CN109824908A - A kind of bimetallic metal organic frame thin layer and preparation method thereof - Google Patents
A kind of bimetallic metal organic frame thin layer and preparation method thereof Download PDFInfo
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- CN109824908A CN109824908A CN201910134715.9A CN201910134715A CN109824908A CN 109824908 A CN109824908 A CN 109824908A CN 201910134715 A CN201910134715 A CN 201910134715A CN 109824908 A CN109824908 A CN 109824908A
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Abstract
The invention discloses a kind of bimetallic metal organic frame thin layers and preparation method thereof.This method includes the preparation of metal salt solution A and ligand solution B, the bimetallic metal organic frame ZIF-8 of additional constant current synthesisx- 67 thin layers.The present invention is prepared by additional constant current method, and operating procedure is easy, generated time is short, input cost is low and high production efficiency, it is also possible to synthesize other metallic organic frame films.The ZIF-8 prepared by additional constant current methodx- 67 film surfaces are continuous, contacted with substrate closely without lamination, two kinds of metallic elements are evenly distributed in thin layer, good mixing.Anodised aluminium (AAO) substrate used in the present invention has good supporting role to film, and thinner aperture is also beneficial to the formation of film nucleus.
Description
Technical field
The invention belongs to thin-film device technical fields, and in particular to a kind of bimetallic metal organic frame thin layer and its system
Preparation Method.
Background technique
Metal-organic framework material Recent study is very burning hot, and the adjustability of structure with superelevation makes it each
Field all has great application potential.Metal organic framework film is formed by metal ion and organic ligand periodic arrangement, existing
Organic speciality has inorganic nature again, is the research hotspot of recent years.The film of ZIF series is one kind of metallic organic frame films,
There are good thermal stability and self-framework stable performance, research application is all very extensively.
More often, in order to make bigger its application potential of performance of metal-organic framework material, need to be prepared into thin
Layer device.In prepared metal organic frame thin layer, the selection of metallic element has great decision to the application range of thin layer
Property effect.The type of metal ion or ion cluster greatly influences the frame topological structure and physicochemical properties of film, Jin Erying
Ring the performance that they are shown in different application field.
By taking zeolite imidazole frame material as an example, central metal is zinc ion or cobalt ions, and single metal material is
It is proved to that there is very extensive purposes.Such as zeolite imidazole material ZIF-8, metal ion are zinc ion, this material has fine
Chemical stability, be widely used in gas separation field.Another metal ion species are the metal organic frame material of cobalt ions
Expect ZIF-67, center ionic cobalt ion has preferable chemical catalysis performance, but its stability ratio ZIF-8 is slightly weak.Therefore
If the cobalt ions with catalytic activity can be introduced, then such material will be greatly facilitated under the premise of keeping its stability
Application field.Therefore prepare that bimetallic organic backbone thin layer is very promising, and mixed metal can effectively adjust thin layer institute
The property shown.
On the other hand, due to preparing the limitation of thin-bed technique at present, common law such as hydro-thermal method: the operation cycle is long, experiment
Complex steps, therefore be badly in need of proposing new thin layer technology of preparing, faster and better prepares metal organic frame thin layer.
Summary of the invention
It is an object of the invention to overcome deficiency existing for existing masking technique, providing a kind of bimetallic metal has machine frame
Frame thin layer and preparation method thereof.
The object of the invention is achieved through the following technical solutions.
A kind of preparation method of bimetallic metal organic frame thin layer, preparation process the following steps are included:
(1) two kinds of metal salts are dissolved in solvent, are uniformly mixed and obtain metal salt solution A:
(2) organic ligand is dissolved in solvent, is uniformly mixed and obtains ligand solution B；
(3) it is stood after mixing above-mentioned metal salt solution A and ligand solution B and obtains mixed solution, and substrate is placed in described fit
It measures in mixed solution, additional constant current synthesizes the bimetallic metal organic frame thin layer.
Preferably, the metal salt solution is the methanol solution of zinc nitrate hexahydrate and cabaltous nitrate hexahydrate.
It is further preferred that the metal salt solution concentration is 0.05-0.1 mol/L, zinc nitrate hexahydrate and six water
The molar ratio for closing cobalt nitrate is (0.25 ~ 4): 1.
Preferably, the ligand solution is the methanol solution of 2-methylimidazole, and concentration is the mol/L of 0.1mol/L ~ 0.2.
Preferably, described to mix metal salt solution A and ligand solution B, time of repose is 12 ~ 24 hours.
Preferably, the substrate is anodised aluminium (AAO) substrate, has good supporting role to film, and AAO substrate has
There is the thinner aperture 40-70nm, is also beneficial to the formation of film nucleus.It is further preferred that impressed current required for described
For 0.5 ~ 2 mA.
Still more preferably, the reaction time is 12 ~ 24 minutes.
The bimetallic metal organic frame thin layer of this method preparation, process is simple, and production efficiency is high.
The bimetallic metal organic frame thin layer that the present invention is prepared is expected to be applied to each side such as catalysis sensing separation
Face.
