CN110694604A - TiO 22-PPy super-wetting photocatalytic composite material and preparation method thereof - Google Patents
TiO 22-PPy super-wetting photocatalytic composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000009736 wetting Methods 0.000 title claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 31
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract 9
- 238000004729 solvothermal method Methods 0.000 claims abstract 6
- 238000011068 loading method Methods 0.000 claims abstract 4
- 239000000758 substrate Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 238000001764 infiltration Methods 0.000 claims description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 8
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims 3
- 229920001940 conductive polymer Polymers 0.000 abstract description 12
- 239000003344 environmental pollutant Substances 0.000 abstract description 10
- 231100000719 pollutant Toxicity 0.000 abstract description 10
- 238000001228 spectrum Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000007795 chemical reaction product Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 229910010446 TiO2-a Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- 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
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Abstract
TiO 22The preparation method of the-PPy super-wetting photocatalytic composite material comprises the following steps: taking a material with a sponge structure as a matrix, and uniformly loading titanium dioxide particles on the surface of the matrix by a solvothermal method; loading ferric trichloride on a substrate loaded with titanium dioxide particles to obtain a precursor, and performing chemical vapor deposition on the precursorForming a polypyrrole film on the surface. The titanium dioxide film generated in situ on the sponge has uniform thickness and forms a good composite interface with the vapor-deposited conductive polymer, so that the composite material has more active sites, and the excellent full-spectrum photocatalytic performance is endowed by the synergistic effect and the heterostructure of the titanium dioxide and the conductive polymer, and the titanium dioxide film is used for rapidly degrading water-soluble pollutants. In addition, the modified composite sponge has high surface energy and a micro-nano coarse structure, so that the material has underwater super-oleophobic performance, and can be used for continuously separating wastewater containing hydrophobic pollutants.
Description
Technical Field
The invention belongs to the field of nano composite material preparation, and particularly relates to TiO2A preparation method of a PPy super-infiltration photocatalytic composite material.
Background
Water is a source of life and is an irreplaceable resource for maintaining the functions of an ecosystem and supporting the development of socioeconomic development. However, with the acceleration of urbanization and the rapid development of modern agriculture and industry, water pollution is becoming more serious, especially the types and the amount of organic pollutants are increasing, various organic pollutants with different properties such as water solubility, hydrophobicity and the like coexist in wastewater, and the traditional separation material is usually only used for a certain type of pollutants, has single function and is difficult to remove different types of organic pollutants simultaneously.
The Chinese patent with the application number of CN201811251260.0 discloses a preparation method of an easily prepared underwater super-oleophobic high-flow-rate oil-water separation net, and the Chinese patent with the application number of CN201710924555.9 discloses a preparation method and an application method of an oil-water separation net film with different wettability. Therefore, it is necessary to develop a composite material having high efficiency of oil-water separation and degradation of water-soluble pollutants to solve the above environmental problems.
An important measure for solving the organic pollution in water is the photocatalysis technology. The traditional photocatalyst mainly has powder and a supported type, but the traditional photocatalyst has a plurality of defects. If the powder catalyst is difficult to recover and cannot be reused (science 2001.293.261-71); the mechanical strength of the supported catalyst is better enhanced, but most of the selected matrixes are weak and cannot perform continuous work with high strength (chem. Soc. Rev. 2012.41.666-686). Therefore, the development of the high-efficiency photocatalytic material with excellent mechanical property has great practical significance in water pollution treatment.
Disclosure of Invention
Therefore, the project proposes to use TiO2And the conductive polymer is used as a construction element, and the porous material with visible light catalysis and underwater super oleophobic function is prepared through in-situ growth, surface modification and structure regulation. On one hand, the underwater super-oleophobic property of the material is utilized to selectively allow water to pass through, and the removal of insoluble pollutants in water is realized in a water-passing and oil-blocking manner; on the other hand, the high adsorption performance of the material is utilized to enrich the soluble pollutants in water, and the loaded photocatalytic material is used for quickly catalyzing and degrading the soluble pollutants so as to achieve the purpose of removing the water-soluble pollutants. Therefore, by designing the super-wetting material with photocatalytic performance, the selective wetting property of the material surface to oil and water and the synergistic effect of photocatalysis can be exerted to synchronously remove various mixed organic pollutants in water, the defects of easy generation of secondary pollution and difficult recovery of photocatalytic powder are overcome, and the super-wetting material has wide application prospect in the aspects of oily wastewater treatment and water environment purification.
