CN107794767B - Method for preparing metal organic framework compound coated fibers by using spraying method - Google Patents
Method for preparing metal organic framework compound coated fibers by using spraying method Download PDFInfo
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- CN107794767B CN107794767B CN201710994152.1A CN201710994152A CN107794767B CN 107794767 B CN107794767 B CN 107794767B CN 201710994152 A CN201710994152 A CN 201710994152A CN 107794767 B CN107794767 B CN 107794767B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/687—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing atoms other than phosphorus, silicon, sulfur, nitrogen, oxygen or carbon in the main chain
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
- D06B1/02—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by spraying or projecting
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/02—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fibres, slivers or rovings
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a method for preparing metal organic framework compound coated fibers by using a spraying method, which comprises the steps of taking a metal cation solution as a spraying solution and an organic ligand solution as a solution for soaking fibers, injecting the metal cation solution to be atomized into a spraying device through an automatic sample injection pump, dispersing the metal cation solution into liquid small particles in a nozzle through ultrasonic waves, spraying the liquid small particles out of the nozzle in a mist form, uniformly dropping the atomized solution on the surfaces of the fibers soaked with the organic ligand solution under the action of gravity, and reacting the two substances on the surfaces of the fibers after contacting to form the metal organic framework compound and coat the metal organic framework compound on the surfaces of the fibers. The invention has the advantages that: the operation is simple, and the control and the industrial production are convenient; normal temperature and pressure, mild experimental conditions, environmental protection and energy conservation; the reaction speed is high, and the preparation period is short; the product collection method is simple and convenient, and is convenient for subsequent use.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a method for preparing a metal organic framework compound coated fiber by using a spraying method.
Background
The metal organic framework compound is a novel nano-pore crystalline material, and the structure of the metal organic framework compound is formed by combining metal ions or metal clusters with various organic ligands in a strong coordination bond form. The metal organic framework compound has excellent physicochemical properties such as uniform aperture, ultrahigh specific surface area, stronger adsorption affinity and the like. The fiber wrapped by the metal organic framework compound is a composite material, integrates the excellent properties of the metal organic framework compound and the fiber, enhances the physical and chemical properties of the fiber, and expands the application field of the fiber. The common method for preparing the metal organic framework compound coated fiber comprises the following steps: direct sedimentation in precursor solution; a free diffusion method. However, these methods are complicated in operation, long in synthesis period, and large in energy consumption in the preparation process, and are not suitable for industrial production.
Disclosure of Invention
In order to solve the technical problems, the invention utilizes the ultrasonic spraying technology to prepare the metal organic framework compound on the surface of the fiber, realizes the synchronous synthesis of the metal organic framework nanosheet and the synchronous wrapping on the surface of the fiber, and has the advantages of simple operation, short synthesis period and convenient large-scale production in industry.
The specific technical scheme is as follows:
a method for preparing a metal organic framework compound coated fiber by using a spraying method comprises the following steps:
(1) two reaction solutions were prepared by selecting one of the following cases:
the first condition is as follows:
the first solution is a metal cation solution, the solute is copper acetate, the concentration is 0.015mol/L-0.025mol/L, the solvent is a mixture of N, N-dimethylformamide and acetonitrile with the volume ratio of 1:2,
the second is organic ligand solution; the solute is terephthalic acid, the concentration is 0.005mol/L-0.015mol/L, and the solvent is a mixture of N, N-dimethylformamide and acetonitrile with the volume ratio of 2: 1;
case two:
the first solution is a metal cation solution, the solute is zinc acetate, the concentration is 0.0055mol/L-0.0065mol/L, the solvent is a mixture of N, N-dimethylformamide and acetonitrile with the volume ratio of 1:2,
the second is organic ligand solution; the solute is terephthalic acid, the concentration is 0.005mol/L-0.015mol/L, and the solvent is a mixture of N, N-dimethylformamide and acetonitrile with the volume ratio of 2: 1;
case three:
the first solution is a metal cation solution, the solute is cobalt acetate, the concentration is 0.15mol/L, the solvent is N, N-dimethylformamide,
the second is organic ligand solution; the solute is terephthalic acid, the concentration is 0.15mol/L, and the solvent is N, N-dimethylformamide;
(2) soaking: soaking the substrate fiber in an organic ligand solution, and taking out the substrate fiber after soaking;
(3) spraying: injecting the metal cation solution as a spray solution into a spray head, dispersing the metal cation solution into small liquid drop particles through ultrasonic waves, and spraying the small liquid drop particles out of the spray head in a mist form; the atomized solution uniformly falls on the underlying substrate fiber soaked with the organic ligand solution, and the two solutions start to construct a metal-organic framework compound after contacting the surface of the fiber, so that the fiber wrapped by the metal-organic framework compound is obtained; the obtained fiber wrapped by the metal organic framework compound is washed and purified by repeatedly soaking in N, N-dimethylformamide.
