CN104841407B - Method and device for realizing in-situ synthesis of metal organic framework compound coating - Google Patents
Method and device for realizing in-situ synthesis of metal organic framework compound coating Download PDFInfo
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- CN104841407B CN104841407B CN201510280366.3A CN201510280366A CN104841407B CN 104841407 B CN104841407 B CN 104841407B CN 201510280366 A CN201510280366 A CN 201510280366A CN 104841407 B CN104841407 B CN 104841407B
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Abstract
The invention discloses a method and a device for realizing in-situ synthesis of a metal organic framework compound coating. A serum bottle serves as a reaction container, so that the quartz fiber surface is carboxyl-functionalized; and the metal organic framework compound coating is synthesized in a solution with a metal organic framework material by adopting an oil bath solvothermal method with stirring. The reaction device achieves an effect of synthesizing the coating, and the quartz fibers can be protected. According to the synthesis device, the design is unique, the structure is novel, the metal organic framework material coating fibers prepared by utilizing the device have the advantages of coating growth visualization, fiber length controllability and the like, and the problems that the quartz fibers are easily broken because an organic solvent is corrosive at high temperature and the like are solved in the using process; and moreover, the prepared MOFs coating fiber is uniform in coating, and the thickness of the coating is controllable.
Description
Technical field
The invention belongs in sample pre-treatments SPME coatings preparation field, and in particular to a kind of fabricated in situ metal is organic
The method and device of framework compound coating.
Background technology
Solid phase micro-extraction technique（SPME）Nineteen ninety by Canadian professor Pawliszyn propose first it is a kind of solvent-free
Sample Pretreatment Technique Used.Compared with conventional art, solid phase micro-extraction technique has that high sensitivity, operating process be simple, low cost
The features such as, can be used to fast and effeciently analyze trace organic substance in sample.Therefore, SPME is widely used in environment, food, biology
Etc. every field.The fiber coat of commercialization at present mainly has dimethyl silicone polymer（PDMS）, dimethyl silicone polymer/diethyl
Alkenyl benzene (PDMS/DVB), polyacrylate（PA）Deng macromolecule and its composite coating.These commercialization extracting fibers are
It is widely used, but there are some inevitable latent defects in use.For example, thermally-stabilised and solvent resistant stability
Difference, coating select the limitation such as limited, expensive.In order to overcome disadvantage mentioned above, in recent years people are primarily focused on out
SPME fiber coats that send out new, with function admirable.
Metallic organic framework（Metal-Organic Frameworks, MOFs）Material, is matched somebody with somebody with organic by metal ion
The porous material that body is self-assembly of by covalent bond or other intramolecular interactions.This kind of material have high-specific surface area,
Size is controllable, duct it is regular it is homogeneous, can carry out after modification, excellent thermally-stabilised and chemical stability the advantages of, current MOFs
Widely used in analytical chemistry, such as achieve application well in solid phase micro-extraction technique field and develop.Prepare
MOFs coatings have various methods, are to ensure that what is prepared applies to the uniformity and fastness of the MOFs coatings of SPME, profit
MOFs coatings with hydro-thermal or solvent heat growth in situ are the most reliably to select.The device of the MOFs coatings of conventional fabricated in situ
All it is in the reactor of polytetrafluoroethylene (PTFE), there are many inherences, such as coatings growth process is invisible, synthetic fibers
Length limited in reactor size, fiber at high temperature, it is easy to by organic reaction solvent corrosion, need the fiber surface for retaining
Polyimide coating come off that to cause fiber to become fragile easily broken etc., badly influence the preparation in situ of MOFs coatings.Using serum bottle
Surrogate response kettle as growth in situ reaction unit, under magnetic stirring oil bath synthesis MOFs coatings, have the advantages that it is a lot,
As coatings growth is process visualized, coated fiber uniformity is good, coated fiber length can arbitrarily regulate and control as needed, fiber
Surface macromolecule layer preserves good etc., so as to solve the great number of issues existing for the coating using reactor fabricated in situ.
But so far it is not yet reported that adopting serum bottle as the reaction unit of growth in situ, under magnetic stirring oil bath synthesis MOFs paintings
The method of layer.
The content of the invention
It is an object of the invention to provide a kind of method and device of fabricated in situ metal organic framework compound coating, closes
It is simple, economical, visualized into method so that the MOFs coated fibers that composition length is controllable, pliability is good are possibly realized.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of method of fabricated in situ metal organic framework compound coating, the oil bath solvent-thermal method stirred using band is closed
Into.