The invention provides a TiO2A preparation method of a PPy super-infiltration photocatalytic composite material. The method prepares TiO by simple hydrothermal synthesis and chemical vapor deposition process2-a PPy super-infiltrated photocatalytic composite material. And the growth process is regulated and controlled by regulating and controlling the reaction, the reaction time and the reaction temperature. The composite material has high-efficiency full-spectrum photocatalytic performance and can have a good separation effect on insoluble oil stains.
The titanium dioxide film generated in situ on the sponge has uniform thickness and forms a good composite interface with the vapor-deposited conductive polymer, so that the composite material has more active sites, and the excellent full-spectrum photocatalytic performance is endowed by the synergistic effect and the heterostructure of the titanium dioxide and the conductive polymer, and the titanium dioxide film is used for rapidly degrading water-soluble pollutants. In addition, the modified composite sponge has high surface energy and a micro-nano coarse structure, so that the material has underwater super-oleophobic performance, and can be used for continuously separating wastewater containing hydrophobic pollutants.
In order to achieve the purpose, the invention adopts the following technical scheme:
a simple two-step method is provided, the influence of the type and concentration of a titanium dioxide precursor and hydrothermal synthesis conditions on the appearance of titanium dioxide is changed, and TiO is realized2Controllable preparation on the surface of the melamine sponge. And depositing a thin conductive polymer layer on the surface of the sponge on which the titanium dioxide grows by a chemical vapor deposition method to regulate and control the photocatalytic performance and wettability of the titanium dioxide. The prepared titanium dioxide is tightly covered by the conductive polymer film, a heterojunction structure is formed at the interface of the titanium dioxide and the conductive polymer film, and the surface of the titanium dioxide photocatalyst can be uniformly covered by the conductive polymer film by adopting a vapor deposition method, so that the composite material has higher mechanical stability, and the catalytic performance of the composite material under the full-spectrum light wavelength is efficiently enhanced. The material has the characteristics of simple preparation, low cost and environmental friendliness.
Further, the method specifically comprises:
mixing ethanol and titanium trichloride (TiCl)3) Aqueous solution and tin tetrachloride (SnCl)4) Adding the ethanol solution into a polytetrafluoroethylene reaction kettle, uniformly mixing, adding melamine sponge, and reacting for a period of time under certain conditions. Drying the resultant, and soaking in ferric chloride (FeCl)3) Drying the ethanol solution, dripping a conductive polymer as a monomer, depositing for a period of time under a certain condition, washing and drying to obtain TiO2-a PPy super-infiltrated photocatalytic composite material.
In a further improvement of the invention, the melamine sponge is commercial grade, washed with deionized water and air dried at room temperature prior to use.
The further improvement of the invention is that the concentration of the titanium trichloride aqueous solution is 10-25 percent, and the dosage is 0.1-2 mL.
The further improvement of the invention is that the concentration of the stannic chloride aqueous solution is 0.01-1.5mol/L, and the dosage is 0.5-3 mL.
The further improvement of the invention is that the concentration of the ferric trichloride ethanol solution is 0.01-1mol/L, and the dosage is 40-60 mL.
The further improvement of the invention is that the conductive polymer is pyrrole, the vapor deposition reaction time is 2-24h, and the deposition reaction temperature is 20-60 ℃.
The further improvement of the invention is that the solvent thermal reaction vessel is a polytetrafluoroethylene reaction kettle, the reaction temperature is 40-120 ℃, and the reaction time is 2-10 h.
Compared with the prior art, the invention has the advantages that:
1) by adopting the method of titanium dioxide in-situ growth, the titanium dioxide uniformly grows on the surface of the melamine sponge, and a layer of solid cladding titanium dioxide nano structure is formed.
