CN109847702A - A method of the cage diameter modulation of the poromerics containing basket structure - Google Patents
A method of the cage diameter modulation of the poromerics containing basket structure Download PDFInfo
- Publication number
- CN109847702A CN109847702A CN201711233038.3A CN201711233038A CN109847702A CN 109847702 A CN109847702 A CN 109847702A CN 201711233038 A CN201711233038 A CN 201711233038A CN 109847702 A CN109847702 A CN 109847702A
- Authority
- CN
- China
- Prior art keywords
- poromerics
- cage
- zif
- ionic liquid
- basket structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a kind of method of the cage diameter modulation of poromerics containing basket structure, synthesis obtains the poromerics with basket structure first, the poromerics obtained again to synthesis is activated, then the poromerics after activation is immersed in ionic liquid, ionic liquid is introduced into the cage of poromerics by Vacuum Heat dipping in vacuum drying oven, it will be taken out impregnated poromerics in ionic liquid, alcohols supersound washing is used again, the poromerics after washing is dried again, obtains the poromerics of cage diameter modulation.The present invention is by being introduced into the stable molecule of the big physicochemical properties of the steric hindrances such as ionic liquid in the cage of the poromerics with basket structure, the cage diameter and gas absorption property of fine modulation poromerics, so that cage diameter accurately sieves field with broader practice prospect in gas-selectively absorption and molecule by the poromerics of fine modulation.
Description
Technical field
The invention belongs to molecules accurately to sieve field, and in particular to a kind of cage diameter modulation of the poromerics containing basket structure
Method.
Background technique
The isolation and purification of gas is very important process in industrial production, at present gas membrane Seperation Technology and absorption point
Have the advantages that low energy consumption, pollution-free and equipment is simple from technology, is favored extensively by global researchers.In order to develop film
Isolation technics and adsorption separation technology, the material that there is high adsorptive selectivity and molecular dimension to sieve for design, screening and synthesis
It is the emphasis that we study.
Inorganic microporous material is that one kind has the characteristics that biggish specific surface area, low-density, lower thermal conductivity, high porosity
Material rich in pore structure has broad application prospects in fields such as catalysis, absorption, gas separation.Inorganic microporous material
Generally comprise micro porous molecular sieve and metal-organic framework materials etc..Metal-organic framework materials (metal-organic
Frameworks, hereinafter referred to as MOFs) it is a kind of novel poromerics, generally there is grade pore structure abundant, it is biggish
Specific surface area, higher thermal stability and the characteristic modified after being easy to.The pore structure size of MOFs is normally at micro-molecular gas
Kinetic diameter region has certain molecule sieving capacity；And the specific functional group of organic ligand is also to certain in MOFs
Micro-molecular gas (such as H2、CO2、CH4Deng) there is good compatibility.This be just this kind of poromerics of MOFs in gas absorption and
The application of separation field is had laid a good foundation.
However, find under study for action, it is some according to pore structure size to there is the MOFs material of separation effect to be applied to reality
Expected selectivity is not achieved when separating in border mixture.By taking ZIF-8 as an example, it is by Zn2+With 2-methylimidazole anion binding
The material with sodalite SOD structure formed, hexa-atomic hole window diameter are 0.34nm, and sodalite cage diameter is 1.10nm, by
Molecular dynamics diameter data is it is found that theoretically, when gas molecule passes through the pore structure of ZIF-8, hexa-atomic hole window can be cut
Stay larger-size CH4、N2, and make CO2It passes through.However, skeleton caused by being vibrated due to imidazole ligands is flexible, ZIF-8 tool
There is aperture effect, hole window magnifies to form a bigger dynamic aperture.The dynamic aperture effect of the MOFs poromerics such as ZIF-8, meeting
Hole window is reduced to macromolecular interception capacity, separation selectivity declines when it being caused to form molecular screen membrane.It would therefore be desirable to fine
The pore structure size of modulation MOFs material makes it have obvious excellent molecule sieve performance.
Currently, the pore structure modulation strategy of MOFs has the sides such as crystal engineering means, metal (ligand) exchange and hole cage occupies
Method.The method that hole cage occupies is that the biggish guest molecule of steric hindrance is put into the cage of MOFs material, in this way, MOFs
Molecule retention size just becomes the cage diameter being obstructed in space from original hole window diameter, improves the molecule screening energy of flexible MOFs
Power.The size that the thought that foundation hole cage occupies adjusts cage is more simple and easy to do, and does not destroy the intrinsic structure of crystal.
There is ionic liquid extremely-low vapor pressure and excellent chemistry and thermal stability, anion or cationic portion to have
Enough steric hindrances can effectively occupy space in cage.Correlative study the result shows that, confinement in small size nanocages from
Sub- liquid, voltage endurance capability significantly improve, and will not escape and come out of steamer because of excessive pressure-bearing.Furthermore the result table of some theoretical calculations
It is bright, there is strong interaction, this point similarly serves to favor stabilization immobilized in ionic liquid cage between ionic liquid and MOFs material
Property.Therefore we select ionic liquid as the immobilized cage diameter to fine modulation MOFs material next in MOFs cage of guest molecule.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that fine modulation has the cage diameter of the poromerics of basket structure, pass through
The composite material of the fine modulation of cage diameter will be prepared in the hole cage of ionic liquid supported to MOFs material.
