CN110564186A - Visible light photocatalytic functional topcoat containing quantum dots and preparation method thereof - Google Patents
Visible light photocatalytic functional topcoat containing quantum dots and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
the invention discloses a visible light photocatalytic functional surface coating containing quantum dots and a preparation method thereof, wherein the visible light photocatalytic functional surface coating comprises the following components in percentage by weight: 1-10% of silicate coating resin, 1-10% of titanium dioxide quantum dots doped with noble metal ions, 0.02-2% of silicon nanoparticles, 0-1% of FeOOH nanoparticles, 0.1-1% of flatting agent, 0.1-1% of dispersing agent, 0.1-1% of thickening agent, 0.1-1% of defoaming agent and the balance of water. Compared with the traditional photocatalytic coating, the visible light photocatalytic functional surface coating containing the quantum dots can obviously improve the photocatalytic effect, can continuously and efficiently remove harmful substances such as formaldehyde, benzene, ammonia, TVOC (total volatile organic compound), PM (particulate matter) 2.5 and the like, purify the indoor air environment, remove haze outdoors, kill bacteria, viruses, fungi, microorganisms and the like in a broad spectrum, is coated once, is used for the whole life, and is safe to use.
Description
Technical Field
The invention relates to the field of coatings, in particular to a visible light photocatalytic functional surface coating containing quantum dots and a preparation method thereof.
Background
Since the discovery of the photodecomposition phenomenon of titanium dioxide single crystal under ultraviolet irradiation in 1972 by Taeniculia of photochemistry, photocatalysis has gradually become a novel environment-friendly environmental pollution cleaning technology. The photocatalyst absorbs light, electrons on the surface of the photocatalyst absorb enough energy to be separated, positive holes are formed at the positions where the electrons are separated, the electrons and the holes react with oxygen, water and hydroxyl groups to generate superoxide ions with strong oxidizing property and hydroxyl radicals with strong reducing property, and the superoxide ions and the hydroxyl radicals oxidize and decompose organic pollutants and bacteria into harmless water and carbon dioxide, so that the aims of removing pollutants and reducing bacteria are fulfilled.
The photocatalyst materials are numerous, including oxides such as titanium dioxide, zinc oxide and tin dioxide, and sulfides such as cadmium sulfide and zinc sulfide, wherein the titanium dioxide is the most important photocatalyst material at present because of strong oxidizing ability, chemical stability and no toxicity. However, the forbidden band width of titanium dioxide is large, and the photocatalyst has higher catalytic activity only under the irradiation of ultraviolet light. The reality is that the solar energy is mainly concentrated in the visible light range of 400-700nm, the ultraviolet light accounts for only about 4% of the sunlight, and the ultraviolet light wavelength, the diffraction capability and the penetration capability are relatively weak; ultraviolet rays entering the room are very little after being blocked and filtered by the wall and the glass. There are also conditions of oblique sun rays, and less ultraviolet rays in winter and cloudy days. Thus, conventional coatings using titanium dioxide have a low availability to visible light and are substantially catalytically inactive in the visible range.
