CN111952010B - Flexible metal organic framework compound film and preparation method and application thereof - Google Patents

Flexible metal organic framework compound film and preparation method and application thereof Download PDF

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CN111952010B
CN111952010B CN202010641558.3A CN202010641558A CN111952010B CN 111952010 B CN111952010 B CN 111952010B CN 202010641558 A CN202010641558 A CN 202010641558A CN 111952010 B CN111952010 B CN 111952010B
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organic framework
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CN111952010A (en
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王维科
查通
穆雪阳
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Shaanxi University of Science and Technology
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    • H01—ELECTRIC ELEMENTS
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    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract

The invention provides a flexible metal organic framework compound film and a preparation method and application thereof, wherein the method comprises the following steps of 1, sequentially loading an aluminum source and an oxygen source on the upper surface of polyester fiber cloth through an atomic layer deposition system, and forming an alumina film on the polyester fiber cloth after the aluminum source and the oxygen source react; step 2, sequentially immersing the surface-modified polyester fiber cloth in a BTC solution and a copper acetate solution; and 3, removing impurities in the flexible thin film with the Cu-BTC to obtain the flexible metal organic framework compound thin film. And drying the film, soaking the film in a TCNQ solution or pyrrole solution, taking out the dried film, soaking the dried film in an iodine n-hexane solution, and finally taking out the dried film to obtain the flexible conductive metal organic framework compound film. The defect that a metal organic framework compound film in the prior art is easy to fall off on a flexible base material is effectively overcome, and the stability and the conductivity of the flexible metal organic framework compound material are greatly improved.

Description

Flexible metal organic framework compound film and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of flexible conductive materials, in particular to a flexible metal organic framework compound film and a preparation method and application thereof.
Background
The metal organic framework has good porosity and large specific surface area, and the synthesis and electronic design can be used for producing a framework with permanent pores and long-distance charge transport characteristics, and the excellence is proved.
The metal organic framework material is mostly an insulator, but compared with the conventional material, the material has more reactive sites, provides conditions for the attachment of charged particles and provides possibility for the migration of charges. At present, one important problem limiting the application of this material is that it is difficult to compromise between flexibility and stability. Therefore, how to increase the flexibility of the product to the maximum extent on the premise of ensuring the stability of the product becomes one of the research hotspots of researchers at present.
In the preparation of the metal organic framework compound, a hydrothermal method is used for preparing a powder material, but the powder material is difficult to apply to product devices after the preparation of the material is finished, and the ex-situ growth mode has great difficulty in application. The prepared film material mostly uses glass and other hard materials as substrates, and the grown material has fixed shape and insufficient flexibility and is difficult to be applied in actual production. When the conventional flexible material is used as a substrate, the metal organic framework compound is easy to fall off, the structural stability of the material is poor, and the quality is difficult to ensure.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the flexible metal organic framework compound film and the preparation method and the application thereof, which effectively make up for the defect that the metal organic framework compound film in the prior art is easy to fall off on a flexible base material, and greatly improve the stability and the conductivity of the flexible metal organic framework compound material.
The invention is realized by the following technical scheme:
a method for preparing a flexible metal organic framework compound film comprises the following steps,
step 1, sequentially loading an aluminum source and an oxygen source on the upper surface of polyester fiber cloth through an atomic layer deposition system, wherein the loading time ratio of the aluminum source to the oxygen source is (0.01-0.03): (0.1-0.3), wherein the exposure time ratio of the aluminum source to the oxygen source is (6-10): (6-10) reacting an aluminum source and an oxygen source to form an aluminum oxide film on the polyester fiber cloth to obtain the surface-modified polyester fiber cloth;
step 2, sequentially immersing the surface-modified polyester fiber cloth into a BTC solution and a copper acetate solution to obtain a flexible film with Cu-BTC;
and 3, removing impurities in the flexible thin film with the Cu-BTC to obtain the flexible metal organic framework compound thin film.
Preferably, the aluminum source and the oxygen source in step 1 are trimethyl aluminum and water, respectively.
Preferably, in the step 1, the aluminum source and the oxygen source are sequentially loaded on the upper surface of the polyester fiber cloth at 70-85 ℃.
Preferably, in the step 1, after loading the aluminum source, purging is carried out for 20-30 s by using a carrier gas, and after loading the oxygen source, purging is carried out for 25-40 s.
Preferably, in the step 2, the mass ratio of BTC to copper acetate is 0.95: 0.89; the solvents of the BTC solution and the copper acetate solution are absolute ethyl alcohol.
Preferably, in the step 2, the surface modified polyester fiber cloth is firstly immersed in the BTC solution for 5-10 minutes, then taken out and immersed in absolute ethyl alcohol for 3-8 minutes, and then the obtained composite is immersed in the copper acetate solution for 3-8 minutes, so as to obtain the flexible film with the Cu-BTC growing.
