CN113289574A - Titanium dioxide-carbon nanotube flexible composite film and preparation method and application thereof - Google Patents
Titanium dioxide-carbon nanotube flexible composite film and preparation method and application thereof Download PDFInfo
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- CN113289574A CN113289574A CN202010110239.XA CN202010110239A CN113289574A CN 113289574 A CN113289574 A CN 113289574A CN 202010110239 A CN202010110239 A CN 202010110239A CN 113289574 A CN113289574 A CN 113289574A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 103
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 16
- 239000010865 sewage Substances 0.000 claims abstract description 14
- 230000000593 degrading effect Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000000779 smoke Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 81
- 239000004408 titanium dioxide Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 17
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 10
- 239000002344 surface layer Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 239000010408 film Substances 0.000 description 75
- 239000000243 solution Substances 0.000 description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 27
- 239000000463 material Substances 0.000 description 24
- 238000006136 alcoholysis reaction Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002238 carbon nanotube film Substances 0.000 description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 9
- 239000003755 preservative agent Substances 0.000 description 9
- 230000002335 preservative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a titanium dioxide-carbon nano tube flexible composite film and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1, adding a pure carbon tube film into absolute ethyl alcohol, and dropwise adding titanium tetrachloride under the stirring condition; after the dropwise adding is finished, continuously stirring until white smoke above the solution is scattered to obtain a solution soaked with the film; step 2, taking out the film obtained in the step 1, transferring the film into deionized water, dropwise adding the solution obtained in the step 1 under the stirring condition, continuously stirring after dropwise adding, placing into an oven after stirring, and carrying out hydrothermal reaction at the temperature of 50 ℃; and 3, taking out the film obtained in the step 2, washing and drying to obtain the titanium dioxide-carbon nano tube flexible composite film. The titanium dioxide-carbon nano tube flexible composite film obtained by the invention has good adsorption performance and can be used for degrading organic matters in sewage.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a titanium dioxide-carbon nano tube flexible composite film and a preparation method and application thereof.
Background
With the development of economy in China, the discharge amount of sewage in the industries of textile, printing and dyeing and the like is obviously increased, and the sewage contains a large amount of organic pollutants which are difficult to biodegrade besides dyeing auxiliaries and heavy metal salts, so that the environmental resources such as land, fresh water and the like can be seriously polluted. Because the traditional wastewater treatment technology has high production cost and low efficiency, the development of novel materials capable of being recycled is the research direction in the future to perfect the wastewater treatment technology. Among various degradation methods, the adsorption method has high removal efficiency for organic matters with high concentration, and is simple and convenient to operate. However, most of the adsorption materials such as activated carbon are in powder particles, are difficult to recover after being put into water and are easy to cause new pollution, and meanwhile, the adsorption materials can only adsorb and remove organic dye molecules and cannot degrade the organic dye molecules. Therefore, in order to meet the actual requirements, the adsorption material needs to have high adsorption efficiency, flexible self-supporting performance, reusability, no new pollution and certain self-cleaning performance.
However, in view of the current state of the materials, most of them exist in the form of powder, and cannot meet the requirements of industrial applications such as recycling and easy utilization of materials in sewage treatment.
The carbon nano tube is used as a unique one-dimensional material, has excellent mechanical properties (flexibility), high conductivity and high specific surface area, has strong adsorption effect on organic matters, and can be used as a novel adsorption material. However, the strong hydrophobicity of the carbon nanotube limits its application in related fields.
Disclosure of Invention
The invention aims to provide a titanium dioxide-carbon nanotube flexible composite film aiming at the problem that Carbon Nanotubes (CNTs) in the prior art are poor in hydrophilicity as an adsorbing material, and the introduction of titanium dioxide can improve the hydrophilicity of the carbon nanotubes.
The invention also aims to provide a preparation method of the titanium dioxide-carbon nano tube flexible composite film, and the titanium dioxide-carbon nano tube flexible composite film prepared by the alcoholysis method can be produced continuously and in large scale.