Comprise the following steps that：
1）The pretreatment of quartz fibre
Take a length be 20 cm, the quartz fibre that internal diameter is 125 μm, the cm of front end 3 is partly submerged in 10 in acetone
Min, divests the polyimide coating of fiber surface, and secondary washing three times is dried；It is 1 by exposed quartz portions immersion concentration
1 h is activated in the sodium hydroxide solution of M, makes surface produce substantial amounts of silicone hydroxyl, then secondary washing three times, then immerse 0.1 M
Hydrochloric acid solution in half an hour, remove remaining alkali lye, secondary washing, drying for standby；
2）The carboxyl-functional of quartz fibre
Pretreated quartz fibre is dipped in 24 hours in 3- aminopropyl triethoxysilane solution, 120 after taking-up
It is dried 30 minutes at a temperature of DEG C, is then placed in being soaked 6 hours in the glutaric anhydride ethanol solution that concentration is 0.1g/mL, so that stone
English fiber surface carries a large amount of carboxylic groups, finally with ethanol and water washing, drying for standby；
3）The structure of coating reaction device
The black polytetrafluoroethylene (PTFE) bottle cap of a serum bottle is taken, in the lid a suitable aperture is made a call in centre, lay injection glue
Plug, takes a syringe needle through plug, by step 2）The quartz fibre handled well passes through syringe needle, and in tip portion a sealing is installed
Dottle pin, in the quartz fibre of dottle pin bare front end carboxylated；
4）Quartz fiber surface key and metal organic framework compound
It is put in serum bottleN ,NZirconium chloride and organic ligand be by-dimethylformamide with mol ratio as solvent
1:1 is dissolved in solvent, adds acetic acid；By step 3）The quartz fibre handled well is put in the reactant liquor of serum bottle, 800rpm
2-24 hours, quartz fiber surface key and metal organic framework compound are reacted in 120-130 DEG C of oil bath under magnetic agitation
Coating.
Reaction vessel is the 25mL serum bottles with black polytetrafluoroethylene (PTFE) lid, and white injection glue is laid on lid
Plug.
Described syringe needle is 5 μ L of gas-chromatography without dead volume microsyringe syringe needle.
The thickness of sealing dottle pin is 0.3-1.0cm, and top half wraps up syringe needle, the latter half parcel quartz fibre.
Described organic ligand is 2- amino terephthalic acid (TPA)s, 2- nitroterephthalics, terephthalic acid (TPA), equal benzene front three
One or more in acid, imidazoles -2- formaldehyde, 2-methylimidazole.
Key and quartz fiber surface metal organic framework compound coating thickness be 25 μm.
Quartz fibre leading portion is apart from serum bottle bottom 0.8-1.5cm.
Sealing dottle pin lower end distance reaction liquid level 0.2cm.
A kind of device of fabricated in situ metal organic framework compound coating, including be arranged in oil bath pan for holding
The serum bottle of metal organic framework compound reactant liquor, the serum bottle includes the polytetrafluoroethylene (PTFE) lid at upper end open, institute
State polytetrafluoroethylene (PTFE) lid and be provided with perforate, injection piston is embedded with hole, syringe needle is inserted in serum bottle through injection piston, function
The quartz fibre front end of change is through syringe needle and stretches in metal organic framework compound reactant liquor, in the syringe needle insertion serum bottle
End be provided with sealing dottle pin to protect quartz fibre；Magnetic particle is provided with serum bottle, it is permanent that oil bath pot bottom is provided with heat collecting type
Temperature heating magnetic stirring apparatus.
The present invention remarkable advantage be：
1）Method design is simple, economical, and the coating uniform of the MOFs coated fibers of preparation, coating layer thickness are controllable.
2）Device design is unique, structure is novel, and the metal-organic framework materials coating prepared using the method and device is fine
Dimension has coatings growth visualization, fibre length controllable, and quartz fibre is overcome in use because of organic solvent under high temperature
Corrosion causes the problems such as easily wrecking；
3）Device volume is little, is easy to lay.Device manufacturing process is simply convenient, and instrument is cheap, material source
Extensively, it is easy to which each laboratory, each scientific research department promote the use of.
Description of the drawings
Fig. 1 is the reaction unit structural representation.In figure：1. quartz fibre, 2. microsyringe syringe needle, 3. injects glue
Fill in, 4. polytetrafluoroethylene (PTFE) lid with holes, 5. serum bottle, 6. seal dottle pin, 7. oil bath pan, 8. magnetic particle, 9. heat collecting type constant temperature adds
Pyromagnetic force agitator.
Fig. 2 is that the UiO-66 coatings that the growth of serum bottle situ is obtained amplify 1000 times of scanning electron microscope (SEM) photographs.
Fig. 3 is that the UiO-66 little particles on fiber coat amplify 30000 times of scanning electron microscope (SEM) photographs.
