CN105148969A - Self-cleaning nitrogen-doped titanium oxide film as well as preparation method and applications thereof - Google Patents
Self-cleaning nitrogen-doped titanium oxide film as well as preparation method and applications thereof Download PDFInfo
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- CN105148969A CN105148969A CN201510503921.4A CN201510503921A CN105148969A CN 105148969 A CN105148969 A CN 105148969A CN 201510503921 A CN201510503921 A CN 201510503921A CN 105148969 A CN105148969 A CN 105148969A
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Abstract
The invention discloses a self-cleaning nitrogen-doped titanium oxide film as well as a preparation method and applications thereof. The preparation method comprises steps as follows: butyl titanate, absolute ethyl alcohol and acetylacetone are evenly mixed, and a solution A is obtained; deionized water, hydrochloric acid, absolute ethyl alcohol and polyvinylpyrrolidone are evenly mixed, and a solution B is obtained; the solution A is added to the solution B dropwise, stirring is performed, and sol C is obtained through ageing or without ageing; a to-be-coated substrate which is washed clean is soaked in the sol C and lifted vertically at the constant speed for coating, then drying and calcination are performed, and the self-cleaning nitrogen-doped titanium oxide film with the thickness ranging from 0.2 mu m to 10 mu m is obtained. According to the method, technological equipment is simple, the cost is low, the film-forming property and the repeatability are good, the prepared film has the good hydrophilia, and the hydrophilia and the methylene blue degradation efficiency of the film are obviously higher than those of a common titanium oxide film under visible light irradiation.
Description
Technical field
The present invention relates to a kind of self-cleaning film, be specifically related to a kind of nitrogen-doped titanium dioxide self-cleaning film and preparation method thereof and application.
Background technology
Titanium dioxide has photocatalytic effect under UV-irradiation, a lot of organic matter is had to the function of degraded, plates at pottery or glass surface the automatic cleaning action that titanium deoxid film effectively can improve their surfaces.But titanium dioxide only just has catalytic performance under UV-irradiation, lower to the utilization rate of visible ray, greatly have impact on it to general organic degradation efficiency.In order to widen the range of application of titanium dioxide and improve the photocatalysis effect of titanium dioxide, many scholars have carried out metal cations Fe to titanium dioxide
3+, Co
2+, Cr
3+, Ni
+, Mo
5+, Cu
2+, Pb
2+with nonmetallic ion N
3-, F
-, S
2-deng doping, wherein N can replace TiO
2oxygen atom in lattice and produce visible light photoactivated activity, to the effect of having greatly improved of the photocatalytic activity of titanium dioxide.When degrade acetaldehyde, mix N
3-tiO
2at not only activity under ultraviolet light and pure TiO
2close, and the former still has significant photocatalytic activity under visible light.General N doping manufacture craft, as sputtering method, vapour deposition process or at NH
3or calcine in Ar atmosphere, technics comparing is complicated, and cost compare is high, and visible light catalytic efficiency also has much room for improvement.The nitrogenous source that sol-gal process makes nitrogen-doped titanium dioxide film is generally urea, triethanolamine etc., although the visible light catalytic efficiency of film increases, improve and not obvious.
Summary of the invention
The object of the invention is to overcome prior art Problems existing, there is provided a kind of preparation technology easy, film automatically cleaning Be very effective, cost is lower, good hydrophilic property, 8h radiation of visible light is to the degradation rate of methylene blue nitrogen-doped titanium dioxide film that can reach 55% and preparation method thereof;
Another object of the present invention is to provide the application of nitrogen-doped titanium dioxide self-cleaning film in photocatalysis to degrade organic matter and exterior wall tile automatically cleaning.
The present invention plates nitrogen-doped titanium dioxide film by the mode of Best-Effort request in ceramic substrate surface, and then dry, calcining successively, and the efficiency of obtained film hydrophily under visible light illumination and degradation of methylene blue is apparently higher than ordinary titanium dioxide film.Film is labile organic compound (as methylene blue, formaldehyde, benzene, methyl orange, benzene etc.) under the irradiation of ultraviolet light and visible ray, also there is the effect of sterilizing, under the irradiation of the sunshine of 24h, can more than 80% be reached to the degradation rate of methylene blue; Film can be degraded the pollutant on its surface by Reusability, can be used for the automatically cleaning of exterior wall tile, indoor air purification etc.