The present invention provides a kind of method of the cage diameter modulation of poromerics containing basket structure, specific steps are as follows:
(1) poromerics synthesized first is the material of crystallization or amorphous, and hole cage size is less than 2nm, micropore material
Material is selected from ZIF-8, ZIF-11, CuBTC, IRMOF-1, UiO-66, MOF-74 etc..
(2) poromerics then obtained to synthesis is activated, and activation processing is the vacuum shape in vacuum drying oven
It is carried out under state, activation temperature is 50~350 DEG C, and being activated the time is 12~96 hours.
(3) poromerics after activation is immersed in ionic liquid again, is impregnated under vacuum state in vacuum drying oven, very
Temperature is 60~300 DEG C in empty dipping process, and the vacuum impregnation time is 12~120 hours.
During poromerics is immersed in ionic liquid, the cation for impregnating the ionic liquid of poromerics is season
One of ammonium type cation, season phosphine type cation, pyridine type cation, imidazole cation, anion is [PF6] (hexafluoro
Change phosphorus), [BF4] (tetrafluoride boron), [Br], [I], [Tf2N] (bis-trifluoromethylsulfoandimide salt), [OTF] (fluoroform sulphonate)
One of.
(4) it will be taken out impregnated poromerics in ionic liquid, then use alcohols supersound washing, alcohols used is C1-4
One kind of alcohols, then the poromerics after washing is dried, the drying temperature is 40~150 DEG C.Obtain the micro- of cage diameter modulation
Porous materials.
Ionic liquid is introduced into poromerics cage by the present invention, is occupied by the various sizes of zwitterion of ionic liquid
The hole basket structure of poromerics realizes the modulation to available gas retention size in poromerics cage, and to gas with various
Adsorptive selectivity.
The method of modifying of the micropore MOFs cage diameter of the guest molecules such as solid-loaded ionic-liquid in this cage, survivable crystal
Intrinsic structure is readily extended in other MOFs crystalline materials with basket structure.The zwitterion of ionic liquid has very
Numerous types and adjustable functional group, in the present invention ionic liquid used in embodiment be all glyoxaline cation type and point
The sub- huge anion of size difference, in addition to this immobilized ionic liquid in MOFs cage can also be extended to and have by we
The quaternary ammonium cation type of different sizes and different functional groups, season phosphine cationic, ionic liquid of pyridylium type etc..We
The ionic liquid for selecting a variety of steric hindrances different is expected to occupy the cage diameter of different materials, and it is continuously adjustable to obtain a series of cage diameters
MOFs material, pass through size difference realize gas molecule screening；Furthermore by the ionic liquid for containing different functional groups
The modification to microenvironment in the cage of the MOFs material with basket structure is realized in the selection of body zwitterion, improves MOFs material
Gas absorption selectivity.Therefore, the present invention in micropore MOFs material cage in solid-loaded ionic-liquid modulation cage diameter method in gas
The screening of body size and adsorbing separation field will have in future to be more widely applied.
Detailed description of the invention
Fig. 1 is the x-ray diffraction pattern that embodiment 1 synthesizes obtained poromerics ZIF-8；
Fig. 2 is the scanning electron microscope diagram that embodiment 1 synthesizes obtained poromerics ZIF-8；
N under the 77K that Fig. 3 is the poromerics ZIF-8 that the synthesis of embodiment 1 obtains2Adsorption isotherm map, wherein filled circles
Absorption is represented, open circles represent desorption；
Fig. 4 is [BMIM] [Tf prepared by embodiment 12N]@ZIF-8 x-ray diffraction pattern；
Fig. 5 is [BMIM] [Tf prepared by embodiment 12N]@ZIF-8 scanning electron microscope diagram；
Fig. 6 is [BMIM] [Tf prepared by embodiment 12N]@ZIF-8 and ZIF-8 X-ray diffraction comparison diagram；
Fig. 7 is [BMIM] [Tf prepared by embodiment 12N]@ZIF-8 and ZIF-8 infrared signature peak comparison diagram；
Fig. 8 is [BMIM] [Tf prepared by embodiment 12N]@ZIF-8 N at 77K2Adsorption isotherm map, wherein filled circles generation
Table absorption, open circles represent desorption；
Fig. 9 is [BMIM] [Tf prepared by embodiment 12N]@ZIF-8 and ZIF-8 pore-size distribution comparison diagram, wherein L1It is corresponding
The hexa-atomic hole window diameter of ZIF-8, L2The dynamic aperture that the hexa-atomic hole window cell breath of corresponding ZIF-8 is formed, L3The hole of corresponding ZIF-8
