CN107880275A - A kind of preparation method of Zn MOF nanometer sheets - Google Patents
A kind of preparation method of Zn MOF nanometer sheets Download PDFInfo
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- CN107880275A CN107880275A CN201711161954.0A CN201711161954A CN107880275A CN 107880275 A CN107880275 A CN 107880275A CN 201711161954 A CN201711161954 A CN 201711161954A CN 107880275 A CN107880275 A CN 107880275A
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- nanometer sheets
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Abstract
The invention discloses a kind of method that self-assembly method prepares Zn MOF nanometer sheets, belong to metal-organic framework material preparing technical field.The amino terephthalic acid (TPA) of organic ligand 2 and zinc source are dissolved in water by the present invention, conditioning agent is used as using the aqueous solution of TMAH (TMAH) 25%, two kinds of solution are mixed under condition of heating and stirring, after reacting a period of time, add ethanol and mixed liquor is cooled to room temperature, be centrifugally separating to obtain white solid powder.Zn MOF obtained by preparation method of the present invention are a kind of flake nano material.
Description
Technical field
The present invention relates to a kind of method for preparing Zn-MOF nanometer sheets, belongs to metal-organic framework material technology of preparing neck
Domain.
Background technology
Ultra-thin two-dimension (2D) nano material has some for being different from stratiform persursor material due to the change of structural dimension
Unique physico-chemical property, makes it receive much concern.Ultra-thin 2D MOF materials are a kind of new class grapheme materials, in recent years,
Researcher's extensive concern is just caused.With traditional stratiform MOF crystal phase ratios, ultra-thin 2D MOF materials have bigger ratio table
The advantages such as area, more avtive spots and smaller resistance to mass tranfer, in electrooptical device, catalysis, bio-sensing, UF membrane
Had broad application prospects Deng field.
" from bottom to top " method refers to, using molecule or ion unit as predecessor, pass through coordinate bond or weak interaction
Self assembly directly obtains ultra-thin two-dimension material.The ultra-thin porous porphyrin MOF reported is prepared using the method for self assembly more, still
The ultra-thin 2D MOF materials of gained are attached in particular substrate mostly, and direct-assembling generates the report of the ultra-thin 2D MOF materials of stable dispersion
Road is also extremely limited.Lotsch etc. is by reverse micelle method, in the micro emulsion that cetyltrimethyl ammonium/heptane/n-hexyl alcohol is formed
In liquid, self assembly obtains the ultra-thin 2D MOF materials that thickness is 8nm.Rodenas etc. is in N,N-dimethylformamide and acetonitrile
In the mixed solvent grows to obtain ultra-thin 2D CuBDC and ZnBDC MOF materials by spreading control MOF.Therefore, exploitation is " from lower
On " dicyandiamide solutions of the ultra-thin 2D MOF nanometer sheets of assembling, there is extensively application prospect.
The content of the invention
The purpose of the present invention is to prepare Zn-MOF nanometer sheets using the method for self assembly, there is provided one kind prepares Zn-MOF and received
The dicyandiamide solution of rice piece.
The technical scheme that the present invention prepares Zn-MOF nanometer sheets comprises the following steps：
1. metal zinc salt and organic ligand 2- amino terephthalic acid (TPA) are distinguished into wiring solution-forming, certain temperature is heated to, will
The solution of zinc ion is added dropwise to the solution of 2- amino terephthalic acid (TPA)s, and it is water-soluble to add appropriate TMAH (TMAH) 25%
As conditioning agent, mixed liquor reacts 1~12 hour liquid at 40~120 DEG C, and stopping heating after addition ethanol is cooled to room temperature, from
The separating obtained product of the heart, obtains Zn-MOF nanometer sheets.
2. a kind of method for preparing Zn-MOF nanometer sheets of the present invention, zinc ion and 2- amino terephthalic acid (TPA)s in mixed liquor
Mol ratio is 5:1~1:3, preferably 2:1~1:2.
