CN110975904A - CFs @ TiC/TiO2Composite material and preparation method and application thereof - Google Patents

CFs @ TiC/TiO2Composite material and preparation method and application thereof Download PDF

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CN110975904A
CN110975904A CN201911408169.XA CN201911408169A CN110975904A CN 110975904 A CN110975904 A CN 110975904A CN 201911408169 A CN201911408169 A CN 201911408169A CN 110975904 A CN110975904 A CN 110975904A
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cfs
composite material
tio
preparation
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CN110975904B (en
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张福勤
吕波
王小明
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Central South University
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof

Abstract

The invention discloses CFs @ TiC/TiO2Composite material, preparation method and application thereof, and CFs @ TiC/TiO2The preparation process of the composite material comprises the following steps: (1) carbon Fibers (CFs) are used as carbon raw materials, and are subjected to degumming treatment by a Soxhlet extraction method to obtain single dispersed fibers; (2) growing porous titanium carbide on the surface of the carbon fiber by using a molten salt method with titanium hydride as titanium; (3) converting the titanium carbide part growing on the surface of the carbon fiber into a potassium titanate nanosheet by using a potassium hydroxide hydrothermal method; (4) obtaining CFs @ TiC/TiO through acid treatment and heat treatment2And (3) a composite functional material. The invention has simple process, easy regulation and control of material structure, excellent performance of the prepared composite material and convenient industrial production and engineering application.