The invention also aims to provide application of the titanium dioxide-carbon nanotube flexible composite film as a material for degrading organic matters in sewage.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a titanium dioxide-carbon nano tube flexible composite film is characterized in that titanium dioxide is agglomerated on the surface layer of a carbon nano tube in a fusiform shape, the diameter of the titanium dioxide agglomerate is 50-200nm, and the crystal form of the titanium dioxide is rutile type.
In another aspect of the present invention, the method for preparing the titanium dioxide-carbon nanotube flexible composite film comprises the following steps:
step 1, adding a pure carbon tube film into absolute ethyl alcohol, and dropwise adding titanium tetrachloride under the stirring condition; after the dripping is finished, continuously stirring for 10-15min, and obtaining a solution soaked with the film after white smoke above the solution is scattered;
step 2, taking out the film obtained in the step 1, transferring the film into deionized water, dropwise adding the solution obtained in the step 1 under the stirring condition, continuously stirring for 20-40min after the dropwise adding is finished, putting the film into an oven after the stirring is finished, and carrying out hydrothermal reaction at the temperature of 50-80 ℃ for 20-28 h;
wherein: the mass ratio of the deionized water, the absolute ethyl alcohol, the titanium tetrachloride and the pure carbon tube film is (280-290): 20-25): 1: 5-30;
and 3, taking out the film obtained in the step 2, washing and drying to obtain the titanium dioxide-carbon nano tube flexible composite film.
In the technical scheme, the washing is respectively carried out by deionized water and absolute ethyl alcohol in the step 3, and the washing is put into an oven to be dried, wherein the drying time is 12-18h, and the drying temperature is 60-80 ℃.
In the technical scheme, the dropping rate of the titanium tetrachloride in the step 1 is 6-8 ml/min.
In the technical scheme, the solution obtained in the step 1 is dropwise added in the step 2 at the dropping rate of 6-8 ml/min.
In the above technical scheme, the absolute ethyl alcohol in the step 1 is GR high-purity absolute ethyl alcohol.
In another aspect of the invention, the titanium dioxide-carbon nanotube flexible composite film prepared by the method is also included.
In the technical scheme, titanium dioxide is agglomerated on the surface layer of the carbon nano tube in a shuttle shape, the diameter of the titanium dioxide agglomerate is 50-200nm, and the crystal form of the titanium dioxide is rutile.
In another aspect of the invention, the titanium dioxide-carbon nanotube flexible composite film is applied.
In the technical scheme, the titanium dioxide-carbon nanotube flexible composite film is applied to adsorbing and degrading organic matters in sewage.
In the technical scheme, under the illumination condition with the wavelength of 664nm, when the titanium dioxide-carbon nano tube flexible composite film adsorbs and degrades organic matters in sewage, the effective time is longer than 1500min, and when 1500min happens, the removal rate of 10mg/L methylene blue by the titanium dioxide-carbon nano tube flexible composite film is higher than 25%.
Compared with the prior art, the invention has the beneficial effects that:
1. TiO prepared by the process of the invention2the/CNTs flexible composite film material can be produced continuously in large scale, is easy to recover, and can meet the requirements of industrial application such as material circulation, simple utilization and the like in sewage treatment.
2. The method of the invention compounds the titanium dioxide and the carbon nano tube film, increases the contact area of the carbon nano tube film and the methylene blue solution, thereby exerting the strong adsorbability of the carbon nano tube film to a greater extent and improving the efficiency of adsorbing organic matters in sewage degradation.
3. The titanium dioxide nanoparticles are introduced to the carbon nano tubes to form a novel composite system, the titanium dioxide can improve the hydrophilicity of the carbon nano tubes, the efficiency of the carbon nano tubes for adsorbing organic molecules in sewage is improved, and the organic substances adsorbed on the carbon nano tubes are degraded by utilizing the photocatalytic property of the titanium dioxide, so that self-cleaning and recycling are realized.
4. The titanium dioxide powder in the titanium dioxide-carbon nano tube flexible composite film is uniformly coated on the carbon nano tube film, thereby hindering the self-aggregation of the titanium dioxide powder to a certain extent and being beneficial to the degradation treatment of the organic pollutants by the titanium dioxide powder by utilizing illumination.