2) The chemical vapor deposition method can enable the conductive polymer to uniformly form a layer of film on the titanium dioxide film, can effectively inhibit the polymer from blocking a porous structure, and can form a good bonding interface with the catalyst.
3) The titanium dioxide polymer composite material is simple in preparation method and mild in condition, can perform catalytic reaction under full-spectrum illumination, performs oil-water separation, and has a very high application prospect.
Drawings
FIG. 1 shows TiO prepared according to the present invention2SEM of PPy composite.
FIG. 2 shows TiO prepared according to the present invention2-infrared spectrum of PPy composite.
FIG. 3 shows TiO prepared according to the present invention2The photocatalytic degradation rate of the PPy composite material to 20mL rhodamine B dye with the concentration of 20 mg/L.
Detailed Description
In order to make the content of the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1 was carried out: 20mg of melamine sponge was added to 30mL of ethanol, 1.5mL of a mixed solution of titanium trichloride and 1mL of tin tetrachloride. The mixed solution is poured into a 100mL polytetrafluoroethylene reaction kettle and reacted for 6h at 100 ℃. Taking out the reaction product, drying at 60 ℃, then soaking in 0.05mol/L ferric trichloride solution for 20min, taking out and drying at 40 ℃. Three drops of pyrrole monomer are dripped into the bottom of the deposition container, and the precursor soaked with ferric trichloride is hung on the upper part of the reaction container to react for 5 hours at the temperature of 40 ℃. After the reaction is finished, the mixture is taken out and washed by ethanol and deionized water, and dried. The obtained black solid is TiO2-a PPy super-infiltrated photocatalytic composite material.
Example 2 was carried out: 15mg of melamine sponge was added to a mixed solution of 60mL of ethanol, 2mL of titanium trichloride and 1mL of tin tetrachloride. The mixed solution is poured into a 100mL polytetrafluoroethylene reaction kettle and reacted for 8h at 120 ℃. Taking out the reaction product, drying at 60 ℃, then putting the reaction product into 0.2mol/L ferric trichloride solution, soaking for 20min, taking out the reaction product, and drying at 40 ℃. Dripping four drops of pyrrole monomer to the bottom of the deposition container, hanging the precursor soaked with ferric trichloride on the upper part of the reaction container, and reacting for 6h at 40 ℃. After the reaction is finished, the mixture is taken out and washed by ethanol and deionized water, and dried. The obtained black solid is TiO2-a PPy super-infiltrated photocatalytic composite material.
Example 3 was carried out: 20mg of melamine sponge was added to a mixed solution of 30mL of ethanol, 1.5mL of titanium trichloride and 1mL of tin tetrachloride. The mixed solution is poured into a 100mL polytetrafluoroethylene reaction kettle and reacted for 5h at 80 ℃. Taking out the reaction product, drying at 60 ℃, then putting the reaction product into 0.1mol/L ferric trichloride solution, soaking for 10min, taking out the reaction product, and drying at 40 ℃. Three drops of aniline monomer are dropped into the bottom of the deposition container, and the precursor soaked with ferric trichloride is hung on the upper part of the reaction container and reacts for 24 hours at 60 ℃. After the reaction is finished, the mixture is taken out and washed by ethanol and deionized water, and dried. The obtained black solid is TiO2-a PPy super-infiltrated photocatalytic composite material.
FIG. 1 shows TiO prepared by the method of example 1 of the present invention2SEM images of PPy super-infiltrated photocatalytic composite material. It can be seen from fig. 1 that the titanium dioxide and polypyrrole are tightly coated on the sponge matrix.
Please refer to fig. 2, which illustrates a method of the present inventionProcess example 1 preparation of TiO2-infrared spectrogram of a PPy super-infiltrated photocatalytic composite material. FIG. A shows the IR spectrum of pure titanium dioxide and FIG. B shows TiO2-infrared spectrum of PPy composite. As can be seen from fig. 2: titanium dioxide and polypyrrole form a good hybrid structure.