Compared with prior art, the present invention has the advantage that one step of additional constant current method of the present invention preparation is double
The metal organic frame thin layer of metal compared with traditional hydro-thermal method, greatly simplifies operating procedure in actual operation.
And the thin double metal layers synthesized are contacted with substrate closely to be occurred without lamination.Metal organic frame thin layer is expanded to be catalyzed
Application in the fields such as sensing.
Detailed description of the invention
Fig. 1 is ZIF-8 prepared by embodiment 180The exterior view of -67 thin layers；
Fig. 2 is ZIF-8 prepared by embodiment 180The sectional view of -67 thin layers；
Fig. 3 is ZIF-8 prepared by embodiment 180The section energy spectrum diagram of -67 thin layers；
Fig. 4 is ZIF-8 prepared by embodiment 250The exterior view of -67 thin layers；
Fig. 5 is ZIF-8 prepared by embodiment 250The sectional view of -67 thin layers；
Fig. 6 is ZIF-8 prepared by embodiment 250The section energy spectrum diagram of -67 thin layers；
Fig. 7 is ZIF-8 prepared by embodiment 320The exterior view of -67 thin layers；
Fig. 8 is ZIF-8 prepared by embodiment 320The sectional view of -67 thin layers；
Fig. 9 is ZIF-8 prepared by embodiment 320The section energy spectrum diagram of -67 thin layers.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Bimetallic ratio is determined by carrying out power spectrum characterization to bimetallic metallic organic frame films in following embodiments
And distribution situation, required power spectrum voltage are the kV of 15 kV ~ 20, the energy-spectrum scanning time is 1 ~ 3 minute.
Embodiment 1
The present embodiment prepares ZIF-8 using one step of additional constant current method80- 67 thin layers, comprising the following steps:
(1) zinc nitrate hexahydrate (1.19g) and cabaltous nitrate hexahydrate (0.29g) are dissolved in 100 mL methanol, obtain metal salt
Solution A；
(2) 2-methylimidazole (0.82g) is dissolved in 100 mL methanol, obtains ligand solution B；
(3) metal salt solution A and ligand solution B is mixed, stands 12 hours and obtains mixed solution,；
(4) anodised aluminium (AAO) substrate is immersed in the mixed solution of step (3) preparation, the electric current of additional 0.5 mA, reaction
24min obtains ZIF-880- 67 thin layers；
The ZIF-8 that will be obtained80- 67 thin layers are scanned electron microscope characterization, as shown in Figure 1, coating granules are continuous；
The ZIF-8 that will be obtained80- 67 thin layer sections are scanned electron microscope characterization, as shown in Fig. 2, thin layer is connect with substrate
Well without tomography；
The ZIF-8 that will be obtained80- 67 thin layer sections carry out energy spectrum analysis, as shown in figure 3, Zn-ef ficiency content is greater than cobalt element, and
Two kinds of Elemental redistributions are uniform.
Embodiment 2
The present embodiment prepares ZIF-8 using one step of additional constant current method50- 67 thin layers, comprising the following steps:
(1) zinc nitrate hexahydrate (1.12 g) and cabaltous nitrate hexahydrate (1.09 g) are dissolved in 100 mL methanol, obtain metal
Salting liquid A.
(2) 2-methylimidazole (1.23 g) is dissolved in 100 mL methanol, obtains ligand solution B.
(3) metal salt solution A and ligand solution B is mixed, stands 18 hours and obtains mixed solution,；
(4) anodised aluminium (AAO) substrate is immersed in the mixed solution of step (3) preparation, the electric current of additional 1.25 mA, instead
18 min are answered, ZIF-8 is obtained50- 67 thin layers.
The ZIF-8 that step (4) is obtained50- 67 thin layers are scanned electron microscope characterization, as shown in figure 4, coating granules
Continuously.
The ZIF-8 that step (4) is obtained50- 67 thin layer sections are scanned electron microscope characterization, as shown in figure 5, thin layer
It is connect with substrate well without tomography.
The ZIF-8 that step (4) is obtained50- 67 thin layer sections carry out energy spectrum analysis, as shown in fig. 6, Zn-ef ficiency content is greater than
Cobalt element, and two kinds of Elemental redistributions are uniform.
Embodiment 3
The present embodiment prepares ZIF-8 using one step of additional constant current method20- 67 thin layers, comprising the following steps:
(1) zinc nitrate hexahydrate (0.59 g) and cabaltous nitrate hexahydrate (2.33 g) are dissolved in 100 mL methanol, obtain metal
Salting liquid A.
(2) 2-methylimidazole (1.64 g) is dissolved in 100 mL methanol, obtains ligand solution B.
(3) metal salt solution A and ligand solution B is mixed, stands 24 hours and obtains mixed solution,；
(4) anodised aluminium (AAO) substrate is immersed in the mixed solution of step (3) preparation, the electric current of additional 2 mA, reaction 12
Min obtains ZIF-820- 67 thin layers.