5. The titanium dioxide-carbon nano tube flexible composite film has excellent performance of adsorbing and degrading organic matters in sewage, and the adsorption capacity of the material is obviously higher than that of a carbon nano tube film and a CVD titanium dioxide/carbon nano tube within the adsorption time of 10-1500 min. Even if the adsorption time is 300min-1500min, the adsorption quantity of the material is slowly increased along with the increase of the time, and the phenomenon of adsorption saturation does not occur, thereby proving the good adsorption performance of the material. More particularly, the removal rate of the material to methylene blue is far higher than that of a carbon nanotube film and CVD titanium dioxide/carbon nanotubes within the adsorption time of 10-1500min, and the material is proved to have excellent degradation performance.
Drawings
FIG. 1 is a schematic representation of alcoholysis of TiO in example 12-low power SEM images of surface layer titanium dioxide in CNTs;
FIG. 2 is the alcoholysis of TiO in example 12-high power SEM images of surface layer titanium dioxide in CNTs;
FIG. 3 is the alcoholysis of TiO in example 12-low magnification TEM images of surface layer titanium dioxide in CNTs;
FIG. 4 is the alcoholysis of TiO in example 12-high magnification TEM images of surface layer titanium dioxide in CNTs;
FIG. 5 shows alcoholysis of TiO from example 12CNTs, Pure CNTs obtained in comparative example 1 and CVD-TiO obtained in comparative example 22-XRD of CNTs;
FIG. 6 shows alcoholysis of TiO from example 12CNTs, Pure CNTs obtained in comparative example 1 and CVD-TiO obtained in comparative example 22-the amount of CNTs adsorbed at different times to 10mg/L methylene blue;
FIG. 7 shows alcoholysis of TiO from example 12CNTs, Pure CNTs obtained in comparative example 1 and CVD-TiO obtained in comparative example 22-CNTsThe removal rate of the methylene blue of 10mg/L is the same time.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The ferrocene and the thiophene are produced by Tianjin photoresistive fine chemical research institute and are analytical pure reagents; the ethanol and the ethyl orthosilicate are produced by Yuanli chemical technology limited company in Tianjin, wherein the ethanol is a superior pure reagent, and the ethyl orthosilicate is an analytical pure reagent.
Example 1
1.008g of deionized water, 0.072g of GR high-purity absolute ethanol, 0.0036g of titanium tetrachloride and 0.02g of a pure carbon tube film were weighed. Wherein, titanium tetrachloride is used as a titanium source of the reaction, the carbon tube film is used as a carbon source, and absolute ethyl alcohol is used for alcoholysis.
A method for preparing a titanium dioxide-carbon nanotube flexible composite film comprises the following steps:
(1) adding GR high-purity absolute ethyl alcohol into a drying beaker, adding a carbon tube film, and starting magnetic stirring; dropwise adding titanium tetrachloride solution, and continuously stirring for 10min after the dropwise adding;
(2) after the solution is transparent, transferring the carbon tube film into a beaker filled with deionized water by using clean tweezers, starting magnetic stirring, transferring the solution into the beaker filled with deionized water in a dropwise adding mode for 30 min; after the solution is dropwise added, covering the solution with a preservative film, continuously stirring for 30min, taking out the magnetons, poking 4-6 holes in the preservative film, putting the beaker into a drying oven, and reacting for 24h at 50 ℃.
(3) Taking out the carbon tube film after hydrothermal treatment, placing the carbon tube film in a culture dish, washing the carbon tube film for three times by using deionized water and absolute ethyl alcohol respectively, then sealing and punching the hole by using a preservative film, placing the carbon tube film in an oven for drying, and preparing the titanium dioxide-carbon nano tube flexible composite film which is recorded as alcoholysis TiO2-CNTs。
The titanium dioxide-carbon nanotube flexible composite film obtained by the embodiment can be used as a self-cleaning composite film material for adsorbing and degrading organic matters.
