CN113943488B - Composite material based on polytetrafluoroethylene-coated MOFs material and preparation method thereof - Google Patents
Composite material based on polytetrafluoroethylene-coated MOFs material and preparation method thereof Download PDFInfo
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- CN113943488B CN113943488B CN202111014781.6A CN202111014781A CN113943488B CN 113943488 B CN113943488 B CN 113943488B CN 202111014781 A CN202111014781 A CN 202111014781A CN 113943488 B CN113943488 B CN 113943488B
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- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention discloses a composite material based on polytetrafluoroethylene-coated MOFs material and a preparation method thereof. The composite material is formed by wrapping MOFs material by polytetrafluoroethylene. The preparation method of the composite material comprises the following steps: and dripping the polytetrafluoroethylene emulsion into the MOFs material suspension in an ultrasonic state, then placing the MOFs material suspension in liquid nitrogen for freezing, removing moisture after thawing, and drying to obtain the composite material based on the MOFs material wrapped by the polytetrafluoroethylene. The method also comprises the step of placing the composite material in an inert atmosphere to carry out annealing treatment so as to remove moisture and nonionic surfactants in the composite material. According to the invention, the PTFE/ZIF-8-370 composite material is obtained by combining the high polymer material polytetrafluoroethylene and ZIF-8 for the first time, and has excellent performances of water stability, high pressure resistance, less loss under catalytic reaction and the like, so that a new building block is provided for an unstable metal organic frame, and a new idea is provided for the design of a metal organic frame material.
Description
Technical Field
The invention relates to the technical field of metal organic frameworks protected by high molecular polymers, in particular to a composite material based on a polytetrafluoroethylene-coated MOFs material and a preparation method thereof.
Background
Because Metal Organic Frameworks (MOFs) have the structural characteristics of large specific surface area, high porosity and the like, the MOFs is widely applied to the fields of gas storage and separation, biosensors, catalysis, biological medicine release and the like. The zeolite imidazolate framework material ZIF-8 shows a special pore structure and high hydrothermal stability and chemical stability, so that the ZIF-8 becomes a research hotspot in multiple fields. The use of ZIF-8 has been extended to aqueous solutions (removal of heavy metal ions from water, photocatalytic degradation of dyes).
Nevertheless, it has been reported in the literature that ZIF-8 crystallites are unstable in water and also produce new species. Therefore, it is a problem to be solved in the art to protect ZIF-8 from decomposition in aqueous solution applications or other reactions.
The high molecular polymer Polytetrafluoroethylene (PTFE) has excellent mechanical toughness, chemical stability, corrosion resistance, high temperature resistance, high lubrication non-adhesiveness, electric insulation, good ageing resistance and high endurance capacity, and is also a super-hydrophobic material.
Different from the traditional metal organic framework material, the metal organic framework material is combined with a high molecular polymer, so that the metal organic framework material not only retains the characteristics of the metal organic framework material, but also has the characteristics of the high molecular material. The composite material combining polytetrafluoroethylene and ZIF-8 can improve the characteristics of ZIF-8 such as water stability, high pressure resistance, hydrophobicity and the like, so that the composite material has wide application prospect in more fields.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a composite material based on a polytetrafluoroethylene-coated MOFs material and a preparation method thereof, wherein the composite material can prevent ZIF-8 from being decomposed in aqueous solution application or other reactions.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A composite material based on polytetrafluoroethylene-coated MOFs is formed by coating a MOFs material with polytetrafluoroethylene.
Preferably, the polytetrafluoroethylene accounts for 20wt% -70wt% of the composite material, and the MOFs material accounts for 30wt% -80wt% of the composite material.
Preferably, the polytetrafluoroethylene accounts for 20wt% -50wt% of the composite material, and the MOFs material accounts for 50wt% -80wt% of the composite material.
Preferably, the MOFs material is ZIF-8.
The preparation method of the composite material based on the polytetrafluoroethylene-coated MOFs material comprises the following steps:
and (3) dripping the polytetrafluoroethylene emulsion into the MOFs material suspension in the ultrasonic state, continuously carrying out ultrasonic treatment, then placing the MOFs material suspension in liquid nitrogen for freezing, removing moisture after thawing, and drying to obtain the composite material based on the MOFs material wrapped by the polytetrafluoroethylene.
Preferably, the composite material based on the polytetrafluoroethylene-coated MOFs material is subjected to annealing treatment under an inert atmosphere so as to remove moisture and nonionic surfactants in the composite material.