In order to achieve the above object, the present invention adopts following technical scheme:
A preparation method for nitrogen-doped titanium dioxide self-cleaning film, comprises the steps:
1) butyl titanate, absolute ethyl alcohol, acetylacetone,2,4-pentanedione are mixed acquisition solution A; Controlling the volume fraction of acetylacetone,2,4-pentanedione in solution A is 2%-4%;
2) deionized water, hydrochloric acid, absolute ethyl alcohol, polyvinylpyrrolidone are mixed acquisition solution B; Controlling the mass percent of polyvinylpyrrolidone in solution B is 1%-5%;
3) described solution A is dripped enter in solution B, stir, ageing or without ageing, obtain colloidal sol C;
4) vertically at the uniform velocity lift in the substrate immersion colloidal sol C to be coated cleaned up with plated film, then through super-dry, calcining, obtain the nitrogen-doped titanium dioxide self-cleaning film that thickness is 0.2-10 μm.
For realizing the object of the invention further, preferably, in solution A, described butyl titanate and absolute ethyl alcohol volume ratio are 1:(2-5); In solution B, the volume ratio of described ionized water, hydrochloric acid, absolute ethyl alcohol is 1:(0.2-0.5): (5-15).
Preferably, described solution A and solution B volume ratio are 1:(0.5-2).
Preferably, the time of described ageing is 0-36h.
Preferably, the described speed at the uniform velocity lifted is 1cm/min-10cm/min.
Preferably, the temperature of described drying is 80-150 DEG C, and the time is 2-12h.
Preferably, the temperature of described calcining is 200-700 DEG C, and the time is 1-5h.
Preferably, described substrate to be coated adopts ceramic substrate.
A kind of nitrogen-doped titanium dioxide self-cleaning film, is obtained by above-mentioned preparation method.
The application of described nitrogen-doped titanium dioxide self-cleaning film in the automatically cleaning of photocatalysis to degrade organic matter and exterior wall tile.
The general organic matter of described nitrogen-doped titanium dioxide self-cleaning film degradable methylene blue, formaldehyde, benzene, methyl orange or benzene etc. under the irradiation of ultraviolet light or visible ray, and there is the effect of sterilizing, under the irradiation of the sunshine of 24h, can more than 80% be reached to the degradation rate of methylene blue.Described nitrogen-doped titanium dioxide self-cleaning film can be degraded the pollutant on its surface by Reusability, for automatically cleaning or the indoor air purification of exterior wall tile.
Adding polyvinylpyrrolidone (PVP) in preparation method of the present invention, is a kind of non-ionic macromolecule compound, has colloid protective effect; and good film forming, caking property, hygroscopicity etc.; be widely used in health care, food processing, coating and pigment etc.PVP nitrogen content 12-12.8%, is a kind of well nitrogenous source, can promotes Lacking oxygen and Ti
3dthe generation of valence state, the band gap of titanium dioxide reduces, and the electronics under visible light illumination in titanium dioxide can be excited, and transits to conduction band from valence band, produces electron hole pair, improves organic catalytic efficiency.Nitrogen-doped titanium dioxide film obtained by the present invention has the effect of good degradation of organic substances under ultraviolet light and radiation of visible light, gas chromatography can be prevented the pollution of matrix surface, can be used for the automatically cleaning of exterior wall tile.Under the effect of sunshine, the exterior wall tile being coated with nitrogen-doped titanium dioxide film has good automatic cleaning action, and due to illumination effect, the contact angle of film and rainwater is very little, even if polluted, also can be cleaned by rainwater very soon; Film also has the prospect and possibility that are applied to indoor.
Compared with prior art, beneficial effect of the present invention is:
1. the present invention adopts sol-gal process, pulling film forming method plates nitrogen-doped titanium dioxide film at clean substrate surface, preparation technology is easy, film automatically cleaning Be very effective, and cost is lower, good hydrophilic property, Sometimes When It Rains more easy cleaning falls the pollutant on its surface.
