阅读说明：本技术 一种有机-无机杂化的抗静电自清洁膜及其制备方法 (Organic-inorganic hybrid antistatic self-cleaning film and preparation method thereof ) 是由 罗伟 任辉彩 庞茂印 曹原 贺伟 辛晓明 于 2019-11-27 设计创作，主要内容包括：本发明涉及一种有机-无机杂化的抗静电自清洁膜,所述的抗静电自清洁膜包括PEDOT/PSS·TiO<Sub>2</Sub>或PEDOT/PSS·TiO<Sub>2</Sub>-Er.N、水、有机溶剂、分散剂和导电性增强剂,所述的抗静电自清洁膜由抗静电超亲水自清洁涂料涂布制得。所述抗静电自清洁膜既能超亲水光催化降解,起到自清洁作用,又能抗静电防污。应用到玻璃幕墙或太阳能电池上具有重要意义；PEDOT/PSS·TiO<Sub>2</Sub>-Er.N,能在TiO<Sub>2</Sub>中同时引入施主能级和受主能级,能加速光生电子和空穴的分离,降低复合几率,增加光降解活性；本发明采用所述涂布方式为喷涂、旋涂、刮涂或辊涂,操作简单适宜产业化生产。(The invention relates to an organic-inorganic hybrid antistatic self-cleaning film, which comprises PEDOT/PSSTiO 2 Or PEDOT/PSS TiO 2 The 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 TiO 2 Er.N, can be in TiO 2 The 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.)

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.

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.