CN111826018A - Organic-inorganic hybrid antistatic self-cleaning film and preparation method thereof - Google Patents
Organic-inorganic hybrid antistatic self-cleaning film and preparation method thereof Download PDFInfo
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- CN111826018A CN111826018A CN201911183038.6A CN201911183038A CN111826018A CN 111826018 A CN111826018 A CN 111826018A CN 201911183038 A CN201911183038 A CN 201911183038A CN 111826018 A CN111826018 A CN 111826018A
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- 238000004140 cleaning Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 47
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 11
- 238000004528 spin coating Methods 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 46
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 42
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 42
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000003623 enhancer Substances 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910052691 Erbium Inorganic materials 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 7
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007888 film coating Substances 0.000 claims description 2
- 238000009501 film coating Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 150000001298 alcohols Chemical group 0.000 claims 2
- 150000002170 ethers Chemical class 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000001782 photodegradation Methods 0.000 abstract description 4
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 238000007761 roller coating Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 9
- 239000010936 titanium Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 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 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 pollen Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- C03C2217/00—Coatings on glass
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
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- C03C2218/112—Deposition methods from solutions or suspensions by spraying
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Abstract
The invention relates to an organic-inorganic hybrid antistatic self-cleaning film, which comprises PEDOT/PSSTiO2Or PEDOT/PSS TiO2The antistatic self-cleaning film is prepared by coating an antistatic super-hydrophilic self-cleaning coating. The antistatic self-cleaning film can be degraded by super-hydrophilic photocatalysis to play a self-cleaning role, and can also be antistatic and antifouling. The method has important significance when being applied to glass curtain walls or solar cells; PEDOT/PSS TiO2Er.N, can be in TiO2The donor level and the acceptor level are introduced simultaneously, so that the separation of photo-generated electrons and holes can be accelerated, the recombination probability is reduced, and the photodegradation activity is increased; the coating mode adopted by the invention is spraying, spin coating, blade coating or roller coating, the operation is simple, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to an organic-inorganic hybrid antistatic self-cleaning film and a preparation method thereof, belonging to the technical field of organic-inorganic semiconductors.
Background
According to statistics of relevant departments, nearly 50% of cities in China have more than moderate pollution, 18% of the cities have severe pollution, and a thick atmospheric pollution layer covers 15% of the regions of the country. It is estimated that the economic loss of China caused by pollution is about 2000 billion yuan each year. The increasingly serious haze, oily smoke, industrial waste gas, automobile exhaust and acid rain bring about a great deal of pollution to the outer wall of the building, and the attractiveness, functionality and durability of the building are greatly influenced. The stain resistance is an important index for inspecting the performance of the building exterior wall coating. The solar cell industry also faces the same problem. At present, the application of solar cells in various countries in the world is rapidly increased, and the light transmittance of general glass is about 90 percent. The transmittance of sand dust, pollen, oil stain, bird droppings and the like is reduced to 50-70% after being attached to the surface, so that the power generation rate is reduced, and the pollutants are unevenly attached to the surface of the solar cell, so that the hot spot effect is easily caused, and the cell is damaged. How to maintain the power generation efficiency for a long time after the installation of the solar facility becomes a major issue of the right and left benefits. The solar cell panel can efficiently absorb sunlight, the light absorption angle is certain, but pollution cannot be prevented. How to self-clean or simply clean regularly becomes the biggest future point of sale for the solar energy industry.
In order to improve the stain resistance and self-cleaning capability of the surface of a glass curtain wall or a solar cell, technicians develop a stain-resistant self-cleaning coating which is not easy to attach pollutants or can remove the attached pollutants by means of natural action of rainwater, wind power and the like. But the gains are far from the expected routes so far. The main reason is that the antifouling film can exert the super-hydrophilic effect only after being irradiated for more than two hours, and stains on curtain walls, solar cells and vehicle bodies have various factors such as carbon dust, soot, pollen, NOX, SOX and the like, wherein most stains are the carbon dust and the soot, and cannot be effectively removed due to the fact that the stains cannot be decomposed by the photocatalyst, and the photocatalyst cannot exert the effect in places without light rays such as backlight walls, underground streets, tunnels and the like.
