CN108707237A - A kind of universal method preparing hollow metal organic frame - Google Patents
A kind of universal method preparing hollow metal organic frame Download PDFInfo
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- CN108707237A CN108707237A CN201810620708.5A CN201810620708A CN108707237A CN 108707237 A CN108707237 A CN 108707237A CN 201810620708 A CN201810620708 A CN 201810620708A CN 108707237 A CN108707237 A CN 108707237A
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Abstract
The invention discloses a kind of universal methods preparing hollow metal organic frame, include the following steps：(1) MOF materials are dissolved in ethyl alcohol, form suspension C；(2) 2-methylimidazole is dissolved in ethyl alcohol, forms solution D；(3) solution D is placed in water-bath after being heated to 45~55 DEG C, pours into suspension C, stir 23~25h, product is centrifuged, then it is washed successively with ethyl alcohol and deionized water, is finally placed in 80~100 DEG C of baking ovens after drying 10~20h, obtains hollow ZIF-8 powders.This hollow-core construction ZIF-8 can obtain hollow mesoporous carbon after high temperature cabonization, and have excellent electrochemical energy storage performance.The present invention is easy to operate, at low cost, and process is easily controllable with observation, can be produced in enormous quantities, and the hollow MOF materials of preparation will have broad application prospects, and can be used for detaching, sense, being catalyzed, the fields such as medicament slow release and the energy.
Description
Technical field
The invention belongs to the synthesis technical fields of functional material hollow metal organic frame, and in particular to a kind of difference MOFs
Material prepares the universal method of hollow metal organic frame as presoma.
Background technology
In recent years, the metal organic framework with periodic network structure that metal ion is self-assembly of with organic ligand
(MOFs, Metal-Organic Framework) causes more and more concerns.MOFs materials have high porosity, big ratio
The advantages that surface area, regular pore canal, skeleton size be adjustable and the diversity and modifiability of organic ligand, in separation, storage
Hydrogen, catalysis, sensing and energy conversion have obtained extremely wide application with storage art, show to be better than Conventional porous crystal knot
The performance of structure material.Particularly, MOF materials can be used as mould material, in conditions such as different subsequent anneal temperatures and atmosphere
Under, corresponding porous metal oxide/hydroxide, porous carbon materials and metal/metal oxide/metal hydrogen-oxygen can be obtained
The composite material of compound and carbon.On the one hand, the structure of the MOF materials of existing synthesis is relatively simple, is essentially all solid
Kernel structure；On the other hand, the solid construction of this MOF particles can greatly limit the promotion of its performance, and hollow-core construction
MOF particles be proved to show the advantage of bigger at many aspects.Therefore, the MOF with hollow-core construction that prepared by the present invention
The application boundary of MOF materials will be further expanded, and in fields such as separation, catalysis, sensing and the energy there is the reality of bigger to answer
With value.
Invention content
It is an object of the invention to：A kind of universal method preparing hollow metal organic backbone, material preparation process are provided
Simply, at low cost, can large-scale production, potential application field is wide.
To achieve the goals above, the present invention provides the following technical solutions：
A kind of universal method preparing hollow metal organic frame, includes the following steps：
(1) MOF materials are scattered in ethyl alcohol, form suspension C；
(2) 2-methylimidazole is dissolved in ethyl alcohol, forms solution D；
(3) solution D is placed in water-bath after being heated to 45~55 DEG C, pours into suspension C, stir 23~25h, by product from
The heart detaches, and is then washed successively with ethyl alcohol and deionized water, is finally placed in 80~100 DEG C of baking ovens after drying 10~20h, obtains
Hollow ZIF-8 powders.
Preferably, a concentration of 20g L of the suspension C-1, a concentration of 1.5mmol L of solution D-1；In step (3)
Solution D and the volume ratio of suspension C are 3:1.
Preferably, MOF materials are ZIF-7 powders, ZIF-71 powders, one kind in MOF-5 powders in step (1).
Preferably, ZIF-7 raw powder's production technologies are as follows：
Benzimidazole being dissolved in after ethyl alcohol, ammonium hydroxide formation solution A 1 is added, zinc nitrate hexahydrate is dissolved in ethyl alcohol and forms solution B 1,
Solution A 1 is poured into solution B 1, and 8~12min is stirred at room temperature, and product is centrifuged, and then ethyl alcohol and deionization is used to wash successively
It washs, is placed in 80~100 DEG C of baking ovens after drying 10~20h, obtains ZIF-7 powders.
