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CN113522262A - Recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material and preparation method and application thereof - Google Patents

Recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material and preparation method and application thereof Download PDF

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Publication number
CN113522262A
CN113522262A CN202110802958.2A CN202110802958A CN113522262A CN 113522262 A CN113522262 A CN 113522262A CN 202110802958 A CN202110802958 A CN 202110802958A CN 113522262 A CN113522262 A CN 113522262A
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carbon fiber
fiber felt
carbon
pyrolytic carbon
titanium dioxide
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杨艳玲
刘佳隽
陈华军
锁国权
冯雷
叶晓慧
侯小江
和茹梅
薛帆
张荔
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Shaanxi University of Science and Technology
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2305/10—Photocatalysts

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Abstract

The invention discloses a recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material and a preparation method and application thereof, and relates to the field of photocatalytic materials. By putting carbon fiber felt into the containerSoaking in ketone, and drying to obtain a clean carbon fiber felt; heating the clean carbon fiber felt in an inert atmosphere, and then depositing pyrolytic carbon at high temperature in a methane atmosphere to obtain pyrolytic carbon/carbon fiber felt; uniformly mixing acetone, ethylene glycol and tetrabutyl titanate to obtain a mixed solution, mixing the obtained pyrolytic carbon/carbon fiber felt with the mixed solution to perform hydrothermal reaction, and cleaning and drying the obtained product after the reaction is finished to obtain the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material. The invention effectively solves the problem of TiO in the prior art2The traditional powder photocatalyst has the problems of low solar energy utilization rate and difficult recovery.