Description

CFs @ TiC/TiO2Composite material and preparation method and application thereof
Technical Field
The invention relates to CFs @ TiC/TiO2A composite material and a preparation method and application thereof, belonging to the technical field of composite material preparation.
Background
The carbon fiber is expected to be a good catalyst carrier material, which is due to good chemical stability and excellent mechanical property. The good chemical stability can enable the catalyst to be used for a long time under the more extreme chemical environment such as acid-base salt, and the good mechanical property and flexibility enable the catalyst to be better supported. However, the inertness of the surface of the carbon fiber causes the application of the carbon fiber to be limited, and particularly, the application of the carbon fiber is more prominent in the aspect of loading and using the catalyst.
With the discharge of industrial wastewater and organic wastewater, human health and living environment are polluted and damaged, scientific and technical progress and energy requirements are met, solar energy is widely concerned as a renewable energy source, and the method for degrading organic wastewater by utilizing solar photocatalysis is a good method.
Titanium dioxide is used as a semiconductor for photocatalysis and can be found by decomposing water under the irradiation of ultraviolet light, and then a plurality of researches find that cavities on the surface of titanium dioxide powder can activate oxygen in water and oxygen in air to form active oxygen substances which can oxidize organic matters so as to be widely concerned and researched. On the other hand, nanoparticles dispersed in a solution are difficult to recover and reuse.
Currently, titanium dioxide is supported on some carriers to overcome the problems of agglomeration and recycling. The carriers of nano titanium dioxide which are researched more mainly comprise: silicon dioxide, aluminum oxide, ceramics, quartz glass, activated carbon, natural minerals and organic high molecular polymers, and the like. There are few reports of using carbon fibers as carriers, mainly due to: 1. the surface of the carbon fiber is of a disordered graphite structure, the surface is smooth and inert, good wetting and combination cannot be realized between the carbon fiber and the catalyst, and the carbon fiber is easy to fall off when the catalyst is loaded. 2. The surface area of the carbon fiber is not large enough, and the contact area of the carbon fiber and the catalytic degradation organic solvent is not enough.
The main method for introducing the nano titanium dioxide on the carbon fiber comprises the following steps: the surface of the fiber is activated to carry out chemical modification, which is usually completed by chemical treatment means, such as concentrated sulfuric acid, nitric acid or hydrofluoric acid is used to oxidize the surface of the fiber into hydroxyl, carboxyl or etching, so as to provide conditions for chemical modification grafting, but toxic organic solvents are introduced through series of chemical treatments, so that serious environmental pollution is caused, in addition, the stable structure of the surface layer of the fiber needs to be activated under extreme conditions, and the strength and the performance of the fiber are also damaged; the nano titanium dioxide can also be introduced by chemical vapor deposition, surface spraying and sol-gel, and the methods are complex, require professional equipment and are not firm to fix on the surface.
Disclosure of Invention
In view of the deficiencies of the prior art, it is a first object of the present invention to provide a CFs @ TiC/TiO catalyst having excellent catalytic properties2A composite material.
The second purpose of the invention is to provide CFs @ TiC/TiO2A method for preparing a composite material.
The third purpose of the invention is to provide CFs @ TiC/TiO2Application of the composite material.
The invention relates to CFs @ TiC/TiO2The composite material has a structure from inside to outside: carbon fiber is used as a core material, a TiC intermediate layer coated with the carbon fiber and TiC-coated TiO2Nanosheets.
The composite material provided by the invention contains the titanium carbide transition layer, so that the composite material has stronger binding force with fibers, can effectively prevent the falling of a film layer, can also be used as a raw material for generating titanium dioxide, enables titanium dioxide nanosheets and lines to be uniformly distributed, avoids secondary agglomeration in the use process, and effectively exerts the catalytic performance.
In a preferred scheme, the TiC intermediate layer is in a porous structure. The porous titanium carbide greatly improves the adhesive force of the titanium dioxide, simultaneously improves the specific surface area of the composite material, and well exerts the catalytic performance.
The invention relates to CFs @ TiC/TiO2The preparation method of the composite material comprises the following steps: the method comprises the following steps:
step 1
Mixing carbon fibers with a titanium source and molten salt to obtain a mixture, and carrying out molten salt reaction on the mixture to obtain a CFs @ TiC composite material;
step 2
Placing the CFs @ TiC composite material obtained in the step 1 in potassium hydroxideIn the solution, carrying out hydrothermal reaction to obtain CFs @ TiC/K2Ti6O13A composite material;
step 3
The CFs @ TiC/K obtained in the step 22Ti6O13The composite material is sequentially subjected to acid treatment and heat treatment to obtain CFs @ TiC/TiO2A composite material.
The preparation method comprises the steps of directly generating a porous titanium carbide transition layer on the surface of carbon fiber, placing the obtained titanium carbide coated carbon fiber (CFs @ TiC) composite material in a potassium hydroxide solution, and converting the titanium carbide part on the surface of the carbon fiber into a potassium titanate nanosheet through a hydrothermal method to form the CFs @ TiC/K2Ti6O13A composite material; by acid treatment, K is2Ti6O13K in the (1) is replaced by H to form CFs @ TiC/H2Ti6O13Composite material, finally heat-treated H2Ti6O13Decomposing and converting into titanium dioxide nanosheets to obtain CFs @ TiC/TiO2A composite material.
The invention relates to CFs @ TiC/TiO2In the preparation method of the composite material, in the step 1, the carbon fibers are single dispersed carbon fibers.
As a preferred scheme, the invention relates to CFs @ TiC/TiO2The preparation method of the composite material comprises the following steps of: and (3) washing the bundled carbon fibers for 48-96h at the temperature of 60-100 ℃ by using acetone steam, and drying to obtain the single dispersed carbon fibers.