The addition of an antistatic function on a glass curtain wall or a solar panel is an effective method for effectively preventing the attachment of pollutants such as wind sand and the like. However, most studied self-cleaning materials in the market are hydrophobic, hydrophilic or photocatalyst self-cleaning coatings, among which the most studied is TiO which is super-hydrophilic and has the function of photocatalytic degradation of organic matters2(titanium dioxide) film. And meanwhile, the research on the coating with the antistatic effect is less. Organic-inorganic hybrid PEDOT/PSS TiO2Not only can resist static electricity, but also has super-hydrophilic photodegradation self-cleaning effect. Further doped with erbium and nitrogen, prepared PEDOT/PSS TiO2Er.N, can be in TiO2The donor level and the acceptor level are introduced simultaneously, so that the separation of photo-generated electrons and holes can be accelerated, the recombination probability is reduced, and the photodegradation activity is increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an organic-inorganic hybrid antistatic self-cleaning film and a preparation method thereof.
The technical scheme for solving the technical problems is as follows: an organic-inorganic hybrid antistatic self-cleaning film, which comprises PEDOT/PSS TiO2Or PEDOT/PSS TiO2The antistatic self-cleaning film is prepared by coating an antistatic super-hydrophilic self-cleaning coating.
Preference is given toThe PEDOT/PSS TiO2Or PEDOT/PSS TiO20.1-5 parts of Er.N, 20-60 parts of water, 20-60 parts of organic solvent, 0-1 part of dispersant and 0-5 parts of conductivity enhancer.
Preferably, the organic solvent is alcohol or ether or a mixture of the alcohol and the ether; the dispersing agent is one or a mixture of sodium dodecyl sulfate, polyvinylpyrrolidone, polyalcohol and polycarboxylic acid; the conductivity enhancer is ethylene glycol.
The invention also discloses a preparation method of the organic-inorganic hybrid antistatic self-cleaning film, which comprises the following steps:
A. treatment of the substrate: cleaning a substrate needing film coating to remove dust and oil stains on the surface;
B. preparing an antistatic super-hydrophilic coating: the PEDOT/PSS TiO2Solution or PEDOT/PSS2Adding an Er.N solution, water, an organic solvent, a dispersing agent and a conductivity enhancer into a reactor, magnetically stirring at normal temperature to fully mix the components, and aging for 24 hours to obtain the antistatic super-hydrophilic self-cleaning coating;
C. preparing an antistatic self-cleaning film: and (D) coating the antistatic super-hydrophilic self-cleaning coating obtained in the step (B) on the substrate obtained in the step (A), and drying at normal temperature or annealing at a certain temperature to obtain the antistatic self-cleaning film.
Further, in step a, the substrate is a glass curtain wall or a solar cell surface.
Further, in step B, the PEDOT/PSS TiO2The preparation method of the solution comprises the following steps: dropwise adding acetylacetone and butyl titanate into ethanol under magnetic stirring, dropwise adding concentrated nitric acid to adjust the pH of the solution to 2-5, stirring, aging for 0.5-10h to obtain a solution A, dropwise adding the solution A into a 0.1-1 mol/L PSS (polystyrene sulfonate) aqueous solution, stirring, adding an EDOT (3, 4-ethylenedioxythiophene) monomer, dropwise adding concentrated nitric acid to adjust the pH of the solution to 2-5, and adding (NH)4)S2O8And Fe2(SO4)3Stirring the mixed solution to obtain PEDOT/PSS TiO2Solutions ofFiltering, washing the precipitate, calcining at 600 ℃ for 3h to obtain PEDOT/PSS TiO2Nanoparticles, followed by mixing PEDOT/PSS TiO2Dissolving in deionized water to prepare an aqueous solution with the mass fraction of 1-10%;
the PEDOT/PSS TiO2The preparation method of the Er.N solution comprises the following steps: erbium nitrate Er (NO)3)3Adding the solution A into the solution A, stirring and dissolving to obtain a solution B, dropwise adding the solution B into 0.1-1 mol/L aqueous solution of urea, and stirring to obtain erbium and nitrogen co-doped TiO2Adding the solution C into 0.1-1 mol/L polystyrene sulfonate aqueous solution, stirring, then adding 3, 4-ethylenedioxythiophene monomer, dropwise adding concentrated nitric acid to adjust the pH value of the solution to 2-5, and adding (NH)4)S2O8And Fe2(SO4)3Stirring the mixed solution to obtain PEDOT/PSS TiO2Filtering Er.N solution, washing the precipitate, calcining the precipitate at 600 ℃ for 3h to obtain PEDOT/PSS TiO2-Er.N nanoparticles, followed by PEDOT/PSS TiO2Dissolving Er.N in deionized water to prepare an aqueous solution with the mass fraction of 1-10%.
