CN107022095A - A kind of method that utilization spray-on process prepares metal organic framework film - Google Patents
A kind of method that utilization spray-on process prepares metal organic framework film Download PDFInfo
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- CN107022095A CN107022095A CN201710286896.8A CN201710286896A CN107022095A CN 107022095 A CN107022095 A CN 107022095A CN 201710286896 A CN201710286896 A CN 201710286896A CN 107022095 A CN107022095 A CN 107022095A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The present invention discloses a kind of method that utilization spray-on process prepares metal organic framework film, spray solution and undertaking liquid are used as using metal cation solution and organic ligand solution, spray solution to be atomized is entered in sprayer unit by auto injection infusion, it is set to be dispersed into liquid little particle by ultrasonic wave in the showerhead, and sprayed with mist from shower nozzle, solution after atomization falls on the undertaking liquid of lower section by the even action of gravity, reacted after two kinds of material contacts at interface, construct copper terephthalic acid metal organic backbone film.It is an advantage of the invention that：It is simple to operate, be easy to control and industrialized production；Normal temperature and pressure, experiment condition is gentle, environmental protection and energy saving；Reaction speed is fast, short preparation period；The limitation of substrate is broken through, can be deposited in any substrate；Collection of products method is easy, convenient subsequently to use.
Description
Technical field
The present invention relates to chemical field, and in particular to a kind of method that utilization spray-on process prepares metal organic framework film.
Background technology
Metal organic framework compound is a kind of novel nano-pore crystalline material, and its structure is by metal ion or metal
Cluster is constituted in strong coordinate bond form with reference to diversified organic ligand.Metal organic framework compound has uniform pore diameter, surpassed
The excellent physicochemical properties such as high-specific surface area and stronger absorption affinity, therefore the film that its assembling is formed has brilliance
Performance.The common method for preparing metal organic framework film has：In-situ crystallization method, LBL sedimentations, electrochemical deposition method and
Secondary growth method etc..But these method generally existing complex operations, synthesis cycle is long, energy consumption is big in preparation process and is unsuitable for
The shortcomings of industrial production.
The content of the invention
In order to solve the above technical problems, the present invention prepares the metal organic framework film of large area using ultrasonic spray technology
Method, the method achieve metal organic framework nanometer sheet synthesis with assembling it is synchronous carry out, with it is simple to operate, synthesize
Cycle is short and is easy to the advantage that is mass produced in industry.
Concrete technical scheme is as follows：
A kind of method that utilization spray-on process prepares metal organic framework film, preparation process is as follows：
(1) two kinds of reaction solutions are prepared：The first solution is metal cation solution, and its solute is mantoquita, and solvent is body
Product is than being 1:2 N,N-dimethylformamide and acetonitrile mixture；Second is organic ligand solution, and its solute is terephthaldehyde
Acid, solvent is that volume ratio is 2:1 N,N-dimethylformamide and acetonitrile mixture；Mantoquita is 3 with terephthalic acid (TPA) mol ratio:
1~1:3；
(2) spray process：It is dispersed into as spray solution by ultrasonic wave in the showerhead metal cation solution
Liquid little particle, is sprayed with mist from shower nozzle；The undertaking liquid terephthalic acid (TPA) that solution after atomization uniformly falls in lower section is molten
On liquid liquid level, two kinds of materials start to construct copper-terephthalic acid metal organic backbone film after the liquid level contact of liquid is accepted；
(3) collection and purifying of film：Metal organic framework film is swum in as self-supporting film on the liquid level for accepting liquid, is made
Film is picked up from liquid level with hollow copper mesh；Or solid substrate is put into undertaking liquid in advance, question response is careful after terminating
Sucking liquid, makes film fall into substrate；Obtained film by being immersed in N,N-dimethylformamide with being washed in methanol repeatedly
Wash purifying.
The mantoquita can be one kind in Salicylaldoxime, anhydrous cupric chloride, anhydrous copper bromide, cupric sulfate pentahydrate.