Preferably, ZIF-71 raw powder's production technologies are as follows：
Two water zinc acetates are dissolved in methanol formation 2,4,5- dichloro-imidazole of solution A and are dissolved in methanol formation solution B 2, solution A 2
It pours into solution B 2,23~25h is stirred at room temperature, product is centrifuged, then washed successively with methanol and deionized water, is placed in
After drying 10~20h in 80~100 DEG C of baking ovens, ZIF-71 powders are obtained.
Preferably, MOF-5 raw powder's production technologies are as follows：
Two water zinc acetates are dissolved in DMF and form solution A 3, terephthalic acid (TPA) is dissolved in methanol and forms solution B 3, and solution A 3 is poured into
Solution B 3, is transferred in autoclave, in 90~100 DEG C, keeps the temperature 9~11h, product is centrifuged, is then washed successively with ethyl alcohol
It washs, obtains MOF-5 powders.
Compared with prior art, the present invention its advantageous effects is shown：
1, the insolid particle of the metal organic frame of the invention prepared, has unique hollow-core construction；
2, preparation method of the present invention is easy to operate, and the time is short, and raw material and device category demand are few, at low cost
It is honest and clean；
3, the method applied in the present invention can realize that the organic large-scale production and preparation of hollow metal, yield are high.Possible
Potential application in, the hollow porous carbon material obtained through high temperature cabonization can direct plunge into production using existing equipment and apply
In electrochemical energy storage, excellent chemical property is shown, there is good industrial applications foreground, can be used for detaching, sense,
The fields such as catalysis, medicament slow release and the energy.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture of ZIF-7 prepared by embodiment 1.
Fig. 2 is scanning electron microscopic picture of the embodiment 1 by the ZIF-7 ZIF-8 prepared.
Fig. 3 is transmission electron microscope picture of the embodiment 1 by the ZIF-7 ZIF-8 prepared.
Fig. 4 is the scanning electron microscopic picture of ZIF-71 prepared by embodiment 1.
Fig. 5 is scanning electron microscopic picture figure of the embodiment 1 by the ZIF-71 ZIF-8 prepared.
Fig. 6 is transmission electron microscope picture of the embodiment 1 by the ZIF-71 ZIF-8 prepared.
Fig. 7 is the scanning electron microscopic picture of MOF-5 prepared by embodiment 1.
Fig. 8 is scanning electron microscopic picture of the embodiment 1 by the MOF-5 ZIF-8 prepared.
Fig. 9 is transmission electron microscope picture of the embodiment 1 by the MOF-5 ZIF-8 prepared.
Specific implementation mode
In order to facilitate the understanding of those skilled in the art, the present invention will be described with reference to the accompanying drawings and examples.
Embodiment 1
A kind of universal method preparing hollow metal organic frame, includes the following steps：
(1) ZIF-7 raw powder's production technologies are as follows：
0.72g benzimidazoles are dissolved in after 38ml ethyl alcohol, 3ml ammonium hydroxide formation solution A 1 is added, 0.9g zinc nitrate hexahydrates are dissolved in
12.5ml ethyl alcohol forms solution B 1, and solution A 1 is poured into solution B 1,10min is stirred at room temperature, product is centrifuged, then successively
It is washed with ethyl alcohol and deionized water, is placed in 80 DEG C of baking ovens after drying 10h, obtains ZIF-7 powders；
(2) 0.2g ZIF-7 powders are dissolved in 10ml ethyl alcohol, form suspension C；
(3) 4g 2-methylimidazoles are dissolved in 30ml ethyl alcohol, form solution D；
(4) solution D being placed in water-bath after being heated to 50 DEG C, pours into suspension C, for 24 hours, product is centrifuged for stirring,
Then it is washed successively with ethyl alcohol and deionized water, is finally placed in 80 DEG C of baking ovens after drying 10h, obtains hollow ZIF-8 powders.
Embodiment 2
A kind of universal method preparing hollow metal organic frame, includes the following steps：
(1) ZIF-71 raw powder's production technologies are as follows：
Bis- water zinc acetates of 0.4458g are dissolved in 90mL methanol and form solution A 2,1.3152g 4,5- dichloro-imidazoles are dissolved in
90ml methanol forms solution B 2, and solution A 2 is poured into solution B 2, is stirred at room temperature for 24 hours, product is centrifuged, then use first successively
Alcohol and deionized water washing, are placed in 80 DEG C of baking ovens after drying 10h, obtain ZIF-71 powders；
(2) 0.2g ZIF-71 powders are dissolved in 10ml ethyl alcohol, form suspension C；
(3) 4g 2-methylimidazoles are dissolved in 30ml ethyl alcohol, form solution D；
(4) solution D being placed in water-bath after being heated to 50 DEG C, pours into suspension C, for 24 hours, product is centrifuged for stirring,
Then it is washed successively with ethyl alcohol and deionized water, is finally placed in 80 DEG C of baking ovens after drying 10h, obtains hollow ZIF-8 powders.