Further, the volume ratio of the acetylacetone to the butyl titanate is 1: 2-5, the volume ratio of the butyl titanate to the ethanol is 5-20:100, and the 3, 4-ethylenedioxythiophene monomer and (NH)4)S2O8The molar ratio is 1: 1-5, the 3, 4-ethylenedioxythiophene monomer and Fe2(SO4)3The molar ratio is 1: 0.01-0.05, wherein the molar ratio of the 3, 4-ethylenedioxythiophene monomer to the polystyrene sulfonate is 1: 1-2. Er (NO)3)3And C16H30O4The molar ratio of Ti is 1-5: 100, CH4N2O and C16H30O4The molar ratio of Ti is 2.5-10: 100, EDOT and C16H30O4The molar ratio of Ti is 1: 1 to 5.
Further, in the step C, the coating mode is spray coating, spin coating, blade coating or roll coating, the annealing temperature is 50-250 ℃, and the annealing time is 10-60 min.
Further, in the step C, the thickness of the antistatic self-cleaning film is 20-2000 nm.
The invention has the beneficial effects that:
(1) the main component of the invention is organic-inorganic hybrid PEDOT/PSS TiO2Or PEDOT/PSS TiO2And the-Er.N can be degraded by super-hydrophilic photocatalysis, has a self-cleaning effect, and can be antistatic and antifouling. The method has important significance when being applied to glass curtain walls or solar cells;
(2)PEDOT/PSS·TiO2in TiO of Er.N2Erbium and nitrogen are simultaneously doped, and position defects can be introduced into titanium oxide by the erbium to become traps of electrons or holes, so that the service life of the photocatalytic free radicals is prolonged. And the doping of nitrogen can generate an energy level for absorbing visible light in the band gap of titanium dioxide, so that the forbidden bandwidth is narrowed. The co-doping of nitrogen and erbium introduces a donor level and an acceptor level simultaneously, can accelerate the separation of photo-generated electrons and holes, reduce the recombination probability and increase the photodegradation activity, thereby enhancing the PEDOT/PSS TiO2Self-cleaning function of Er.N photocatalytic degradation;
(3) the coating mode adopted by the invention is spraying, spin coating, blade coating or roller coating, the operation is simple, and the method is suitable for industrial production.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Organic-inorganic hybridAn antistatic self-cleaning film, which mainly comprises PEDOT/PSS TiO2The film is prepared by spin coating of antistatic super-hydrophilic self-cleaning paint.
The preparation method of the organic-inorganic hybrid antistatic self-cleaning film comprises the following steps:
A. treatment of the substrate: cleaning the surface of the curtain wall glass to remove dust and oil stains on the surface;
B. preparing an antistatic super-hydrophilic coating: dropwise adding 5mL of acetylacetone and 10mL of butyl titanate into 100mL of ethanol under magnetic stirring, dropwise adding concentrated nitric acid to adjust the pH to 2.5, stirring for 3h, sealing, standing and aging for 8h to obtain TiO2And (3) sol. Adding TiO into the mixture2The sol is dripped into 0.1mol/L PSS (polystyrene sulfonate) aqueous solution and stirred, then EDOT (3, 4-ethylenedioxythiophene) monomer is added, concentrated nitric acid is dripped to adjust the pH value of the solution to 2.5, and (NH) is added4)S2O8And Fe2(SO4)3Stirring the mixed solution to obtain PEDOT/PSS TiO2Solution, wherein the molar ratio EDOT: (NH)4)S2O8＝1：1.5，EDOT：Fe2(SO4)3＝1：0.03，EDOT：PSS＝1：2，EDOT：C16H30O4And Ti is 1: 2. filtering the solution, washing the solution to precipitate, and calcining the solution for 3 hours at the temperature of 600 ℃ to obtain PEDOT/PSS TiO2Nanoparticles, followed by mixing PEDOT/PSS TiO2Dissolving in deionized water to prepare an aqueous solution with the mass fraction of 1%.
0.05% of PEDOT/PSS TiO2Adding 40.95% of water, 49.9% of ethanol, 8% of ethylene glycol monomethyl ether, 0.1% of dispersant sodium dodecyl sulfate and 1% of conductivity enhancer ethylene glycol into a reactor, magnetically stirring at normal temperature to fully mix the components, and aging for 24 hours to obtain the antistatic super-hydrophilic self-cleaning coating.