Fig. 1 and 2 are SEM images of surface layer titanium dioxide in the titanium dioxide-carbon nanotube flexible composite film prepared by the alcoholysis process in example 1, and it can be seen from fig. 1 that the titanium dioxide prepared by the alcoholysis process is in the form of leaf-like agglomerates, and the diameter of the agglomerates is about 2 μm. Fig. 3 is a low-power TEM image of the titanium dioxide-carbon nanotube flexible composite film, and fig. 4 is a high-power TEM image of the titanium dioxide-carbon nanotube flexible composite film.
Example 2
1.008g of deionized water, 0.072g of GR high-purity absolute ethanol, 0.0036g of titanium tetrachloride and 0.05g of a pure carbon tube film were weighed. Wherein, titanium tetrachloride is used as a titanium source of the reaction, the carbon tube film is used as a carbon source, and absolute ethyl alcohol is used for alcoholysis.
A method for preparing a titanium dioxide-carbon nanotube flexible composite film comprises the following steps:
(1) adding GR high-purity absolute ethyl alcohol into a drying beaker, adding a carbon tube film, and starting magnetic stirring; dropwise adding titanium tetrachloride solution, and continuously stirring for 15min after dropwise adding;
(2) after the solution is transparent, transferring the carbon tube film into a beaker filled with deionized water by using clean tweezers, starting magnetic stirring, transferring the solution into the beaker filled with deionized water in a dropwise adding mode for 35 min; after the solution is dropwise added, covering the solution with a preservative film, continuously stirring for 35min, taking out the magnetons, poking 4-6 holes in the preservative film, putting the beaker into a drying oven, and reacting for 20h at 80 ℃.
(3) And taking out the carbon tube film after hydrothermal treatment, placing the carbon tube film in a culture dish, washing the carbon tube film for three times by using deionized water and absolute ethyl alcohol respectively, sealing the hole by using a preservative film, poking the hole, and placing the carbon tube film in an oven for drying to prepare the titanium dioxide-carbon nanotube flexible composite film.
The titanium dioxide-carbon nanotube flexible composite film obtained by the embodiment can be used as a self-cleaning composite film material for adsorbing and degrading organic matters.
Example 3
1.008g of deionized water, 0.072g of GR high-purity absolute ethanol, 0.0036g of titanium tetrachloride and 0.1g of a pure carbon tube film were weighed. Wherein, titanium tetrachloride is used as a titanium source of the reaction, the carbon tube film is used as a carbon source, and absolute ethyl alcohol is used for alcoholysis.
A method for preparing a titanium dioxide-carbon nanotube flexible composite film comprises the following steps:
(1) adding GR high-purity absolute ethyl alcohol into a drying beaker, adding a carbon tube film, and starting magnetic stirring; dropwise adding titanium tetrachloride solution, and continuously stirring for 15min after dropwise adding;
(2) after the solution is transparent, transferring the carbon tube film into a beaker filled with deionized water by using clean tweezers, starting magnetic stirring, transferring the solution into the beaker filled with deionized water in a dropwise adding mode for 40 min; after the solution is dropwise added, covering the solution with a preservative film, continuously stirring for 40min, taking out the magnetons, poking 4-6 holes in the preservative film, putting the beaker into a drying oven, and reacting for 20h at 80 ℃.
(3) And taking out the carbon tube film after hydrothermal treatment, placing the carbon tube film in a culture dish, washing the carbon tube film for three times by using deionized water and absolute ethyl alcohol respectively, sealing the hole by using a preservative film, poking the hole, and placing the carbon tube film in an oven for drying to prepare the titanium dioxide-carbon nanotube flexible composite film.
The titanium dioxide-carbon nanotube flexible composite film obtained by the embodiment can be used as a self-cleaning composite film material for adsorbing and degrading organic matters.
The titanium dioxide-carbon nanotube flexible composite film of the present invention can be prepared by adjusting the process parameters according to the contents of the present invention, and examples 2 and 3 show substantially the same properties as example 1.