Preferably, the annealing treatment is to place the composite material based on the polytetrafluoroethylene-coated MOFs material in a tube furnace with argon flow, heat to 120 ℃ for 20min, and then heat to 370 ℃ for 30min.
Preferably, the polytetrafluoroethylene emulsion comprises 60wt% polytetrafluoroethylene, 30wt% nonionic surfactant and 10wt% water. The nonionic surfactant is.
Preferably, the concentration of the MOFs material suspension is 11mg/ml.
Preferably, the time of the ultrasound is 2min.
Preferably, the temperature of the drying is 100 ℃.
Because the polytetrafluoroethylene has excellent mechanical toughness, chemical stability, corrosion resistance, hydrophobicity and other properties, the problem that the ZIF-8 is decomposed in an aqueous solution can be effectively solved, and the original characteristics of the ZIF-8 are kept.
Compared with the prior art, the invention has the following beneficial effects:
(1) The composite material disclosed by the invention has excellent performances of high pressure resistance, good water stability, less loss under catalytic reaction and the like, so that a new building block is provided for an unstable metal organic frame, and a new idea is provided for the design of a metal organic frame material.
(2) The composite material has higher hydrophobicity than ZIF-8, and the hydrophobicity of the composite material is further improved after annealing treatment.
Drawings
FIG. 1a is a scanning electron micrograph (left) and a transmission electron micrograph (right) of 80% PTFE/ZIF-8 according to example 2 of the present invention.
FIG. 1b is a scanning electron micrograph (left) and a transmission electron micrograph (right) of 80% PTFE/ZIF-8-370 in example 3 of the present invention.
FIG. 1c is a scanning electron micrograph (left) and a transmission electron micrograph (right) of 50% PTFE/ZIF-8 in example 2 of the present invention.
FIG. 1d is a scanning electron micrograph (left) and a transmission electron micrograph (right) of 50% PTFE/ZIF-8-370 in example 3 of the present invention.
FIG. 2 is a graph showing the results of water stability tests on the ZIF-8 of example 1 and the PTFE/ZIF-8-370 composite of example 3 of the present invention.
FIG. 3 is a graph of the results of the high pressure stability tests of the ZIF-8 of example 1, the PTFE/ZIF-8 composite of example 2, and the PTFE/ZIF-8-370 composite of example 3 in accordance with the present invention.
FIG. 4 is a graph showing the results of recovery of the catalyst used as the ZIF-8 of example 1, the PTFE/ZIF-8 composite of example 2, and the PTFE/ZIF-8-370 composite of example 3 in accordance with the present invention.
FIG. 5 is a graph of the water contact angle of the ZIF-8 of example 1 of the present invention, the PTFE/ZIF-8 composite of example 2, and the PTFE/ZIF-8-370 composite of example 3.
Detailed Description
The following examples further illustrate the practice of the present invention, but the practice of the present invention is not limited thereto.
The experimental procedures in the following examples are all conventional procedures unless otherwise specified; the chemical reagents and raw materials used are all conventional raw materials in the field and are all commercially available unless otherwise specified.
The main reagent sources are as follows:
zinc nitrate hexahydrate: CAS registry number 10196-18-6;
2-methylimidazole: CAS registry number 693-98-1;
polytetrafluoroethylene emulsion: CAS registry number 9002-84-0;
tetrahydrofuran (CAS registry number: 109-99-9), benzaldehyde (CAS registry number: 100-52-7), malononitrile (CAS registry number: 109-77-3), acetonitrile (CAS registry number 75-05-8), ethanol (CAS registry number 64-17-5);
EXAMPLE 1 preparation of ZIF-8
(1) Weighing 1.17g of zinc nitrate hexahydrate in a 20mL glass bottle, adding 8mL of deionized water, adding 20.27g of 2-methylimidazole in a 250mL conical bottle, and adding 80mL of deionized water;
(2) Performing ultrasonic treatment on the glass bottle and the conical bottle in the step (1) until the solid is dissolved;
(3) Slowly dripping the solution in the glass bottle in the step (2) into the solution of 2-methylimidazole, and then stirring for 5min;
(4) And (4) centrifuging the turbid liquid obtained in the step (3) to obtain a white solid product, washing the white solid product with ethanol for three times, and drying the white solid product in a vacuum drying oven at 100 ℃ for 12 hours to obtain ZIF-8 powder.