A flexible metal organic framework compound film obtained by the method for preparing a flexible metal organic framework compound film according to any one of the above.
The application of the flexible metal organic framework compound film comprises the steps of drying the flexible metal organic framework compound film, soaking the dried flexible metal organic framework compound film in a TCNQ solution, taking out the dried flexible metal organic framework compound film and drying the dried flexible metal organic framework compound film to obtain a flexible conductive metal organic framework compound film;
the flexible metal organic framework compound film is firstly dried and then soaked in pyrrole, then taken out and soaked in iodine normal hexane solution, and finally taken out and dried to obtain the flexible conductive metal organic framework compound film.
Further, the flexible metal organic framework compound film is dried and then soaked in the TCNQ solution for 48-72 hours.
Further, the flexible metal organic framework compound film is dried and then soaked in pyrrole for 18-24 hours, and then taken out and soaked in an iodine n-hexane solution for 48-72 hours.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a flexible metal organic framework compound film, which adopts the Atomic Layer Deposition (ALD) technology to coat a film on a common flexible substrate polyester fiber cloth, prepares an aluminum oxide film on the surface of the polyester fiber cloth by limiting the loading time ratio and the exposure time ratio of an aluminum source and an oxygen source so as to obtain enough attachment active sites, and then immerses the obtained surface-modified polyester fiber cloth in a BTC solution and a copper acetate solution in sequence to react BTC and copper acetate, so that the formed metal organic framework compound Cu-BTC can stably exist on the surface of the polyester fiber cloth. The preparation method adopts the similar idea of ALD method to prepare the invention, and effectively reduces the impurity concentration in the material and improves the stability and quality of the material by timely removing the redundant reactants on the surface of the polyester fiber cloth. The transition layer is prepared between the metal organic framework compound and the base material in a mode of coating the surface of the base material, so that the defect that a metal organic framework compound film is easy to fall off on a flexible base material in the prior art is effectively overcome, the stability of the flexible metal organic framework compound material is greatly improved, the problem of compatibility is effectively avoided, favorable conditions are provided for completing doping modification, and more possibilities are provided for the application of the flexible metal organic framework compound material in production. The transition layer is reasonably changed, so that the preparation method can be popularized to the preparation process of various film materials, and has quite important inspiration significance for the flexibility of the conductive material. Meanwhile, the preparation of the metal organic framework compound through the similar idea of the ALD method is an expansion and attempt of the existing preparation method of the material, and can also be applied to the preparation of other metal organic framework compound materials.
According to the invention, a mode of coating a film on the polyester fiber cloth is adopted, and the transition layer alumina is prepared between the metal organic framework compound Cu-BTC and the base material polyester fiber cloth, so that the obtained film material not only ensures the mode of in-situ growth of the material, but also increases the flexibility of the material.
According to the invention, reasonable electron acceptors or functional materials with high conductivity are doped on the flexible metal organic framework compound thin film, so that the flexibility of the MOFs Cu-BTC thin film is improved, and meanwhile, the electron acceptors and the functional materials with high conductivity are doped, so that the conductivity of the MOFs Cu-BTC thin film is obviously improved, and a greater possibility is provided for the application of the MOFs Cu-BTC in the aspect of electricity.
Drawings
FIG. 1 is an I-V curve obtained by TCNQ doping of flexible MOFs Cu-BTC films with different cycle numbers (10, 20, 30, 40) using polyester cloth as a base material.
FIG. 2 is an I-V curve obtained by PPy doping of flexible MOFs Cu-BTC films with different cycle numbers (10, 20, 30, 40) using polyester fiber cloth as a base material.
FIG. 3 is an XRD diffraction pattern of MOFs Cu-BTC thin film using the polyester fiber cloth obtained in example 4 as a substrate and TCNQ and PPy obtained in example 8 after doping modification.
Fig. 4 is a partial enlarged view of fig. 3 showing the modified TCNQ doping 2 θ of 5 to 7.
FIG. 5 is a partial enlarged view of the PPy doping modified 2 θ of FIG. 3, which is 6-8.
FIG. 6 is a schematic diagram of a MOFs Cu-BTC film using the polyester fiber cloth obtained in example 4 as a substrate.
FIG. 7 is a diagram of a TCNQ-doped modified sample obtained in example 8.
FIG. 8 is a diagram showing a modified example of the doping of PPy obtained in example 8.
FIG. 9 is an SEM image of a MOFs Cu-BTC film based on polyester cloth at 100 μm under 40 cycles.
FIG. 10 is an SEM image of a MOFs Cu-BTC film based on polyester fiber cloth at 25 μm cycle at 40.
FIG. 11 is an SEM image of MOFs Cu-BTC film based on polyester cloth at 10 μm under 40 cycles.
FIG. 12 is an SEM image of 2.5 μm at 40 cycles of MOFs Cu-BTC film based on polyester cloth.