Comparative example 1
A preparation method of a carbon nanotube film comprises the following steps:
(1) 24.03g of ethanol, 0.432g of ferrocene and 0.22g of thiophene are weighed, wherein the ethanol is used as a carbon source of the reaction, the ferrocene is used as a catalyst, and the thiophene is used as an accelerator, so that the three materials are mixed into an ethanol solution and placed in a beaker; continuously carrying out ultrasonic dispersion on the solution at the temperature of 50 ℃ for 60min to obtain uniform dispersion liquid, and transferring the uniform dispersion liquid to an injector to be used as precursor solution;
(2) completely sealing the vertical CVD furnace in a water seal mode, continuously introducing 100sccm Ar, completely removing residual air in the furnace, heating the vertical CVD furnace to 1150 ℃, and preserving heat for 5 hours to provide a constant temperature environment with enough time for the continuous growth of subsequent carbon nanotube thin film materials (CNTs);
(3) after the step (2) is finished, Ar is closed, and 800sccm of H is continuously injected into the furnace2Wait for H2Filling the whole vertical CVD furnace cavity, and injecting the precursor solution into the furnace cavity at the injection rate of 8 ml/h; and collecting the cylindrical carbon nanotube film at the bottom of the hearth about 20min after the reaction is started, and recording the film as Pure CNTs.
Comparative example 2
A preparation method of CVD titanium dioxide/carbon nano-tubes comprises the following steps:
(1) 24.03g of ethanol, 0.432g of ferrocene and 0.22g of thiophene are weighed according to the mass ratio of 95:1.5: 1-100: 2:1, wherein ethanol is used as a carbon source of the reaction, ferrocene is used as a catalyst, and thiophene is used as an accelerator, and the three materials are mixed to form an ethanol solution and placed in a beaker; in addition, 4% (-2.145 g) of tetrabutyl titanate was weighed out as the titanium source for the reaction in the total mass fraction and placed in the solution beaker. Continuously carrying out ultrasonic dispersion on the solution at the temperature of 50 ℃ for 60min to obtain uniform dispersion liquid, and transferring the uniform dispersion liquid to an injector to be used as precursor solution;
(2) completely sealing the vertical CVD furnace in a water seal mode, continuously introducing 100sccm Ar, completely removing residual air in the furnace, heating the vertical CVD furnace to 1150 ℃, and preserving heat for 5 hours to obtain a subsequent titanium dioxide/carbon nano tube composite film material (TiO)X/CNTs) provides a constant temperature environment for a sufficient time;
(3) after the step (2) is finished, Ar is closed, and 800sccm of H is continuously injected into the furnace2Wait for H2Filling the whole vertical CVD furnace cavity, and injecting the precursor solution into the furnace cavity at the injection rate of 8 ml/h; collecting the cylindrical titanium oxide/carbon nano tube film at the bottom of the hearth within about 20min after the reaction startsTo produce uniform and continuous CVD titanium dioxide/carbon nano-tube which can be directly used for organic matter degradation and is marked as CVD-TiO2-CNTs。
FIG. 5 shows alcoholysis of TiO from example 12CNTs, Pure CNTs obtained in comparative example 1 and CVD-TiO obtained in comparative example 22XRD of CNTs, it can be seen that the alcoholysis TiO obtained in example 1 of the figure2CNTs and CVD-TiO from comparative example 12CNTs all contain a crystalline phase of titanium oxide and carbon tubes, but alcoholyzed TiO2The crystalline form of titanium oxide in the-CNTs is the rutile form, while CVD-TiO2The titanium oxide in the CNTs has a mixed phase of rutile and anatase.
2.1mg of alcoholysis TiO, respectively2CNTs, 1.4mg Pure CNTs, 1.0mg CVD-TiO2The CNTs are respectively added into 100ml of 10mg/L methylene blue, and under the illumination condition of a wavelength of 664nm, the results of FIG. 6 and FIG. 7 are obtained.