The ZIF-8 that step (4) is obtained20- 67 thin layers are scanned electron microscope characterization, as shown in fig. 7, coating granules
Continuously.
The ZIF-8 that step (4) is obtained20- 67 thin layer sections are scanned electron microscope characterization, as shown in figure 8, thin layer
It is connect with substrate well without tomography.
The ZIF-8 that step (4) is obtained20- 67 thin layer sections carry out energy spectrum analysis, as shown in figure 9, Zn-ef ficiency content is greater than
Cobalt element, and two kinds of Elemental redistributions are uniform.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of bimetallic metal organic frame thin layer, which comprises the following steps:
(1) two kinds of metal salts are dissolved in solvent, are uniformly mixed and obtain metal salt solution A:
(2) organic ligand is dissolved in solvent, is uniformly mixed and obtains ligand solution B；
(3) it is stood after mixing above-mentioned metal salt solution A and ligand solution B and obtains mixed solution, substrate is placed in the mixing
In solution, additional constant current synthesizes the bimetallic metal organic frame thin layer.
2. the method according to claim 1, wherein two kinds of metal salts of the step (1) are respectively six hydrations
Zinc nitrate and cabaltous nitrate hexahydrate, solvent are methanol.
3. according to the method described in claim 2, it is characterized in that, the metal salt solution concentration of the step (1) is 0.05-
The molar ratio of 0.1 mol/L, zinc nitrate hexahydrate and cabaltous nitrate hexahydrate is (0.25 ~ 4): 1.
4. the method according to claim 1, wherein the step (2) organic ligand is 2-methylimidazole, and dense
Degree is the mol/L of 0.1mol/L ~ 0.2, and solvent is methanol.
5. the method according to claim 1, wherein substrate is anodic oxidation aluminium substrate in the step (3).
6. the method according to claim 1, wherein standing 12 ~ 24 hours in the step (3).
7. according to the method described in claim 6, it is characterized in that, required impressed current is 0.5 ~ 2 in the step (3)
MA, reaction time are 12 ~ 24 minutes.
8. the metal organic framework thin layer that any one of claim 1-7 the method is prepared.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112808027A (en) * | 2020-12-23 | 2021-05-18 | 华南理工大学 | Method for rapidly growing ZIF-8 film on stainless steel substrate |
| CN113105646A (en) * | 2021-04-20 | 2021-07-13 | 广东药科大学 | Preparation method and application of bimetallic-organic infinite coordination polymer nano-microsphere |
| CN113501966A (en) * | 2021-07-29 | 2021-10-15 | 武汉理工大学 | Two-dimensional zinc-cobalt bimetallic ZIF catalyst and preparation method and application thereof |
| CN113828169A (en) * | 2021-10-20 | 2021-12-24 | 嘉兴哲夫埃特环保科技有限公司 | polycoFs/bimetal MOFs composite membrane and preparation method thereof |
| CN114105486A (en) * | 2021-12-24 | 2022-03-01 | 广西大学 | Preparation method of bimetallic center metal organic framework electrochromic film |
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| CN107398187A (en) * | 2017-07-26 | 2017-11-28 | 华南理工大学 | It is a kind of to utilize the supper-fast method for preparing metal organic framework film of electric field poling |
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| CN108745285A (en) * | 2018-06-08 | 2018-11-06 | 盐城工学院 | The preparation method of the magnetic porous carbon adsorbing material of antibiotic in a kind of adsorbed water body |
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| CN107398187A (en) * | 2017-07-26 | 2017-11-28 | 华南理工大学 | It is a kind of to utilize the supper-fast method for preparing metal organic framework film of electric field poling |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112808027A (en) * | 2020-12-23 | 2021-05-18 | 华南理工大学 | Method for rapidly growing ZIF-8 film on stainless steel substrate |
| CN113105646A (en) * | 2021-04-20 | 2021-07-13 | 广东药科大学 | Preparation method and application of bimetallic-organic infinite coordination polymer nano-microsphere |
| CN113105646B (en) * | 2021-04-20 | 2022-09-16 | 广东药科大学 | Preparation method and application of bimetallic-organic infinite coordination polymer nano-microsphere |
| CN113501966A (en) * | 2021-07-29 | 2021-10-15 | 武汉理工大学 | Two-dimensional zinc-cobalt bimetallic ZIF catalyst and preparation method and application thereof |
| CN113828169A (en) * | 2021-10-20 | 2021-12-24 | 嘉兴哲夫埃特环保科技有限公司 | polycoFs/bimetal MOFs composite membrane and preparation method thereof |
| CN113828169B (en) * | 2021-10-20 | 2023-10-20 | 苏州清李新材料科技有限公司 | PolyCOFs/bimetal MOFs composite film and preparation method thereof |
| CN114105486A (en) * | 2021-12-24 | 2022-03-01 | 广西大学 | Preparation method of bimetallic center metal organic framework electrochromic film |
| CN114105486B (en) * | 2021-12-24 | 2024-02-20 | 广西大学 | Preparation method of bimetallic center metal organic framework electrochromic film |
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Application publication date: 20190531 |