Description

Recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material and preparation method and application thereof
Technical Field
The invention relates to the field of photocatalytic materials, in particular to a recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material and a preparation method and application thereof.
Background
With the rapid development of productivity, large-scale industrial production processes generate a large amount of industrial wastewater, and the discharge of the wastewater not only pollutes the ecological environment, but also has great harm to human health, and the wastewater can be discharged after being treated. The traditional industrial wastewater treatment method mainly comprises a physical method, a chemical method and a biological method, and has the defects of limited treatment capacity, higher treatment cost and the like.
In recent years, photocatalytic oxidation technology has been widely used for the treatment of industrial wastewater. TiO22Has strong oxidative degradation capability, stable performance,Low treatment cost, no secondary pollution and the like, but has wider band gap (3.2eV) and lower utilization rate of solar energy. The traditional powder photocatalyst has the problem of difficult recovery in the application of water treatment, and the large-scale application of the traditional powder photocatalyst in the field of photocatalytic degradation is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material and a preparation method and application thereof, and solves the problems that a TiO 2-based traditional powder photocatalyst is low in solar energy utilization and difficult to recycle in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material, which comprises the following steps:
1) soaking the carbon fiber felt in acetone and drying to obtain a clean carbon fiber felt; heating the clean carbon fiber felt in an inert atmosphere, and then depositing pyrolytic carbon at high temperature by using methane to obtain pyrolytic carbon/carbon fiber felt; 2) uniformly mixing acetone, ethylene glycol and tetrabutyl titanate to obtain a mixed solution, mixing the obtained pyrolytic carbon/carbon fiber felt with the mixed solution to perform hydrothermal reaction, and cleaning and drying an obtained product after the hydrothermal reaction is finished to obtain the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Preferably, the specific operation of step 1) comprises: and putting the clean carbon fiber felt into a tubular furnace, introducing argon at a rate of 150-300 mL/min, heating to 1000-1100 ℃, introducing methane at a flow rate of 50-100 mL/min, performing high-temperature deposition on pyrolytic carbon in a mixed atmosphere of methane and argon, and performing deposition for 10-60 min to obtain the pyrolytic carbon/carbon fiber felt.
Further preferably, the temperature rise rate is 8-10 ℃/min.
Further preferably, after the deposition is finished, the methane valve is closed, and the temperature is naturally cooled in an inert atmosphere.
Preferably, in the step 2), the volume ratio of acetone, ethylene glycol and tetrabutyl titanate is 20: 10: 1-20: 10: 2.
preferably, in the step 2), the hydrothermal reaction temperature is 150-180 ℃ and the time is 10-16 h.
Preferably, in the step 2), the drying temperature is 60-80 ℃ and the time is 10-14 h.
The invention discloses a recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material prepared by the preparation method.
The invention discloses an application of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material in photocatalytic degradation of water.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material, which adopts a carbon fiber felt as a substrate, is simple and low in cost, and adopts acetone to carry out simple pretreatment on the carbon fiber felt and then carry out deposition of pyrolytic carbon, so that the photoresponse range of a photocatalyst is enlarged, and the charge transmission efficiency is improved. The invention selects the carbon fiber felt as the substrate, and mainly the carbon fiber felt has low price, stable property and flexibility and can be bent at will. After simple acetone cleaning treatment, the growth of the photocatalyst is still limited by the chemical properties of the surface of the carbon fiber felt, and after deposition treatment and hydrothermal growth, the amount of the catalyst on the surface of the carbon fiber is obviously improved. The pyrolytic carbon-coated carbon fiber is used as a carrier of the catalyst, so that the light absorption range of the catalyst is widened, the charge transmission efficiency is improved, and the recombination of electrons and holes is inhibited. The preparation method disclosed by the invention has the advantages of simple experimental method and low cost.
The invention discloses a recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material prepared by the preparation method, which is characterized in that the carbon fiber felt is used as a substrate, a carbon layer is deposited on the surface of carbon fiber through a CVD (chemical vapor deposition) tube furnace, and TiO is grown through hydrothermal growth2Nanoparticles of increased TiO2Nano-particlesThe range of particle absorption, the rate of electron transfer, and thus the electron-hole recombination. Meanwhile, with the deposition of the carbon layer, the uniform growth of titanium dioxide on the surface of the carbon fiber can be promoted. And the mechanical property of the carbon fiber sample can be improved, the structural stability of the carbon fiber three-dimensional space is enhanced, and the recycling capability of the sample is improved. Recyclable flexible TiO thus produced2The/pyrolytic carbon/carbon fiber felt composite photocatalytic material well reserves the good flexibility of the carbon fiber felt, can be cut according to the working environment, has the advantages of wide photoresponse range, recyclability and low cost, improves the mechanical property of the material along with the deposition of the pyrolytic carbon layer, enhances the stability of a fiber three-dimensional frame structure, and can realize the sustainable development and cyclic utilization of resources.
The invention also discloses application of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material in photocatalytic degradation of water. The recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material has the advantages of flexibility, recoverability and wide photoresponse range, and is widely applied to photocatalytic pollutant degradation.
Drawings
FIG. 1 shows that TiO is grown by 30min CVD methane deposition and hydrothermal method under the conditions of 18KV and 5mL/h2The SEM image of 20000 times of the recoverable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material;
FIG. 2 shows that TiO is grown by 30min CVD methane deposition and hydrothermal method under the conditions of 18KV and 5mL/h2SEM image of 3000 times of the recoverable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material;
FIG. 3 shows that TiO is grown by 30min CVD methane deposition and hydrothermal method under the conditions of 18KV and 5mL/h2The SEM image of 500 times of the recoverable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material;
FIG. 4 is an EDS energy spectrum of Ti element on the surface of the fiber of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material at 3000 times;
FIG. 5 shows degradation of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material to a rhodamine B aqueous solution.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses a recyclable flexible titanium dioxide (TiO)2) The preparation method of the/pyrolytic carbon/carbon fiber felt composite photocatalytic material comprises the following steps: soaking a carbon fiber felt in acetone for pretreatment, drying to obtain a clean carbon fiber felt, putting the clean carbon fiber felt into a CVD (chemical vapor deposition) tube furnace, introducing methane and argon, depositing pyrolytic carbon at high temperature to obtain pyrolytic carbon/carbon fiber felt, adding a certain amount of tetrabutyl titanate into a mixed solution of acetone and ethylene glycol, adding the pyrolytic carbon/carbon fiber felt and the mixed solution into a reaction kettle lined with polytetrafluoroethylene, cleaning, drying to obtain the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material. Comprises the following stepsThe method comprises the following steps:
step 1: soaking the carbon fiber felt in acetone for 12 hours, and drying to obtain a clean carbon fiber felt;
step 2: putting the pretreated clean carbon fiber felt into a tubular furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1000-1100 ℃;
and step 3: when the temperature of the furnace reaches 1000-1100 ℃, continuously introducing methane at the flow rate of 50-100 mL/min for high-temperature deposition pyrolysis carbon to form a methane: argon gas is 1: 3, introducing mixed gas of methane and argon, depositing for 10-60 min, and naturally cooling to obtain pyrolytic carbon/carbon fiber felt;
