl -3- methylimidazoles ion (BMIM).
Composition ionic liquid in the cage of the invention described above described in the zeolitic imidazolate framework material of solid-loaded ionic-liquid
Anion be selected from phosphorus hexafluoride ion ([PF6]), tetrafluoride boron ion ([BF4]), bromide ion ([Br]), iodide ion ([I]),
Bis-trifluoromethylsulfoandimide salt ion ([Tf2N]) or trifluoromethanesulfonic acid ion ([OTF]).Wherein particularly preferred tetrafluoride boron from
Son ([BF4]) or bis-trifluoromethylsulfoandimide salt ion ([Tf2N])。
More preferably, the ion in the cage of the invention described above described in the zeolitic imidazolate framework material of solid-loaded ionic-liquid
Liquid is selected from [BMIM] [Tf2N] or [BMIM] [BF4]。
It is further preferred that in the cage of the invention described above described in the zeolitic imidazolate framework material of solid-loaded ionic-liquid
Zeolitic imidazolate framework material is ZIF-8.
Ionic liquid is introduced into zeolitic imidazolate framework material cage in the present invention, it is various sizes of by ionic liquid
Zwitterion occupies functional group different on the gas transport passage and zwitterion of zeolitic imidazolate framework material, realizes to boiling
The modulation of available gas retention size and the adsorptive selectivity to gas with various in stone imidazate framework material cage.
Based on this, the zeolite imidazole ester bone for being designed to provide solid-loaded ionic-liquid in the cage of another aspect of the present invention
Application of the frame material in gas separation.
The ZIFs method of modifying of the guest molecules such as solid-loaded ionic-liquid in this cage, the intrinsic structure of survivable crystal,
It is readily extended in other MOFs crystalline materials, such as pore passage structure size suitable ZIF-11, IRMOF-1, UiO-66, MOF-
74 (Mg) etc..The zwitterion of ionic liquid has very various species and the functional group that can be adjusted, used in of the invention
Ionic liquid be all glyoxaline cation type and the huge anion of molecular size differences, in addition we can also will be immobilized
The quaternary ammonium cation type with different sizes and different functional groups, season phosphine cation are extended to the ionic liquid in MOFs cages
The ionic liquid of type, pyridylium type.We expect the ionic liquid for selecting a variety of steric hindrances different to occupy different materials
The cage footpath of material obtains a series of continuously adjustable MOFs materials in cage footpaths, and the screening of gas molecule is realized by size difference；In addition
We are realized by the selection of the ionic liquid zwitterion to containing different functional groups to the MOFs materials with basket structure
Cage in microenvironment modification, improve MOFs materials gas absorption selectivity.Therefore, the present invention in ZIFs cages in it is immobilized from
The method of sub- liquid will have in the screening of gas size and adsorbing separation field in future to be more widely applied.