in order to improve the responsiveness of titanium dioxide to visible light, patents with publication numbers CN101153137A and CN100335578C propose a method of adding metal or doping nonmetal to titanium dioxide, but the visible light-responsive photocatalyst obtained in this way has weak light absorption capability and low catalytic activity, and the use of noble metal increases the cost, and the doping element is easy to run off, which easily results in losing the catalytic activity. In this method, the chemical bond of the photosensitizing dye is broken and separated by the photocatalytic action even when the photosensitizing dye is an organic substance, and thus the responsiveness to visible light is not durable, and the lifetime of the photosensitizing dye gradually decreases with the passage of time. Further, as proposed in patent publication No. CN1013756376B, a semiconductor with a narrow energy gap such as modified iron oxide is added to absorb visible light, and the refractive index of the iron oxide material is generally 2.8 to 2.9, and compared with a paint base material having a refractive index of generally only about 1.4 to 1.6, iron oxide particles scatter visible light strongly, so that there is a defect that the photocatalytic activity is not high when visible light is irradiated, although visible light is absorbed. In addition, the document also proposes that semiconductors with narrow energy gap widths such as cadmium sulfide and tin dioxide are added, but the cadmium sulfide and the tin dioxide have certain toxicity and cannot meet the requirement of environmental protection. Furthermore, the photocatalytic effect of these coatings is limited by the fact that the light absorption is substantially concentrated at the surface of the coating and hence the photocatalytic degradation is limited. How to improve the photocatalytic effect of the coating is a problem to be solved urgently. And the photocatalytic coating and the organic components in the wall coating applied by the photocatalytic coating are difficult to avoid bond breaking under the action of photocatalysis, so that how to avoid the deterioration of the coating and protect the original wall coating is also very important.
disclosure of Invention
the invention aims to overcome the defects and provide the visible light photocatalytic functional surface coating containing quantum dots, which has high photocatalytic efficiency, good visible light responsiveness and stable performance.
The invention also aims to provide a preparation method of the quantum dot-containing visible light photocatalytic functional surface coating, which has high photocatalytic efficiency, good visible light responsiveness and stable performance.
one of the objects of the invention is achieved by: the visible light photocatalytic functional top coat comprises the following components in percentage by weight:
the balance being water.
The titanium dioxide is doped with the noble metal ions, and the titanium dioxide particles are subjected to quantum dot formation, so that the titanium dioxide has responsiveness to visible light; the added silicon nanoparticles are used for converting ultraviolet light and low-wavelength visible light into high-wavelength visible light in a matched mode, so that titanium dioxide in a system can absorb natural light from the environment and can also receive self-generated visible light from the photocatalytic functional treatment liquid after the photocatalytic functional treatment liquid is cured into a film, the photocatalytic effect of the coating is limited to a light source absorbed by the surface of the coating, the light absorption efficiency is greatly improved, and the catalytic efficiency is greatly improved.
In addition, the inorganic resin using water as a dispersion medium is used as a base material, so that the coating has good weather resistance and can maintain good stability under the illumination condition. After the visible light photocatalytic surface coating is solidified, a swelling crystallization reaction occurs, and the formed microcrystalline structure can fully absorb organic matters in the environment, thereby being beneficial to photocatalytic degradation. More importantly, the silicate coating resin in the visible light photocatalytic functional surface coating can penetrate into the original coating which is coated and covered by the visible light photocatalytic functional surface coating to block the pores of the original coating, so that corrosive molecules such as water, oxygen and the like are difficult to contact the original coating, and the covered original coating also has good light stability.
The further preferable technical scheme is that the particle size of the titanium dioxide quantum dots is 2-10 nm. The noble metal is preferably one of Pt, Au and Pd.
The silicon nano-particles have rich resources, low price and no toxicity to human bodies, and the surface of the silicon nano-particles is provided with Si-H bonds, can generate Si-OH and Si-O-Si bonds which are well compatible with silicate coating resin when meeting water, and has good compatibility with base materials. Bulk silicon can only fluoresce weakly. The preferable technical scheme is that the particle size of the silicon nano-particles is less than 8 nm. When the particle size of the silicon nano-particles is less than 8nm, the fluorescence effect is enhanced, and the visible light photocatalytic functional surface coating shows higher photocatalytic performance.
in order to improve the photocatalytic effect, the preferable technical scheme is that the weight percentage of the FeOOH nano particles is 0.02-1%. The FeOOH nano particles can absorb visible light to generate photoproduction electrons and photoproduction holes, and can endow the photoproduction electrons with higher reduction capability by matching with the noble metal ions doped with the titanium dioxide quantum dots, widen the absorption wavelength range of the visible light and improve the photocatalytic activity. It is preferred here that the FeOOH nanoparticles have a particle size of less than 20 nm.