Cage diameter；
Figure 10 is [BMIM] [Tf prepared by embodiment 12N]@ZIF-8 CO at 273K2Adsorption isotherm map, wherein solid
Circle represents absorption, and open circles represent desorption；
Figure 11 is [BMIM] [Tf prepared by embodiment 12N]@ZIF-8 N at 273K2Adsorption isotherm map, wherein filled circles
Absorption is represented, open circles represent desorption；
Figure 12 is composite material [BMIM] [Tf prepared by embodiment 12N]@ZIF-8 and ZIF-8 CO at 273K2With N2's
Adsorption isotherm comparison diagram, wherein square represents CO2, circle represents N2, solid representative absorption, hollow representative desorption.Pass through benefit
Ideal adsorptive selectivity is calculated with the slope ratio of adsorption isotherm the initial segment, i.e. Henry adsorptive selectivity calculates discovery,
[BMIM] [Tf of solid-loaded ionic-liquid in cage2N]@ZIF-8 its CO2/N2Ideal Henry adsorptive selectivity be up to 2760, it is remote high
In the CO of ZIF-82/N2Ideal adsorption selectivity 32；
Figure 13 is [BMIM] [BF prepared by embodiment 24]@ZIF-8 and ZIF-8 XRD spectra comparison；
Figure 14 is [BMIM] [BF prepared by embodiment 24]@ZIF-8 and ZIF-8 infrared signature peak comparison；
Figure 15 is [BMIM] [BF prepared by embodiment 24] N of the@ZIF-8 at 77K2Adsorption isotherm map；
Figure 16 is [BMIM] [BF prepared by embodiment 24]@ZIF-8 and ZIF-8 pore-size distribution comparison diagram, wherein L1It is corresponding
The hexa-atomic hole window diameter of ZIF-8, L2The dynamic aperture that the hexa-atomic hole window cell breath of corresponding ZIF-8 is formed, L3The hole of corresponding ZIF-8
Cage diameter；
Figure 17 is [EMIM] [BF prepared by embodiment 34] N of the@ZIF-8 at 77K2Adsorption isotherm map；
Figure 18 is [EMIM] [BF prepared by embodiment 34]@ZIF-8 and ZIF-8 pore-size distribution comparison diagram, wherein L1It is corresponding
The hexa-atomic hole window diameter of ZIF-8, L2The dynamic aperture that the hexa-atomic hole window cell breath of corresponding ZIF-8 is formed, L3The hole of corresponding ZIF-8
Cage diameter.
Specific embodiment
The present invention provides a kind of method of the fine modulation poromerics cage diameter of solid-loaded ionic-liquid in cage.
Constituted in solid-loaded ionic-liquid in cage described in the embodiment of the present invention cation of ionic liquid be imidazole type sun from
Son.It may be selected from but not limited to 1,3- methylimidazole ion, 1- ethyl-3-methylimidazole ion ([EMIM]), 1- propyl -3- first
Base imidazol ion, 1- butyl -3- methylimidazole ion ([BMIM]), 1- hexyl -3- methylimidazole ion.Anion is selected from hexafluoro
Change phosphonium ion ([PF6]), tetrafluoride boron ion ([BF4]), bromide ion ([Br]), iodide ion ([I]), bis-trifluoromethylsulfoandimide
Salt ion ([Tf2N]) or trifluoromethanesulfonic acid ion ([OTF]).
The preferential 1- ethyl-3-methylimidazole ion ([EMIM]) of cation or 1- butyl -3- methyl miaow in specific embodiment
Oxazolinium ion ([BMIM]), preferred tetrafluoride the boron ion ([BF of anion4]) or bis-trifluoromethylsulfoandimide salt ion ([Tf2N])。
In specific embodiment, the preferred ionic liquid of institute is selected from [BMIM] [Tf2N] or [BMIM] [BF4] or [EMIM]
[BF4]。
In specific embodiment, preparation method includes the following steps:
(1) it prepares micropore MOFs material and cleans；
(2) by the MOFs being prepared, vacuum activating is handled in vacuum drying oven, and activation pressure is 0~-0.1MPa, activation
Temperature is 50~350 DEG C, and being activated the time is 12~96 hours
(3) the MOFs material after activation is immersed in preferred ionic liquid, hot submersion is carried out in vacuum drying oven, impregnated
0~-0.1MPa of pressure process, dip time 12~120 hours, 60~300 DEG C of dipping temperature.
(4) it will be taken out impregnated poromerics in ionic liquid, then use alcohols supersound washing, alcohols used is C1-4
One kind of alcohols, then the poromerics after washing is dried, drying temperature is 40~150 DEG C, obtains the micropore material of cage diameter modulation
Material.
The present invention will be by that will obtain solid-loaded ionic-liquid modulation cage diameter in cage in ionic liquid supported to micropore MOFs cage
Poromerics.The modification that occupies of MOFs cage is realized to the modulation of MOFs cage diameter by ionic liquid zwitterion, is improved
The molecule sieving capacity in the duct MOFs；In addition, real by the selection to guest molecule ionic liquid zwitterion immobilized in cage
Now to the modification of microenvironment in the cage of MOFs, improve its gas absorption selectivity.