Description of the drawings
14 width of attached drawing of the present invention：
Attached drawing 1 synthesizes the x-ray diffraction pattern of obtained fertile material ZIF-8 for embodiment 1；
Attached drawing 2 synthesizes the scanning electron microscope diagram of obtained fertile material ZIF-8 for embodiment 1；
N under the 77K for the fertile material ZIF-8 that attached drawing 3 obtains for the synthesis of embodiment 12Adsorption isotherm line chart, wherein, it is solid
Circle represents absorption, and open circles represent desorption；
Attached drawing 4 is composite material IL prepared by embodiment 11The x-ray diffraction pattern of@ZIF-8；
Attached drawing 5 is composite material IL prepared by embodiment 11The scanning electron microscope diagram of@ZIF-8；
Attached drawing 6 is composite material IL prepared by embodiment 11The X-ray diffraction of@ZIF-8 and fertile material ZIF-8 compares
Figure；
Attached drawing 7 is composite material IL prepared by embodiment 11The infrared signature peak of@ZIF-8 and fertile material ZIF-8 compares
Figure；
Attached drawing 8 is composite material IL prepared by embodiment 11@ZIF-8 N under 77K2Adsorption isotherm line chart, wherein filled circles
Absorption is represented, open circles represent desorption；
Attached drawing 9 is composite material IL prepared by embodiment 11@ZIF-8 CO under 273K2Adsorption isotherm line chart, wherein solid
Circle represents absorption, and open circles represent desorption；
Attached drawing 10 is composite material IL prepared by embodiment 11@ZIF-8 N under 273K2Adsorption isotherm line chart, wherein solid
Circle represents absorption, and open circles represent desorption；
Attached drawing 11 is composite material IL prepared by embodiment 11@ZIF-8 CO under 273K2With N2Adsorption isotherm comparison
Figure, wherein square represents CO2, circle represents N2, solid to represent absorption, hollow represent is desorbed.It is risen by using adsorption isotherm
The slope ratio of beginning section calculates preferable adsorptive selectivity, i.e., Henry adsorptive selectivities, which calculate, finds, immobilized ionic liquid in cage
The IL of body1Its CO of@ZIF-82/N2Preferable Henry adsorptive selectivities be up to 3110, far above the CO of fertile material ZIF-82/N2's
Ideal adsorption selectivity 32；
Attached drawing 12 is composite material IL prepared by embodiment 22The XRD spectra of@ZIF-8 and fertile material ZIF-8 compares；
Attached drawing 13 is composite material IL prepared by embodiment 22The infrared signature peak pair of@ZIF-8 and fertile material ZIF-8
Than；
Attached drawing 14 is composite material IL prepared by embodiment 22Ns of the@ZIF-8 under 77K2Adsorption isotherm line chart.
Specific embodiment
The present invention provides a kind of zeolitic imidazolate framework material of solid-loaded ionic-liquid in cage, the material be ionic liquid with
The composite material that zeolitic imidazolate framework material is formed.
In the composite material, ionic liquid occupies the basket structure of zeolitic imidazolate framework material, to microenvironment in its cage into
Row modification, so as to fulfill the limitation to imidazole skeleton, to realize to the separated purpose of mixed gas.
In cage of the present invention in the zeolitic imidazolate framework material of solid-loaded ionic-liquid form ionic liquid sun from
Son is imidazole cation.It may be selected from but be not limited to 1,3- methylimidazoles ion, 1- ethyl-3-methylimidazoles ion, 1- third
Base -3- methylimidazoles ion, 1- butyl -3- methylimidazoles ions (BMIM), 1- hexyl -3- methylimidazole ions.Anion selects
From phosphorus hexafluoride ion ([PF6]), tetrafluoride boron ion ([BF4]), bromide ion ([Br]), iodide ion ([I]), double fluoroform sulphurs
Imide salts ion ([Tf2N]) or trifluoromethanesulfonic acid ion ([OTF]).It is preferred that tetrafluoride boron ion ([BF4]) or double fluoroforms
Sulfimide salt ion ([Tf2N])。
In specific embodiment, the zeolitic imidazolate framework material of solid-loaded ionic-liquid, feature exist in the cage
In the ionic liquid is selected from [BMIM] [Tf2N] or [BMIM] [BF4]。
In another specific embodiment, the zeolitic imidazolate framework material is ZIF-8.
Another aspect of the present invention also provides the zeolitic imidazolate framework material of solid-loaded ionic-liquid in the cage of the invention described above
Preparation method：Zeolitic imidazolate framework material (ZIFs) is dipped under the conditions of 50 DEG C~180 DEG C processing 1 in dipping solution~
96 it is small when, be washed out and dry；The wherein described dipping solution is ionic liquid or by C1-4Low-carbon alcohols and ionic liquid according to
The mixed solution of arbitrary proportion composition.
