CN109293937A - A method of tradition ZIF-90 material is prepared using bimetal salt room temperature - Google Patents
A method of tradition ZIF-90 material is prepared using bimetal salt room temperature Download PDFInfo
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Abstract
The invention discloses a kind of methods using bimetal salt room temperature preparation tradition ZIF-90 material, can successfully reduce generated time using this method.The synthetic method includes the following steps: one, Zinc diacetate dihydrate and zinc oxide difference is soluble in water；Two, the suspension of the aqueous solution of Zinc diacetate dihydrate and zinc oxide is mixed and is dissolved in N,N-dimethylformamide solvent；Three, imidazoles dicarbaldehyde is dissolved in N,N-dimethylformamide；Four, imidazoles dicarbaldehyde solution is added into the mixed solution of Zinc diacetate dihydrate and zinc oxide, is sufficiently stirred；Five, products therefrom is filtered, it is dry, obtain traditional ZIF-90 material.The present invention only passes through addition (Zn-Zn) bimetal salt, not only easy to operate, mild condition, and substantially reduces generated time, is suitble to the demand of industrialization and commercialization.
Description
Technical field
The invention belongs to the quick preparation fields of metal organic framework, and in particular to a kind of to be prepared using bimetal salt room temperature
The method of traditional ZIF-90 material.
Background technique
Metal-organic framework materials (Metal-Organic Framework, MOFs), also referred to as coordination polymer
(Coordination Polymers, CPs), be biometallic joint assembled with organic ligand by coordinate bond to be formed one kind it is novel
Crystalline, porous material [Yaghi O M, O ' Keeffe M, Ockwig N W, et al.Reticular synthesis and
the design of new materials[J].Nature 2003,423(6941):705-714].Since discovery metal has
Since machine frame frame material (MOFs), since the feature in its structure causes the extensive concern of people, quantity is also with surprising finger
Number form formula increases, the metal-organic framework materials direction one of most active as material and chemical field, and in new material
Design, preparation and application etc. are rapidly developed.The preparation method of bimetallic coordination polymer also more and more attention has been paid to.
The characteristics of MOFs is that there is very high interior surface area (to be generally greater than 1000m2·g-1) and lower crystal density, therefore
They are stored in gas, molecule separation, catalysis, and the application fields such as sensing and drug conveying possess huge potential and important grind
Study carefully meaning [Long J R, Yaghi O M.The pervasive chemistry of metal-organic frameworks
[J].Chemical Society Reviews,2009,38(5):1213-1214.].And micropore MOFs is in gas absorption and storage
Deposit, molecule separation and catalysis aspect have very big application prospect [Seo, J.S., Whang, D., Lee, H., Jun, S.I., Oh,
J.,Jeon,Y.J.,and Kim,K.Nature 2000,404,982].It is synthesizing high-sequential, different length that there is difference
The mesoporous or large pore material of structural integrity is still an important target, especially in terms of MOFs material [P.Yang,
D.Zhao,D.I.Margolese,B.F.Chmelka,G.D.Stucky,Nature 396,152-155(1998)]
[S.Inagaki,S.Guan,T.Ohsuna,O.Terasaki,Nature 416,304-307(2002)].But it is nowadays many
MOFs material is limited by micropore, hinders the extensive use and development of MOFs material.[J.-R.Li,R.J.Kuppler,H.-
C.Zhou,Chem.Soc.Rev.38,1477-1504(2009)][S.Furukawa,J.Reboul,S.Diring,
K.Sumida,S.Kitagawa,Chem.Soc.Rev.43,5700-5734(2014)]。
According to the literature, nowadays more mature MOFs preparation method there are several types of.One, solvent evaporation method passes through gold
Belong to salt, organic ligand and solvent mixing, solvent volatilizees under optimum conditions, causes generated MOFs crystal gradually from solvent
It is precipitated.[Li H,Eddaoudi M,et al.,Design and synthesis of an exceptionally stable
and highly porous metal-organic framework[J],Nature,1999,402(6759):276-279.]