Further, spraying in the step (3): the spraying solution is injected into the nozzle by an automatic sample injection pump, the parameter of the automatic sample injection pump is set to be 30 mu L/min of flow, and the spraying time is 400 s.
Further, the substrate fiber is one of carbon felt fiber, cotton fabric fiber or organic fiber.
The invention successfully synthesizes the fiber wrapped by the metal organic framework compound by a spraying method. At present, the fiber wrapped by the metal framework compound has good application in the aspects of gas sensing, adsorption, catalysis and the like. Compared with the traditional wrapping method, the method has the advantages that: (1) the operation is simple and convenient, the control is easy, and the industrial production is facilitated; (2) the reaction is carried out at normal temperature and normal pressure, the experimental conditions are mild, and the energy is saved and the environment is protected; (3) the reaction is fast and the period is short; (5) the product is convenient to collect and is beneficial to subsequent use.
Drawings
FIG. 1 is an SEM photograph of carbon felt fibers wrapped by a metal organic framework compound prepared by a spraying method when anhydrous copper acetate is used as a solute of a metal cation solution and the concentration is 0.02 mol/L;
FIG. 2 is an in-situ X-ray diffraction spectrum of a metal organic framework compound coated carbon felt fiber prepared by a spraying method when anhydrous copper acetate is used as a solute of a metal cation solution and the concentration is 0.02 mol/L;
FIG. 3 is an SEM picture of a metal organic framework compound coated cotton fiber prepared by a spraying method when anhydrous copper acetate is used as a solute of a metal cation solution and the concentration is 0.02 mol/L;
FIG. 4 is an SEM picture of nylon cloth fiber wrapped by metal organic framework compound prepared by spraying method when anhydrous copper acetate is used as the solute of the metal cation solution and the concentration is 0.02 mol/L. Fig. 4(1) is a wide-range view at 12000 times magnification, and fig. 4(2) is a partial parcel view at 80000 times magnification.
FIG. 5 is an SEM picture of carbon felt fiber coated with metal organic framework compound prepared by spraying method when anhydrous zinc acetate is used as the solute of the metal cation solution and the concentration is 0.006 mol/L;
FIG. 6 is an SEM picture of carbon felt fiber coated with metal organic framework compound prepared by spraying method when cobalt acetate tetrahydrate is used as the solute of metal cation solution and the concentration is 0.15 mol/L.
Detailed Description
Example 1
(1) Two reaction solutions were prepared: the first one is copper acetate solution with the concentration of 0.015mol/L, the solute is anhydrous copper acetate, and the solvent is a mixed solvent of 1:2N, N-dimethylformamide and acetonitrile in volume ratio; the second one is terephthalic acid solution with the concentration of 0.005mol/L, the solute is terephthalic acid, and the solvent is a mixed solvent of N, N-dimethylformamide and acetonitrile with the volume ratio of 2: 1.
(2) The soaking process comprises the following steps: soaking 2 x 2cm carbon felt fiber in terephthalic acid solution, and taking out for later use after completely wetting;
(3) and (3) spraying process: injecting anhydrous copper acetate solution serving as spray solution into a spray head of a spraying device through an injector of an automatic sample injection pump, dispersing the anhydrous copper acetate solution into small liquid particles in the spray head through ultrasonic waves, and spraying the small liquid particles out of the spray head in a mist form; the atomized solution evenly falls on a carbon felt soaked with terephthalic acid under the action of self gravity, and the two substances start to construct a copper-terephthalic acid metal organic framework compound after contacting the surface of carbon felt fibers; setting parameters of an automatic sample injection pump:
flow rate: 30 mu L/min
10 times of distribution
Distribution time: 100s
Amount of liquid to be dispensed 50. mu.L
The interval time is 0.1min
Selecting an injector: 4.25mm
(4) Purification of fibers coated with metal organic framework compounds: the obtained copper-terephthalic acid coated carbon felt fiber is washed and purified by repeatedly soaking in N, N-dimethylformamide.
Example 2
The concentration of copper acetate in example 1 was changed to 0.025mol/L and the concentration of terephthalic acid was changed to 0.015mol/L, and the other procedures were the same as in example 1.