In specific embodiment, above-mentioned preparation method includes the following steps：
(1) ZIFs materials are prepared and are cleaned；
(2) ZIFs materials are dipped under the conditions of 50 DEG C~180 DEG C in dipping solution processing 1~96 it is small when, be washed out
And it dries；
The wherein described dipping solution is ionic liquid or by C1-4What low-carbon alcohols were formed with ionic liquid according to arbitrary proportion
Mixed solution；It is preferable to use C1-4Low-carbon alcohols percentage composition is no more than 95% mixed solution；
(3) product obtained by step (2) is cleaned and dried.
Clean the low-carbon alcohols used in dipping solution in preferred steps (2).After 3~5 washings, product 30~
When drying 12~48 is small under the conditions of 100 DEG C, you can obtain the zeolite imidazole ester bone of solid-loaded ionic-liquid in cage of the present invention
Frame material.
In another specific embodiment, using ZIF-8 as fertile material, the ZIF-8 of solid-loaded ionic-liquid in cage is prepared
Composite material (IL@ZIF-8).Its preparation method includes the following steps：
(1) fertile material ZIF-8 is synthesized：ZIF-8 is to be coordinated the institute's shape that is connected with 2-methylimidazole (mIm) by metallic zinc (Zn)
Into the ZIFs materials with sodalite (SOD) topological structure, chemical composition be Zn (mIm)2.The original of ZIF-8 is synthesized at room temperature
Expect that mol ratio is：Zn2+：xmIm：yCH3OH, wherein, Zn2+Represent soluble zinc salt, in particular to Zn (NO3)2·6H2O,
Zn(NO3)2·4H2O, ZnCl2, Zn (OAc)2·2H2One kind in O, mIm represent 2-methylimidazole, CH3OH represents solvent first
Alcohol, x=2~8, y=200~800, when generated time is 1~24 small；
(2) the washing drying of fertile material ZIF-8：Above-mentioned steps (1) synthesize obtained ZIF-8 solids and are washed with alcohols
3~5 times, solid and alcohols washing lotion are centrifuged each time after washing, and alcohols is methanol, one kind in ethyl alcohol.Dry temperature after washing
It spends for 30~100 DEG C, when drying time is 12~48 small.
(3) composite material IL@ZIF-8 are prepared：By step (2) prepare fertile material ZIF-8 be impregnated in low-carbon alcohols with from
The in the mixed solvent of sub- liquid composition, the low-carbon alcohols are selected from methanol, ethyl alcohol, propyl alcohol, butanol, account for the volume ratio of mixed solvent
For 20%~60%；Cation is 1,3- methylimidazoles, 1- ethyl-3-methylimidazoles, 1- propyl -3- methyl in ionic liquid
One kind in imidazoles, 1- butyl -3- methylimidazoles, 1- hexyl -3- methylimidazoles, anion are [PF6] (phosphorus hexafluoride), [BF4]
(tetrafluoride boron), [Br], [I], [Tf2N] (bis-trifluoromethylsulfoandimide salt), one kind in [OTF] (fluoroform sulphonate)；Leaching
Stain temperature is 50 DEG C~180 DEG C, when dip time is 1~96 small.
(4) composite material IL@ZIF-8 washing and dryings:Above-mentioned steps (3) obtained solid product is washed with methanol or ethyl alcohol
It washs 3~5 times, centrifuges solid and alcohols washing lotion each time after washing.Dry after washing, drying temperature is 30~100 DEG C, drying
When time is 12~48 small.
The present invention by ionic liquid supported to ZIFs cages by that will obtain the ZIFs composite woods of solid-loaded ionic-liquid in cage
Material.Modification realization is occupied to the modulation in ZIFs cages footpath to ZIFs cages by ionic liquid zwitterion, improves ZIFs ducts
Molecule sieving capacity；In addition, by realizing the selection of guest molecule ionic liquid zwitterion immobilized in cage to ZIFs
Cage in microenvironment modification, improve its gas absorption selectivity.
Following non-limiting example is not construed as the present invention is described further to the present invention
Any form of restriction.