3. a kind of method for preparing Zn-MOF nanometer sheets of the present invention, Zn solions concentration is 20~100mmol/L, preferably
For 40~80mmol/L；The concentration of 2- amino terephthalic acid solutions is 40~120mmol/L, preferably 50~100mmol/L.
4. a kind of method for preparing Zn-MOF nanometer sheets of the present invention, the rate of addition of Zn solions is 10~50ml/
Min, preferably 20~30ml/min.
5. a kind of method for preparing Zn-MOF nanometer sheets of the present invention, in Zn solions solute be selected from zinc acetate, zinc nitrate,
One kind in zinc sulfate.
The TMAH (TMAH) added 6. a kind of method for preparing Zn-MOF nanometer sheets of the present invention, during reaction
The amount of 25% aqueous solution conditioning agent is 50~500 μ L, preferably 100~300 μ L.
Stirred 7. a kind of method for preparing Zn-MOF nanometer sheets of the present invention, during reaction, mixing speed is 500~1000r/
min。
The present invention obtains nanometer using tetramethylammonium hydroxide aqueous solution as conditioning agent, control MOF epitaxis
Piece.
Brief description of the drawings
Fig. 1 is the XRD of Zn-MOF nanometer sheets prepared by embodiment 1.
Fig. 2 is the transmission electron microscope picture of Zn-MOF nanometer sheets prepared by embodiment 1.
Embodiment
The embodiment of the present invention is described further below in conjunction with the accompanying drawings.
Embodiment 1
40mmol/L zinc nitrate solution and 60mmol/L 2- amino terephthalic acid solutions is respectively configured.Take 10ml
For 2- amino terephthalic acid solutions in round-bottomed flask, 600r/min is stirred and heated to 100 DEG C, by the solution of 10ml zinc ions with
20ml/min speed is added dropwise in the solution of 2- amino terephthalic acid (TPA)s, adds 100 μ L tetramethylammonium hydroxide aqueous solutions, is mixed
Close liquid to react 8 hours at 100 DEG C, stopping heating after addition ethanol is cooled to room temperature, centrifuges products therefrom, vacuum drying
Obtain Zn-MOF nanometer sheets.
Comparative example 1
40mmol/L zinc nitrate solution and 60mmol/L 2- amino terephthalic acid solutions is respectively configured.Take 10ml
For 2- amino terephthalic acid solutions in round-bottomed flask, 600r/min is stirred and heated to 100 DEG C, by the solution of 10ml zinc ions with
20ml/min speed is added dropwise in the solution of 2- amino terephthalic acid (TPA)s, does not add tetramethylammonium hydroxide aqueous solution, mixing
Liquid reacts 8 hours at 100 DEG C, and stopping heating after addition ethanol is cooled to room temperature, no product.
Embodiment 2
50mmol/L zinc nitrate solution and 50mmol/L 2- amino terephthalic acid solutions is respectively configured.Take 10ml
For 2- amino terephthalic acid solutions in round-bottomed flask, 600r/min is stirred and heated to 100 DEG C, by the solution of 10ml zinc ions with
20ml/min speed is added dropwise in the solution of 2- amino terephthalic acid (TPA)s, adds 100 μ L tetramethylammonium hydroxide aqueous solutions, is mixed
Close liquid to react 8 hours at 100 DEG C, stopping heating after addition ethanol is cooled to room temperature, centrifuges products therefrom, vacuum drying
Obtain Zn-MOF nanometer sheets.
Embodiment 3
40mmol/L zinc nitrate solution and 60mmol/L 2- amino terephthalic acid solutions is respectively configured.Take 10ml
For 2- amino terephthalic acid solutions in round-bottomed flask, 600r/min is stirred and heated to 100 DEG C, by the solution of 10ml zinc ions with
40ml/min speed is added dropwise in the solution of 2- amino terephthalic acid (TPA)s, adds 100 μ L tetramethylammonium hydroxide aqueous solutions, is mixed
Close liquid to react 8 hours at 100 DEG C, stopping heating after addition ethanol is cooled to room temperature, centrifuges products therefrom, vacuum drying
Obtain Zn-MOF nanometer sheets.