Specific embodiment
The inventive method and device operation are further illustrated with reference to the accompanying drawings and examples.
Embodiment 1：
A kind of device of fabricated in situ metal organic framework compound coating, including be arranged in oil bath pan for holding
The serum bottle of metal organic framework compound reactant liquor, the serum bottle includes the polytetrafluoroethylene (PTFE) lid at upper end open, institute
State polytetrafluoroethylene (PTFE) lid and be provided with perforate, injection piston is embedded with hole, syringe needle is inserted in serum bottle through injection piston, function
The quartz fibre front end of change is through syringe needle and stretches in metal organic framework compound reactant liquor, in the syringe needle insertion serum bottle
End be provided with sealing dottle pin to protect quartz fibre；Magnetic particle is provided with serum bottle, it is permanent that oil bath pot bottom is provided with heat collecting type
Temperature heating magnetic stirring apparatus.
A kind of method of fabricated in situ metal organic framework compound coating, the oil bath solvent-thermal method stirred using band is closed
Into.
Comprise the following steps that：
1）The pretreatment of quartz fibre
Take a length be 20 cm, the quartz fibre that internal diameter is 125 μm, the cm of front end 3 is partly submerged in 10 in acetone
Min, divests the polyimide coating of fiber surface, and secondary washing three times is dried；It is 1 by exposed quartz portions immersion concentration
1 h is activated in the sodium hydroxide solution of M, makes surface produce substantial amounts of silicone hydroxyl, then secondary washing three times, then immerse 0.1 M
Hydrochloric acid solution in half an hour, remove remaining alkali lye, secondary washing, drying for standby；
2）The carboxyl-functional of quartz fibre
Pretreated quartz fibre is dipped in 24 hours in 3- aminopropyl triethoxysilane solution, 120 after taking-up
It is dried 30 minutes at a temperature of DEG C, is then placed in being soaked 6 hours in the glutaric anhydride ethanol solution that concentration is 0.1g/mL, so that stone
English fiber surface carries a large amount of carboxylic groups, finally with ethanol and water washing, drying for standby；
3）The structure of coating reaction device
The black polytetrafluoroethylene (PTFE) bottle cap of a serum bottle is taken, in the lid a suitable aperture is made a call in centre, lay injection glue
Plug, takes a syringe needle through plug, by step 2）The quartz fibre handled well passes through syringe needle, and in tip portion a sealing is installed
Dottle pin, in the quartz fibre of dottle pin bare front end carboxylated；
4）Quartz fiber surface key and metal organic framework compound
20 mL are put in serum bottleN ,N- dimethylformamide as solvent, by 0.160 g zirconium chlorides and
0.114 g terephthalic acid (TPA)s are dissolved in solvent, add 0.6mL acetic acid；By step 3）The quartz fibre handled well is put into serum
In the reactant liquor of bottle, react 6 hours in 120 DEG C of oil baths under 800rpm magnetic agitations, quartz fiber surface key has with metal
Machine framework compound coating.
Reaction vessel is the 25mL serum bottles with black polytetrafluoroethylene (PTFE) lid, and white injection glue is laid on lid
Plug.
Described syringe needle is 5 μ L of gas-chromatography without dead volume microsyringe syringe needle.
The thickness of sealing dottle pin is 0.5cm, and top half wraps up syringe needle, the latter half parcel quartz fibre.
Key and quartz fiber surface metal organic framework compound coating thickness be 25 μm.
Quartz fibre leading portion is apart from serum bottle bottom 1.0cm.
Sealing dottle pin lower end distance reaction liquid level 0.2cm.