EXAMPLE 2 preparation of PTFE/ZIF-8 composites
1. 80% preparation of PTFE/ZIF-8 composite
(1) Dispersing the ZIF-8 prepared in the example 1 in deionized water, performing ultrasonic treatment to obtain 5ml of suspension with the concentration of 11mg/ml, taking 20% of PTFE/ZIF-8 composite material in polytetrafluoroethylene emulsion according to the mass ratio of the PTFE to the ZIF-8 of 2:8, slowly dropping the obtained polytetrafluoroethylene emulsion into the ZIF-8 suspension in an ultrasonic state, and performing ultrasonic treatment (with the power of 100%) for 2min to obtain a mixture of the polytetrafluoroethylene and the ZIF-8.
(2) And (2) completely freezing the mixture obtained in the step (1) in liquid nitrogen, taking out, placing at normal temperature for thawing, and removing water after thawing.
(3) Drying the dewatered mixture of step (2) in a vacuum oven at 100 deg.C for 6h to obtain a white, marshmallow-touch, fluffy product, which is 80% PTFE/ZIF-8 composite.
2. 50% preparation of PTFE/ZIF-8 composite
(1) Dispersing the ZIF-8 prepared in the example 1 in deionized water, performing ultrasonic treatment to obtain 5ml of suspension with the concentration of 11mg/ml, taking 50% of PTFE/ZIF-8 composite material in polytetrafluoroethylene emulsion according to the mass ratio of the PTFE to the ZIF-8 of 5:5, slowly dropping the obtained polytetrafluoroethylene emulsion into the ZIF-8 suspension in an ultrasonic state, and performing ultrasonic treatment (with the power of 100%) for 2min to obtain a mixture of the polytetrafluoroethylene and the ZIF-8.
(2) And (2) completely freezing the mixture obtained in the step (1) in liquid nitrogen, taking out, placing at normal temperature for thawing, and removing water after thawing.
(3) And (3) placing the mixture subjected to moisture removal in the step (2) in a vacuum drying oven at 100 ℃ for drying for 6h to obtain a white, marshmallow-touch fluffy product, namely the 50-percent PTFE/ZIF-8 composite material.
EXAMPLE 3 preparation of PTFE/ZIF-8-370 composite
And (3) putting the PTFE/ZIF-8 composite material obtained in the step (a) into a tubular furnace, and annealing by using argon flow.
(1) The sample was placed in a tube furnace and heated to 120 ℃ for 20min.
(2) After the step (1) is finished, the temperature is raised to 370 ℃ and kept for 30min.
(3) Finally obtaining brown solid which is the PTFE/ZIF-8-370 composite material.
TABLE 1
From the SEM image (left) of FIG. 1a, it can be seen that when the ratio of the mass fraction of PTFE: ZIF-8 was 2:8 and 80% of the amount of PTFE/ZIF-8 synthesized was not annealed, the ZIF-8 was unevenly wrapped with PTFE, and the ball-shaped wrapping was not possible.
From the SEM image (left) of FIG. 1c, it can be seen that when the mass fraction ratio of PTFE: ZIF-8 is 5:5 and 50% by weight of the synthesized PTFE/ZIF-8 is not annealed, the PTFE can uniformly wrap the ZIF-8 to form spherical shapes.
Example 4 PTFE/ZIF-8 and PTFE/ZIF-8-370 composite Performance testing
The PTFE/ZIF-8 and PTFE/ZIF-8-370 composite materials prepared in the embodiments 2 and 3 are subjected to stability tests under the following test conditions:
1. and (3) testing the water stability: deionized water (3 ml) and the number of stirring revolutions was 750rpm.
FIG. 2 is a graph showing the stability in water of ZIF-8 and PTFE/ZIF-8-370 composites of examples 1 and 3. As can be seen from FIG. 2, after 24h of stirring, the ZIF-8 framework had collapsed, but the PTFE/ZIF-8-370 retained essentially the original diffraction peak and the framework remained stable. The result shows that the PTFE/ZIF-8-70 composite material has better stability when stirred in water for 24 hours under the same condition compared with ZIF-8 microcrystal. Encapsulation of the teflon coating was shown to protect ZIF-8.
2. Stability test under high pressure: 10mg sample, 10Mpa, hold for 2min
FIG. 3 is a graph showing stability test of ZIF-8 and its composite material in examples 1, 2 and 3 maintained at 10MPa for 2min. As can be seen from FIG. 3, the framework of ZIF-8 had completely collapsed under a pressure of 10MPa, but the original diffraction peak was still retained in the composite materials of PTFE/ZIF-8 and PTFE/ZIF-8-370, and the framework was stable. The PTFE/ZIF-8 and PTFE/ZIF-8-370 composite material prepared by the invention has high pressure resistance.