Embodiment 4
40mmol/L zinc nitrate solution and 60mmol/L 2- amino terephthalic acid solutions is respectively configured.Take 10ml
For 2- amino terephthalic acid solutions in round-bottomed flask, 600r/min is stirred and heated to 100 DEG C, by the solution of 10ml zinc ions with
20ml/min speed is added dropwise in the solution of 2- amino terephthalic acid (TPA)s, adds 100 μ L tetramethylammonium hydroxide aqueous solutions, is mixed
Close liquid to react 8 hours at 40 DEG C, stopping heating after addition ethanol is cooled to room temperature, centrifuges products therefrom, vacuum drying
Obtain Zn-MOF nanometer sheets.
Embodiment 5
40mmol/L zinc nitrate solution and 60mmol/L 2- amino terephthalic acid solutions is respectively configured.Take 10ml
For 2- amino terephthalic acid solutions in round-bottomed flask, 600r/min is stirred and heated to 100 DEG C, by the solution of 10ml zinc ions with
20ml/min speed is added dropwise in the solution of 2- amino terephthalic acid (TPA)s, adds 100 μ L tetramethylammonium hydroxide aqueous solutions, is mixed
Close liquid to react 4 hours at 100 DEG C, stopping heating after addition ethanol is cooled to room temperature, centrifuges products therefrom, vacuum drying
Obtain Zn-MOF nanometer sheets.
Embodiment 6
40mmol/L zinc nitrate solution and 60mmol/L 2- amino terephthalic acid solutions is respectively configured.Take 10ml
For 2- amino terephthalic acid solutions in round-bottomed flask, 600r/min is stirred and heated to 100 DEG C, by the solution of 10ml zinc ions with
20ml/min speed is added dropwise in the solution of 2- amino terephthalic acid (TPA)s, adds 400 μ L tetramethylammonium hydroxide aqueous solutions, is mixed
Close liquid to react 8 hours at 100 DEG C, stopping heating after addition ethanol is cooled to room temperature, centrifuges products therefrom, vacuum drying
Obtain Zn-MOF nanometer sheets.
Embodiment 7
40mmol/L zinc acetate solution and 60mmol/L 2- amino terephthalic acid solutions is respectively configured.Take 10ml
For 2- amino terephthalic acid solutions in round-bottomed flask, 600r/min is stirred and heated to 100 DEG C, by the solution of 10ml zinc ions with
20ml/min speed is added dropwise in the solution of 2- amino terephthalic acid (TPA)s, adds 100 μ L tetramethylammonium hydroxide aqueous solutions, is mixed
Close liquid to react 8 hours at 100 DEG C, stopping heating after addition ethanol is cooled to room temperature, centrifuges products therefrom, vacuum drying
Obtain Zn-MOF nanometer sheets.
Embodiment 8
40mmol/L zinc nitrate solution and 60mmol/L 2- amino terephthalic acid solutions is respectively configured.Take 10ml
For 2- amino terephthalic acid solutions in round-bottomed flask, 1000r/min is stirred and heated to 100 DEG C, by the solution of 10ml zinc ions
It is added dropwise to 20ml/min speed in the solution of 2- amino terephthalic acid (TPA)s, adds 100 μ L tetramethylammonium hydroxide aqueous solutions,
Mixed liquor reacts 8 hours at 100 DEG C, and stopping heating after addition ethanol is cooled to room temperature, centrifuges products therefrom, vacuum is done
It is dry to obtain Zn-MOF nanometer sheets.