The parameter of the auto injection pump is set to：
Flow：30μL/min
The distribution time：100s
Distribute liquid measure：50μL
Interval time：0.1min
Syringe bore：4.25mm
The spray solution can be any one in metal ion solution and organic ligand solution, another to be used as institute
State undertaking liquid.
The solid substrate can be one kind in glass, filter membrane, carbon cloth or silicon chip.
Described two reaction solutions can be adjusted according to required film thickness to distribution number of times.
The present invention successfully synthesizes metal organic framework film by spray-on process.At present, metal organic framework film is in gas
The field such as body absorption and sensing, battery, catalysis is all widely used.Compared with traditional synthetic method, this method it is excellent
Putting is：(1) it is simple to operate, be easy to control and industrialized production.(2) normal temperature and pressure, experiment condition is gentle, environmental protection and energy saving.(3) it is anti-
Answer speed fast, short preparation period.(4) limitation of substrate is broken through, can be deposited in any substrate.(5) collection of products method letter
Just, subsequent use is facilitated.
Brief description of the drawings
Fig. 1 is the solute using Salicylaldoxime as metal cation solution, the organic bone of metal prepared by spray-on process
Frame film SEM photograph；
Fig. 2 is the solute using Salicylaldoxime as metal cation solution, the organic bone of metal prepared by spray-on process
Frame film situ X-Ray Diffraction spectrogram；
Fig. 3 is the solute using Salicylaldoxime as metal cation solution, and when distribution number of times is 10 times, prepared by spray-on process
Metal organic framework film SEM photograph；
Fig. 4 is the solute using Salicylaldoxime as metal cation solution, and when distribution number of times is 5 times, prepared by spray-on process
Metal organic framework film SEM photograph.
Fig. 5 is the solute using anhydrous cupric chloride as metal cation solution, the organic bone of metal prepared by spray-on process
Frame film SEM photograph；
Fig. 6 is the solute using anhydrous cupric chloride as metal cation solution, the organic bone of metal prepared by spray-on process
Frame film situ X-Ray Diffraction spectrogram；
Fig. 7 is the solute using anhydrous copper bromide as metal cation solution, the organic bone of metal prepared by spray-on process
Frame film SEM photograph；
Fig. 8 is the solute using anhydrous copper bromide as metal cation solution, the organic bone of metal prepared by spray-on process
Frame film situ X-Ray Diffraction spectrogram；
Fig. 9 is the solute using cupric sulfate pentahydrate as metal cation solution, the organic bone of metal prepared by spray-on process
Frame film SEM photograph.
Embodiment
Embodiment 1
(1) two kinds of reaction solutions are prepared：The first is acetic acid copper solution, and solute is Salicylaldoxime, and solvent is volume ratio
For 1:2 N,N-dimethylformamide and acetonitrile mixed solvent；Second is terephthalic acid solution, and solute is terephthaldehyde
Acid, solvent is that volume ratio is 2:1 N,N-dimethylformamide and acetonitrile mixed solvent；Salicylaldoxime rubs with terephthalic acid (TPA)
You are than being 3:1；
(2) spray process：Acetic anhydride copper solution is injected as spray solution by the syringe of auto injection pump and sprayed
In the shower nozzle of mist device, it is dispersed into liquid little particle by ultrasonic wave in the showerhead, sprayed with mist from shower nozzle；Mist
Solution after change falls on undertaking liquid terephthalic acid solution's liquid level of lower section by the even action of gravity, and two kinds of materials are being held
Start to construct copper-terephthalic acid metal organic backbone film after the liquid level contact for connecing liquid；Keep lower section catching device to stand, hold
The continuous careful shower nozzle that rocks makes the solution after atomization uniformly fall on lower section undertaking liquid liquid level；The parameter setting of auto injection pump：
Flow：30μL/min
Distribute number of times:10 times
The distribution time：100s
Distribute liquid measure:50μL
Interval time:0.1min
Syringe is selected：4.25mm
(3) collection and purifying of film：Metal organic framework film is swum in as self-supporting film on the liquid level for accepting liquid, can
So that film to be picked up from liquid level using hollow copper net；Solid substrate can also be put into undertaking liquid in advance, question response terminates
Careful sucking liquid, makes film fall in substrate afterwards；Obtained film by being immersed in N,N-dimethylformamide and first repeatedly
Purifying is washed in alcohol.