The drying adopts vacuum drying, the temperature of the vacuum drying is 105 ℃, and the time of the vacuum drying is 12-24 h.
In the actual operation, the bundled carbon fibers are placed in a soxhlet extractor, and acetone vapor is adopted for reflux to wash away the resin on the fiber surface.
In the present invention, the carbon fiber of the prior art is suitable for use in the present invention, and the type, diameter, etc. thereof are not limited, for example, a conventional T700 carbon fiber having a diameter of about 7 μm is used.
The invention relates to CFs @ TiC/TiO2Method for preparing a composite material, step 1, the methodThe titanium source is titanium hydride powder. The grain diameter of the titanium hydride powder is less than or equal to 200 meshes.
In the invention, the titanium source is preferably titanium hydride powder, and compared with the titanium powder, the titanium carbide film layer formed by using the titanium hydride as the titanium source is more porous and is more beneficial to the improvement of the catalytic performance.
The invention relates to CFs @ TiC/TiO2The preparation method of the composite material comprises the step 1, wherein the molten salt is selected from one or more of KCl, NaCl and LiCl, and is preferably KCl. The molten salt used in the present invention is analytically pure.
The invention relates to CFs @ TiC/TiO2A method of preparing a composite material, step 1, wherein, in the mixture, in terms of mole ratios, Ti: and C is 0.5-2.0. Preferably, in the mixture, the molar ratio of Ti: and C is 0.5-1.0.
The invention relates to CFs @ TiC/TiO2In the step 1, the adding amount of the molten salt in the mixture is 5-20 times of the sum of the mass of the carbon fiber and the mass of the titanium hydride powder.
The invention relates to CFs @ TiC/TiO2In the step 1, the molten salt reaction is carried out in a protective atmosphere, and the protective atmosphere is preferably an argon atmosphere.
The invention relates to CFs @ TiC/TiO2The preparation method of the composite material comprises the step 1, wherein the temperature of the molten salt reaction is 800-1200 ℃, and the time of the molten salt reaction is 1-5 h.
As a preferred scheme, the invention relates to CFs @ TiC/TiO2The preparation method of the composite material has the temperature rise rate of 5-20 ℃/min and the temperature drop rate of 5-20 ℃/min during the molten salt reaction.
In the actual operation process, after sintering is completed, the obtained CFs @ TiC composite material fiber is taken out, boiling distilled water is adopted, washing is carried out for multiple times, salt and unreacted residual titanium raw materials are dried in vacuum for 24 hours, and then the potassium hydroxide hydrothermal reaction is carried out.
According to the invention, the CFs @ TiC composite fiber is formed by adopting a molten salt reaction, and compared with other systems, a molten salt system is easier to separate, and the fiber can be well separated by using simple water.
The invention relates to CFs @ TiC/TiO2In the step 2, the concentration of the potassium hydroxide solution is 0.2-2 mol/L.
The invention relates to CFs @ TiC/TiO2In the step 2, the solid-liquid mass volume ratio of the CFs @ TiC composite material to the potassium hydroxide solution is 0.1g:10-50 ml.
The invention relates to CFs @ TiC/TiO2The preparation method of the composite material comprises the step 2, wherein the temperature of the hydrothermal reaction is 150-200 ℃, and the time of the hydrothermal reaction is 1-5 h.
The invention relates to CFs @ TiC/TiO2The preparation method of the composite material comprises the following steps of 2, placing the CFs @ TiC composite material in a potassium hydroxide solution, heating to 150-.
In the actual operation process, after the hydrothermal reaction is finished and cooled, taking out the obtained CFs @ TiC/K2Ti6O13The composite material is repeatedly washed to be neutral by distilled water and then is subjected to acid treatment.
The invention relates to CFs @ TiC/TiO2The preparation method of the composite material comprises the step 3 of carrying out acid treatment on CFs @ TiC/K2Ti6O13The composite material is soaked in acid solution for 1-10h at room temperature. After soaking, the obtained CFs @ TiC/H2Ti6O13After the composite material is taken out, the composite material is repeatedly washed to be neutral by adopting distilled water and then is subjected to heat treatment.
As a preferred scheme, the invention relates to CFs @ TiC/TiO2Preparation method of composite material, step 3, in acid solution used in acid treatment, H+The concentration of (A) is 0.2-2 moL/L.
As a preferred scheme, the invention relates to CFs @ TiC/TiO2In the step 3, the acid solution used in the acid treatment is hydrochloric acid solution.
The invention relates to CFs @ TiC/TiO2The preparation method of the composite material comprises the steps of carrying out heat treatment at the temperature of 300-600 ℃, carrying out heat treatment for 1-6h and carrying out temperature rise at the rate of 1-5 ℃/min.
The invention relates to CFs @ TiC/TiO2Application of composite material, namely applying the CFs @ TiC/TiO2The composite material is applied to a catalytic functional material.
Advantageous effects
The invention provides titanium dioxide and titanium carbide loaded carbon fiber (CFs @ TiC/TiO)2) The composite material contains the titanium carbide transition layer, can not only have stronger binding force with fibers and effectively prevent the falling of a film layer, but also can be used as a raw material for generating titanium dioxide, so that titanium dioxide nanosheets and lines are uniformly distributed, secondary agglomeration in the use process is avoided, and the catalytic performance of the composite material is effectively exerted.
In addition, TiC has an electronic structure and catalytic activity similar to those of platinum, and the anisotropic structural characteristics of the one-dimensional nano material can provide a favorable transmission channel for a current carrier, so that the synergistic effect of titanium dioxide and titanium carbide is realized, and the catalytic performance of the composite material can be exerted under visible light.