This readily available MOF monocrystalline of method, but preparation time is relatively long.Two, slow diffusion method utilizes two kinds of immiscible, boilings
Different solvents is put to the dissolubility difference of MOF, the solvent of low boiling point low solubility enters higher boiling Gao Rong under certain condition
In the solvent of Xie Du, the solubility of the MOF formed in the solvent of higher boiling high-dissolvability is reduced, MOF monocrystalline is precipitated
[Furukawa H.Miller M A,et al.Independent verification of the saturation on
hydrogen uptake in MOF-177and establishment of a benchmark for hydrogen
adsorption in metal-organic frameworks[J].Journal of Materials Chemistry,
2007,17(30):3197-3204].Three, extend ligand method, by changing the length of ligand, introduce mesoporous [Wang X for material
S,Ma S Q,Sun D F,Parkin S,and Zhou H C.A Mesoporous Metal-Organic Framework
with Permanent Porosity[J].J.AM.CHEM.SOC.2006,128(51):16474-16475.].Removing visitor
After body molecule, metal framework is easy to collapse, and bad stability needs to post-process material to improve its stability.Four,
Template.Template can induce MOFs material to be formed mesoporous as structure directing agent, after forming MOFs material, remove template
Agent can form MOFs material [Do X D, Hoang V T, Kaliaguine S.MIL-53 (Al) mesostructured
metal-organic frameworks[J].Microporous and Mesoporous Materials.2011；141(1-
3):135.].Template is the mesoporous method of most common introducing.
ZIF-90 is raw by solvent thermal reaction by zinc (II) salt and imidazoles -2- formaldehyde (ICA) by Yaghi and its colleague
At.[Morris,W.,Doonan,C.J.,Furukawa,H.,Banerjee,R.,and Yaghi,
O.M.J.Am.Chem.Soc.2008,130,12626].Due to the permanent porosity that ZIF-90 material has, brilliant thermostabilization
Property and chemical stability and uniform pore size, have nowadays caused the extensive concern of numerous researchers.
The present invention uses bimetal salt, a kind of metal-organic framework materials of room temperature rapid synthesis.
Summary of the invention
The purpose of the present invention is to provide a kind of using Zn-Zn bimetal salt room temperature rapid synthesis tradition ZIF-90 material
Method.
Raw material of the present invention is Zinc diacetate dihydrate, zinc oxide, imidazoles dicarbaldehyde, n,N-Dimethylformamide, uses two water
It closes zinc acetate and zinc oxide forms Zn-Zn bimetal salt, imidazoles dicarbaldehyde is ligand, rapid synthesis can go out tradition at normal temperature
ZIF-90 material.
The purpose of the invention is achieved by the following technical solution.
A method of tradition ZIF-90 material being prepared using bimetal salt room temperature, is included the following steps:
(1) Zinc diacetate dihydrate and zinc oxide difference is soluble in water, stirring respectively obtains Zinc diacetate dihydrate aqueous solution
With zinc oxide suspension；
(2) Zinc diacetate dihydrate aqueous solution and zinc oxide suspension are mixed and are dissolved in n,N-Dimethylformamide, stirred,
Obtain Zn-Zn bimetal salt solution；
(3) imidazoles dicarbaldehyde is dissolved in n,N-Dimethylformamide, stirs, obtains imidazoles dicarbaldehyde solution；
(4) the imidazoles dicarbaldehyde solution is added into the Zn-Zn bimetal salt solution, is sufficiently stirred；
(5) step (4) products therefrom is filtered, washing, places into drying in vacuum oven, obtains ZIF-90 material.
Preferably, the mixing time in step (1) is 10-20 minutes.
Preferably, the mixing time in step (2) is 16-20 hours.
Preferably, the mixing time in step (3) is 5-10 minutes.
Preferably, the mixing time in step (4) is 1-5 minutes, and further preferably 1 minute.
Preferably, the temperature of step (5) described drying is 100-120 DEG C, and drying time is 20-24 hours.
Preferably, the Zinc diacetate dihydrate, zinc oxide, imidazoles dicarbaldehyde molar ratio be (4.9-5.1): (5.0-
5.2):(5.9-6.1)。
Preferably, step (1), step (2), step (3), step (4) are to carry out at normal temperature.
Compared with the existing technology, the invention has the advantages that and effect:
(1) high-specific surface area is possessed using the material that method of the invention synthesizes, material itself has micropore and mesoporous knot
Structure, thermal stability are good.
(2) present invention is by being added bimetal salt, can rapid synthesis tradition ZIF-90 material at normal temperature, operation letter
Single, mild condition avoids heating, ultrasound, energy saving.
(3) generated time can be substantially reduced using method synthesis ZIF-90 material of the invention, space time yield is high, can
Realize industrialized production.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of the ZIF-90 material of computer simulation and the ZIF-90 material of the preparation of embodiment 1.
Fig. 2 is the stereoscan photograph of ZIF-90 material prepared by embodiment 1.
Fig. 3 is the hot weight curve of ZIF-90 material prepared by embodiment 1.
Fig. 4 is the N of ZIF-90 material prepared by embodiment 12Adsorption-desorption isothermal figure.
Fig. 5 is the graph of pore diameter distribution of ZIF-90 material prepared by embodiment 1.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the range of embodiment statement.