Following non-limiting embodiment is not construed as to the present invention for the present invention is described further
Any form of restriction.
Embodiment 1
Vacuum ionic liquid hot submersion prepares solid-loaded ionic-liquid in cage [BMIM] [Tf2N] ZIF-8 material (composite wood
Material is denoted as [BMIM] [Tf2N]@ZIF-8), the specific steps are as follows:
(1) poromerics ZIF-8 is prepared:
To 1.8g solid Zn (NO3)2·6H2It is anhydrous that 100ml is added in O and 4.0g solid 2-methylimidazole (mim) mixture
Methanol, stirring make reactant sufficiently dissolve and be uniformly mixed in 30 minutes, reaction mixture are then stood to 24 hours at room temperature.
The formula of ZIF-8 is synthesized at room temperature are as follows: Zn2+: xmIm:yCH3OH, wherein x is 8, y 400.
(2) the washing drying of material ZIF-8:
It reacts obtained product to be centrifugally separating to obtain, and three times with the ultrasonic cleaning of a large amount of anhydrous methanols, is cleaned by ultrasonic every time
Centrifuge separation product and methanol washing lotion afterwards.Obtained ZIF-8 solid is dried at room temperature for 12 hours, is then done in 60 DEG C of baking ovens
Dry 24 hours.
(3) activation of ZIF-8 poromerics:
The obtained ZIF-8 solid material of previous step (2) is put into vacuum tank, at 120 DEG C, vacuum pressure-
It is activated 24 hours under 0.1MPa.
(4) the ZIF-8 composite material of solid-loaded ionic-liquid modulation cage diameter in synthesis cage is impregnated under vacuum ionic hot submersion:
By the obtained ZIF-8 solid impregnating of step (3) in ionic liquid [BMIM] [Tf2N] in, it is put into vacuum drying oven
In, it is impregnated 24 hours at vacuum -0.1MPa, 120 DEG C.
(5) the washing drying for the ZIF-8 material that cage diameter modulation is crossed:
Step (4) obtained product is centrifugally separating to obtain, and three times with the ultrasonic cleaning of a large amount of anhydrous methanols, it is super every time
Centrifuge separation product and methanol washing lotion after sound cleaning.Obtained ZIF-8 solid is dried at room temperature for 12 hours, is then dried at 60 DEG C
It is 24 hours dry in case.
(6) [BMIM] [Tf that poromerics ZIF-8 and cage diameter modulation are crossed respectively2N] the multinomial characterization of@ZIF-8 progress, table
Result is levied as shown in attached drawing 1~12.
To ZIF-8 and [BMIM] [Tf2N]@ZIF-8 does X-ray diffraction, respectively attached drawing 1, attached drawing 4, pair of the two
Than for attached drawing 6.X-ray diffraction shows [BMIM] [Tf2N] both@ZIF-8 and ZIF-8 have identical crystal phase structure,
And [BMIM] [Tf2N]@ZIF-8 its characteristic diffraction peak (100) compared with ZIF-8 peak intensity significantly reduce, this is because from
Sub- liquid [BMIM] [Tf2N] enter in ZIF-8 cage and causes caused by cloud density changes.
To ZIF-8 and [BMIM] [Tf2N]@ZIF-8 does scanning electron microscope characterization, respectively attached drawing 2,5 institute of attached drawing
Show.
To material ZIF-8 and [BMIM] [Tf2N]@ZIF-8 be Fourier decay total reflection spectrum, the two is in feature official
The comparison in the area Neng Tuan is attached drawing 7.Compared with ZIF-8, [BMIM] [Tf2N]@ZIF-8 is in 1350,1230,1200,1065cm-1Out
Now new vibration band, these vibration bands are ionic liquid [BMIM] [Tf2N] in anion part eigen vibration band, it is right respectively
Answer SO2Antisymmetric stretching vibration, CF3Antisymmetric stretching vibration, SO2Symmetrical stretching vibration and SNS antisymmetric stretching vibration mode.
To ZIF-8 and [BMIM] [Tf2N]@ZIF-8 powder is made in the N under 77K2Adsorption isotherm, respectively 3 He of attached drawing
Attached drawing 8；In addition, to [BMIM] [Tf2N]@ZIF-8 powder is made in the CO under 273K2、N2Adsorption isotherm, respectively attached drawing 10
With attached drawing 11, and ideal CO is calculated using the slope ratio of adsorption isotherm the initial segment2/N2Adsorptive selectivity, and and ZIF-
8 ideal CO2/N2Adsorptive selectivity comparison.By attached drawing 3 and attached drawing 8 it was found that ZIF-8 and [BMIM] [Tf2N]@ZIF-8
The N at 77K2Adsorption isotherm is the absorption of typical I- type.According to N under 77K2Corresponding specific surface is calculated in adsorption isotherm
Product is also from the 1821m of original ZIF-82g-1It is down to [BMIM] [Tf2N]@ZIF-8 875m2g-1, pore volume is from 0.65ml g-1Drop
To 0.37ml g-1,[BMIM][Tf2N]@ZIF-8 compared to ZIF-8 specific surface area significantly reduce.