Embodiment 3
A kind of universal method preparing hollow metal organic frame, includes the following steps：
(1) MOF-5 raw powder's production technologies are as follows：
Bis- water zinc acetates of 1.528g are dissolved in 35mL DMF and form solution A 3,0.15g terephthalic acid (TPA)s are dissolved in 15ml methanol
Solution B 3 is formed, solution A 3 is poured into solution B 3, is transferred in autoclave, in 95 DEG C, keeps the temperature 10h, product is centrifuged, then
It is washed successively with ethyl alcohol, obtains MOF-5 powders；
(2) 0.2g MOF-5 powders are dissolved in 10ml ethyl alcohol, form suspension C；
(3) 4g 2-methylimidazoles are dissolved in 30ml ethyl alcohol, form solution D；
(4) solution D being placed in water-bath after being heated to 50 DEG C, pours into suspension C, for 24 hours, product is centrifuged for stirring,
Then it is washed successively with ethyl alcohol and deionized water, is finally placed in 80 DEG C of baking ovens after drying 10h, obtains hollow ZIF-8 powders.
It can be seen that from embodiment 1,2,3：The present invention may be implemented to pass through the MOF materials such as ZIF-7, ZIF-71, MOF-5
Same process is converted into hollow metal-organic framework material.
Above example is the more typical embodiment of the present invention, not any limitation of the invention, such as 2- first
Base imidazoles dosage, soaking time, the speed of heating, solvent type and and centrifugation rotating speed and time of drying can be into one
Successive step.Therefore, according to general thought of the present invention, affiliated those skilled in the art adjust described technological parameter
It is whole and modification, as long as it does not deviate from the concept of invention or beyond the scope defined by this claim, this hair should all be belonged to
Bright protection domain.
It can be seen that from Fig. 1-9：
Fig. 1 is the scanning electron microscopic picture of ZIF-7, it can be seen that about 5 microns of ZIF-7 particle sizes are substantially in spherical, surface
It is essentially smooth.Fig. 2 is by the scanning electron microscopic picture of the ZIF-7 ZIF-8 prepared, it can be seen that thus of prepared ZIF-8
Grain keeps spherical, and size is still about 5 microns, but its surface becomes coarse, is accumulated by small ZIF-8 nano particles, from
It can be found that being hollow-core construction by the ZIF-8 prepared by ZIF-7 in the transmission electron microscope picture of Fig. 3；Fig. 4 is the ZIF-71 prepared
Scanning electron microscopic picture, it can be seen that ZIF-71 shows the dodecahedron of rule, and size is about 2 microns.Fig. 5 is by ZIF-71 systems
The scanning electron microscopic picture of standby ZIF-8, it can be seen that prepared ZIF-8 still keeps the dodecahedron of the rule of initial ZIF-71
And size is still about 2 microns, but its surface is more coarse, and structure is also to be accumulated by small ZIF-8 nano particles.From figure
6 transmission electron microscope picture, it can be seen that by the ZIF-8 prepared by ZIF-71 be hollow-core construction；Fig. 7 is sweeping for the MOF-5 prepared
Retouch electron microscopic picture, it can be seen that MOF-5 shows regular square or cuboid, and size is about 400nm, and surface is smooth.Fig. 8 is
By the scanning electron microscopic picture of the MOF-5 ZIF-8 prepared, it can be seen that prepared ZIF-8 still maintains square or cuboid
Shape, but size slightly increases to 1 micron and rough surface, from the transmission electron microscope picture of Fig. 9, it can be seen that made by MOF-5
Standby ZIF-8 is hollow-core construction.
Claims (6)
1. a kind of universal method preparing hollow metal organic frame, it is characterised in that：Include the following steps：
(1) MOF materials are scattered in ethyl alcohol, form suspension C；
(2) 2-methylimidazole is dissolved in ethyl alcohol, forms solution D；
(3) solution D is placed in water-bath after being heated to 45~55 DEG C, pours into suspension C, stir 23~25h, by product centrifugation point
From, then washed successively with ethyl alcohol and deionized water, be finally placed in 80~100 DEG C of baking ovens dry 10~20h after, obtain hollow
ZIF-8 powders.