In order to facilitate construction and improve film-forming performance, the preferable technical scheme is that the leveling agent is carboxymethyl cellulose, the dispersing agent is an organic phosphonic acid scale inhibition and dispersion agent, the thickening agent is a nonionic polyurethane associated thickening agent, and the defoaming agent is a silicon dioxide derivative.
The second purpose of the invention is realized by the following steps: a preparation method of a visible light photocatalytic functional topcoat containing quantum dots comprises the following steps:
a) Adding the silicon nano-particles into water for activation and then stirring for later use; adding titanium dioxide quantum dots doped with noble metal ions and FeOOH nano particles according to the proportion, and ball-milling uniformly by using a ball mill to form a suspension;
b) Adding silicate coating resin into the suspension obtained in the step a), and uniformly ball-milling by using a ball mill; and adding a flatting agent, a dispersing agent, a thickening agent and a defoaming agent, ball-milling uniformly by using a ball mill to obtain the visible light photocatalytic functional surface coating containing the quantum dots, and packaging.
The process disperses silicon nanoparticles in water to form Si-OH and Si-O-Si bonds compatible with silicate coating resin, then uniformly grinds titanium dioxide quantum dots doped with noble metal ions, FeOOH nanoparticles and the like, then mixes the silicon nanoparticles with the silicate coating resin, and finally mixes the silicon nanoparticles with organic components.
Compared with the traditional photocatalytic coating, the visible light photocatalytic functional surface coating containing the quantum dots has the following advantages.
(1) the photocatalysis effect is obviously improved. Because the noble metal ions are doped with titanium dioxide quantum dots, silicon nanoparticles and the like, the photocatalytic reaction activity is improved, the photodecomposition capability is greatly enhanced, the photocatalytic efficiency is improved, the coating is decomposed when light is emitted, and the coating has multispectral responsiveness, so that harmful substances such as formaldehyde, benzene, ammonia, TVOC (total volatile organic compound), PM (particulate organic compound) 2.5 and the like can be continuously and efficiently removed, the indoor air environment is purified, the outdoor haze is removed, the removal rate of volatile organic compounds can reach more than 90%, bacteria, viruses, fungi, microorganisms and the like can be killed in a broad spectrum, and the killing rate of virus protobacteria such as cold viruses and the like can reach more than 90%.
(2) Has the function of protecting the original decorative coating. According to the visible light photocatalytic functional surface coating containing the quantum dots, the silicate coating resin can permeate into the wall coating applied by the visible light photocatalytic functional surface coating, so that the pores of the original wall coating are closed, and the original wall coating is protected from photodegradation to a great extent.
(3) And (3) food-grade safety: the coating can decompose harmful substances to clean air purely by means of sunlight or illumination, can realize active air purification without any energy consumption, has no secondary pollution, is nontoxic and tasteless, and does not contain substances harmful to the environment.
(4) The photocatalyst has long service life, the coating has uniform and stable performance, and the photocatalyst is coated once and is used for the whole life.
(5) the coating also has a self-cleaning effect. The coating has small contact angle, good self-cleaning effect and long-term self-cleaning effect.
Detailed Description
The following further describes the embodiments of the present invention with reference to the accompanying examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
A visible light photocatalytic functional surface coating containing quantum dots comprises the following components in percentage by weight:
5 percent of silicate coating resin,
5 percent of 2-10nm Au ion doped titanium dioxide quantum dots,
0.5 percent of silicon nano-particles with the particle diameter less than 8nm,
0.2 percent of carboxymethyl cellulose leveling agent,
0.2 percent of organic phosphonic acid dirt dispersion agent,
0.2 percent of nonionic polyurethane associated thickening agent,
0.2 percent of silicon dioxide derivative defoaming agent,
The balance being water.