FIG. 13 is an SEM image of MOFs Cu-BTC film based on polyester cloth at 200 μm after being doped with TCNQ at 30 cycles.
FIG. 14 is an SEM image of MOFs Cu-BTC film based on polyester cloth at 10 μm after being doped with TCNQ at 30 cycles.
FIG. 15 is an SEM image of MOFs Cu-BTC film based on polyester cloth at 5 μm after being doped with TCNQ at 30 cycles.
FIG. 16 is an SEM image of 2.5 μm MOFs Cu-BTC film based on polyester cloth after being doped with TCNQ at 30 cycles.
FIG. 17 is an SEM image at 50 μm of a MOFs Cu-BTC film based on polyester fiber cloth after being doped with TCNQ at 40 cycles.
FIG. 18 is an SEM image at 15 μm of a MOFs Cu-BTC film based on polyester fiber cloth after being doped with TCNQ at 40 cycles.
FIG. 19 is an SEM image of MOFs Cu-BTC film based on polyester cloth at 10 μm after being doped with TCNQ at 40 cycles.
FIG. 20 is an SEM image of MOFs Cu-BTC film based on polyester cloth at 8 μm after being doped with TCNQ at 40 cycles.
FIG. 21 is an SEM image of a MOFs Cu-BTC film with polyester cloth as a substrate, which is doped with PPy at 30 cycles and then reaches 300 μm.
FIG. 22 is an SEM image of a MOFs Cu-BTC film with polyester cloth as a substrate, which is doped with PPy at 30 cycles and then reaches 100 μm.
FIG. 23 is an SEM image of 25 μm MOFs Cu-BTC film based on polyester cloth doped with PPy at 30 cycles.
FIG. 24 is an SEM image of 2.5 μm after PPy doping of MOFs Cu-BTC film based on polyester cloth at 30 cycles.
FIG. 25 is an SEM image of a MOFs Cu-BTC film with polyester cloth as the substrate after being doped with PPy at 40 cycles and 200 μm.
FIG. 26 is an SEM image of 50 μm MOFs Cu-BTC film based on polyester cloth doped with PPy at 40 cycles.
FIG. 27 is an SEM image of a MOFs Cu-BTC film with polyester cloth as the substrate after being doped with PPy at 40 cycles and then at 10 μm.
FIG. 28 is an SEM image of MOFs Cu-BTC film with polyester cloth as the substrate, doped by PPy at 40 cycles, different at 5 μm.
Fig. 29 is an absorption curve of the MOFs Cu-BTC thin film based on the polyester cloth obtained in example 4 and the TCNQ doping-modified thin films obtained in examples 7 and 8.
Fig. 30 shows absorption curves of the MOFs Cu-BTC thin film based on the polyester cloth obtained in example 4 and the PPy doping modified thin film obtained in examples 7 and 8.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a preparation method of a flexible metal organic framework compound film, which utilizes an atomic layer deposition method to modify the surface of polyester fiber so that a metal organic framework compound can stably grow on the surface of the polyester fiber, and the specific method comprises the following steps:
step 1, cutting purchased polyester fiber cloth into 20mm multiplied by 20mm, alternately cleaning three to five times by using deionized water and ethanol through ultrasonic waves, drying, and placing in an atomic layer deposition system;
and 2, respectively taking Trimethylaluminum (TMA) and deionized water as an aluminum source and an oxygen source, loading the aluminum source and the oxygen source into the system through nitrogen, carrying out fixed time pulse at the temperature of 70-85 ℃, counting as a cycle, and purging by using nitrogen at the reaction interval of the Trimethylaluminum (TMA) and the deionized water. Specifically, 0.01-0.03 s of trimethylaluminum is loaded, the exposure time is 6-10 s, the nitrogen purging time is 20-30 s, the deionized water introducing time is 0.1-0.3 s, the exposure time is 6-10 s, and the nitrogen purging time is 25-40 s. The nitrogen is introduced in a cycle with a flow rate of 40-60 sccm.
Generally, the reaction process is carried out for 100-300 cycles, an alumina film is prepared on the surface of the polyester fiber cloth, the thickness of the film is 1-2 nm in each 10-cycle reaction, the thickness of 100-300 cycles is 10-60 nm, and the cycle times can be selected according to actual requirements.
Step 3, preparing the metal organic framework compound by taking copper acetate and 1,3, 5-benzene tricarboxylic acid (BTC) as raw materials, wherein the specific method comprises the following steps:
a, respectively dissolving 0.95g of BTC and 0.89g of copper acetate in 100ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 20-45 minutes to fully dissolve the BTC and the copper acetate. Taking 100ml of absolute ethyl alcohol in a beaker to obtain liquid A;
b, placing the polyester fiber cloth plated with the alumina film in a BTC solution of absolute ethyl alcohol for treatment for 5-10 minutes under an ultrasonic condition to enable the BTC to be adsorbed in the alumina film to obtain a compound, then taking out the compound and placing the compound in a liquid A for treatment for 3-8 minutes to remove redundant BTC, then taking out the compound and placing the compound in a copper acetate solution of absolute ethyl alcohol for treatment for 5-10 minutes to enable the BTC and the copper acetate to react, and then taking out the compound and placing the compound in the liquid A soaked in the compound for treatment for 1 minute. The above-mentioned treatment process is used as a circulation, and can treat different circulations so as to prepare the metal organic framework compound with required thickness.