2. a kind of universal method preparing hollow metal organic frame according to claim 1, it is characterised in that：Described
A concentration of 20g L of suspension C-1, a concentration of 1.5mmol L of solution D-1；The volume of solution D and suspension C in step (3)
Than being 3:1.
3. a kind of universal method preparing hollow metal organic frame according to claim 1, it is characterised in that：Step
(1) MOF materials are one kind in ZIF-7 powders, ZIF-71 powders, MOF-5 powders in.
4. a kind of universal method preparing hollow metal organic frame according to claim 3, it is characterised in that：ZIF-7
Raw powder's production technology is as follows：
Benzimidazole is dissolved in after ethyl alcohol, ammonium hydroxide formation solution A 1 is added, zinc nitrate hexahydrate is dissolved in ethyl alcohol and forms solution B 1, solution
A1 is poured into solution B 1, and 8~12min is stirred at room temperature, and product is centrifuged, and is then washed successively with ethyl alcohol and deionized water,
It is placed in 80~100 DEG C of baking ovens after drying 10~20h, obtains ZIF-7 powders.
5. a kind of universal method preparing hollow metal organic frame according to claim 3, it is characterised in that：ZIF-71
Raw powder's production technology is as follows：
Two water zinc acetates are dissolved in methanol formation 2,4,5- dichloro-imidazole of solution A and are dissolved in methanol formation solution B 2, solution A 2 is poured into
In solution B 2,23~25h is stirred at room temperature, product is centrifuged, is then washed successively with methanol and deionized water, it is placed in 80~
After drying 10~20h in 100 DEG C of baking ovens, ZIF-71 powders are obtained.
6. a kind of universal method preparing hollow metal organic frame according to claim 3, it is characterised in that：MOF-5
Raw powder's production technology is as follows：
Two water zinc acetates are dissolved in DMF and form solution A 3, terephthalic acid (TPA) is dissolved in methanol and forms solution B 3, and solution A 3 pours into solution
B3 is transferred in autoclave, in 90~100 DEG C, keeps the temperature 9~11h, product is centrifuged, is then washed successively with ethyl alcohol, is obtained
To MOF-5 powders.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110423358A (en) * | 2019-08-14 | 2019-11-08 | 合肥工业大学 | The preparation and application of the porous carbon nano-tube material of the preparation method and one-dimensional N doping of one-dimensional tubulose MOF material |
| CN113651970A (en) * | 2021-08-24 | 2021-11-16 | 合肥工业大学 | Universal method for preparing multi-shell hollow metal organic framework |
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| WO2010012660A1 (en) * | 2008-07-31 | 2010-02-04 | Shell Internationale Research Maatschappij B.V. | Process for producing alcohol |
| CN103694260A (en) * | 2013-12-02 | 2014-04-02 | 南京工业大学 | High-stability metal organic skeleton hybrid material, preparation method and application thereof |
| US9375678B2 (en) * | 2012-05-25 | 2016-06-28 | Georgia Tech Research Corporation | Metal-organic framework supported on porous polymer |
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2018
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| WO2010012660A1 (en) * | 2008-07-31 | 2010-02-04 | Shell Internationale Research Maatschappij B.V. | Process for producing alcohol |
| US9375678B2 (en) * | 2012-05-25 | 2016-06-28 | Georgia Tech Research Corporation | Metal-organic framework supported on porous polymer |
| CN103694260A (en) * | 2013-12-02 | 2014-04-02 | 南京工业大学 | High-stability metal organic skeleton hybrid material, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
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| CHAO-HSIANG KANG ET AL: "Synthesis of ZIF-7/chitosan mixed-matrix membranes with improved separation performance of water/ethanol mixtures", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| RYAN P. LIVELY ET AL: "Ethanol and water adsorption in methanol-derived ZIF-71", 《CHEMICAL COMMUNICATIONS》 * |
| XIAONA XU ET AL: "Synthesis of ZIF-8 Hollow Spheres via MOF-to-MOF Conversion", 《CHEMISTRY SELECT》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110423358A (en) * | 2019-08-14 | 2019-11-08 | 合肥工业大学 | The preparation and application of the porous carbon nano-tube material of the preparation method and one-dimensional N doping of one-dimensional tubulose MOF material |
| CN113651970A (en) * | 2021-08-24 | 2021-11-16 | 合肥工业大学 | Universal method for preparing multi-shell hollow metal organic framework |
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