Example 3
The concentration of copper acetate in example 1 was changed to 0.02mol/L and the concentration of terephthalic acid was changed to 0.01mol/L, and the other procedures were the same as in example 1.
Example 4
The soaked fibers were changed to cotton, and the other procedure was the same as in example 1.
Example 5
The soaked fibers were changed to cotton, and the other procedure was the same as in example 2.
Example 6
The soaked fibers were changed to cotton, and the other procedure was the same as in example 3.
Example 7
The soaked fiber was changed to nylon cloth, and the other procedure was the same as in example 1.
Example 8
The soaked fiber was changed to nylon cloth, and the other procedure was the same as in example 2.
Example 9
The soaked fiber was changed to nylon cloth, and the other procedure was the same as in example 3.
Example 10
(1) Two reaction solutions were prepared: the first one is zinc acetate solution with the concentration of 0.0055mol/L, the solute is anhydrous zinc acetate, and the solvent is a mixed solvent of 1:2N, N-dimethylformamide and acetonitrile in volume ratio; the second one is terephthalic acid solution with the concentration of 0.05mol/L, the solute is terephthalic acid, and the solvent is a mixed solvent of N, N-dimethylformamide and acetonitrile with the volume ratio of 2: 1;
(2) the soaking process comprises the following steps: soaking 2 x 2cm carbon felt fiber in terephthalic acid solution, and taking out for later use after completely wetting;
(3) and (3) spraying process: injecting an anhydrous zinc acetate solution serving as a spray solution into a spray head of a spraying device through an injector of an automatic sample injection pump, dispersing the anhydrous zinc acetate solution into small liquid particles in the spray head through ultrasonic waves, and spraying the small liquid particles out of the spray head in a mist form; the atomized solution evenly falls on the carbon felt soaked with the terephthalic acid under the action of self gravity, and the two substances start to construct a zinc-terephthalic acid metal organic framework compound after contacting the surface of the carbon felt fiber; setting parameters of an automatic sample injection pump:
flow rate: 30 mu L/min
10 times of distribution
Distribution time: 100s
Amount of liquid to be dispensed 50. mu.L
The interval time is 0.1min
Selecting an injector: 4.25mm
(4) Purification of fibers coated with metal organic framework compounds: the obtained carbon felt fiber wrapped by the zinc-terephthalic acid is washed and purified by repeatedly soaking in N, N-dimethylformamide.
Example 11
The concentration of zinc acetate in example 10 was changed to 0.0065mol/L, and the concentration of terephthalic acid was changed to 0.015mol/L, in the same manner as in example 10.
Example 12
The concentration of zinc acetate in example 10 was changed to 0.006mol/L, and the concentration of terephthalic acid was changed to 0.01mol/L, and the other procedures were the same as in example 10.
Example 13
(1) Two reaction solutions were prepared: the first one is cobalt acetate solution with the concentration of 0.15mol/L, the solute is cobalt acetate tetrahydrate, and the solvent is N, N-dimethylformamide; the second is terephthalic acid solution with concentration of 0.15mol/L, the solute is terephthalic acid and the solvent is N, N-dimethylformamide.
(2) The soaking process comprises the following steps: soaking 2 x 2cm carbon felt fiber in terephthalic acid solution, and taking out for later use after completely wetting;
(3) and (3) spraying process: injecting a cobalt acetate solution serving as a spray solution into a spray head of a spraying device through an injector of an automatic sample injection pump, dispersing the cobalt acetate solution into small liquid particles in the spray head through ultrasonic waves, and spraying the small liquid particles out of the spray head in a mist form; the atomized solution evenly falls on a carbon felt soaked with terephthalic acid under the action of self gravity, and the two substances start to construct a copper-terephthalic acid metal organic framework compound after contacting the surface of carbon felt fibers; setting parameters of an automatic sample injection pump:
flow rate: 30 mu L/min
10 times of distribution
Distribution time: 100s
Amount of liquid to be dispensed 50. mu.L
The interval time is 0.1min
Selecting an injector: 4.25mm
(4) Purification of fibers coated with metal organic framework compounds: the obtained carbon felt fiber wrapped by the zinc-terephthalic acid is washed and purified by repeatedly soaking in N, N-dimethylformamide.
The invention will now be described with reference to the accompanying drawings, wherein fig. 1 is an SEM photograph of a metal organic framework compound-coated carbon fiber prepared by a spraying method with anhydrous copper acetate as a metal cation solution at a concentration of 0.02mol/L, and as shown in the drawing, the metal organic framework compound-coated carbon fiber prepared by the spraying method is uniform.