and 4, step 4: weighing a certain amount of acetone, ethylene glycol and tetrabutyl titanate, putting the acetone, the ethylene glycol and the tetrabutyl titanate and the pyrolytic carbon/carbon fiber felt obtained in the step 3 into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, and collecting a product after the reaction is finished;
and 5: washing the solid product obtained in the step 4 with deionized water, and then putting the solid product into an oven for drying to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
And in the step 2, the heating rate of the argon is 8-10 ℃/min.
And (3) closing the methane valve after the deposition is finished in the step 3, and naturally cooling in an argon environment.
The volume ratio of the ethylene glycol to the acetone to the tetrabutyl titanate in the step 4 is 20: 10: 1-20: 10: 2, the hydrothermal reaction temperature is 150-180 ℃, and the time is 10-16 h.
In the step 5, the drying temperature is 60-80 ℃, and the drying time is 10-14 h.
The recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material prepared by the preparation method has the advantage of convenient recycling, and avoids the processes of centrifugation, washing and drying for reusing the traditional powder photocatalyst. Relevant tests show that the degradation performance of the rhodamine B solution reaches 70% -75% in 30 min.
The invention is further illustrated by the following specific examples:
example 1
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1000 ℃ at the temperature of 8 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 10min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: adding the mixture into a beaker according to the volume ratio of 1, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 16 hours at 150 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven at 80 ℃ for 12 hours to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 2
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And (3) putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1100 ℃ at the temperature of 9 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for depositing for 20min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: adding the mixture into a beaker according to the volume ratio of 1, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 12 hours at 160 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven at 80 ℃ for 10 hours to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 3
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1000 ℃ at the temperature of 8 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 30min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: adding the mixture into a beaker according to the volume ratio of 1.5, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 12 hours at 160 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven for 14 hours at the temperature of 60 ℃ to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 4
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1030 ℃ at the temperature of 8 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 40min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: adding the mixture into a beaker according to the volume ratio of 1, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 12 hours at 160 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven at 70 ℃ for 13 hours to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 5
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1050 ℃ at the temperature of 8 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 50min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: adding the mixture into a beaker according to the volume ratio of 1.3, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 14 hours at 155 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven at 65 ℃ for 12 hours to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 6
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1000 ℃ at the temperature of 10 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 60min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: adding the mixture into a beaker according to the volume ratio of 1, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 12 hours at 160 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven at 80 ℃ for 12 hours to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 7
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1000 ℃ at the temperature of 8 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 10min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: 2, adding the mixture into a beaker, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 11 hours at 170 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven at 80 ℃ for 12 hours to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 8
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1080 ℃ at the temperature of 9 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for depositing for 20min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: adding the mixture into a beaker according to the volume ratio of 1.8, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 10 hours at 180 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven for 14 hours at 64 ℃ to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 9
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1000 ℃ at the temperature of 8 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 30min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: 2, adding the mixture into a beaker, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 12 hours at 155 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven at 80 ℃ for 12 hours to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 10
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1090 ℃ at the temperature of 8 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 40min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: adding the mixture into a beaker according to the volume ratio of 1.6, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 12 hours at 160 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven at 75 ℃ for 12 hours to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 11
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1000 ℃ at the temperature of 8 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 50min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: adding the mixture into a beaker according to the volume ratio of 1.2, and stirring for 30min to obtain a prepared solution.
(5) And (3) adding the pyrolytic carbon/carbon fiber felt obtained in the carbon step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 12 hours at 160 ℃, and collecting a product after the reaction is finished.
(6) Taking out the collected product, cleaning the product with deionized water, and drying the product in an oven at 80 ℃ for 12 hours to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
Example 12
(1) And (3) soaking the carbon fiber felt in acetone for 12 hours, removing impurities on the surface, and drying to obtain the clean carbon fiber felt.
(2) And putting the clean carbon fiber felt pretreated by acetone into a CVD (chemical vapor deposition) tube furnace, introducing argon at the rate of 150-300 mL/min, and heating to 1000 ℃ at the temperature of 10 ℃ per minute in the atmosphere of argon.
(3) When the furnace is kept warm, introducing methane at a flow rate of 50-100 mL/min to form a methane: argon gas is 1: and 3, introducing mixed gas of methane and argon, keeping the temperature at 1000 ℃ for deposition for 60min, and naturally cooling to obtain the pyrolytic carbon/carbon fiber felt.
(4) Mixing ethylene glycol, acetone and tetrabutyl titanate according to the weight ratio of 20: 10: 2, adding the mixture into a beaker, and stirring for 30min to obtain a prepared solution.
(5) And (4) adding the pyrolytic carbon/carbon fiber felt obtained in the step (3) and the solution prepared in the step (4) into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, reacting for 12 hours at 160 ℃, and collecting a product after the reaction is finished.
(6) Taking out the product collected by the carbon, cleaning the product with deionized water, and drying the product in an oven for 11 hours at the temperature of 80 ℃ to prepare the recyclable flexible TiO2Pyrolytic carbon/carbon fiber felt composite photocatalytic material.
The invention is described in further detail below with reference to the accompanying drawings:
referring to FIGS. 1-4, TiO can be seen2The growth on the surface of the carbon fiber is relatively uniform, which shows that the C layer has a relatively good promoting effect on the growth of the catalyst on the surface of the carbon fiber, and figure 5 shows that the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material prepared by the invention has a relatively good degradation performance on rhodamine B solution.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (9)

