CN110791045A - Metal organic framework film, preparation thereof and application thereof in identifying nitro explosives - Google Patents
Metal organic framework film, preparation thereof and application thereof in identifying nitro explosives Download PDFInfo
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- CN110791045A CN110791045A CN201810866836.8A CN201810866836A CN110791045A CN 110791045 A CN110791045 A CN 110791045A CN 201810866836 A CN201810866836 A CN 201810866836A CN 110791045 A CN110791045 A CN 110791045A
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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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- 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
- C08J2487/00—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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
The invention discloses a metal organic framework film, a preparation method thereof and application thereof in identifying nitro explosives, wherein the metal organic framework film is formed by copolymerizing metal organic framework material MOF and polyvinylidene fluoride PVDF, and the mass ratio of the metal organic framework material MOF to the polyvinylidene fluoride PVDF is 1-10: 1; the metal organic framework material MOF is a coordination polymer of a microporous network structure formed by self-assembly of metal ions and a compound A, is ZIF-8, UIO-66, MIL-101, MOF-5 or HKUST-1 and has the advantage of rapid identification of nitro explosives.
Description
Technical Field
The invention relates to the field of chiral polysaccharide recognition, in particular to a metal organic framework film, preparation thereof and application thereof in recognition of nitro explosives.
Background
Most nitro compounds can be used as explosives, and nitro-containing explosives such as trinitrotoluene (TNT), trinitrophenol (PA), hexogen (RDX), cyclone explosive (PETN), nitroglycerin and compound explosives containing the above compounds account for more than 80% of the explosives. The detection of nitro compounds has therefore long been a research hotspot in the field of sensors. Metal Organic Frameworks (MOFs) are one of the hot spots in the field of functional materials. The MOF has the advantages of highly ordered pore channel structure, adjustable pore diameter, larger specific surface area, various synthetic methods, easy functional modification and the like, is a new crystal material, and is rarely reported in the detection neighborhood of nitro compounds.
Disclosure of Invention
A first object of the present invention is to provide a metal organic framework film having the advantage of rapidly recognizing nitro explosives.
The technical purpose of the invention is realized by the following technical scheme:
a metal organic framework membrane is formed by copolymerizing metal organic framework materials MOF and polyvinylidene fluoride PVDF, wherein the mass ratio of the metal organic framework materials MOF to the polyvinylidene fluoride PVDF is 1-10: 1; the metal organic framework material MOF is a coordination polymer of a microporous network structure formed by self-assembly of metal ions and a compound A, and is selected from ZIF-8, UIO-66, MIL-101, MOF-5 or HKUST-1.
ZIF-8, UIO-66, MIL-101, MOF-5 or HKUST-1 are all existing MOF metal organic framework materials, and can be directly purchased from the market.
The second purpose of the invention is to provide a preparation method of the metal organic framework film.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of a metal organic framework film comprises the following steps:
dissolving polyvinylidene fluoride (PVDF) in DMF, adding metal organic framework material MOF, uniformly mixing, and controlling the temperature to be 80-120 ℃ until the solvent is dried; the mass ratio of polyvinylidene fluoride PVDF to MOF is 1: 1-10.
The third purpose of the invention is to provide an application of the metal organic framework film in the rapid identification of nitro explosives.
The technical purpose of the invention is realized by the following technical scheme:
an application of a metal organic framework film in the fast identification of nitro explosives.
More preferably: adding a solution of nitro explosives into the solution of the metal organic framework film, recording the fluorescence intensity in the process, and observing the degree of quenching of fluorescence to a final state and the time used, thereby rapidly identifying the nitro explosives.
In conclusion, the invention has the following beneficial effects:
(1) nitro explosives can be identified quickly: because the monomer compound A has axial chirality, the hydroxyl of the chiral framework can be identified with the specific hydrogen bond of the nitro explosive;
(2) the synthesis method is a common solvothermal reaction in a laboratory, is simple and convenient to operate, easy to amplify, high in yield and capable of quickly identifying various nitro explosives.
Detailed Description
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the present invention.
Example 1: dissolving 10g of polyvinylidene fluoride (PVDF) in DMF, adding 3g of ZIF-8, paving on a glass plate, controlling the temperature at 100 ℃ by program and maintaining for 12 hours, after the solvent is volatilized and dried, putting the glass plate into water, and naturally stripping the membrane. Washing with distilled water for several times, drying for later use, wherein the yield is 95%, and nuclear magnetic verification shows that ZIF-8 and polyvinylidene fluoride PVDF are successfully polymerized. Compared with ZIF-8, the melting point of the product is increased by 125 ℃.
Example 2
Dissolving 10g of polyvinylidene fluoride PVDF in DMF, adding 3g of UIO-66, paving on a glass plate, controlling the temperature by program to be 100 ℃ and maintaining for 12 hours, after the solvent is volatilized and dried, putting the glass plate into water, and naturally stripping the membrane. Washing with distilled water for several times, drying for later use, wherein the yield is 97%, and the polymerization of UIO-66 and polyvinylidene fluoride PVDF is successful through nuclear magnetic verification. The melting point of the product was increased by 110 ℃ compared to UIO-66.
Example 3
Dissolving 10g of polyvinylidene fluoride (PVDF) in DMF, adding 3g of MIL-101, spreading on a glass plate, controlling the temperature by program to be 100 ℃ and maintaining for 12 hours, after the solvent is volatilized and dried, putting the glass plate into water, and naturally stripping the membrane. Washing with distilled water for several times, drying for later use, wherein the yield is 98%, and the polymerization of MIL-101 and polyvinylidene fluoride PVDF is successfully verified through nuclear magnetism. Compared with MIL-101, the melting point of the product is raised by 150 ℃.