C. Preparing an antistatic self-cleaning film: and B, spraying the antistatic super-hydrophilic self-cleaning film obtained in the step B on the surface of the glass obtained in the step A, and annealing at 120 ℃ for 30min to obtain the antistatic self-cleaning film with the thickness of 50 nm.
Example 2
An organic-inorganic hybridized antistatic self-cleaning film contains PEDOT/PSS TiO as main component2Er.N, and in addition, auxiliary agents such as a dispersant and a conductivity enhancer. The film is prepared by spin coating of antistatic super-hydrophilic self-cleaning paint.
The preparation method of the organic-inorganic hybrid antistatic self-cleaning film comprises the following steps:
A. treatment of the substrate: cleaning the surface of the curtain wall glass to remove dust and oil stains on the surface;
B. preparing an antistatic super-hydrophilic coating: dropwise adding 5mL of acetylacetone and 10mL of butyl titanate into 100mL of ethanol under magnetic stirring, dropwise adding concentrated nitric acid to adjust the pH to 2.5, stirring for 3h, sealing, standing and aging for 8h to obtain TiO2And (3) solution. Erbium nitrate Er (NO)3)3Adding the TiO2Stirring the sol for 24 hours to obtain erbium-doped TiO solution2And (3) solution. The solution is dripped into 0.1mol/L aqueous solution of urea and stirred for 24 hours to obtain the TiO codoped with erbium and nitrogen2And (3) solution. The solution is dripped into 0.5mol/L PSS (polystyrene sulfonate) aqueous solution and stirred, then EDOT (3, 4-ethylenedioxythiophene) monomer is added, concentrated nitric acid is dripped to adjust the pH value of the solution to 2.5, and (NH4) S is added2O8And Fe2(SO4)3Stirring the mixed solution to obtain PEDOT/PSS TiO2-er.n solution. Wherein, the molar ratio EDOT: (NH)4)S2O8＝1：1.5，EDOT：Fe2(SO4)3＝1：0.03，EDOT：PSS＝1：2，Er(NO3)3：C16H30O4Ti＝1：100，CH4N2O：C16H30O4Ti＝20：100，EDOT：C16H30O4Ti＝1：2。
Filtering, washing the precipitate, calcining at 600 ℃ for 3h to obtain PEDOT/PSS TiO2-Er.N nanoparticles, followed by PEDOT/PSS TiO2Dissolving Er.N in deionized water to prepare an aqueous solution with the mass fraction of 1%.
0.1% of PEDOT/PSS TiO2-Er.N, 40.9 percent of water, 49.9 percent of ethanol, 8 percent of ethylene glycol monomethyl ether, 0.1 percent of dispersant sodium dodecyl sulfate and 1 percent of conductivity enhancer ethylene glycol are added into a reactor, and are stirred magnetically at normal temperature to be mixed fully and aged for 24 hours to obtain the antistatic super-hydrophilic self-cleaning coating.
C. Preparing an antistatic self-cleaning film: and B, spraying the antistatic super-hydrophilic self-cleaning film obtained in the step B on the surface of the glass obtained in the step A, and annealing at 120 ℃ for 30min to obtain the antistatic self-cleaning film with the thickness of 50 nm.
The examples were subjected to surface resistance, contact angle, transmittance and photocatalytic degradation (test solution of 0.02mol/L methylene blue, 3 mW/cm)2Ultraviolet light irradiation for 20min, and the test absorbance range of 600-700nm), the obtained data are shown in the following table:
watch 1
As can be seen from the table I, the surface resistance of the organic-inorganic hybrid antistatic self-cleaning films prepared in examples 1 and 2 is in the antistatic range of 106-109Omega/□, and has good antistatic performance. The contact angles of the photocatalyst are less than 5 degrees, the photocatalyst is super-hydrophilic, the photocatalytic degradation rates are high and are respectively 37% and 42%, and the photocatalyst has good super-hydrophilic photocatalytic self-cleaning performance. Further, the transmittances were 88.5% and 88.3%, respectively, and the light transmittance was hardly affected.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. An organic-inorganic hybrid antistatic self-cleaning film, which is characterized in that the antistatic self-cleaning film comprises PEDOT/PSS TiO2Or PEDOT/PSS TiO2The antistatic self-cleaning film is prepared by coating an antistatic super-hydrophilic self-cleaning coating.