Embodiment 1
High temperature mixed solvent dipping prepares solid-loaded ionic-liquid in cage [BMIM] [Tf2N] ZIF-8 composite materials it is (compound
Material IL1@ZIF-8), specific synthesis step is as follows：
(1) fertile material ZIF-8 is prepared：
To 1.8g solid Zn (NO3)2·6H2It is anhydrous that 100ml is added in O and 4.0g solids 2-methylimidazole (mim) mixture
Methanol, stirring make reactant fully dissolve and be uniformly mixed in 30 minutes, then reaction mixture is stood at room temperature 24 it is small when.
The formula of synthesis ZIF-8 is at room temperature：Zn2+：xmIm：yCH3OH, wherein x are 8, y 400.
(2) the washing drying of fertile material ZIF-8：
Product obtained by the reaction is centrifugally separating to obtain, and is cleaned by ultrasonic three times with a large amount of absolute methanols, is cleaned by ultrasonic every time
Product and methanol washing lotion are centrifuged afterwards.Obtained ZIF-8 solids be dried at room temperature for 12 it is small when, then in 60 DEG C of baking ovens do
It is dry 24 it is small when.
(3) the ZIF-8 composite materials of solid-loaded ionic-liquid in synthesis cage are impregnated under high temperature：
The obtained ZIF-8 solid materials of previous step (2) are added in ionic liquid [BMIM [Tf2N] it is formed with butanol
In the mixed solvent, wherein ionic liquid [BMIM [Tf2N] with the volume ratio of butanol it is 6:4, butanol volume integral of the total volume
Number is 40%, is then placed it in 120 DEG C of baking ovens, and dipping temperature is 120 DEG C, when dip time is 12 small.
(4) mixed solvent impregnates the drying for synthesizing the ZIF-8 composite materials of solid-loaded ionic-liquid in cage under high temperature：
Step (3) obtained solid product is centrifugally separating to obtain, and is cleaned by ultrasonic three times, often with a large amount of absolute methanols
Product and methanol washing lotion are centrifuged after secondary ultrasonic cleaning.Obtained composite products be first dried at room temperature for 12 it is small when,
Then it is immobilized in obtained cage when finally drying 12 is small in 60 DEG C of vacuum drying chambers when drying 24 is small in 60 DEG C of baking ovens
Ionic liquid [BMIM [Tf2N] ZIF-8 composite materials, be denoted as composite material IL1@ZIF-8。
(5) respectively to fertile material ZIF-8 and composite material IL1@ZIF-8 carry out multinomial characterization, characterization result such as attached drawing 1
Shown in~11.
To fertile material ZIF-8 and composite material IL1@ZIF-8 do X-ray diffraction, respectively attached drawing 1, attached drawing 4, and two
The comparison of person is attached drawing 6.X-ray diffraction shows composite material IL1Both@ZIF-8 and fertile material ZIF-8 have complete phase
Same crystal phase structure, and composite material IL1@ZIF-8 peak intensities of its characteristic diffraction peak (100) compared with ZIF-8 significantly drop
It is low, cause this is because ionic liquid enters in ZIF-8 cages caused by cloud density changes.
To fertile material ZIF-8 and composite material IL1@ZIF-8 do scanning electron microscope characterization, be respectively attached drawing 2,
Shown in attached drawing 5.
To fertile material ZIF-8 and composite material IL1@ZIF-8 do Fourier's attenuation total reflection spectrum, and the two is in feature
The comparison of functional group region is attached drawing 7.Compared with ZIF-8, composite material IL1@ZIF-8 are 1350,1230,1200,1065cm-1Go out
Now new vibration band, these vibration bands are ionic liquid [BMIM] [Tf2N] in anionicsite eigen vibration band, it is right respectively
Answer SO2Antisymmetric stretching vibration, CF3Antisymmetric stretching vibration, SO2Symmetrical stretching vibration and SNS antisymmetric stretching vibration patterns.