The absolute ethyl alcohol is replaced once every 3-6 cycles, and the absolute ethyl alcohol BTC solution and the absolute ethyl alcohol copper acetate solution are replaced once every 8-12 cycles.
The flexible metal organic framework compound film which has a stable structure and takes the polyester fiber cloth as the base material, namely the flexible MOFs Cu-BTC film can be obtained through the steps.
Example 1
The invention relates to a preparation method of a flexible metal organic framework compound film with 10 cycles, which specifically comprises the following steps:
step 1, cleaning 20mm × 20mm polyester fiber cloth, drying and placing in an atomic layer deposition system;
step 2, Trimethylaluminum (TMA) and deionized water are used as the aluminum source and the oxygen source, respectively, and loaded into the system by nitrogen, a fixed time pulse is carried out at 75 ℃, counted as one cycle, and purging is carried out by using nitrogen at the interval of the two reactions. Specifically, trimethylaluminum is loaded for 0.02s, the exposure time is 8s, the nitrogen purging time is 25s, the deionized water introducing time is 0.1s, the exposure time is 8s, and the nitrogen purging time is 40 s. This was a cycle with a nitrogen flow of 50 sccm. For a total of 10 cycles.
And 3, respectively putting 0.89g of copper acetate and 0.95g of BTC in 100ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 20min to fully dissolve the copper acetate and the BTC. Placing 100ml of absolute ethyl alcohol in a beaker;
step 4, plating Al2O3Cutting polyester fiber cloth of the film into squares (20mm multiplied by 20mm), and soaking in BTC absolute ethyl alcohol solution for 5 min;
step 5, taking out and placing in absolute ethyl alcohol for soaking treatment for 3 min;
step 6, taking out the mixture, and soaking the mixture in an absolute ethyl alcohol solution of copper acetate for 5 min;
and 7, taking out, and soaking in an absolute ethanol solution for 1 min. Repeating the process for 10 times to prepare the flexible metal organic framework compound film with 10 cycles.
Example 2
The invention relates to a preparation method of a flexible metal organic framework compound film with 20 cycles, which comprises the following steps:
step 1, cleaning 20mm × 20mm polyester fiber cloth, drying and placing in an atomic layer deposition system;
and 2, respectively taking Trimethylaluminum (TMA) and deionized water as an aluminum source and an oxygen source, loading the aluminum source and the oxygen source into the system through nitrogen, carrying out fixed time pulse at 70 ℃, counting as one cycle, and purging by using the nitrogen at the interval of the two reactions. Specifically, 0.02s of trimethylaluminum is loaded, the exposure time is 6s, the nitrogen purging time is 20s, the deionized water introducing time is 0.1s, the exposure time is 8s, and the nitrogen purging time is 35 s. This was a cycle with a nitrogen flow of 40 sccm. For a total of 20 cycles.
And 3, respectively putting 0.89g of copper acetate and 0.95g of BTC in 100ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 20min to fully dissolve the copper acetate and the BTC. Placing 100ml of absolute ethyl alcohol in a beaker;
step 4, plating Al2O3Cutting polyester fiber cloth of the film into squares (20mm multiplied by 20mm), and soaking in BTC absolute ethyl alcohol solution for 10 min;
step 5, taking out and placing in absolute ethyl alcohol for soaking treatment for 5 min;
step 6, taking out the copper acetate, and soaking the copper acetate in an absolute ethyl alcohol solution for 7 min;
and 7, taking out the mixture, and then soaking the mixture in an absolute ethyl alcohol solution for 1 min. Repeating the process for 20 times to prepare the flexible metal organic framework compound film with 20 cycles.
Example 3
The invention relates to a preparation method of a 30-cycle flexible metal organic framework compound film, which specifically comprises the following steps:
step 1, cleaning 20mm × 20mm polyester fiber cloth, drying and placing in an atomic layer deposition system;
and 2, respectively taking Trimethylaluminum (TMA) and deionized water as an aluminum source and an oxygen source, loading the aluminum source and the oxygen source into the system through nitrogen, carrying out fixed time pulse at 85 ℃, counting as one cycle, and purging by using the nitrogen at the interval of the two reactions. Specifically, 0.01s of trimethylaluminum is loaded, the exposure time is 10s, the nitrogen purging time is 25s, the deionized water introducing time is 0.3s, the exposure time is 6s, and the nitrogen purging time is 25 s. This was a cycle with a nitrogen flow of 55 sccm. For a total of 30 cycles.