By N of two kinds of materials at 77K2Adsorption isotherm simulates to obtain ZIF-8 material and [BMIM] by H-K method
[Tf2N]@ZIF-8 graph of pore diameter distribution, the two comparing result is attached drawing 9, wherein L1The hexa-atomic hole window diameter of corresponding ZIF-8, L2
The dynamic aperture that the hexa-atomic hole window cell breath of corresponding ZIF-8 is formed, L3The hole cage diameter of corresponding ZIF-8.Pass through origin normalizing
Change the percentage in the simulation total hole available three kinds of hole Zhan.By simulating we have found that hexa-atomic hole window L1Accounting increases, dynamic aperture L2
With hole cage L3Accounting is reduced, and further illustrates ionic liquid [BMIM] [Tf2N] it occupies in ZIF-8 cage, it being capable of effectively modulation ZIF-8
Cage diameter.Accordingly result is shown in table 1.
Table 1:ZIF-8 and [BMIM] [Tf2N]@ZIF-8 difference hole accounting
Furthermore to composite material under 273K to CO2And N2Adsorption isotherm carry out data analysis, by utilize adsorption isotherm
The slope ratio of line the initial segment calculates ideal adsorptive selectivity, i.e., Henry adsorptive selectivity calculates discovery, [BMIM]
[Tf2N]@ZIF-8 CO2/N2Ideal Henry adsorptive selectivity be up to 2760, the CO much higher than ZIF-82/N2Ideal adsorption
Selectivity 32, also considerably beyond other MOFs crystal reported in the literature so far.Corresponding absorption result is listed in table 2
Table 2:[BMIM] [Tf2N]@ZIF-8 and IF-8 absorption property comparison
Embodiment 2
Vacuum ionic liquid hot submersion prepares solid-loaded ionic-liquid in cage [BMIM] [BF4] ZIF-8 material (composite material
It is denoted as [BMIM] [BF4]@ZIF-8, the specific steps are as follows:
(1) poromerics ZIF-8 is prepared: identical as step (1) in embodiment 1；
(2) the washing drying of material ZIF-8: identical as step (2) in embodiment 1；
(3) activation of ZIF-8 poromerics: identical as step (3) in embodiment 1；
(4) the ZIF-8 composite material of solid-loaded ionic-liquid modulation cage diameter in synthesis cage is impregnated under vacuum ionic hot submersion:
By the obtained ZIF-8 solid impregnating of step (3) in ionic liquid [BMIM] [BF4] in, it is put into vacuum drying oven,
It is impregnated 48 hours at vacuum -0.1MPa, 140 DEG C.
(5) the washing drying for the ZIF-8 material that cage diameter modulation is crossed:
Step (4) obtained product is centrifugally separating to obtain, and three times with the ultrasonic cleaning of a large amount of anhydrous methanols, it is super every time
Centrifuge separation product and methanol washing lotion after sound cleaning.Obtained ZIF-8 solid is dried at room temperature for 12 hours, is then dried at 60 DEG C
It is 24 hours dry in case.
(6) [BMIM] [BF that poromerics ZIF-8 and cage diameter modulation are crossed respectively4] the multinomial characterization of@ZIF-8 progress, table
Result is levied as shown in attached drawing 13~16.
To obtained [BMIM] [BF4]@ZIF-8 sample is X-ray diffraction and Fourier and decays total reflection spectrum, and with
The spectrogram of ZIF-8 compares, respectively attached drawing 13 and attached drawing 14.
By X-ray diffraction as a result, it has been found that [BMIM] [BF4] both@ZIF-8 and ZIF-8 have identical crystal phase
Structure, and [BMIM] [BF4]@ZIF-8 its characteristic diffraction peak (100) compared with ZIF-8 peak intensity significantly reduce, this be by
Entering in ZIF-8 cage in ionic liquid causes caused by cloud density changes.This result is similar with result in embodiment 1,
Show the repeatability of the method.
Pass through the comparison graph discovery in characteristic group area, [BMIM] [BF4]@ZIF-8 is in 1060cm-1Place has new wider
Absorption peak, this is [BF4 -1] eigen vibration peak, neighbouring 1129cm-1Also there is new vibration peak at place, this vibration peak is stretching for B-F key
Contracting vibration peak, this is the result shows that ionic liquid has successfully loaded in the cage of ZIF-8.
To obtained [BMIM] [BF4]@ZIF-8 is the N under 77K2Adsorption isotherm is attached drawing 15.By to its adsorption number
It is found according to analysis, the 1821m of the specific surface area of composite material from ZIF-82g-1It is reduced to 371m2g-1, this is also further demonstrated
Ionic liquid [BMIM] [BF4] really immobilized into ZIF-8 cage.
By N of two kinds of materials at 77K2Adsorption isotherm simulates to obtain ZIF-8 material and [BMIM] by H-K method
[BF4]@ZIF-8 graph of pore diameter distribution, the two comparing result be attached drawing 16, by simulate we have found that hexa-atomic hole window L1Accounting increases
Add, dynamic aperture L2With hole cage L3Accounting is reduced, and similar with result in embodiment 1, accordingly result is in table 3.