The preparation method comprises the following steps:
a) adding the silicon nano-particles into water for activation and then stirring for later use; adding titanium dioxide quantum dots doped with noble metal ions, and ball-milling for 0.25-1 hour by using a ball mill at the speed of 70-1500 rpm until the mixture is uniform to form a suspension;
b) Adding silicate coating resin into the suspension obtained in the step a), and ball-milling for 0.25-1 hour at the speed of 70-1500 rpm by using a ball mill; and adding a flatting agent, a dispersing agent, a thickening agent and a defoaming agent, ball-milling for 0.5-6 hours by using a ball mill until the mixture is uniform to obtain the visible light photocatalytic functional surface coating containing the quantum dots, filling the visible light photocatalytic functional surface coating into a packaging container, and filling nitrogen with the pressure of 0.10-0.13MPa for packaging.
Example 2
The formulation and preparation method in this example are similar to example 1, except that silicon nanoparticles having a particle size of 20-200nm are used instead of silicon nanoparticles having a particle size of less than 8nm, and the rest is the same as example 1.
Example 3
A visible light photocatalytic functional surface coating containing quantum dots comprises the following components in percentage by weight:
5 percent of silicate coating resin,
5 percent of 2-10nm Au ion doped titanium dioxide quantum dots,
0.5 percent of silicon nano-particles with the particle diameter less than 8nm,
0.6 percent of FeOOH nano-particles with the particle diameter of less than 20nm,
0.2 percent of carboxymethyl cellulose leveling agent,
0.2 percent of organic phosphonic acid dirt dispersion agent,
0.2 percent of nonionic polyurethane associated thickening agent,
0.2 percent of silicon dioxide derivative defoaming agent,
The balance being water.
The preparation method comprises the following steps:
a) Adding the silicon nano-particles into water for activation and then stirring for later use; adding titanium dioxide quantum dots doped with noble metal ions and FeOOH nano particles, and ball-milling for 0.25-1 hour by using a ball mill at the speed of 70-1500 rpm until the mixture is uniform to form a suspension;
b) Adding silicate coating resin into the suspension obtained in the step a), and ball-milling for 0.25-1 hour at the speed of 70-1500 rpm by using a ball mill; and adding a flatting agent, a dispersing agent, a thickening agent and a defoaming agent, ball-milling for 0.5-6 hours by using a ball mill until the mixture is uniform to obtain the visible light photocatalytic functional surface coating containing the quantum dots, filling the visible light photocatalytic functional surface coating into a packaging container, and filling nitrogen with the pressure of 0.10-0.13MPa for packaging.
Example 4
A visible light photocatalytic functional surface coating containing quantum dots comprises the following components in percentage by weight:
10 percent of silicate coating resin,
10 percent of Pt ion doped titanium dioxide quantum dots with the particle size of 2-10nm,
2 percent of silicon nano-particles with the particle size less than 8nm,
1 percent of FeOOH nano-particles with the particle size of less than 20nm,
0.1 percent of carboxymethyl cellulose leveling agent,
0.1 percent of organic phosphonic acid dirt dispersion agent,
0.1 percent of nonionic polyurethane associated thickening agent,
0.1 percent of silicon dioxide derivative defoaming agent,
The balance being water.
The preparation method of this example is the same as that of example 3, and is not described herein again.
Example 5
a visible light photocatalytic functional surface coating containing quantum dots comprises the following components in percentage by weight:
1 percent of silicate coating resin,
1 percent of 2-10nm Pd ion doped titanium dioxide quantum dots,
0.02 percent of silicon nano-particles with the particle diameter of less than 8nm,
0.02 percent of FeOOH nano-particles with the particle diameter of less than 20nm,
1 percent of carboxymethyl cellulose leveling agent,
1 percent of organic phosphonic acid dirt dispersion agent,
1 percent of nonionic polyurethane associative thickener,
1 percent of silicon dioxide derivative defoaming agent,
the balance being water.
The preparation method of this example is the same as that of example 3, and is not described herein again.