Embodiment 1
0.4069g zinc oxide and 1.0976g Zinc diacetate dihydrate are dissolved in respectively in 5mL deionized water, stirred 10 minutes,
Zinc oxide suspension and zinc acetate solution is made, then zinc oxide suspension and zinc acetate solution are mixed, 5mLN, N- diformazan is added
It in base formamide, stirs 16 hours, (Zn-Zn) bimetal salt solution is made；0.576g imidazoles dicarbaldehyde is dissolved in 9mLN, N- bis-
It in methylformamide, stirs 5 minutes, imidazoles dicarbaldehyde solution is made；Imidazoles diformazan is added into (Zn-Zn) bimetal salt solution
Aldehyde solution stirs 1 minute；Products therefrom is filtered again, is added soaked in absolute ethyl alcohol 12 hours, is repeated 3 times；Institute will be washed
The substance obtained dries 20 hours in 120 DEG C of baking oven, obtains ZIF-90 material.The material space time yield is 9.3X103kg·m-3·d-1。
Embodiment 2
0.4151g zinc oxide and 1.1195g Zinc diacetate dihydrate are dissolved in respectively in 5mL deionized water, stirred 15 minutes,
Zinc oxide suspension and zinc acetate solution is made, then zinc oxide suspension and zinc acetate solution are mixed, 5mLN, N- diformazan is added
It in base formamide, stirs 18 hours, (Zn-Zn) bimetal salt solution is made；0.567g imidazoles dicarbaldehyde is dissolved in 9mLN, N- bis-
It in methylformamide, stirs 7.5 minutes, imidazoles dicarbaldehyde solution is made；Imidazoles two is added into (Zn-Zn) bimetal salt solution
Formalin stirs 1 minute；Products therefrom is filtered again, is added soaked in absolute ethyl alcohol 12 hours, is repeated 3 times；It will washing
Resulting substance dries 22 hours in 120 DEG C of baking oven, obtains ZIF-90 material.The material space time yield is 8.9X103kg·m-3·d-1。
Embodiment 3
0.4232g zinc oxide and 1.1195g Zinc diacetate dihydrate are dissolved in respectively in 5mL deionized water, stirred 20 minutes,
Zinc oxide suspension and zinc acetate solution is made, then zinc oxide suspension and zinc acetate solution are mixed, 5mLN, N- diformazan is added
It in base formamide, stirs 20 hours, (Zn-Zn) bimetal salt solution is made；0.586g imidazoles dicarbaldehyde is dissolved in 9mLN, N- bis-
It in methylformamide, stirs 10 minutes, imidazoles dicarbaldehyde solution is made；Imidazoles two is added into (Zn-Zn) bimetal salt solution
Formalin stirs 1 minute；Products therefrom is filtered again, is added soaked in absolute ethyl alcohol 12 hours, is repeated 3 times；It will washing
Resulting substance dries 24 hours in 120 DEG C of baking oven, obtains ZIF-90 material.The material space time yield is 8.7X103kg·m-3·d-1。
It is analyzed using traditional ZIF-90 material prepared by embodiment 1 as representative, traditional ZIF- of other embodiments preparation
The analysis result of 90 materials does not provide one by one substantially with embodiment 1.
(1) crystal structure properties of bimetal salt room temperature rapid synthesis ZIF-90 material are utilized
Using the D8-ADVANCE model X-ray diffractometer of German Bruker company production to the crystalline substance of the embodiment of the present invention 1
Body structure is characterized.
Fig. 1 spreads out for the wide-angle x-ray of ZIF-90 material prepared by the ZIF-90 material and the embodiment of the present invention 1 of computer simulation
Penetrate figure.The ZIF-90 of computer simulation is zinc ion and the perfect cystal that imidazoles dicarbaldehyde is formed, and can fully demonstrate its crystal form knot
Structure can be compareed with experimental result.From figure 1 it appears that compared with the ZIF-90 material of simulation, sample that embodiment 1 is prepared
There is the characteristic diffraction peak of stronger ZIF-90 metal organic framework in product A, illustrates the ZIF-90 in product there are high-crystallinity
Component.
(2) schemed using the SEM of bimetal salt room temperature rapid synthesis ZIF-90 material.
Product is characterized using JSM-6330F type scanning electron microscope (electronics corporation JEOL, Japan), as a result such as Fig. 2 institute
Show.It can be seen that the sample of preparation is in polyhedron, material morphology is almost the same, is evenly distributed, and material surface has micropore abundant
With it is mesoporous.
(3) thermogravimetric analysis of bimetal salt room temperature rapid synthesis ZIF-90 material is utilized
Fig. 3 is the thermogravimetric analysis song for being heated to 898.94K from 35.44K using 209 thermogravimetric analyzer of TG (Netzsch)
Line.Between 35 DEG C to 100 DEG C, Free water abjection, 1 weightlessness 13% of embodiment.When temperature reaches 100 DEG C, deviate from conjunction with water,
1 weightlessness 5% of embodiment.At 300 DEG C, the thermogravimetric curve of embodiment 1 sharply declines, and material skeleton starts to collapse at this time, and temperature reaches
When to 900 DEG C, curve tends to be horizontal, and material collapses completely illustrates material thermodynamic stability with higher.