Table 1:ZIF-8 and [BMIM] [BF4]@ZIF-8 difference hole accounting
Embodiment 3
Vacuum ionic liquid hot submersion prepares solid-loaded ionic-liquid in cage [EMIM] [BF4] ZIF-8 material (composite material
It is denoted as [EMIM] [BF4]@ZIF-8, the specific steps are as follows:
(1) poromerics ZIF-8 is prepared: identical as step (1) in embodiment 1；
(2) the washing drying of material ZIF-8: identical as step (2) in embodiment 1；
(3) activation of ZIF-8 poromerics: identical as step (3) in embodiment 1；
(4) the ZIF-8 composite material of solid-loaded ionic-liquid modulation cage diameter in synthesis cage is impregnated under vacuum ionic hot submersion:
By the obtained ZIF-8 solid impregnating of step (3) in ionic liquid [EMIM] [BF4] in, it is put into vacuum drying oven,
It is impregnated 24 hours at vacuum -0.1MPa, 120 DEG C.
(5) the washing drying for the ZIF-8 material that cage diameter modulation is crossed:
Step (4) obtained product is centrifugally separating to obtain, and three times with the ultrasonic cleaning of a large amount of anhydrous methanols, it is super every time
Centrifuge separation product and methanol washing lotion after sound cleaning.Obtained ZIF-8 solid is dried at room temperature for 12 hours, is then dried at 60 DEG C
It is 24 hours dry in case.
(6) [EMIM] [BF that poromerics ZIF-8 and cage diameter modulation are crossed respectively4]@ZIF-8 is the N under 77K2Absorption etc.
Warm line is attached drawing 17.By being found to its adsorpting data analysis, the 1821m of the specific surface area of composite material from ZIF-82g-1Drop
As low as 808m2g-1, this also further demonstrates ionic liquid [BMIM] [BF4] really immobilized into ZIF-8 cage.
By N of two kinds of materials at 77K2Adsorption isotherm simulates to obtain ZIF-8 material and [EMIM] by H-K method
[BF4]@ZIF-8 graph of pore diameter distribution, the two comparing result be attached drawing 18, it is similar with result in embodiment 1.
Embodiment 4
Vacuum ionic liquid hot submersion prepares solid-loaded ionic-liquid in cage [BMIM] [BF4] Mg-MOF-74 material it is (compound
Material is denoted as [BMIM] [BF4]@Mg-MOF-74, the specific steps are as follows:
(1) poromerics Mg-MOF-74 is prepared:
To 6.0g solid Mg (NO3)2·6H220ml first is added in 2,5 dihydric para-phthalic acid's mixture of O and 2.0g
Alcohol, 20ml deionized water and 100mlDMF, stirring make reactant sufficiently dissolve and be uniformly mixed in 30 minutes, then mix reaction
Object reacts 24 hours at 120 DEG C in a kettle.
(2) the washing drying of poromerics Mg-MOF-74:
By steps are as follows (1), the middle obtained product that reacts is centrifugally separating to obtain, and is cleaned by ultrasonic three with a large amount of anhydrous methanols
It is secondary, product and methanol washing lotion are centrifugated after ultrasonic cleaning every time.It is small that obtained Mg-MOF-74 solid is dried at room temperature for 12
When, it is then 24 hours dry in 120 DEG C of baking ovens.
(3) activation of Mg-MOF-74 poromerics:
The obtained Mg-MOF-74 solid material of previous step (2) is put into vacuum tank, at 150 DEG C, vacuum pressure-
It is activated 24 hours under 0.1MPa.
(4) the Mg-MOF-74 composite wood of solid-loaded ionic-liquid modulation cage diameter in synthesis cage is impregnated under vacuum ionic hot submersion
Material:
By the obtained Mg-MOF-74 solid impregnating of step (3) in ionic liquid [BMIM] [BF4] in, it is put into vacuum baking
In case, impregnated 36 hours at vacuum -0.1MPa, 150 DEG C.
(5) the washing drying for the Mg-MOF-74 material that cage diameter modulation is crossed:
Step (4) obtained product is centrifugally separating to obtain, and three times with the ultrasonic cleaning of a large amount of anhydrous methanols, it is super every time
Centrifuge separation product and methanol washing lotion after sound cleaning.Obtained solid is dried at room temperature for 12 hours, then in 120 DEG C of baking ovens
It is 24 hours dry.
(6) respectively to [BMIM] [BF of poromerics Mg-MOF-74 and cage diameter modulation4]@Mg-MOF-74 makees the N under 77K2
Adsorption isotherm.By being found to its adsorpting data analysis, the 1108m of the specific surface area of composite material from Mg-MOF-742g-1Drop
As low as 340m2g-1, this demonstrates ionic liquid [BMIM] [BF4] really immobilized into Mg-MOF-74 cage, it also demonstrates such
Supported quantity ionic liquid adjusts the universality of cage gauge structure in poromerics MOFs cage, can be applied to other with suitable
In the MOFs of microcellular structure.