3. And (3) testing the recovery rate of the catalyst: 20mg of ZIF-8 and composite materials PTFE/ZIF-8 and PTFE/ZIF-8-370 thereof are used as catalysts, and benzaldehyde and malononitrile are subjected to catalytic test at normal temperature.
FIG. 4 is a graph showing recovery of ZIF-8 and its composite catalyzed in example 2. As can be seen from FIG. 4, ZIF-8 and its composites PTFE/ZIF-8 and PTFE/ZIF-8-370 were used as catalysts, and after the catalytic reaction, the catalysts were washed with ethanol and dried at 60 ℃ to reduce the ZIF-8 recovery to less than 50%,80% PTFE/ZIF-8 recovery to about 65%, 50% PTFE/ZIF-8 recovery to 75%, 80% PTFE/ZIF-8 recovery to 92.75%, and 50% PTFE/ZIF-8-370 recovery to 96.5%. The recovery rate of ZIF-8 is the lowest in the catalytic stirring process, and the recovery rate of the annealed composite material PTFE/ZIF-8-370 is higher.
Example 5, ZIF-8 and composite hydrophobicity testing thereof
And (3) testing the hydrophobicity of the ZIF-8 and the composite material thereof: and (3) placing the ZIF-8 and the composite material thereof on a glass sheet, flattening, and testing by a contact angle tester.
TABLE 2
FIG. 5 is a graph of water contact angles of ZIF-8 and its composites in examples 1, 2, and 3. It can be seen that ZIF-8 does not exhibit hydrophobicity. The water contact angle of the PTFE/ZIF-8 is 140-150 degrees, the water contact angle of the PTFE/ZIF-8-370 is 150-160 degrees, and the super-high hydrophobicity is shown.
Claims (8)
1. A composite material based on polytetrafluoroethylene-coated MOFs material is characterized in that the composite material is formed by coating the MOFs material with polytetrafluoroethylene;
the MOFs material is ZIF-8;
the polytetrafluoroethylene accounts for 20-70 wt% of the composite material, and the MOFs material accounts for 30-80% of the composite material.
2. The composite material of claim 1, wherein the polytetrafluoroethylene constitutes 20wt% -50wt% of the composite material, and the MOFs material constitutes 50wt% -80wt% of the composite material.
3. Method for preparing a composite material based on polytetrafluoroethylene-coated MOFs material according to any of the claims 1-2, comprising the following steps:
and (3) dripping the polytetrafluoroethylene emulsion into the MOFs material suspension in the ultrasonic state, continuously carrying out ultrasonic treatment, then placing the MOFs material suspension in liquid nitrogen for freezing, removing moisture after thawing, and drying to obtain the composite material based on the MOFs material wrapped by the polytetrafluoroethylene.
4. The method according to claim 3, wherein the composite material based on the polytetrafluoroethylene-coated MOFs is subjected to an annealing treatment under an inert atmosphere to remove moisture and nonionic surfactants from the composite material.
5. The method according to claim 4, characterized in that the annealing treatment consists in placing the composite material based on polytetrafluoroethylene-coated MOFs in a tube furnace with argon flow, heating to 120 ℃ for 20min, and then raising the temperature to 370 ℃ for 30min.
6. The method of claim 3, wherein the polytetrafluoroethylene emulsion comprises 60wt% polytetrafluoroethylene, 30wt% nonionic surfactant, and 10wt% water.
7. The method according to claim 3, characterized in that the concentration of said MOFs material suspension is 11mg/ml.
8. The method of claim 3, wherein the sonication time is 2min.
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| CN114621545B (en) * | 2022-04-18 | 2022-12-16 | 中国科学院兰州化学物理研究所 | High-wear-resistance composite material and preparation method and application thereof |
| WO2024004664A1 (en) * | 2022-06-30 | 2024-01-04 | パナソニックＩｐマネジメント株式会社 | Composite material, articles made using same, and method for producing composite material |
| WO2024004663A1 (en) * | 2022-06-30 | 2024-01-04 | パナソニックＩｐマネジメント株式会社 | Composite material, articles made using same, and method for producing composite material |
| CN115181380B (en) * | 2022-08-15 | 2023-10-31 | 兰州中科聚润新材料有限公司 | High-temperature-resistant polytetrafluoroethylene-based composite material, preparation method thereof and application of composite material as high-temperature sealing material |
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| CN103230777A (en) * | 2013-05-06 | 2013-08-07 | 北京化工大学 | Large-scale adsorbing material ZIF-8 preparation method and forming method |
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| CN103230777A (en) * | 2013-05-06 | 2013-08-07 | 北京化工大学 | Large-scale adsorbing material ZIF-8 preparation method and forming method |
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