FIG. 2 is an in-situ X-ray diffraction spectrum of a metal organic framework compound coated carbon fiber prepared by a spraying method when anhydrous copper acetate is used as a metal cation solution and the concentration is 0.02 mol/L.
FIG. 3 is an SEM photograph of cotton fiber wrapped with metal organic framework compound prepared by spraying method with anhydrous copper acetate as metal cation solution and concentration of 0.02mol/L, and as shown in the figure, the cotton fiber wrapped with metal organic framework compound prepared by spraying method is uniform.
FIG. 4 is an SEM photograph of nylon fibers wrapped with metal organic framework compound prepared by spraying method with anhydrous copper acetate as metal cation solution at a concentration of 0.02mol/L, and as shown in the figure, the nylon fibers wrapped with metal organic framework compound prepared by spraying method are uniform.
FIG. 5 is an SEM photograph of carbon fiber wrapped with metal organic framework compound prepared by spraying method with zinc acetate as metal cation solution at concentration of 0.006mol/L, and the carbon fiber wrapped with metal organic framework compound prepared by spraying method is uniform.
Fig. 6 is an SEM photograph of the metal-organic framework compound-coated carbon fiber prepared by the spraying method at a concentration of 0.15mol/L using cobalt acetate as the metal cation solution, and as shown in the figure, the metal-organic framework compound-coated carbon fiber prepared by the spraying method is uniform.
Claims (2)
1. A method for preparing a metal organic framework compound coated fiber by using a spraying method is characterized by comprising the following steps:
(1) two reaction solutions were prepared by selecting one of the following cases:
the first condition is as follows:
the first solution is a metal cation solution, the solute is copper acetate, the concentration is 0.015mol/L-0.025mol/L, the solvent is a mixture of N, N-dimethylformamide and acetonitrile with the volume ratio of 1:2,
the second is organic ligand solution; the solute is terephthalic acid, the concentration is 0.005mol/L-0.015mol/L, and the solvent is a mixture of N, N-dimethylformamide and acetonitrile with the volume ratio of 2: 1;
case two:
the first solution is a metal cation solution, the solute is zinc acetate, the concentration is 0.0055mol/L-0.0065mol/L, the solvent is a mixture of N, N-dimethylformamide and acetonitrile with the volume ratio of 1:2,
the second is organic ligand solution; the solute is terephthalic acid, the concentration is 0.005mol/L-0.015mol/L, and the solvent is a mixture of N, N-dimethylformamide and acetonitrile with the volume ratio of 2: 1;
case three:
the first solution is a metal cation solution, the solute is cobalt acetate, the concentration is 0.15mol/L, the solvent is N, N-dimethylformamide,
the second is organic ligand solution; the solute is terephthalic acid, the concentration is 0.15mol/L, and the solvent is N, N-dimethylformamide;
(2) soaking: soaking the substrate fiber in an organic ligand solution, and taking out the substrate fiber after soaking;
(3) spraying: injecting the metal cation solution as a spray solution into a spray head, dispersing the metal cation solution into small liquid drop particles through ultrasonic waves, and spraying the small liquid drop particles out of the spray head in a mist form; the spraying solution is injected into the nozzle by an automatic sample injection pump, the parameter of the automatic sample injection pump is flow 30 mu L/min, and the spraying time is 400 s; the atomized solution uniformly falls on the underlying substrate fiber soaked with the organic ligand solution, and the two solutions start to construct a metal-organic framework compound after contacting the surface of the fiber, so that the fiber wrapped by the metal-organic framework compound is obtained; the obtained fiber wrapped by the metal organic framework compound is washed and purified by repeatedly soaking in N, N-dimethylformamide.
2. The method for preparing the metal organic framework compound coated fiber by using the spraying method according to claim 1, wherein the metal organic framework compound coated fiber comprises the following steps: the substrate fiber is one of a carbon felt fiber or an organic fiber.
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| CN113437279B (en) * | 2021-08-26 | 2021-11-16 | 河南师范大学 | Preparation method of MOFs-coated high-conductivity multi-wall carbon nanotube composite material and application of MOFs-coated high-conductivity multi-wall carbon nanotube composite material in potassium ion battery |
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| CN105133317A (en) * | 2015-08-16 | 2015-12-09 | 哈尔滨工业大学宜兴环保研究院 | Method for modification of carbon fiber surface by use of metal organic framework |
| CN107201645A (en) * | 2017-04-28 | 2017-09-26 | 东华大学 | A kind of metal organic frame/carbon nano-fiber composite film material and preparation method thereof |
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