Claims (10)
1. a kind of method of the cage diameter modulation of poromerics containing basket structure, it is characterised in that this method specifically: close first
At the poromerics for obtaining having basket structure, then the poromerics obtained to synthesis is activated, then will be after activation
Poromerics is immersed in ionic liquid, and ionic liquid is introduced into the cage of poromerics by Vacuum Heat dipping in vacuum drying oven
It is interior, it will be taken out impregnated poromerics in ionic liquid, then use alcohols supersound washing, then by the poromerics baking after washing
It is dry, obtain the poromerics of cage diameter modulation.
2. a kind of method of the cage diameter modulation of poromerics containing basket structure according to claim 1, it is characterised in that
Poromerics with basket structure is the material of crystallization or amorphous, and hole cage size is less than 2nm.
3. a kind of method of the cage diameter modulation of poromerics containing basket structure according to claim 2, it is characterised in that
Poromerics with basket structure is selected from ZIF-8, ZIF-11, CuBTC, IRMOF-1, UiO-66 or MOF-74.
4. a kind of method of the cage diameter modulation of poromerics containing basket structure according to claim 1, it is characterised in that
The poromerics obtained to synthesis is activated, specifically: it is carried out under vacuum state in vacuum drying oven, activation temperature is
50~350 DEG C, being activated the time is 12~96 hours.
5. a kind of method of the cage diameter modulation of poromerics containing basket structure according to claim 1, it is characterised in that
Poromerics is immersed in ionic liquid, the cation of ionic liquid is quaternary ammonium cation, season phosphine type cation, pyridine type
One of cation or imidazole cation.
6. a kind of method of the cage diameter modulation of poromerics containing basket structure according to claim 1, it is characterised in that
Poromerics is immersed in ionic liquid, the anion of ionic liquid is [PF6]、[BF4]、[Br]、[I]、[Tf2N] or
One of [OTF].
7. a kind of method of the cage diameter modulation of poromerics containing basket structure according to claim 1, it is characterised in that
Poromerics is immersed in ionic liquid, dipping process is carried out in vacuum drying oven, 0~-0.1MPa of dipping process pressure.
8. a kind of method of the cage diameter modulation of poromerics containing basket structure according to claim 1, it is characterised in that
Poromerics is immersed in ionic liquid, during vacuum impregnation temperature be 60~300 DEG C, the vacuum impregnation time be 12~
120 hours.
9. a kind of method of the cage diameter modulation of poromerics containing basket structure according to claim 1, it is characterised in that
The alcohols supersound washing, alcohols used are C1-4One kind of alcohols, the drying temperature are 40~150 DEG C.
10. the poromerics of the fine modulation of cage diameter according to claim 1 is accurately sieved in gas absorption separation and molecule
The application of separation field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711233038.3A CN109847702A (en) | 2017-11-30 | 2017-11-30 | A method of the cage diameter modulation of the poromerics containing basket structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711233038.3A CN109847702A (en) | 2017-11-30 | 2017-11-30 | A method of the cage diameter modulation of the poromerics containing basket structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109847702A true CN109847702A (en) | 2019-06-07 |
Family
ID=66887718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711233038.3A Pending CN109847702A (en) | 2017-11-30 | 2017-11-30 | A method of the cage diameter modulation of the poromerics containing basket structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109847702A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115212735A (en) * | 2022-06-16 | 2022-10-21 | 大连理工大学 | High-efficiency CO 2 Method for producing a screened gas separation membrane |
| CN115957723A (en) * | 2022-11-01 | 2023-04-14 | 浙江理工大学 | Preparation method of IL @ MIL-101 material and application of IL @ MIL-101 material in CO 2 Use in separations |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7943543B1 (en) * | 2006-09-29 | 2011-05-17 | Uop Llc | Ionic liquid-solid-polymer mixed matrix membranes for gas separations |
| US20120264589A1 (en) * | 2009-11-12 | 2012-10-18 | Naiying Du | Polymers of intrinsic microporosity containing tetrazole groups |
| CN103058189A (en) * | 2013-01-28 | 2013-04-24 | 北京化工大学 | Absorption and adsorption coupling method for capturing carbon dioxide |
| CN104722284A (en) * | 2013-12-18 | 2015-06-24 | 中国科学院大连化学物理研究所 | Microporous material loaded ion liquid composite material or film, and preparation thereof |
| CN106582328A (en) * | 2015-10-20 | 2017-04-26 | 中国科学院大连化学物理研究所 | Composite separation film |
| CN106964316A (en) * | 2017-03-17 | 2017-07-21 | 华南理工大学 | A kind of zeolite imidazole ester skeleton functionalized ion liquid composite and its preparation and application |
-
2017