Embodiment 2
The distribution number of times changed in spray process is 5 times, and other processes are same as Example 1.
Embodiment 3
(1) two kinds of reaction solutions are prepared：The first is copper chloride solution, and solute is anhydrous cupric chloride, and solvent is volume ratio
For 1:2 N,N-dimethylformamide and acetonitrile mixed solvent；Second is terephthalic acid solution, and solute is terephthaldehyde
Acid, solvent is that volume ratio is 2:1 N,N-dimethylformamide and acetonitrile mixed solvent；Anhydrous cupric chloride rubs with terephthalic acid (TPA)
You are than being 3:5；
(2) spray process：Filled copper chloride solution as spray solution by the syringe spray injection of auto injection pump
In the shower nozzle put, it is dispersed into liquid little particle by ultrasonic wave in the showerhead, sprayed with mist from shower nozzle；After atomization
Solution fall by the even action of gravity on undertaking liquid terephthalic acid solution's liquid level of lower section, two kinds of materials are accepting liquid
Liquid level contact after start construct copper-terephthalic acid metal organic backbone film；Keep lower section catching device to stand, continue small
The heart, which rocks shower nozzle, makes the solution after atomization uniformly fall on lower section undertaking liquid liquid level；The parameter setting of auto injection pump：
Flow：60μL/min
Distribute number of times:10 times
The distribution time：50s
Distribute liquid measure:50μL
Interval time:0.1min
Syringe is selected：4.25mm
(3) collection and purifying of film：Be the same as Example 1
Embodiment 4
(1) two kinds of reaction solutions are prepared：The first is bromination copper solution, and solute is anhydrous copper bromide, and solvent is volume ratio
For 1:2 N,N-dimethylformamide and acetonitrile mixed solvent；Second is terephthalic acid solution, and solute is terephthaldehyde
Acid, solvent is that volume ratio is 2:1 N,N-dimethylformamide and acetonitrile mixed solvent；Anhydrous copper bromide rubs with terephthalic acid (TPA)
You are than being 1:3；
(2) spray process：Filled bromination copper solution as spray solution by the syringe spray injection of auto injection pump
In the shower nozzle put, it is dispersed into liquid little particle by ultrasonic wave in the showerhead, sprayed with mist from shower nozzle；After atomization
Solution fall by the even action of gravity on undertaking liquid terephthalic acid solution's liquid level of lower section, two kinds of materials are accepting liquid
Liquid level contact after start construct copper-terephthalic acid metal organic backbone film；Keep lower section catching device to stand, continue small
The heart, which rocks shower nozzle, makes the solution after atomization uniformly fall on lower section undertaking liquid liquid level；The parameter setting of auto injection pump：
Flow：30μL/min
Distribute number of times:10 times
The distribution time：100s
Distribute liquid measure:50μL
Interval time:0.1min
Syringe is selected：4.25mm
(3) collection and purifying of film：Be the same as Example 1
Embodiment 5
(1) two kinds of reaction solutions are prepared：The first is copper-bath, and solute is cupric sulfate pentahydrate, and solvent is volume ratio
For 1:2 N,N-dimethylformamide and acetonitrile mixed solvent；Second is terephthalic acid solution, and solute is terephthaldehyde
Acid, solvent is that volume ratio is 2:1 N,N-dimethylformamide and acetonitrile mixed solvent；Cupric sulfate pentahydrate rubs with terephthalic acid (TPA)
You are than being 2:1；
(2) spray process：Filled copper-bath as spray solution by the syringe spray injection of auto injection pump
In the shower nozzle put, it is dispersed into liquid little particle by ultrasonic wave in the showerhead, sprayed with mist from shower nozzle；After atomization
Solution fall by the even action of gravity on undertaking liquid terephthalic acid solution's liquid level of lower section, two kinds of materials are accepting liquid
Liquid level contact after start construct copper-terephthalic acid metal organic backbone film；Keep lower floor's catching device to stand, continue small
The heart, which rocks shower nozzle, makes the solution after atomization uniformly fall on lower section undertaking liquid liquid level；The parameter setting of auto injection pump：
Flow：60μL/min
Distribute number of times:10 times
The distribution time：50s
Distribute liquid measure:50μL
Interval time:0.1min
Syringe is selected：4.25mm
(3) collection and purifying of film：Be the same as Example 1.