Claims (7)
- A kind of 1. method for preparing Zn-MOF nanometer sheets, it is characterised in that：By metal zinc salt and organic ligand 2- amino terephthalic acid (TPA) difference wiring solution-forming, be heated under certain temperature, by zinc from The solution of son is added dropwise to the solution of 2- amino terephthalic acid (TPA)s, adds the aqueous solution of appropriate TMAH (TMAH) 25% work For conditioning agent, mixed liquor reacts 1~12 hour at 40~120 DEG C, stops heating after addition ethanol and is cooled to room temperature, centrifugation point From products therefrom, Zn-MOF nanometer sheets are obtained.
- A kind of 2. method for preparing Zn-MOF nanometer sheets according to claim 1, it is characterised in that：Zinc ion in mixed liquor Mol ratio with 2- amino terephthalic acid (TPA)s is 5:1~1:3, preferably 2:1~1:2.
- A kind of 3. method for preparing Zn-MOF nanometer sheets according to claim 1, it is characterised in that：Zn solion concentration For 20~100mmol/L, preferably 40~80mmol/L；The concentration of 2- amino terephthalic acid solutions is 40~120mmol/L, Preferably 50~100mmol/L.
- A kind of 4. method for preparing Zn-MOF nanometer sheets according to claim 1, it is characterised in that：The drop of Zn solions Acceleration is 10~50ml/min, preferably 20~30ml/min.
- A kind of 5. method for preparing Zn-MOF nanometer sheets according to claim 1-4 any one, it is characterised in that：Zn from The one kind of solute in zinc acetate, zinc nitrate, zinc sulfate in sub- solution.
- A kind of 6. method for preparing Zn-MOF nanometer sheets according to claim 1-5 any one, it is characterised in that：Reaction When the amount of the aqueous solution conditioning agent of TMAH (TMAH) 25% that adds be 50~500 μ L, preferably 100~300 μ L.
- A kind of 7. method for preparing Zn-MOF nanometer sheets according to claim 1-6 any one, it is characterised in that：Reaction When stir, mixing speed is 500~1000r/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776812A (en) * | 2019-02-21 | 2019-05-21 | 河北工业大学 | The preparation method of Cu base two-dimensional sheet MOFs material |
| CN110501487A (en) * | 2019-09-08 | 2019-11-26 | 浙江理工大学 | A kind of construction method of the electrochemical immunosensor based on Au@Zn-MOFs composite material |
| CN111498850A (en) * | 2020-04-26 | 2020-08-07 | 江南大学 | Two-dimensional transition metal carbonitride and preparation method and application thereof |
| CN112250876A (en) * | 2020-09-24 | 2021-01-22 | 温州大学 | Preparation method of two-dimensional IRPY type MOF material and functionalized M @ IRPA-MOF supported catalyst |
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| CN107141491A (en) * | 2017-06-16 | 2017-09-08 | 北京化工大学 | It is a kind of to detect atmosphere pollution SO with fluorescent test paper2And its method for derivative |
| CN107602596A (en) * | 2017-09-14 | 2018-01-19 | 河南城建学院 | A kind of Zn MOF fluorescent sensing materials and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776812A (en) * | 2019-02-21 | 2019-05-21 | 河北工业大学 | The preparation method of Cu base two-dimensional sheet MOFs material |
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| CN110501487A (en) * | 2019-09-08 | 2019-11-26 | 浙江理工大学 | A kind of construction method of the electrochemical immunosensor based on Au@Zn-MOFs composite material |
| CN111498850A (en) * | 2020-04-26 | 2020-08-07 | 江南大学 | Two-dimensional transition metal carbonitride and preparation method and application thereof |
| CN111498850B (en) * | 2020-04-26 | 2021-08-20 | 江南大学 | Two-dimensional transition metal carbonitride and preparation method and application thereof |
| CN112250876A (en) * | 2020-09-24 | 2021-01-22 | 温州大学 | Preparation method of two-dimensional IRPY type MOF material and functionalized M @ IRPA-MOF supported catalyst |
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Application publication date: 20180406 |