1. A preparation method of a recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material is characterized by comprising the following steps:
1) soaking the carbon fiber felt in acetone and drying to obtain a clean carbon fiber felt; heating the clean carbon fiber felt in an inert atmosphere, and then depositing pyrolytic carbon at high temperature by using methane to obtain pyrolytic carbon/carbon fiber felt;
2) uniformly mixing acetone, ethylene glycol and tetrabutyl titanate to obtain a mixed solution, mixing the obtained pyrolytic carbon/carbon fiber felt with the mixed solution to perform hydrothermal reaction, and cleaning and drying an obtained product after the hydrothermal reaction is finished to obtain the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material.
2. The preparation method of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material as claimed in claim 1, wherein the specific operation of the step 1) comprises:
and putting the clean carbon fiber felt into a tubular furnace, introducing argon at a rate of 150-300 mL/min, heating to 1000-1100 ℃, introducing methane at a flow rate of 50-100 mL/min, performing high-temperature deposition on pyrolytic carbon in a mixed atmosphere of methane and argon, and performing deposition for 10-60 min to obtain the pyrolytic carbon/carbon fiber felt.
3. The preparation method of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material as claimed in claim 2, wherein the temperature rise rate is 8-10 ℃/min.
4. The preparation method of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material as claimed in claim 2, wherein a methane valve is closed after deposition is finished, and natural cooling is performed under an inert atmosphere.
5. The method for preparing the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material as claimed in claim 1, wherein in the step 2), the volume ratio of acetone, ethylene glycol and tetrabutyl titanate is 20: 10: 1-20: 10: 2.
6. the preparation method of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material as claimed in claim 1, wherein in the step 2), the hydrothermal reaction temperature is 150-180 ℃ and the time is 10-16 h.
7. The preparation method of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material as claimed in claim 1, wherein in the step 2), the drying temperature is 60-80 ℃ and the drying time is 10-14 h.
8. The recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material prepared by the preparation method of any one of claims 1 to 7.
9. The use of the recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber mat composite photocatalytic material of claim 8 for photocatalytic degradation of water.
CN202110802958.2A 2021-07-15 2021-07-15 Recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material and preparation method and application thereof Pending CN113522262A (en)

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Application publication date: 20211022