In conjunction with accompanying drawing, the present invention will be described, and Fig. 1 is, using Salicylaldoxime as metal cation solution, to pass through spray
Mist method prepare metal organic framework film SEM photograph, as illustrated, spray-on process prepare metal organic framework film be by
A diameter of about 300nm nanometer sheet accumulation is constituted and film surface does not have obvious defect.
Fig. 2 is the metal organic framework film prepared by spray-on process using Salicylaldoxime as metal cation solution
Situ X-Ray Diffraction spectrogram, as illustrated, in XRD only have two 16.9 ° and 34.1 ° sharp of diffraction maximums, it is right respectively
Answer [201] and [402] crystal face.The nanometer sheet for illustrating synthesis is really metal organic framework compound, and the stack measure of nanometer sheet
There is very high directionality to perpendicular to substrate.
Fig. 5, Fig. 6 are the metal organic framework prepared by spray-on process using anhydrous cupric chloride as metal cation solution
The SEM photograph and situ X-Ray Diffraction spectrogram of film.Fig. 7, Fig. 8 are, using anhydrous copper bromide as metal cation solution, to lead to
Cross the SEM photograph and situ X-Ray Diffraction spectrogram of the metal organic framework film of spray-on process preparation.Fig. 9 is with cupric sulfate pentahydrate
As metal cation solution, the SEM photograph of the metal organic framework film prepared by spray-on process.As illustrated, SEM photograph
Show, the metal organic framework film surface prepared does not have in obvious defect, XRD diffraction maximum clearly.
Fig. 3 is the distribution number of times of embodiment 1 when being 10 times, and metal organic framework film SEM photograph prepared by spray-on process is such as schemed
Shown, the prepared metal organic framework film thickness arrived is 4.29 μm, and Fig. 4 is the distribution number of times of embodiment 2 when being 5 times, spray
Metal organic framework film SEM photograph prepared by mist method, as illustrated, it is prepared to metal organic framework film thickness be
1.72μm.It can be seen that, the different metal organic framework of thickness can be prepared thin using spray-on process according to the difference for distributing number of times
Film, solution after atomization forms the film of blueness from undertaking liquid is dropped into after shower nozzle ejection in the liquid level for accepting liquid, with point
Increase with number of times, color and the thickness increase of film.In certain scope, the color of film adds with the increase of straying quatity
It is deep.