And 3, respectively putting 0.89g of copper acetate and 0.95g of BTC in 100ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 20min to fully dissolve the copper acetate and the BTC. Placing 100ml of absolute ethyl alcohol in a beaker;
step 4, plating Al2O3Cutting polyester fiber cloth of the film into squares (20mm multiplied by 20mm), and soaking in BTC absolute ethyl alcohol solution for 8 min;
step 5, taking out and placing in absolute ethyl alcohol for soaking treatment for 4 min;
step 6, taking out the mixture, and soaking the mixture in an absolute ethyl alcohol solution of copper acetate for 10 min;
and 7, taking out the mixture, and then soaking the mixture in an absolute ethyl alcohol solution for 1 min. The above process was repeated 30 times to prepare 30 cycles of flexible metal organic framework compound thin films.
Example 4
The invention relates to a preparation method of a flexible metal organic framework compound film with 40 cycles, which comprises the following steps:
step 1, cleaning 20mm × 20mm polyester fiber cloth, drying and placing in an atomic layer deposition system;
and 2, respectively taking Trimethylaluminum (TMA) and deionized water as an aluminum source and an oxygen source, loading the aluminum source and the oxygen source into the system through nitrogen, carrying out fixed time pulse at 80 ℃, counting as one cycle, and purging by using the nitrogen at the interval of the two reactions. Specifically, 0.03s of trimethylaluminum is loaded, the exposure time is 8s, the nitrogen purging time is 30s, the deionized water introducing time is 0.2s, the exposure time is 10s, and the nitrogen purging time is 30 s. This was a cycle with a nitrogen flow of 60 sccm. For a total of 40 cycles.
And 3, respectively putting 0.89g of copper acetate and 0.95g of BTC in 100ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 20min to fully dissolve the copper acetate and the BTC. Placing 100ml of absolute ethyl alcohol in a beaker;
step 4, plating Al2O3Cutting polyester fiber cloth of the film into squares (20mm multiplied by 20mm), and soaking in BTC absolute ethyl alcohol solution for 6 min;
step 5, taking out the mixture and placing the mixture into absolute ethyl alcohol for soaking treatment for 8 min;
step 6, taking out the mixture, and soaking the mixture in an absolute ethyl alcohol solution of copper acetate for 9 min;
and 7, taking out the mixture, and then soaking the mixture in an absolute ethyl alcohol solution for 1 min. Repeating the process for 40 times to prepare the flexible metal organic framework compound film with 40 cycles.
The invention further applies the flexible MOFs Cu-BTC film to prepare the flexible conductive metal organic framework compound film, and the specific method comprises the following steps:
the method is used for preparing the flexible MOFs Cu-BTC film which is prepared by 10 cycles, 20 cycles, 30 cycles and 40 cycles and takes the polyester fiber cloth as the base material for standby, and two strategies are taken into consideration in a doping manner:
and a, TCNQ doping is carried out on the flexible MOFs Cu-BTC film taking polyester fiber cloth as a base material, wherein TCNQ is a strong electron acceptor, can form a charge transfer compound with a plurality of electron donors, and has high conductivity.
Drying the flexible MOFs Cu-BTC film which is prepared by taking polyester fiber cloth as a base material in 10 cycles, 20 cycles, 30 cycles and 40 cycles, and placing the film in a low-temperature vacuum drying oven for vacuum treatment at 150-200 ℃ for 1-3 h.
4 parts of 0.0090g TCNQ are respectively treated by ultrasonic treatment in 4 parts of 20ml methanol for 1.5 to 3 hours to be fully dissolved. And (3) placing the treated MOFs Cu-BTC in a methanol solution of TCNQ, soaking for 48-72 h, and taking out and drying after the treatment is finished.
b, carrying out polypyrrole (PPy) doping on the flexible MOFs Cu-BTC film taking the polyester fiber cloth as the base material.
Drying the flexible MOFs Cu-BTC film which is prepared by taking polyester fiber cloth as a base material in 10 cycles, 20 cycles, 30 cycles and 40 cycles, and placing the film in a low-temperature vacuum drying oven for vacuum treatment at 150-200 ℃ for 1-3 h.
After the completion, the mixture is respectively placed in 10-25ml of pyrrole for treatment for 18-24 h. And (2) placing 0.15-0.35g of iodine in 20ml of normal hexane for ultrasonic treatment for 45-60 min, preparing 4 parts of solution with the same concentration, respectively placing the treated MOFs Cu-BTC in the normal hexane solution of iodine for treatment for 48-72 h, polymerizing pyrrole on the MOFs Cu-BTC film by using the iodine to form polypyrrole, and taking out and drying after the treatment is finished.