(4) pore properties of bimetal salt room temperature rapid synthesis ZIF-90 material are utilized
Fig. 4 is the N of the ZIF-90 material of preparation of the embodiment of the present invention2Adsorption-desorption isothermal figure is pressed in P/P0 < 0.01
I type adsorption isotherm is shown as under power, adsorbance steeply rises, and shows that sample has microcellular structure.In relative pressure 0.3-0.6
There is IV type adsorption hysteresis ring in left and right, this is mesoporous material in N2Characteristic feature in adsorption desorption curve shows that material contains Jie
Hole.
Fig. 5 is the complete opening graph of pore diameter distribution of the ZIF-90 material of preparation of the embodiment of the present invention, prepared by display embodiment 1
The mesopore orbit that ZIF-90 material possesses the micropore canals of a large amount of 1nm or so, while possessing a large amount of 4nm or so, shows through this
Method can be with rapid synthesis ZIF-90 material.
Above-described embodiment is the comparatively ideal embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination, letter
Change, should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method using bimetal salt room temperature preparation tradition ZIF-90 material, which comprises the steps of:
(1) Zinc diacetate dihydrate and zinc oxide difference is soluble in water, stirring respectively obtains Zinc diacetate dihydrate aqueous solution and oxygen
Change zinc suspension；
(2) Zinc diacetate dihydrate aqueous solution and zinc oxide suspension are mixed and is dissolved in n,N-Dimethylformamide, stirred, obtain
Zn-Zn bimetal salt solution；
(3) imidazoles dicarbaldehyde is dissolved in n,N-Dimethylformamide, stirs, obtains imidazoles dicarbaldehyde solution；
(4) the imidazoles dicarbaldehyde solution is added into the Zn-Zn bimetal salt solution, is sufficiently stirred；
(5) step (4) products therefrom is filtered, washing, places into drying in vacuum oven, obtains ZIF-90 material.
2. according to the method described in claim 1, it is characterized in that: the time of step (1) described stirring is 10-20 minutes.
3. according to the method described in claim 1, it is characterized in that: the time of step (2) described stirring is 16-20 hours.
4. according to the method described in claim 1, it is characterized in that: the time of step (3) described stirring is 5-10 minutes.
5. according to the method described in claim 1, it is characterized in that: the time of step (4) described stirring is 1-5 minutes.
6. according to the method described in claim 5, it is characterized by: the time of the stirring is 1 minute.
7. according to the method described in claim 1, it is characterized in that: the temperature of step (5) described drying is 100-120 DEG C.
8. according to the method described in claim 1, it is characterized in that: the time of step (5) described drying is 20-24 hours.
9. according to the method described in claim 1, it is characterized in that: the Zinc diacetate dihydrate, zinc oxide, imidazoles dicarbaldehyde are rubbed
You are than being (4.9-5.1): (5.0-5.2): (5.9-6.1).
10. according to the method described in claim 1, it is characterized in that: step (1), step (2), step (3), step (4) be
It is carried out under room temperature.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015071A (en) * | 2021-12-07 | 2022-02-08 | 信阳师范学院 | MOFs material controllably synthesized by microemulsion method and preparation method thereof |
| CN114231518A (en) * | 2021-12-17 | 2022-03-25 | 浙江工业大学 | Immobilized carbonic anhydrase and application thereof in preparation of carbon dioxide absorbent |
| CN115947950A (en) * | 2022-12-07 | 2023-04-11 | 电子科技大学长三角研究院(湖州) | Micron-sized single crystal ZIFs and preparation method thereof |
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2018
- 2018-09-28 CN CN201811138245.5A patent/CN109293937A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015071A (en) * | 2021-12-07 | 2022-02-08 | 信阳师范学院 | MOFs material controllably synthesized by microemulsion method and preparation method thereof |
| CN114231518A (en) * | 2021-12-17 | 2022-03-25 | 浙江工业大学 | Immobilized carbonic anhydrase and application thereof in preparation of carbon dioxide absorbent |
| CN115947950A (en) * | 2022-12-07 | 2023-04-11 | 电子科技大学长三角研究院(湖州) | Micron-sized single crystal ZIFs and preparation method thereof |
| CN115947950B (en) * | 2022-12-07 | 2024-02-27 | 电子科技大学长三角研究院(湖州) | Micron-sized monocrystalline ZIFs and preparation method thereof |
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