2. the present invention introduces nitrogen element by adding polyvinylpyrrolidone, and Lacking oxygen is created in titanium dioxide, reduce to know clearly the band gap of titanium dioxide, significantly improve TiO 2 visible light catalytic efficiency, 8h radiation of visible light can reach 55% to the degradation rate of methylene blue, the proportioning of polyvinylpyrrolidone and butyl titanate can be controlled as required, prepare different catalytically active and hydrophilic titanium deoxid film.
Accompanying drawing explanation
Fig. 1 is the curve of titanium deoxid film degradation of methylene blue under visible ray shines.
Detailed description of the invention
For understanding the present invention better, below in conjunction with drawings and Examples, the present invention is further illustrated, but embodiments of the present invention are not limit so.
Embodiment 1
1) butyl titanate and absolute ethyl alcohol are mixed by the volume ratio of 1:2, then under agitation add acetylacetone,2,4-pentanedione, stir 15min, mix, obtained yellow solution A; Wherein the volume fraction of acetylacetone,2,4-pentanedione is 3%.
2) ionized water, hydrochloric acid, absolute ethyl alcohol are mixed according to the volume ratio of 1:0.3:10, add polyvinylpyrrolidone, then stir 10min, obtained clear solution B; Wherein polyvinylpyrrolidone accounts for solution gross mass 2%, and wherein the mass fraction of hydrochloric acid is 36%.
3) clear pale yellow look solution A is dropwise instilled in clear solution B, and the volume ratio of solution A and solution B is 1:1, after stirring 2h under normal temperature, forms even colloidal sol C; Even colloidal sol at room temperature ageing 12h obtains colloidal sol needed for plated film.
4) ceramic substrate to be coated is put into the deionized water that volume ratio is 1:1 and alcohol mixed solution ultrasonic cleaning 15min, by dry at cleaned substrate to be coated 80 DEG C, obtain the substrate cleaned up.
5) 180s is left standstill by the substrate immersion precipitation C cleaned up, then plated film is repeatedly vertically at the uniform velocity lifted until obtain the film that thickness is 0.6 μm with the speed of 5cm/min, by the film plating substrate that obtains in 80 DEG C of dry 2h, then at 600 DEG C, calcine 2h, obtain nitrogen-doped titanium dioxide self-cleaning film.
The hardness of this nitrogen-doped titanium dioxide film is 6H, transparent or micro white, is plated on the surface of ceramic exterior wall dress, can increases the brightness of ceramic substrate, make ceramic substrate have more gloss.Because film is calcined at relatively high temperatures, be combined with exterior wall tile closely, difficult drop-off.The intensity, fracture toughness etc. of the external wall brick of film do not change substantially.After UV-irradiation 12h, more than 80% is reached to the degradation rate of the pollutant such as methylene blue, methyl orange, more than 50% can be reached under the irradiation of light to the organic degradation rate such as methylene blue, methyl orange at 12h.Due to the degradation effect that nitrogen-doped titanium dioxide film is good to organic matter under visible light illumination, the ceramic exterior wall brick being coated with film can have good automatic cleaning action in cloudy or that sunray is more weak place.
Relevant test is below a checking in degraded.
Degradation rate is tested: above drip (0.05ml) methylene blue solution at the ceramic substrate (45 × 45 × 6cm) having plated nitrogen-doped titanium dioxide film, smear evenly, then be under the incandescent lamp of 200w of 400nm-700nm at wavelength, irradiate 8 hours, measure the L (brightness) of not ceramic surface in the same time, a (carmetta is to green), b (yellow to blue) value, calculates degradation rate.
△E＝[(L
0-L
t)
2+(a
0-a
t)
2+(b
0-b
t)
2]
1/2
RE(％)＝△Eo/△Et
L
0the L value of substrate before-illumination; a
0the a value of substrate before-illumination; b
0the b value of substrate before-illumination; L
tthe L value of-illumination different time substrate; a
tthe a value of-illumination different time substrate; b
tthe b value of-illumination different time substrate;
△ E-chroma difference; △ Eo-illumination different time substrate and the difference not by illumination substrate colourity; The chroma difference of △ Et-contaminated front and back substrate; RE (%)-degradation rate.