Example 6
A visible light photocatalytic functional surface coating containing quantum dots comprises the following components in percentage by weight:
6 percent of silicate coating resin,
5 percent of 2-10nm Au ion doped titanium dioxide quantum dots,
0.12 percent of silicon nano-particles with the particle diameter of less than 8nm,
0.12 percent of FeOOH nano-particles with the particle diameter of less than 20nm,
0.2 percent of carboxymethyl cellulose leveling agent,
0.5 percent of organic phosphonic acid dirt dispersion agent,
0.4 percent of nonionic polyurethane associated thickening agent,
0.2 percent of silicon dioxide derivative defoaming agent,
The balance being water.
The preparation method of this example is the same as that of example 3, and is not described herein again.
Example 7
A visible light photocatalytic functional surface coating containing quantum dots comprises the following components in percentage by weight:
7 percent of silicate coating resin,
6 percent of 2-10nm Au ion doped titanium dioxide quantum dots,
0.75 percent of silicon nano-particles with the particle diameter less than 8nm,
1.5 percent of FeOOH nano-particles with the particle diameter of less than 20nm,
0.5 percent of carboxymethyl cellulose leveling agent,
0.2 percent of organic phosphonic acid dirt dispersion agent,
0.2 percent of nonionic polyurethane associated thickening agent,
0.2 percent of silicon dioxide derivative defoaming agent,
The balance being water.
The preparation method of this example is the same as that of example 3, and is not described herein again.
Comparative example 1
Comparative example 1 is similar to the formulation and preparation method of example 1, except that the formulation of comparative example 1 does not contain silicon nanoparticles. During preparation, the titanium dioxide quantum dots doped with noble metal ions and water are ball-milled for 0.25 to 1 hour by a ball mill at the speed of 70 to 1500 revolutions per minute until the mixture is uniform, so as to form a suspension; then adding silicate coating resin into the suspension, and ball-milling for 0.25-1 hour at the speed of 70-1500 r/min by using a ball mill; and adding the flatting agent, the dispersing agent, the thickening agent and the defoaming agent, ball-milling for 0.5-6 hours by using a ball mill until the mixture is uniform, and finally packaging.
comparative example 2
Comparative example 2 is similar to the formulation and preparation method of example 1, and the only difference is that the formulation in comparative example 2 does not contain Au ion doped titanium dioxide quantum dots. During preparation, after the silicon nano particles are added into water for activation, the silicon nano particles are ball-milled for 0.25 to 1 hour by a ball mill at the speed of 70 to 1500 revolutions per minute until a suspension is formed uniformly; then adding silicate coating resin into the suspension, and ball-milling for 0.25-1 hour at the speed of 70-1500 r/min by using a ball mill; and adding the flatting agent, the dispersing agent, the thickening agent and the defoaming agent, ball-milling for 0.5-6 hours by using a ball mill until the mixture is uniform, and finally packaging.
the paint is used as a top coat, has uniform fineness, does not deteriorate at low temperature, and has no obstacle in coating construction.
The preparation of the paint film sample plate is carried out according to the GB1727 specification, the material is selected from base paper (inert material is required), and the weight is 80g/m2Preparation of aGenerally, a spraying method is adopted. And (3) measuring the photolysis index, wherein a light source is LED visible light, the illumination intensity is 145 multiplied by 100LUX, and the methyl blue removal rate is performed according to the GB/T30452-2013. The results are shown in Table 1.
TABLE 1 methyl blue removal rate of coatings obtained in examples 1-7 and comparative examples 1-2
| Group of | Methyl blue removal rate (%) |
| Example 1 | 90.1 |
| Example 2 | 89.2 |
| Example 3 | 94.5 |
| Example 4 | 95.3 |
| example 5 | 89.5 |
| Example 6 | 93.8 |
| Example 7 | 94.4 |
| Comparative example 1 | 67.3 |
| Comparative example 2 | 9.0 |
As can be seen from table 1, compared with the case where only silicon nanoparticles are added to the coating, or only titanium dioxide quantum dots doped with noble metal ions are added to the coating, the photocatalytic degradation efficiency of examples 1 to 7 of the present invention is significantly improved. Comparing examples 1-3, it can be seen that adding FeOOH nanoparticles to reduce the particle size of silicon nanoparticles can further improve the photocatalytic degradation efficiency.