FIG. 6 shows alcoholysis of TiO from example 12CNTs, Pure CNTs obtained in comparative example 1 and CVD-TiO obtained in comparative example 22The adsorption capacity of CNTs to 10mg/L methylene blue at different times can be seen from the figure, the adsorption curves of the three materials are similar, and TiO is alcoholyzed2CNTs adsorption (at 1400 minutes, adsorption of 100-140mg/g)>CVD titanium dioxide/carbon nanotube adsorption amount (adsorption amount of 80mg/g at 1400 minutes)>The amount of carbon nanotube film adsorbed (at 1400 minutes, 20 mg/g).
FIG. 7 shows alcoholysis of TiO from example 12CNTs, Pure CNTs obtained in comparative example 1 and CVD-TiO obtained in comparative example 22The removal rate of 10mg/L methylene blue by CNTs at different times can be seen that the removal rate of methylene blue by alcoholysis of titanium dioxide/carbon nanotube film after a sufficiently long time (after 800-1500 min) is much higher than that of the other two, and at 1500min, alcoholysis of TiO is carried out2The removal rate of-CNTs is 25.2%, the removal rate of Pure CNTs is 2.8%, CVD-TiO2The removal rate of-CNTs was 7.7%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The titanium dioxide-carbon nanotube flexible composite film is characterized in that titanium dioxide is agglomerated on the surface layer of a carbon nanotube in a fusiform shape, the diameter of the titanium dioxide agglomerate is 50-200nm, and the crystal form of the titanium dioxide is rutile type.
2. The preparation method of the titanium dioxide-carbon nanotube flexible composite film is characterized by comprising the following steps:
step 1, adding a pure carbon tube film into absolute ethyl alcohol, and dropwise adding titanium tetrachloride under the stirring condition; after the dripping is finished, continuously stirring for 10-15min, and obtaining a solution soaked with the film after white smoke above the solution is scattered;
step 2, taking out the film obtained in the step 1, transferring the film into deionized water, dropwise adding the solution obtained in the step 1 under the stirring condition, continuously stirring for 20-40min after the dropwise adding is finished, putting the film into an oven after the stirring is finished, and carrying out hydrothermal reaction at the temperature of 50-80 ℃ for 20-28 h;
wherein: the mass ratio of the deionized water, the absolute ethyl alcohol, the titanium tetrachloride and the pure carbon tube film is (280-290): 20-25): 1: 5-30;
and 3, taking out the film obtained in the step 2, washing and drying to obtain the titanium dioxide-carbon nano tube flexible composite film.
3. The method for preparing the titanium dioxide-carbon nanotube flexible composite film according to claim 2, wherein the titanium dioxide-carbon nanotube flexible composite film in the step 3 is washed by deionized water and absolute ethyl alcohol respectively, and is placed into an oven for drying for 12-18h at a drying temperature of 60-80 ℃.
4. The method for preparing a titanium dioxide-carbon nanotube flexible composite film according to claim 2, wherein the dropping rate of titanium tetrachloride in the step 1 is 6 to 8 ml/min;
and in the step 2, dropwise adding the solution obtained in the step 1 at the dropping rate of 6-8 ml/min.
5. The method for preparing the titanium dioxide-carbon nanotube flexible composite film according to claim 2, wherein the absolute ethyl alcohol in the step 1 is GR high-purity absolute ethyl alcohol.
6. The titanium dioxide-carbon nanotube flexible composite film prepared by the method of any one of claims 2 to 5.
7. The titanium dioxide-carbon nanotube flexible composite film as claimed in claim 6, wherein the titanium dioxide is agglomerated on the surface layer of the carbon nanotube in a fusiform, the diameter of the titanium dioxide agglomerate is 50-200nm, and the crystal form of the titanium dioxide is rutile type.
8. The use of the titanium dioxide-carbon nanotube flexible composite film according to claim 1 or 7.
9. The application of claim 8, wherein the titanium dioxide-carbon nanotube flexible composite film is applied to adsorbing and degrading organic matters in sewage.
10. The application of claim 9, wherein the effective time of the titanium dioxide-carbon nanotube flexible composite film for adsorbing and degrading organic matters in sewage is more than 1500min under the illumination condition with the wavelength of 664nm, and the removal rate of 10mg/L methylene blue of the titanium dioxide-carbon nanotube flexible composite film is more than 25% when 1500 min.
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