Example 4
Dissolving 10g of polyvinylidene fluoride PVDF in DMF, adding 3g of MOF-5, paving on a glass plate, controlling the temperature by program to be 100 ℃ and maintaining for 12 hours, after the solvent is volatilized and dried, putting the glass plate into water, and naturally stripping the membrane. Washing with distilled water for several times, drying for later use, wherein the yield is 96%, and the MOF-5 and polyvinylidene fluoride PVDF are successfully polymerized through nuclear magnetic verification. The melting point of the product was raised by 100 ℃ compared to MOF-5.
Example 5
Dissolving 10g of polyvinylidene fluoride PVDF in DMF, adding 3g of HKUST-1, spreading on a glass plate, controlling the temperature by program at 100 ℃ for 12 hours, after the solvent is volatilized and dried, putting the glass plate in water, and naturally stripping the membrane. Washing with distilled water for several times, drying for later use, wherein the yield is 93%, and the HKUST-1 and polyvinylidene fluoride PVDF are successfully polymerized through nuclear magnetic verification. Compared with HKUST-1, the melting point of the product is increased by 80 ℃.
Fluorescence sensing experiment: the fully ground COF was dispersed in acetonitrile to prepare a solution having a concentration of 1.0X 10-5 mol/L. Acetonitrile solutions of 1.0X 10-3mol/L TNT (2,4, 6-trinitrotoluene), PA (1' p-2, 4, 6-trinitrophenol), RDX (cyclotrimethylenetrinitramine) and NGC (nitroglycerin) are prepared respectively. 200. mu.l of the nitro compound solution was added to 2.0mL of the sample solution, and the fluorescence intensity was recorded every 10 seconds. The excitation wavelength for the fluorescence experiment was set at 365nm and the slit width was set at 2nm x 2nm, and the extent of quenching of the fluorescence to the final state and the time used were observed, and nitro explosives were identified according to table 1.
TABLE 1 percent intensity reduction of quenching of nitro-explosives fluorescence in different metal organic framework films to the final state and time used
| TNT | PA | RDX | NGC | |
| Example 1 | 92%/10 seconds | 54%/20 seconds | 73%/10 seconds | 87%/20 seconds |
| Example 2 | 99%/10 seconds | 64%/10 seconds | 43%/30 seconds | 75%/20 seconds |
| Example 3 | 80%/30 seconds | 67%/20 seconds | 63%/10 seconds | 97%/50 seconds |
| Example 4 | 92%/10 seconds | 57%/30 seconds | 73%/20 seconds | 86%/30 seconds |
| Example 5 | 82%/40 seconds | 69%/10 seconds | 83%/10 seconds | 99%/30 seconds |
The above description should not be taken as limiting the invention to the specific embodiments, but rather, as will be readily apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined in the claims appended hereto.
Claims (4)
1. The metal organic framework membrane is characterized by being formed by copolymerizing metal organic framework materials MOF and polyvinylidene fluoride PVDF, wherein the mass ratio of the metal organic framework materials MOF to the polyvinylidene fluoride PVDF is 1-10: 1; the metal organic framework material MOF is a coordination polymer of a microporous network structure formed by self-assembly of metal ions and a compound A, and is selected from ZIF-8, UIO-66, MIL-101, MOF-5 or HKUST-1.
2. The preparation method of the metal organic framework film is characterized by comprising the following steps:
dissolving polyvinylidene fluoride (PVDF) in DMF, adding metal organic framework material MOF, uniformly mixing, and controlling the temperature to be 80-120 ℃ until the solvent is dried; the mass ratio of polyvinylidene fluoride PVDF to MOF is 1: 1-10.
3. Use of the metal-organic framework film according to claim 1 or the metal-organic framework film prepared by the preparation method according to claim 2 for the rapid identification of nitro-explosives.
4. Use according to claim 3, characterized in that: adding a solution of nitro explosives into the solution of the metal organic framework film, recording the fluorescence intensity in the process, and observing the degree of quenching of fluorescence to a final state and the time used, thereby rapidly identifying the nitro explosives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810866836.8A CN110791045A (en) | 2018-08-01 | 2018-08-01 | Metal organic framework film, preparation thereof and application thereof in identifying nitro explosives |
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| CN201810866836.8A CN110791045A (en) | 2018-08-01 | 2018-08-01 | Metal organic framework film, preparation thereof and application thereof in identifying nitro explosives |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578273A (en) * | 2021-07-28 | 2021-11-02 | 长三角(义乌)生态环境研究中心 | Preparation method of metal organic framework film |
| CN115521560A (en) * | 2022-08-18 | 2022-12-27 | 国网黑龙江省电力有限公司电力科学研究院 | Sealing composite material capable of resisting low temperature of-40-15 ℃, preparation method and sensor |
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| WO2009012528A1 (en) * | 2007-07-24 | 2009-01-29 | Adelaide Research & Innovation Pty Ltd | Optical fiber sensor |
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2018
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Patent Citations (5)
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Non-Patent Citations (2)
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| TINGTING CHENG 等: "Luminescent metal-organic frameworks for nitro explosives detection", 《SCIENCE CHINA CHEMISTRY》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578273A (en) * | 2021-07-28 | 2021-11-02 | 长三角(义乌)生态环境研究中心 | Preparation method of metal organic framework film |
| CN115521560A (en) * | 2022-08-18 | 2022-12-27 | 国网黑龙江省电力有限公司电力科学研究院 | Sealing composite material capable of resisting low temperature of-40-15 ℃, preparation method and sensor |
| CN115521560B (en) * | 2022-08-18 | 2023-11-03 | 国网黑龙江省电力有限公司电力科学研究院 | Composite material for sealing resistant to low temperature of-40-15 ℃, preparation method and sensor |
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Application publication date: 20200214 |