The invention also provides CFs @ TiC/TiO2The preparation method of the composite material comprises the steps of directly generating a porous titanium carbide transition layer on the surface of carbon fiber, placing the obtained titanium carbide coated carbon fiber (CFs @ TiC) composite material in a potassium hydroxide solution, and converting the titanium carbide part on the surface of the carbon fiber into a potassium titanate nanosheet through a hydrothermal method to form the CFs @ TiC/K2Ti6O13A composite material; then the mixture is treated by acid and heat to obtain CFs @ TiC/TiO2A composite material. The preparation method is simple and controllable, the material structure is easy to regulate and control, and the prepared composite material has excellent performance and is convenient for industrial production and engineering application.
Drawings
FIG. 1 is a flow chart of a composite material preparation process of the present invention;
FIG. 2 is a scanning electron micrograph of the composite obtained in example 1.
From fig. 2, the microstructure characteristics of the material surface can be clearly observed, and the titanium dioxide lamellar structure is embedded on the surface of the fiber like a blade, so that more reactive sites and larger contact area are provided.
Detailed Description
Example 1
1) Firstly, carrying out degumming treatment on carbon fibers to obtain single dispersed fibers, loading resin-coated fiber bundles by using a Soxhlet extractor, washing away the resin on the surfaces of the fibers back and forth by using acetone steam for reflux, controlling the temperature at 80 ℃ and the time at 72 hours, taking out the fibers, carrying out vacuum drying for 24 hours in a vacuum drying oven at 105 ℃, and taking out the fibers for later use;
2) titanium hydride powder and KCl (analytical grade) particles were thoroughly mixed in a sample mixer, Ti: c is 0.5 (molar ratio), the addition amount of KCl is 10 times of the mass of a reactant, carbon fibers are dispersed in a mixture of titanium hydride and KCl, the mixture is placed in an alumina crucible, the alumina crucible is placed in a tube furnace, argon is introduced as a protective gas, the temperature is programmed to rise, the temperature rise rate is 10 ℃/min, the temperature is raised to 1000 ℃, the temperature is kept for 3h at 1000 ℃, the temperature is cooled to room temperature, the temperature reduction rate is controlled to be 10 ℃/min, the crucible is taken out, boiled distilled water is used for washing for multiple times, fibers are taken out, salt and unreacted residual titanium raw materials are separated, and the fibers are dried for 24h in vacuum.
3) Putting 0.1g of dried titanium carbide modified carbon fiber into a 25mL PL high-pressure reaction kettle liner, adding 20mL of 1mol/L potassium hydroxide solution, putting the mixture into the high-pressure reaction kettle, heating to 180 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 2h, cooling to room temperature at a cooling rate of 5 ℃/min, taking out the fiber, and repeatedly washing the fiber to be neutral by using distilled water.
4) Putting the fiber subjected to high-pressure reaction into 10mL of 1moL/L hydrochloric acid solution, soaking for 1h at room temperature, taking out, repeatedly washing to neutrality, putting the fiber into a crucible, placing the crucible in a muffle furnace, heating to 400 ℃, keeping the temperature at 400 ℃ for 3h at the heating rate of 5 ℃/min, cooling and taking out to obtain the CFs @ TiC/TiO2A composite material.
5) Test for catalytic Performance
Sample CFs @ TiC/TiO2Putting the composite material into a RhB solution, wherein the solid-liquid mass ratio is 50 mg: 50mL of the sample is adsorbed in the dark for 20 minutes, the degradation rate is tested under the illumination of visible light, and the obtained sample of the embodiment 1 is catalyzed for 200minThe chemical degradation rate is 92%.
Example 2
1) Firstly, carrying out degumming treatment on carbon fibers to obtain single dispersed fibers, loading resin-coated fiber bundles by using a Soxhlet extractor, washing away the resin on the surfaces of the fibers back and forth by using acetone steam for reflux, controlling the temperature at 80 ℃ and the time at 72 hours, taking out the fibers, carrying out vacuum drying for 24 hours in a vacuum drying oven at 105 ℃, and taking out the fibers for later use;
2) titanium hydride powder and KCl (analytical grade) particles were thoroughly mixed in a sample mixer, Ti: c is 1.0 (molar ratio), the addition amount of KCl is 10 times of the mass of a reactant, carbon fibers are dispersed in a mixture of titanium hydride and KCl, the mixture is placed in an alumina crucible, the alumina crucible is placed in a tube furnace, argon is introduced as a protective gas, the temperature is programmed to rise, the temperature rise rate is 10 ℃/min, the temperature is raised to 1000 ℃, the temperature is kept for 3h at 1000 ℃, the temperature is cooled to room temperature, the temperature reduction rate is controlled to be 10 ℃/min, the crucible is taken out, boiled distilled water is used for washing for multiple times, fibers are taken out, salt and unreacted residual titanium raw materials are separated, and the fibers are dried for 24h in vacuum.
3) Putting 0.1g of dried titanium carbide modified carbon fiber into a 25mL PL high-pressure reaction kettle liner, adding 20mL of 1mol/L potassium hydroxide solution, putting the mixture into the high-pressure reaction kettle, heating to 160 ℃, keeping the temperature for 4h, cooling to room temperature at the rate of 5 ℃/min, taking out the fiber, and repeatedly washing the fiber to be neutral by using distilled water.
4) Putting the fiber subjected to the high-pressure reaction into 10mL of 1moL/L hydrochloric acid solution, soaking for 1h at room temperature, taking out, repeatedly washing to neutrality, putting the fiber into a crucible, putting the crucible into a muffle furnace, heating to 400 ℃, keeping the temperature at 400 ℃ for 3h at the heating rate of 5 ℃/min, cooling and taking out.
5) Test for catalytic Performance
5) Sample CFs @ TiC/TiO2Putting the composite material into a RhB solution, wherein the solid-liquid mass ratio is 50 mg: 50mL of the catalyst was adsorbed in the dark for 20 minutes, and the degradation rate was measured under visible light, and the catalytic degradation rate of the sample obtained in example 2 was 89% at 200 min.
Example 3
The other conditions were the same as in example 1 except that titanium powder was replaced with titanium hydride powder, and the sample obtained in example 2 was tested to have a catalytic degradation rate of 51% at 200 min.
Comparative example 1
The other conditions were the same as in example 2 except that the potassium hydroxide solution was replaced with a sodium hydroxide solution, and the resulting sample of example 2 was tested to have a catalytic degradation rate of 49% at 200 min. The detection proves that the titanium dioxide lamellar structure formed by the comparative example is insufficient, and the active sites are insufficient.