The visible light photocatalytic functional surface containing quantum dots is coated on a decorative surface coating and a visible light photocatalytic functional base coating and then is coated, can be matched with a functional base coating or a functional treatment solution for use, and can also be independently used on the surfaces of inorganic materials and metal materials. The visible light photocatalytic functional surface coating containing the quantum dots can be used for indoor air purification and outdoor building outer walls, and has significant and remarkable application prospect in the fields of household coating and marine coating.
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 technical 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 visible light photocatalytic functional top coat containing quantum dots is characterized by comprising the following components in percentage by weight:
1-10% of silicate coating resin,
1-10% of titanium dioxide quantum dots doped with noble metal ions,
0.02-2% of silicon nano-particles,
0-1% of FeOOH nano particles,
0.1 to 1 percent of flatting agent,
0.1 to 1 percent of dispersant,
0.1 to 1 percent of thickening agent,
0.1 to 1 percent of defoaming agent,
The balance being water.
2. The visible light photocatalytic functional topcoat containing quantum dots according to claim 1, wherein the particle size of the titanium dioxide quantum dots is 2 to 10 nm.
3. The visible-light photocatalytic functional topcoat containing quantum dots according to claim 1, wherein the noble metal is one of Pt, Au, and Pd.
4. The visible-light-photocatalytic-functional topcoat containing quantum dots according to claim 1, wherein the silicon nanoparticles have a particle size of less than 8 nm.
5. The visible light photocatalytic functional topcoat containing quantum dots according to claim 1, wherein the FeOOH nanoparticles are present in an amount of 0.02 to 1% by weight.
6. the visible light photocatalytic functional topcoat containing quantum dots according to claim 1, wherein the FeOOH nanoparticles have a particle size of less than 20 nm.
7. The visible light photocatalytic functional topcoat containing quantum dots according to claim 1, wherein the leveling agent is carboxymethyl cellulose.
8. The visible light photocatalytic functional topcoat containing quantum dots according to claim 1, wherein the dispersant is an organic phosphonic acid type scale inhibition dispersant, and the thickener is a nonionic polyurethane associative thickener.
9. The visible light photocatalytic functional topcoat containing quantum dots according to claim 1, wherein the defoaming agent is a silica derivative.
10. The method for preparing a visible light photocatalytic functional topcoat containing quantum dots according to any one of claims 1 to 9, characterized by comprising the steps of:
a) Adding the silicon nano-particles into water for activation and then stirring for later use; adding titanium dioxide quantum dots doped with noble metal ions and FeOOH nano particles according to the proportion, and ball-milling uniformly by using a ball mill to form a suspension;
b) Adding silicate coating resin into the suspension obtained in the step a), and uniformly ball-milling by using a ball mill; and adding a flatting agent, a dispersing agent, a thickening agent and a defoaming agent, ball-milling uniformly by using a ball mill to obtain the visible light photocatalytic functional surface coating containing the quantum dots, and packaging.
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| CN113144887A (en) * | 2021-02-07 | 2021-07-23 | 青岛中福高新装备制造有限公司 | Method for improving pollutant degradation effect of photocatalytic coating |
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| CN111442410A (en) * | 2020-04-03 | 2020-07-24 | 青岛海尔空调器有限总公司 | Purification system and purification method of air conditioner and air conditioner |
| CN113144887A (en) * | 2021-02-07 | 2021-07-23 | 青岛中福高新装备制造有限公司 | Method for improving pollutant degradation effect of photocatalytic coating |
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