Example 5
The invention relates to a preparation method of a flexible conductive metal organic framework compound film with 10 cycles, which specifically comprises the following steps:
a, TCNQ doping is carried out on the flexible MOFs Cu-BTC film which takes polyester fiber cloth as a base material,
step 1, placing 10 circulating flexible MOFs Cu-BTC films with polyester fiber cloth as a substrate in a low-temperature vacuum drying oven for vacuum treatment at 190 ℃ for 120 min;
step 2, taking 0.0090g of TCNQ, putting the TCNQ into 20ml of methanol, and carrying out ultrasonic treatment for 120min to fully dissolve the TCNQ;
step 3, placing the treated 10-cycle MOFs Cu-BTC thin films in a methanol solution of TCNQ, and soaking for 72 hours;
and 4, taking out and drying after the treatment is finished.
b, carrying out polypyrrole (PPy) doping on the flexible MOFs Cu-BTC film taking the polyester fiber cloth as the base material.
Step 1, placing 10 circulating flexible MOFs Cu-BTC films with polyester fiber cloth as a substrate in a low-temperature vacuum drying oven for vacuum treatment at 190 ℃ for 120 min;
step 2, after the treatment, placing the mixture in 20ml of pyrrole for treatment for 24 hours;
step 3, placing 0.254g of iodine in 20ml of n-hexane for ultrasonic treatment for 60 min;
and 4, placing the treated 10-cycle flexible MOFs Cu-BTC thin films with the polyester fiber cloth as the substrate into an iodine n-hexane solution for treatment for 66 hours, and taking out and drying after the treatment is finished.
Example 6
The invention relates to a preparation method of a flexible conductive metal organic framework compound film with 20 cycles, which comprises the following steps:
a, TCNQ doping is carried out on the flexible MOFs Cu-BTC film which takes polyester fiber cloth as a base material,
step 1, placing 20 circulating flexible MOFs Cu-BTC films with polyester fiber cloth as a substrate into a low-temperature vacuum drying oven for vacuum treatment at 180 ℃ for 120 min;
step 2, taking 0.0090g of TCNQ, putting the TCNQ into 20ml of methanol, and carrying out ultrasonic treatment for 120min to fully dissolve the TCNQ;
step 3, placing the treated 20-cycle MOFs Cu-BTC thin films in a methanol solution of TCNQ, and soaking for 65 hours;
and 4, taking out and drying after the treatment is finished.
And b, carrying out polypyrrole (PPy) doping on the flexible MOFs Cu-BTC film taking the polyester fiber cloth as the base material.
Step 1, placing 20 circulating flexible MOFs Cu-BTC films with polyester fiber cloth as a substrate into a low-temperature vacuum drying oven for vacuum treatment at 180 ℃ for 120 min;
step 2, after the treatment, placing the mixture in 20ml of pyrrole for treatment for 22 h;
step 3, placing 0.254g of iodine in 20ml of normal hexane for ultrasonic treatment for 60 min;
and 4, placing the treated 20 recycled flexible MOFs Cu-BTC films with the polyester fiber cloth as the substrate in an iodine n-hexane solution for treatment for 48 hours, and taking out and drying after the treatment is finished.
Example 7
The invention relates to a preparation method of a 30-cycle flexible conductive metal organic framework compound film, which specifically comprises the following steps:
a, TCNQ doping is carried out on a flexible MOFs Cu-BTC film which takes polyester fiber cloth as a base material,
step 1, placing 30 circulating flexible MOFs Cu-BTC films with polyester fiber cloth as a substrate in a low-temperature vacuum drying oven for vacuum treatment at 150 ℃ for 360 min;
step 2, taking 0.0090g of TCNQ, putting the TCNQ into 20ml of methanol, and carrying out ultrasonic treatment for 120min to fully dissolve the TCNQ;
step 3, placing the treated MOFs Cu-BTC thin films with 30 cycles in a methanol solution of TCNQ, and soaking for 50 hours;
and 4, taking out and drying after the treatment is finished.
And b, carrying out polypyrrole (PPy) doping on the flexible MOFs Cu-BTC film taking the polyester fiber cloth as the base material.
Step 1, placing 30 circulating flexible MOFs Cu-BTC films with polyester fiber cloth as a substrate in a low-temperature vacuum drying oven for vacuum treatment at 150 ℃ for 360 min;
step 2, after finishing, placing the mixture in 20ml of pyrrole for treatment for 18 h;
step 3, placing 0.254g of iodine in 20ml of normal hexane for ultrasonic treatment for 60 min;
and 4, placing the treated 30 recycled flexible MOFs Cu-BTC films with the polyester fiber cloth as the substrate in an iodine n-hexane solution for treatment for 72 hours, and taking out and drying after the treatment is finished.