Claims (10)

1. CFs @ TiC/TiO2A composite material characterized by: the inside-out structure is: carbon fiber is used as a core material, a TiC intermediate layer coated with the carbon fiber and TiC-coated TiO2Nanosheets.
2. Preparation of a CFs @ TiC/TiO compound as claimed in claim 12A method of compounding a material, comprising the steps of:
step 1
Mixing carbon fibers with a titanium source and molten salt to obtain a mixture, and carrying out molten salt reaction on the mixture to obtain a CFs @ TiC composite material;
step 2
Placing the CFs @ TiC composite material obtained in the step 1 into a potassium hydroxide solution, and carrying out hydrothermal reaction to obtain the CFs @ TiC/K2Ti6O13A composite material;
step 3
The CFs @ TiC/K obtained in the step 22Ti6O13The composite material is sequentially subjected to acid treatment and heat treatment to obtain CFs @ TiC/TiO2A composite material.
3. The CFs @ TiC/TiO of claim 22The preparation method of the composite material is characterized by comprising the following steps: in the step 1, the titanium source is selected from titanium hydride powder, and the molten salt is one or more of KCl, NaCl and LiCl; in the mixture, in terms of molar ratio, Ti: c is 0.5-2.0; the addition amount of the molten salt is carbon fiber and hydrogenation5-20 times of the sum of the mass of the titanium powder.
4. The CFs @ TiC/TiO of claim 22The preparation method of the composite material is characterized by comprising the following steps: in the step 1, the temperature of the molten salt reaction is 800-1200 ℃, and the time of the molten salt reaction is 1-5 h.
5. The CFs @ TiC/TiO of claim 22The preparation method of the composite material is characterized by comprising the following steps: in the step 2, the concentration of the potassium hydroxide solution is 0.2-2 mol/L; the solid-liquid mass-volume ratio of the CFs @ TiC composite material to the potassium hydroxide solution is 0.1g:10-50 ml.
6. The CFs @ TiC/TiO of claim 22The preparation method of the composite material comprises the step 2, wherein the temperature of the hydrothermal reaction is 150-200 ℃, and the time of the hydrothermal reaction is 1-5 h.
7. The CFs @ TiC/TiO of claim 22The preparation method of the composite material is characterized by comprising the following steps: in step 3, the acid treatment refers to the treatment of CFs @ TiC/K2Ti6O13Soaking the composite material in an acid solution at room temperature for 1-10 h; in the acid solution used in the acid treatment, H+The concentration of (A) is 0.2-2 moL/L.
8. A CFs @ TiC/TiO according to claim 1 or 72The preparation method of the composite material is characterized by comprising the following steps: in step 3, the acid solution used in the acid treatment is a hydrochloric acid solution.
9. The CFs @ TiC/TiO of claim 22The preparation method of the composite material is characterized by comprising the following steps: in the step 3, the temperature of the heat treatment is 300-.
10. The CFs @ TiC/TiO of claim 12Use of composite materials, especially for producing a composite materialCharacterized in that: mixing the CFs @ TiC/TiO2The composite material is applied to a catalytic functional material.
CN201911408169.XA 2019-12-31 2019-12-31 CFs @ TiC/TiO2Composite material and preparation method and application thereof Active CN110975904B (en)

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