Obtained UiO-66 fiber coats ESEM is as shown in Figure 2,3.We are it is apparent that made from figure
Coating is abundant, uniform, be by very little UiO-66 build-up of particles into tufted structure, particle diameter is little and uniform.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (6)
1. a kind of method of fabricated in situ metal organic framework compound coating, it is characterised in that：The oil bath stirred using band is molten
The hot method of agent synthesizes metal organic framework compound coating；Comprise the following steps that：
1）The pretreatment of quartz fibre
Take a length be 20 cm, the quartz fibre that internal diameter is 125 μm, the cm of front end 3 is partly submerged in into 10 min in acetone, shell
Except the polyimide coating of fiber surface, secondary washing three times, dry；By the hydrogen that exposed quartz portions immersion concentration is 1 M
1 h is activated in sodium hydroxide solution, makes surface produce substantial amounts of silicone hydroxyl, then secondary washing three times, then the hydrochloric acid for immersing 0.1 M
Half an hour in solution, remove remaining alkali lye, secondary washing, drying for standby；
2）The carboxyl-functional of quartz fibre
Pretreated quartz fibre is dipped in 24 hours in 3- aminopropyl triethoxysilane solution, in 120 DEG C of temperature after taking-up
Degree is lower to be dried 30 minutes, is then placed in being soaked 6 hours in the glutaric anhydride ethanol solution that concentration is 0.1g/mL, so that quartz is fine
Dimension table face carries a large amount of carboxylic groups, finally with ethanol and water washing, drying for standby；
3）The structure of coating reaction device
The black polytetrafluoroethylene (PTFE) bottle cap of a serum bottle is taken, in the lid a suitable aperture is made a call in centre, lay injection piston, taken
One syringe needle passes through plug, by step 2）The quartz fibre handled well passes through syringe needle, and in tip portion a sealing dottle pin is installed,
In the quartz fibre of dottle pin bare front end carboxylated；
4）Quartz fiber surface key and metal organic framework compound
It is put in serum bottleN ,N- dimethylformamide as solvent, by zirconium chloride and organic ligand with mol ratio as 1:1
In being dissolved in solvent, acetic acid is added；By step 3）The quartz fibre handled well is put in the reactant liquor of serum bottle, 800rpm magnetic force
2-24 hours, quartz fiber surface key and metal organic framework compound coating are reacted in 120-130 DEG C of oil bath under stirring；
Reaction vessel is the 25mL serum bottles with black polytetrafluoroethylene (PTFE) lid, and white injection piston is laid on lid；
Described syringe needle is 5 μ L of gas-chromatography without dead volume microsyringe syringe needle；
The thickness of sealing dottle pin is 0.3-1.0cm, and top half wraps up syringe needle, the latter half parcel quartz fibre.
2. method according to claim 1, it is characterised in that：Described organic ligand is 2- amino terephthalic acid (TPA)s, 2-
One or more in nitroterephthalic, terephthalic acid (TPA), trimesic acid, imidazoles -2- formaldehyde, 2-methylimidazole.
3. method according to claim 1, it is characterised in that：Key and the metallic organic framework chemical combination in quartz fiber surface
The thickness of thing coating is 25 μm.
4. method according to claim 1, it is characterised in that：Quartz fibre leading portion is apart from serum bottle bottom 0.8-1.5cm.
5. method according to claim 1, it is characterised in that：Sealing dottle pin lower end distance reaction liquid level 0.2cm.
6. a kind of device of fabricated in situ metal organic framework compound coating, it is characterised in that：Including being arranged in oil bath pan
The serum bottle for holding metal organic framework compound reactant liquor, the serum bottle include upper end open at polytetrafluoroethyl-ne
Alkene lid, the polytetrafluoroethylene (PTFE) lid is provided with perforate, and injection piston is embedded with hole, and syringe needle inserts serum through injection piston
In bottle, the quartz fibre front end of functionalization passes through syringe needle and stretches in metal organic framework compound reactant liquor, and the syringe needle is inserted
Enter the end in serum bottle and be provided with sealing dottle pin to protect quartz fibre；Magnetic particle is provided with serum bottle, oil bath pot bottom is arranged
There are heat collecting type constant-temperature heating magnetic stirring apparatus.
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| CN106111080A (en) * | 2016-06-30 | 2016-11-16 | 华南理工大学 | A kind of Cu BTC@pulp fibre composite material and molding method for preparing thereof |
| CN107174838B (en) * | 2017-06-05 | 2019-02-12 | 武汉大学 | A kind of open tubular capillary column of metal-organic framework materials containing zirconium modification and its application |
| CN108435138B (en) * | 2018-04-04 | 2020-09-01 | 福州大学 | Solid phase micro-extraction device prepared by N-doped carbon nanotube coating synthesized by using MOFs as precursor and application |
| CN108543519B (en) * | 2018-04-24 | 2020-10-09 | 福州大学 | Simple and rapid preparation method and application of covalent organic framework compound solid-phase microextraction coating |
| CN109772268A (en) * | 2019-02-15 | 2019-05-21 | 河北大学 | A kind of solid-phase micro-extraction fibre and preparation method thereof |
| CN110433775A (en) * | 2019-09-10 | 2019-11-12 | 福州大学 | A kind of solid-phase micro-extraction fibre and preparation method of in-situ chemical bond wire organic framework material |
| CN113897786A (en) * | 2020-10-09 | 2022-01-07 | 单中妹 | Anti-static wear-resistant non-woven fabric |
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| CN101332422B (en) * | 2008-06-16 | 2010-06-09 | 福州大学 | Device and use method for preparing molecular engram solid-phase micro-extraction coating |
| CN102989432A (en) * | 2012-12-28 | 2013-03-27 | 南开大学 | Preparation of solid-phase microextraction (SPME) fiber and extraction device assembled by same |
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