- 2017-11-30 CN CN201711233038.3A patent/CN109847702A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7943543B1 (en) * | 2006-09-29 | 2011-05-17 | Uop Llc | Ionic liquid-solid-polymer mixed matrix membranes for gas separations |
| US20120264589A1 (en) * | 2009-11-12 | 2012-10-18 | Naiying Du | Polymers of intrinsic microporosity containing tetrazole groups |
| CN103058189A (en) * | 2013-01-28 | 2013-04-24 | 北京化工大学 | Absorption and adsorption coupling method for capturing carbon dioxide |
| CN104722284A (en) * | 2013-12-18 | 2015-06-24 | 中国科学院大连化学物理研究所 | Microporous material loaded ion liquid composite material or film, and preparation thereof |
| CN106582328A (en) * | 2015-10-20 | 2017-04-26 | 中国科学院大连化学物理研究所 | Composite separation film |
| CN106964316A (en) * | 2017-03-17 | 2017-07-21 | 华南理工大学 | A kind of zeolite imidazole ester skeleton functionalized ion liquid composite and its preparation and application |
Non-Patent Citations (4)
| Title |
|---|
| BAN, YUJIE ET AL.: ""Confinement of Ionic Liquids in Nanocages: Tailoring the Molecular Sieving Properties of ZIF-8 for Membrane-Based CO2 Capture"", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
| HAO LI ET AL.: ""Simultaneous enhancement of mechanical properties and CO2 selectivity of ZIF-8 mixed matrix membranes: Interfacial toughening effect of ionic liquid"", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| LIU, YI ET AL.: ""Microstructural Engineering and Architectural Design of Metal-Organic Framework Membranes"", 《ADVANCED MATERIALS》 * |
| 刘福瑞等: ""离子液体分离膜及其在CO2分离的应用研究进展"", 《应用化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115212735A (en) * | 2022-06-16 | 2022-10-21 | 大连理工大学 | High-efficiency CO 2 Method for producing a screened gas separation membrane |
| CN115957723A (en) * | 2022-11-01 | 2023-04-14 | 浙江理工大学 | Preparation method of IL @ MIL-101 material and application of IL @ MIL-101 material in CO 2 Use in separations |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108114695A (en) | The zeolitic imidazolate framework material of solid-loaded ionic-liquid and its application in cage | |
| Trapani et al. | On the general water harvesting capability of metal-organic frameworks under well-defined climatic conditions | |
| CN104629080B (en) | A kind of method based on the cellulose hard template synthesis aeroges of ZIF 8 | |
| Liu et al. | Metal–organic framework ZIF-8 nanocomposite membrane for efficient recovery of furfural via pervaporation and vapor permeation | |
| CN108114698B (en) | Composite material with porous material loaded with ionic liquid and preparation method and application thereof | |
| Mao et al. | Hierarchical mesoporous metal–organic frameworks for enhanced CO2 capture | |
| CN102408447B (en) | Preparation method of hydrophobic MIL-101 chromium organometallic skeleton material | |
| Sun et al. | Novel MOF-5 derived porous carbons as excellent adsorption materials for n-hexane | |
| CN105418938B (en) | A kind of materials of multi-stage porous HKUST 1 and preparation method and application | |
| CN105854801A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| CN112961370B (en) | Preparation method of fluorescent bimetallic organic JLUE-MOG-7 aerogel material | |
| Wang et al. | Efficient air water harvesting of TpPa-1 COFs@ LiCl composite driven by solar energy | |
| CN113332959B (en) | Novel aluminum-based water-absorbing MOFs material with high stability, preparation method thereof and air water collection application | |
| Lu et al. | Isomer of NU-1000 with a blocking c-pore exhibits high water–vapor uptake capacity and greatly enhanced cycle stability | |
| Cheung et al. | Highly selective uptake of carbon dioxide on the zeolite| Na 10.2 KCs 0.8|-LTA–a possible sorbent for biogas upgrading | |
| Gao et al. | Adsorption breakthrough behavior of 1-butanol from an ABE model solution with high-silica zeolite: comparison with zeolitic imidazolate frameworks (ZIF-8) | |
| CN109847702A (en) | A method of the cage diameter modulation of the poromerics containing basket structure | |
| CN106674118A (en) | Preparation of ZIF-8 adsorption material and application of ZIF-8 adsorption material to de-coloring of malachite green water solution | |
| CN104722284A (en) | Microporous material loaded ion liquid composite material or film, and preparation thereof | |
| CN112076725A (en) | Modified mesoporous molecular sieve, and preparation method and application thereof | |
| Gao et al. | Water confined in MIL-101 (Cr): Unique sorption–desorption behaviors revealed by diffuse reflectance infrared spectroscopy and molecular dynamics simulation | |
| CN105153204B (en) | Micro-diplopore metal-organic framework materials and preparation method in a kind of CuBTC types | |
| CN101816925A (en) | Organic-inorganic hybrid material for CO2 adsorption and preparation method thereof | |
| Zhao et al. | Flexible nanofibrous membranes of dual metallic metal–organic framework with enhanced Lewis basic sites and high loading mass for efficient CO2 capture | |
| CN109851839A (en) | Aerogel material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190607 |
|
| RJ01 | Rejection of invention patent application after publication |