It is deposited on that ZIF-8 surfaces are different from ionic liquid, ionic liquid loaded after in the cage of ZIF-8, SO2Symmetrical stretching vibration band
There is apparent blue shift with SNS antisymmetric stretching vibrations band, this may have with the interaction between ionic liquid and ZIF-8 cages
It closes.
To fertile material ZIF-8 and composite material IL1@ZIF-8 powder is made in the N under 77K2Adsorption isotherm, respectively
Attached drawing 3 and attached drawing 8；In addition, to composite material IL1@ZIF-8 powder is made in the CO under 273K2、N2Adsorption isotherm, be respectively
Attached drawing 9 and attached drawing 10, and preferable CO is calculated using the slope ratio of adsorption isotherm the initial segment2/N2Adsorptive selectivity, and
With the preferable CO of fertile material ZIF-82/N2Adsorptive selectivity compares.By attached drawing 3 and attached drawing 8 it was found that ZIF-8 with it is compound
Material IL1@ZIF-8 N under 77K2Adsorption isotherm adsorbs for typical I- types.Since space is accounted for by ionic liquid in ZIF-8 cages
According to composite material IL1The N of@ZIF-82Adsorbance is substantially reduced, according to N under 77K2Adsorption isotherm is calculated compares table accordingly
Area is also from the 1379m of original ZIF-82g-1It is down to 374m2g-1, pore volume is from 0.67ml g-1It is down to 0.18ml g-1, composite wood
Expect IL1@ZIF-8 are significantly reduced compared to ZIF-8 specific surface areas, this also further demonstrates ionic liquid and enters in ZIF-8 cages,
Reduce the specific surface area of material in itself.In addition to composite material under 273K to CO2And N2Adsorption isotherm carry out data point
Analysis, preferable adsorptive selectivity, i.e. Henry adsorptive selectivities are calculated by using the slope ratio of adsorption isotherm the initial segment
It calculates and finds, composite material IL1The CO of@ZIF-82/N2Preferable Henry adsorptive selectivities be up to 3110, far above fertile material
The CO of ZIF-82/N2Ideal adsorption selectivity 32, also considerably beyond other MOFs crystal of document report so far.It is corresponding to inhale
It is attached that the results are shown in tables 1.
Table 1：The absorption property of composite material and ZIF-8 compare
Embodiment 2
High temperature mixed solvent dipping prepares solid-loaded ionic-liquid in cage [BMIM] [BF4] ZIF-8 composite materials, it is specific to close
It is as follows into step：
(1) fertile material ZIF-8 is prepared：It is identical with step (1) in embodiment 1；
(2) the washing drying of fertile material ZIF-8：It is identical with step (2) in embodiment 1；
(3) mixed solvent dipping synthesizes solid-loaded ionic-liquid [BMIM] [BF in cage under high temperature4] ZIF-8 composite materials,
It is denoted as IL2@ZIF-8：
The obtained dry ZIF-8 solids of previous step (2) are added in into ionic liquid [BMIM] [BF4] formed with butanol
In the mixed solvent, wherein ionic liquid [BMIM [BF4] with the volume ratio of butanol it is 8:2, butanol volume fraction of the total volume is
20%, it then places it in 100 DEG C of baking ovens, dipping temperature is 100 DEG C, when dip time is 48 small.
(4) composite material IL2The drying of@ZIF-8：
Step (3) obtained solid product is centrifugally separating to obtain, and is cleaned by ultrasonic three times, often with a large amount of absolute methanols
Product and methanol washing lotion are centrifuged after secondary ultrasonic cleaning.Obtained composite products be first dried at room temperature for 12 it is small when,
Then in 60 DEG C of baking ovens it is dry 24 it is small when, finally in 60 DEG C of vacuum drying chambers it is dry 12 it is small when, in obtained cage it is immobilized from
Sub- liquid [BMIM] [BF4] ZIF-8 composite materials.