Example 8
The invention relates to a preparation method of a 40-cycle flexible conductive metal organic framework compound film, which specifically comprises the following steps:
a, TCNQ doping is carried out on the flexible MOFs Cu-BTC film which takes polyester fiber cloth as a base material,
step 1, placing 40 circulating flexible MOFs Cu-BTC films with polyester fiber cloth as a substrate in a low-temperature vacuum drying oven for vacuum treatment at 200 ℃ for 60 min;
step 2, 0.0090g of TCNQ is taken and placed in 20ml of methanol, and ultrasonic treatment is carried out for 120min to ensure that the TCNQ is fully dissolved;
step 3, placing the treated 40-cycle MOFs Cu-BTC thin films in a methanol solution of TCNQ, and soaking for 48 hours;
and 4, taking out and drying after the treatment is finished.
And b, carrying out polypyrrole (PPy) doping on the flexible MOFs Cu-BTC film taking the polyester fiber cloth as the base material.
Step 1, placing 40 circulating flexible MOFs Cu-BTC films with polyester fiber cloth as a substrate in a low-temperature vacuum drying oven for vacuum treatment at 200 ℃ for 60 min;
step 2, after finishing, placing the mixture in 20ml of pyrrole for treatment for 20 hours;
step 3, placing 0.254g of iodine in 20ml of normal hexane for ultrasonic treatment for 60 min;
and 4, placing the treated 40-cycle flexible MOFs Cu-BTC thin films with the polyester fiber cloth as the substrate in an iodine n-hexane solution for treatment for 60 hours, and taking out and drying after the treatment is finished.
FIGS. 1 and 2 show the electrical characteristics of the flexible MOFs Cu-BTC film based on polyester fiber cloth doped with electron acceptor and functional material with high conductivity. Fig. 1 shows that the conductivity of the flexible MOFs Cu-BTC thin film doped with TCNQ is significantly improved, and the more cycles, the better conductivity is exhibited after the flexible MOFs Cu-BTC thin film is doped. Fig. 2 shows that the conductivity of the flexible MOFs Cu-BTC thin film doped with PPy with high conductivity is greatly improved, and the flexible MOFs Cu-BTC thin film shows the best conductivity after being doped after 40 cycles.
FIG. 3 is XRD diffraction patterns of MOFs Cu-BTC thin film using polyester fiber cloth obtained in example 4 as a substrate and TCNQ and PPy obtained in example 8 after doping modification. Because the polyester fiber cloth is taken as a substrate in XRD test, the interference generated by diffraction peaks of the substrate material is generated. The characteristic peaks of the MOFs Cu-BTC film shown in the figure have distinct peaks at positions 2 θ ═ 12 °, 17 °, 23 °, and 27 °. The TCNQ-doped MOFs Cu-BTC thin film shows that the peaks at 12 degrees, 17 degrees, 23 degrees and 27 degrees of 2 theta are increased, and the positions of the peaks are not changed obviously. The peak value of 2 theta of the PPy-doped MOFs Cu-BTC thin film is not shown, the peak values at the positions of 2 theta 17 degrees, 23 degrees and 27 degrees are obviously reduced, and new peaks appearing at the positions of 2 theta 43 degrees, 50 degrees, 68 degrees and 77 degrees are also the characteristics of guest molecules PPy doped in the nanometer channels.
Fig. 4 and 5 are partial enlarged views of TCNQ doping-modified 2 θ of 5 to 7 and PPy doping-modified 2 θ of 6 to 8 in fig. 3. Fig. 4 shows that after the MOFs Cu-BTC film using polyester fiber cloth as a substrate is doped with TCNQ, a characteristic peak of TCNQ appears at a position of 2 θ -5.75 °, and it can be judged that TCNQ molecules are bonded to open metal sites in macropores of the film, and the long-range order is shown. Fig. 5 shows that the new peak at 2 θ of 7.2 ° comes from the PPy part in the nano-pore of the MOFs Cu-BTC film based on polyester fiber cloth after doping by PPy.
Fig. 6, 7 and 8 are diagrams of MOFs Cu-BTC thin films based on polyester fiber cloth obtained in example 4 and TCNQ and PPy doped and modified real objects obtained in example 8, respectively. As can be seen from the figure, the polyester fiber cloth shown in figure 6 has obvious blue substance coverage on the surface, uniform surface and good flatness; FIG. 7 shows that the blue covering layer on the surface of the polyester fiber cloth is changed into dark green, the surface is uniform, and the flatness is good; in FIG. 8, it is shown that the blue coating on the surface of the polyester fiber cloth is changed into tan, the surface fibers are slightly damaged, and the surface of the coating is uniform.
SEM images of different magnifications of the MOFs Cu-BTC film taking polyester fiber cloth as a substrate under 40 cycles are respectively shown in the figures 9, 10, 11 and 12. It is obvious from fig. 9 and 10 that the polyester fiber surface is smooth and complete, and has no obvious structural damage and defect. In FIG. 11 and FIG. 12, it can be observed that the polyester fiber surface has a complete surface layer covering, and it can be judged that the MOFs Cu-BTC film is well prepared on the substrate.