Claims (6)
1. a kind of method that utilization spray-on process prepares metal organic framework film, it is characterised in that：Preparation process is as follows：
(1) two kinds of reaction solutions are prepared：The first solution is metal cation solution, and its solute is mantoquita, and solvent is volume ratio
For 1:2 N,N-dimethylformamide and acetonitrile mixture；Second of solution is organic ligand solution, and its solute is terephthaldehyde
Acid, solvent is that volume ratio is 2:1 N,N-dimethylformamide and acetonitrile mixture；Mantoquita is 3 with terephthalic acid (TPA) mol ratio:
1~1:3；
(2) spray process：It is set to be dispersed into liquid by ultrasonic wave in the showerhead as spray solution metal cation solution
Little particle, is sprayed with mist from shower nozzle；Solution after atomization uniformly falls undertaking liquid terephthalic acid solution's liquid in lower section
On face, two kinds of materials start to construct copper-terephthalic acid metal organic backbone film after the liquid level contact of liquid is accepted；
(3) collection and purifying of film：Metal organic framework film is swum in as self-supporting film on the liquid level for accepting liquid, uses sky
Heart copper mesh picks up film from liquid level；Or solid substrate is put into undertaking liquid in advance, question response is careful after terminating to be suctioned out
Liquid, is that film is fallen into substrate；Obtained film is pure with being washed in methanol by being immersed in N,N-dimethylformamide repeatedly
Change.
2. the method for metal organic framework film is prepared using spray-on process according to claim 1, it is characterised in that：Affiliated copper
Salt can be one kind in Salicylaldoxime, anhydrous cupric chloride, anhydrous copper bromide, cupric sulfate pentahydrate.
3. the method for metal organic framework film is prepared using spray-on process according to claim 1, it is characterised in that：It is described from
The parameter of dynamic sampling pump is set to：
Flow：30μL/min
The distribution time：100s
Distribute liquid measure：50μL
Interval time：0.1min
Syringe bore：4.25mm.
4. the method for metal organic framework film is prepared using spray-on process according to claim 1, it is characterised in that：The spray
Mist solution can be any one in metal ion solution and organic ligand solution, another to be used as the undertaking liquid.
5. the method for metal organic framework film is prepared using spray-on process according to claim 1, it is characterised in that：It is described solid
Body substrate can be one kind in glass, filter membrane, carbon cloth or silicon chip.
6. the method for metal organic framework film is prepared using spray-on process according to claim 1, it is characterised in that：Described two
Planting reaction solution can be adjusted according to required film thickness to distribution number of times.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686563A (en) * | 2017-08-17 | 2018-02-13 | 成都新柯力化工科技有限公司 | A kind of method and microballoon foaming agent that microballoon foaming agent is prepared using spray-on process |
| CN107794767A (en) * | 2017-10-23 | 2018-03-13 | 东北大学 | A kind of method that metal organic framework compound parcel fiber is prepared using spray-on process |
| CN110052184A (en) * | 2019-04-16 | 2019-07-26 | 暨南大学 | A kind of method that gas-liquid interface prepares MOF film |
| CN108043459B (en) * | 2017-12-21 | 2021-05-11 | 上海应用技术大学 | Application of copper metal organic framework film in catalytic degradation of organic dye |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478406A (en) * | 2016-08-26 | 2017-03-08 | 东北大学 | A kind of preparation method of nano-grade metal-organic framework materials |
-
2017
- 2017-04-27 CN CN201710286896.8A patent/CN107022095A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478406A (en) * | 2016-08-26 | 2017-03-08 | 东北大学 | A kind of preparation method of nano-grade metal-organic framework materials |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686563A (en) * | 2017-08-17 | 2018-02-13 | 成都新柯力化工科技有限公司 | A kind of method and microballoon foaming agent that microballoon foaming agent is prepared using spray-on process |
| CN107794767A (en) * | 2017-10-23 | 2018-03-13 | 东北大学 | A kind of method that metal organic framework compound parcel fiber is prepared using spray-on process |
| CN108043459B (en) * | 2017-12-21 | 2021-05-11 | 上海应用技术大学 | Application of copper metal organic framework film in catalytic degradation of organic dye |
| CN110052184A (en) * | 2019-04-16 | 2019-07-26 | 暨南大学 | A kind of method that gas-liquid interface prepares MOF film |
| CN110052184B (en) * | 2019-04-16 | 2021-11-23 | 暨南大学 | Method for preparing MOF (Metal organic framework) membrane at gas-liquid interface |
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