The degradation rate of the present embodiment is the results detailed in accompanying drawing 1.The nitrogen-doped titanium dioxide film of different formulations and calcination condition and ordinary titanium dioxide film contrast by Fig. 1, as can be seen from Figure 1, at 8h, illumination can be penetrated that the lower degradation rate to methylene blue is up to by nitrogen-doped titanium dioxide film is 55%, minimum also have 27%, and illumination can be penetrated the lower degradation rate to methylene blue at 8h and only had about 12% by common titanium deoxid film, illustrate that nitrogen-doped titanium dioxide film is illumination can be penetrated the general titanium deoxid film of lower ratio high a lot of to the degradation efficiency of methylene blue.If under the irradiation of sunshine, nitrogen-doped titanium dioxide film is more more abundant to the utilization of sunlight than common titanium deoxid film, higher to organic degradation efficiency, widen the automatically cleaning range of application of exterior wall tile, even if on cloudy day or rainy day, nitrogen-doped titanium dioxide film also has the effect of degradation of organic substances, and has the prospect and possibility that are applied to indoor.
Hydrophily is tested: we use contact angle tester to measure and are coated with the exterior wall tile of titanium deoxid film and the contact angle of water droplet, water droplet is dripped on a solid surface by sessile drop method by from top to down, then by the image analysing computer of instrument, use tangential method to calculate and be coated with the exterior wall tile of titanium deoxid film and the contact angle of water droplet.Every block Ceramic Tiles is got 5 diverse locations and is measured contact angle, averages.
Before illumination and 8 hours visible rays drop in contact angle on film according to rear test water respectively, it is more that contact angle reduces, and illustrates that the hydrophily of film is better.Illustrate can by under the irradiation of light, the contact angle of nitrogen-doped titanium dioxide film and water decreases 27-33 °, and the contact angle of common titanium deoxid film only decreases 7 °, illustrate that nitrogen-doped titanium dioxide film can have obvious enhancing by under the irradiation of light than the hydrophily of common titanium deoxid film, under rainwash, be easy to the pollutant on its surface clean.
The degradation rate of the present embodiment is the results detailed in accompanying drawing 1, and hydrophily is the results detailed in Table 1.
Embodiment 2
1) butyl titanate and absolute ethyl alcohol are mixed by the volume ratio of 1:5, then under agitation add acetylacetone,2,4-pentanedione, stir 15min, mix, obtained yellow solution A; Wherein the volume fraction of acetylacetone,2,4-pentanedione is 2%.
2) ionized water, hydrochloric acid, absolute ethyl alcohol are mixed according to the volume ratio of 1:0.2:5, add polyvinylpyrrolidone, then stir 15min, obtained clear solution B; Wherein polyvinylpyrrolidone accounts for solution gross mass 5%, and wherein the mass fraction of hydrochloric acid is 36%.
3) clear pale yellow look solution A is dropwise instilled in clear solution B, and the volume ratio of solution A and solution B is 1:2, after stirring 3h under normal temperature, forms even colloidal sol C; Even colloidal sol at room temperature ageing 24h obtains colloidal sol needed for plated film.
4) substrate to be coated is put into the deionized water that volume ratio is 1:1 and alcohol mixed solution ultrasonic cleaning 15min, by dry at cleaned substrate to be coated 80 DEG C, obtain the substrate cleaned up.
5) 60s is left standstill by the ceramic substrate immersion precipitation C cleaned up, then plated film is repeatedly vertically at the uniform velocity lifted until obtain the film that thickness is 0.2 μm with the speed of 3cm/min, by the film plating substrate that obtains in 100 DEG C of dry 6h, then at 700 DEG C, calcine 1h, obtain nitrogen-doped titanium dioxide self-cleaning film.
The degradation rate of the present embodiment is the results detailed in accompanying drawing 1, and hydrophily is the results detailed in Table 1.