FIGS. 13, 14, 15 and 16 are SEM images of MOFs Cu-BTC film with polyester cloth as the substrate, after being doped with TCNQ at 30 cycles, at different magnifications; FIGS. 17, 18, 19 and 20 are SEM images of MOFs Cu-BTC film with polyester cloth as the substrate, which is doped with TCNQ at 40 cycles and then under different magnifications. In FIGS. 13 and 14, it can be observed that the surface of the polyester fiber is substantially complete, and the surface roughness is obviously increased compared with that before TCNQ doping; FIG. 15 and FIG. 16 show that the polyester fiber is coated with the layered material, and the tiny powder substances can be observed on the surface; FIGS. 17 and 18 show that the polyester fibers are smoother but have increased surface roughness and less structural damage than before TCNQ doping; fig. 19 and 20 observe that the surface is coated with a distinct layer of material, and the powder material is distinct compared to the increase in thickness of fig. 15 and 16.
In conclusion, the MOFs Cu-BTC film taking the polyester fiber-based composite material as the substrate has obvious micro-morphology change after being doped with TCNQ, and the doping effect is obvious.
FIGS. 21, 22, 23 and 24 are SEM images of MOFs Cu-BTC film with polyester cloth as the substrate, which is doped by PPy at 30 cycles and then under different magnifications; FIGS. 25, 26, 27 and 28 are SEM images of MOFs Cu-BTC film with polyester cloth as the substrate, which is doped by PPy at 40 cycles and then under different magnifications. In FIGS. 21 and 22, it can be observed that the surface of the polyester fiber is basically complete, and the surface roughness is increased compared with the surface roughness before PPy doping; in FIGS. 23 and 24, it can be observed that the polyester fiber surface is coated with the layered material, and the micro particulate matter can be observed on the surface; FIGS. 25 and 26 show that the polyester fiber surface is substantially intact, the structural failure is less, and the roughness is significantly increased; in fig. 27 and 28, the surface is obviously coated by the layered material, and compared with the thickness in fig. 23 and 24, the particle substance is obvious.
In conclusion, after the MOFs Cu-BTC film taking the polyester fiber cloth as the substrate is doped by PPy, the obvious microscopic morphology change is generated, and the doping effect is obvious.
In FIG. 29, 990cm appeared after TCNQ doping-1，1180cm-1，1330cm-1New peak of (2) and TCNQ at 1529cm-1Characteristic peak of (2), especially 2204cm-1Is a C.ident.N extension of TCNQ influenced by adsorption into the framework, from 2223cm-1Move to 2204cm-1And a significant peak broadening occurs, the shift being between-0.4 e for the backbone and TCNQ–In response to charge transfer. 690cm is shown in FIG. 30-1And 1170cm-1The new absorption peak, in particular, the characteristic band of PPy shown, is due to 1039cm-1In-plane deformation vibration of 1458cm-1C-C asymmetric stretching vibration of 1540cm-1Py Ring stretching mode above, and 1292cm exhibited by deformation in CH and CN planes-1The band spectrum of (a).

Claims (1)

1. The application of the flexible metal organic framework compound film is characterized in that the flexible conductive metal organic framework compound film is obtained according to the following step S1 or step S2;
step S1: drying the flexible metal organic framework compound film, soaking the flexible metal organic framework compound film in a methanol solution of TCNQ for 48-72 h, taking out the flexible metal organic framework compound film and drying the flexible metal organic framework compound film to obtain a flexible conductive metal organic framework compound film;
step S2: firstly, drying a flexible metal organic framework compound film, soaking the film in pyrrole for 18-24 hours, taking out the film, soaking the film in a 7.5-17.5 g/L iodine normal hexane solution for 48-72 hours, and finally taking out the film and drying the film to obtain a flexible conductive metal organic framework compound film;
the flexible metal organic framework compound film is obtained by the following steps:
step 1a, sequentially loading trimethylaluminum and water on the upper surface of polyester fiber cloth through an atomic layer deposition system at 70-85 ℃, loading the trimethylaluminum, then purging for 20-30 s with carrier gas, and after loading the water, purging for 25-40 s, wherein the loading time ratio of the trimethylaluminum to the water is (0.01-0.03): (0.1-0.3), wherein the exposure time ratio of the trimethylaluminum to the water is (6-10): (6-10), reacting trimethylaluminum with water to form an aluminum oxide film on the polyester fiber cloth to obtain the surface-modified polyester fiber cloth;
step 1b, firstly, soaking the surface modified polyester fiber cloth in a BTC solution for 5-10 minutes, then taking out and soaking in absolute ethyl alcohol for 3-8 minutes, then soaking the obtained compound in a copper acetate solution for 3-8 minutes, wherein the mass ratio of BTC to copper acetate is 0.95: 0.89, the solvents of the BTC solution and the copper acetate solution are absolute ethyl alcohol, and a flexible film with Cu-BTC grows;
and step 1c, removing impurities in the flexible thin film with the Cu-BTC to obtain the flexible metal organic framework compound thin film.
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