2. The organic-inorganic hybrid antistatic self-cleaning film according to claim 1, wherein the PEDOT/PSS TiO is in parts by weight2Or PEDOT/PSS TiO20.1-5 parts of Er.N, 20-60 parts of water, 20-60 parts of organic solvent, 0-1 part of dispersant and 0-5 parts of conductivity enhancer.
3. The method for preparing an organic-inorganic hybrid antistatic self-cleaning film according to claim 2, wherein the organic solvent is alcohols or ethers or a mixture of the alcohols and the ethers; the dispersing agent is one or a mixture of sodium dodecyl sulfate, polyvinylpyrrolidone, polyalcohol and polycarboxylic acid; the conductivity enhancer is ethylene glycol.
4. A method for preparing an organic-inorganic hybrid antistatic self-cleaning film according to any one of claims 1 to 3, comprising the steps of:
A. treatment of the substrate: cleaning a substrate needing film coating to remove dust and oil stains on the surface;
B. preparing an antistatic super-hydrophilic coating: the PEDOT/PSS TiO2Solutions or PEDOT/PSS TiO2Adding the-Er.N solution, water, organic solvent, dispersant and conductivity enhancer into a reactor, magnetically stirring at normal temperature to fully mix, and agingObtaining the antistatic super-hydrophilic self-cleaning coating after 24 hours;
C. preparing an antistatic self-cleaning film: and (D) coating the antistatic super-hydrophilic self-cleaning coating obtained in the step (B) on the substrate obtained in the step (A), and drying at normal temperature or annealing at a certain temperature to obtain the antistatic self-cleaning film.
5. The method for preparing an organic-inorganic hybrid antistatic self-cleaning film according to claim 4, wherein in step A, the substrate is curtain wall glass or the surface of a solar cell.
6. The method for preparing an organic-inorganic hybrid antistatic self-cleaning film according to claim 4, wherein in step B, the PEDOT/PSS TiO film2The preparation method of the solution comprises the following steps: mixing acetylacetone and butyl titanate C16H30O4Adding Ti dropwise into ethanol under magnetic stirring, adding concentrated nitric acid dropwise to adjust the pH value of the solution to 2-5, stirring, aging for 0.5-10h to obtain a solution A, adding the solution A dropwise into 0.1-1 mol/L polystyrene sulfonate aqueous solution, stirring, adding 3, 4-ethylenedioxythiophene monomer, adding concentrated nitric acid dropwise to adjust the pH value of the solution to 2-5, and adding (NH)4)S2O8And Fe2(SO4)3Stirring the mixed solution to obtain PEDOT/PSS TiO2Filtering the solution, washing the precipitate, calcining the precipitate at 600 ℃ for 3h to obtain PEDOT/PSS TiO2Nanoparticles, followed by mixing PEDOT/PSS TiO2Dissolving in deionized water to prepare an aqueous solution with the mass fraction of 1-10%;
the PEDOT/PSS TiO2The preparation method of the Er.N solution comprises the following steps: erbium nitrate Er (NO)3)3Adding the solution A into the solution A, stirring and dissolving to obtain a solution B, and dropwise adding the solution B into 0.1-1 mol/L urea CH4N2Stirring in O water solution to obtain TiO codoped with erbium and nitrogen2Adding the solution C into 0.1-1 mol/L polystyrene sulfonate aqueous solution, stirring, then adding 3, 4-ethylenedioxythiophene monomer, dropwise adding concentrated nitric acid to adjust the pH value of the solution to 2-5, and adding (NH)4)S2O8And Fe2(SO4)3Stirring the mixed solution to obtain PEDOT/PSS TiO2Filtering Er.N solution, washing the precipitate, calcining the precipitate at 600 ℃ for 3h to obtain PEDOT/PSS TiO2-Er.N nanoparticles, followed by PEDOT/PSS TiO2Dissolving Er.N in deionized water to prepare an aqueous solution with the mass fraction of 1-10%.