(5) fertile material ZIF-8 and composite material IL2The characterization of@ZIF-8, characterization result is as shown in attached drawing 12~14.
To obtained composite material IL2@ZIF-8 do X-ray diffraction and Fourier's attenuation total reflection spectrum, and and parent
The spectrogram of material ZIF-8 compares, and is respectively attached drawing 12 and attached drawing 13.
By X-ray diffraction it turns out that composite material IL2Both@ZIF-8 and fertile material ZIF-8 have complete phase
Same crystal phase structure, and composite material IL2@ZIF-8 peak intensities of its characteristic diffraction peak (100) compared with ZIF-8 significantly drop
It is low, cause this is because ionic liquid enters in ZIF-8 cages caused by cloud density changes.In this result and embodiment 1
As a result it is similar, show the repeatability of the method.
Pass through the comparison graph discovery in characteristic group area, composite material IL2@ZIF-8 are in 1060cm-1Place has new wider
Absworption peak, this is [BF4 -1] eigen vibration peak, neighbouring 1129cm-1Also there is new vibration peak at place, this vibration peak is stretched for B-F keys
Contracting vibration peak, this is the result shows that ionic liquid is successfully loaded in the cage of ZIF-8.
To obtained composite material IL2@ZIF-8 are the N under 77K2Adsorption isotherm is attached drawing 14.By to its adsorption number
It is found according to analysis, the specific surface area of composite material is from the 1379m of ZIF-82g-1It is reduced to 430m2g-1, this is also further demonstrated
Ionic liquid [BMIM] [BF4] really in the immobilized cage to ZIF-8.
Claims (9)
1. the zeolitic imidazolate framework material of solid-loaded ionic-liquid in cage, which is characterized in that be ionic liquid and zeolite imidazole ester
The composite material that framework material is formed.
2. the zeolitic imidazolate framework material of solid-loaded ionic-liquid in cage according to claim 1, which is characterized in that described
The cation of composition ionic liquid be imidazole cation.
3. the zeolitic imidazolate framework material of solid-loaded ionic-liquid in cage according to claim 2, which is characterized in that described
Composition ionic liquid cation be selected from 1,3- methylimidazoles ion, 1- ethyl-3-methylimidazoles ion, 1- propyl -3-
Methylimidazole ion, 1- butyl -3- methylimidazoles ion, 1- hexyl -3- methylimidazole ions.
4. the zeolitic imidazolate framework material of solid-loaded ionic-liquid in cage according to claim 1, which is characterized in that described
Composition ionic liquid anion be selected from phosphorus hexafluoride ion, tetrafluoride boron ion, bromide ion, iodide ion, double fluoroform sulphurs
Imide salts ion or trifluoromethanesulfonic acid ion.
5. the zeolitic imidazolate framework material of solid-loaded ionic-liquid in cage according to claim 4, which is characterized in that described
The anion of composition ionic liquid be tetrafluoride boron ion or bis-trifluoromethylsulfoandimide salt ion.
6. the zeolitic imidazolate framework material of solid-loaded ionic-liquid in cage according to claim 1, which is characterized in that described
Ionic liquid be selected from [BMIM] [Tf2N] or [BMIM] [BF4]。
7. the zeolitic imidazolate framework material of solid-loaded ionic-liquid in cage according to claim 1, which is characterized in that described
Zeolitic imidazolate framework material be ZIF-8.
8. the zeolitic imidazolate framework material of solid-loaded ionic-liquid, is prepared by following methods in cage according to claim 1：
When zeolitic imidazolate framework material to be dipped under the conditions of 50 DEG C~180 DEG C to processing 1~96 is small in dipping solution, it is washed out simultaneously
Drying；
The wherein described dipping solution is ionic liquid or by C1-4The mixing that low-carbon alcohols are formed with ionic liquid according to arbitrary proportion
Solution.
9. application of the zeolitic imidazolate framework material of solid-loaded ionic-liquid in gas separation in cage described in claim 1.
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