FIG. 3 shows TiO prepared by the method of example 1 of the present invention2-photocatalytic degradation rate of PPy super-infiltrated photocatalytic composite material under full spectrum illumination in 20mL of rhodamine B dye with concentration of 20 mg/L. As can be seen from fig. 3: TiO 22PPy shows high-efficiency photocatalytic efficiency in the dye with higher concentration, and the degradation rate can reach 92% after 120 min.
Claims (8)
1. TiO 22The PPy super-wetting photocatalytic composite material is characterized in that a sponge structure is used as a matrix, titanium dioxide particles are uniformly loaded on the surface of the matrix, and a layer of polypyrrole film with a rough structure required by a super-wetting surface is arranged outside the titanium dioxide particles.
2. TiO 22The preparation method of the PPy super-infiltration photocatalytic composite material is characterized by comprising the following steps of:
taking a material with a sponge structure as a matrix, and uniformly loading titanium dioxide particles on the surface of the matrix by a solvothermal method; loading ferric trichloride on a substrate loaded with titanium dioxide particles to obtain a precursor, and forming a polypyrrole film on the surface of the precursor by a chemical vapor deposition method.
3. A TiO according to claim 22The preparation method of the-PPy super-wetting photocatalytic composite material is characterized in that titanium dioxide particles are uniformly loaded on the surface of a matrix through a solvothermal method, titanium trichloride, stannic chloride and melamine sponge are subjected to solvothermal reaction, and the melamine sponge uniformly loaded with titanium dioxide is obtained after drying.
4. A TiO according to claim 32-PPyThe preparation method of the super-infiltration photocatalytic composite material is characterized in that sufficient ethanol is used as a reaction solvent in the solvothermal reaction; before reaction, respectively preparing titanium trichloride and stannic chloride into aqueous solutions, uniformly mixing the aqueous solutions with a reaction solvent, and then immersing melamine sponge in the reaction solvent; the concentration of the titanium trichloride aqueous solution is 10-25%, and the dosage is 0.1-2 mL; the concentration of the stannic chloride aqueous solution is 0.01-1.5mol/L, and the dosage is 0.5-3 mL.
5. A TiO according to claim 22The preparation method of the PPy super-infiltration photocatalytic composite material is characterized in that ferric trichloride is loaded on a matrix loaded with titanium dioxide particles, and the preparation method is obtained by soaking the matrix loaded with the titanium dioxide particles in an ethanol solution of the ferric trichloride, fully soaking and drying; the concentration of the ferric trichloride ethanol solution is 0.01-1mol/L, and the dosage is 40-60 mL.
6. A TiO according to claim 22The preparation method of the PPy super-infiltration photocatalytic composite material is characterized in that the chemical vapor deposition method is to add a proper amount of pyrrole monomer at the bottom of a deposition container, suspend the precursor on the upper part of the deposition container, and fully react at a temperature suitable for chemical vapor deposition.
7. A TiO according to claim 62The preparation method of the-PPy super-infiltration photocatalytic composite material is characterized in that the reaction time of the chemical vapor deposition method is 2-24h, and the reaction temperature is 20-60 ℃.
8. A TiO according to claim 22The preparation method of the-PPy super-infiltration photocatalytic composite material is characterized in that a reaction vessel of solvothermal reaction is a polytetrafluoroethylene reaction kettle, the reaction temperature is 40-120 ℃, and the reaction time is 2-10 h.
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Cited By (3)
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|---|---|---|---|---|
| CN111437886A (en) * | 2020-03-20 | 2020-07-24 | 西安工程大学 | Melamine sponge/TiO2Composite material and preparation method thereof |
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| CN115228470A (en) * | 2022-07-01 | 2022-10-25 | 重庆工商大学 | Preparation method of super-hydrophobic super-oleophylic carbonyl iron loaded nano titanium dioxide photocatalyst |
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| CN111744371A (en) * | 2020-06-23 | 2020-10-09 | 西南石油大学 | Self-cleaning graphene oxide nanofiltration membrane and preparation method thereof |
| CN115228470A (en) * | 2022-07-01 | 2022-10-25 | 重庆工商大学 | Preparation method of super-hydrophobic super-oleophylic carbonyl iron loaded nano titanium dioxide photocatalyst |
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