7. The method for preparing an organic-inorganic hybrid antistatic self-cleaning film according to claim 6, wherein the acetylacetone and butyl titanate C are16H30O4The volume ratio of Ti is 1: 2-5, wherein the volume ratio of the butyl titanate to the ethanol is 5-20:100, the 3, 4-ethylenedioxythiophene monomer and (NH)4)S2O8The molar ratio is 1: 1-5, the 3, 4-ethylenedioxythiophene monomer and Fe2(SO4)3The molar ratio is 1: 0.01-0.05, wherein the molar ratio of the 3, 4-ethylenedioxythiophene monomer to the polystyrene sulfonate is 1: 1-2, Er (NO)3)3And C16H30O4The molar ratio of Ti is 1-5: 100, CH4N2O and C16H30O4The molar ratio of Ti is 2.5-10: 100, 3, 4-ethylenedioxythiophene and C16H30O4The molar ratio of Ti is 1: 1 to 5.
8. The method for preparing an organic-inorganic hybrid antistatic self-cleaning film according to claim 4, wherein in step C, the coating mode is spray coating, spin coating, blade coating or roll coating, the annealing temperature is 50-250 ℃, and the annealing time is 10-60 min.
9. The method for preparing an organic-inorganic hybrid antistatic self-cleaning film according to claim 4, wherein in step C, the thickness of the antistatic self-cleaning film is 20-2000 nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248138A (en) * | 2021-06-03 | 2021-08-13 | 南通腾峰光学仪器有限公司 | High-transmittance anti-radiation optical glass and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928517A (en) * | 2009-06-19 | 2010-12-29 | 北京中科赛纳玻璃技术有限公司 | Nano self-cleaning paint and preparation method thereof |
| CN103861631A (en) * | 2014-03-12 | 2014-06-18 | 北京理工大学 | Preparation method of nitrogen-doped titanium dioxide nanoribbon visible light photocatalyst |
| CN104096576A (en) * | 2014-06-26 | 2014-10-15 | 杭州电子科技大学 | Environmental photocatalytic nano materials and preparation method thereof |
| CN104193972A (en) * | 2014-09-04 | 2014-12-10 | 常州大学 | Preparation method for PEDOT (polymer ethylenedioxy thiophene)/nano titanium dioxide aqueous dispersion |
| CN106366826A (en) * | 2016-08-31 | 2017-02-01 | 浙江润阳新材料科技股份有限公司 | Nano-TiO2 self-cleaning coating and preparation method thereof |
| KR101986607B1 (en) * | 2018-02-01 | 2019-06-10 | (주)기륭산업 | Manufacturing method for antistatic organic-inorganic hybrid composition and organic-inorganic hybrid firm comprising composition manufactured by the same |
-
2019
- 2019-11-27 CN CN201911183038.6A patent/CN111826018B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928517A (en) * | 2009-06-19 | 2010-12-29 | 北京中科赛纳玻璃技术有限公司 | Nano self-cleaning paint and preparation method thereof |
| CN103861631A (en) * | 2014-03-12 | 2014-06-18 | 北京理工大学 | Preparation method of nitrogen-doped titanium dioxide nanoribbon visible light photocatalyst |
| CN104096576A (en) * | 2014-06-26 | 2014-10-15 | 杭州电子科技大学 | Environmental photocatalytic nano materials and preparation method thereof |
| CN104193972A (en) * | 2014-09-04 | 2014-12-10 | 常州大学 | Preparation method for PEDOT (polymer ethylenedioxy thiophene)/nano titanium dioxide aqueous dispersion |
| CN106366826A (en) * | 2016-08-31 | 2017-02-01 | 浙江润阳新材料科技股份有限公司 | Nano-TiO2 self-cleaning coating and preparation method thereof |
| KR101986607B1 (en) * | 2018-02-01 | 2019-06-10 | (주)기륭산업 | Manufacturing method for antistatic organic-inorganic hybrid composition and organic-inorganic hybrid firm comprising composition manufactured by the same |
Non-Patent Citations (3)
| Title |
|---|
| 张明等: "《纳米与新材料专辑V》", 25 November 2005, 材料导报社 * |
| 戴松元: "《薄膜太阳电池关键科学和技术》", 31 January 2013, 上海科学技术出版社 * |
| 杨辉等: "TiO2-PEDT/PSS双层复合膜的制备及其光催化性能", 《催化学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248138A (en) * | 2021-06-03 | 2021-08-13 | 南通腾峰光学仪器有限公司 | High-transmittance anti-radiation optical glass and preparation method thereof |
| CN113248138B (en) * | 2021-06-03 | 2021-10-15 | 南通腾峰光学仪器有限公司 | High-transmittance anti-radiation optical glass and preparation method thereof |
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