Embodiment 3
1) butyl titanate and absolute ethyl alcohol are mixed by the volume ratio of 1:3, then under agitation add acetylacetone,2,4-pentanedione, stir 15min, mix obtained yellow solution A; Wherein the volume fraction of acetylacetone,2,4-pentanedione is 2%.
2) ionized water, hydrochloric acid, absolute ethyl alcohol are mixed according to the volume ratio of 1:0.5:15, add polyvinylpyrrolidone, then stir 30min, obtained clear solution B; Wherein polyvinylpyrrolidone accounts for solution gross mass 1%, and wherein the mass fraction of hydrochloric acid is 36%.
3) clear pale yellow look solution A is dropwise instilled in clear solution B, and the volume ratio of solution A and solution B is 1:0.5, after stirring 3h under normal temperature, forms even colloidal sol C; Even colloidal sol at room temperature ageing 36h obtains colloidal sol needed for plated film.
4) ceramic substrate to be coated is put into the deionized water that volume ratio is 1:1 and alcohol mixed solution ultrasonic cleaning 15min, by dry at cleaned substrate to be coated 80 DEG C, obtain the substrate cleaned up.
5) 360s is left standstill by the ceramic substrate immersion precipitation C cleaned up, then plated film is repeatedly vertically at the uniform velocity lifted until obtain the film that thickness is 10 μm with the speed of 1cm/min, by the film plating substrate that obtains in 150 DEG C of dry 5h, then at 200 DEG C, calcine 5h, obtain nitrogen-doped titanium dioxide self-cleaning film.
The degradation rate of the present embodiment is the results detailed in accompanying drawing 1, and hydrophily is the results detailed in Table 1.
Embodiment 4
1) butyl titanate and absolute ethyl alcohol are mixed by the volume ratio of 1:5, then under agitation add acetylacetone,2,4-pentanedione, stir 15min, mix, obtained yellow solution A; Wherein the volume fraction of acetylacetone,2,4-pentanedione is 4%.
2) hydrochloric acid, deionized water, absolute ethyl alcohol are mixed according to the volume ratio of 1:0.2:12, add polyvinylpyrrolidone, then stir 30min, obtained clear solution B; Wherein polyvinylpyrrolidone accounts for solution gross mass 3%, and wherein the mass fraction of hydrochloric acid is 36%.
3) clear pale yellow look solution A is dropwise instilled in clear solution B, and the volume ratio of solution A and solution B is 1:2, after stirring 2h under normal temperature, forms even colloidal sol C; Even colloidal sol at room temperature ageing 6h obtains colloidal sol needed for plated film.
4) substrate to be coated is put into the deionized water that volume ratio is 1:1 and alcohol mixed solution ultrasonic cleaning 15min, by dry at cleaned substrate to be coated 80 DEG C, obtain the substrate cleaned up.
5) 60s is left standstill by the ceramic substrate immersion precipitation C cleaned up, then plated film is repeatedly vertically at the uniform velocity lifted until obtain the film that thickness is 5 μm with the speed of 5cm/min, by the film plating substrate that obtains in 150 DEG C of dry 8h, then at 500 DEG C, calcine 2h, obtain nitrogen-doped titanium dioxide self-cleaning film.
The degradation rate of the present embodiment is the results detailed in accompanying drawing 1, and hydrophily is the results detailed in Table 1.
Embodiment 5
1) butyl titanate and absolute ethyl alcohol are mixed by the volume ratio of 1:4, then under agitation add acetylacetone,2,4-pentanedione, stir 15min, mix, obtained yellow solution A; Wherein the volume fraction of acetylacetone,2,4-pentanedione is 3%.
2) hydrochloric acid, deionized water, absolute ethyl alcohol are mixed according to the volume ratio of 1:0.4:8, add polyvinylpyrrolidone, then stir 30min, obtained clear solution B; Wherein polyvinylpyrrolidone accounts for solution gross mass 4%, and wherein the mass fraction of hydrochloric acid is 36%.
3) clear pale yellow look solution A is dropwise instilled in clear solution B, and the volume ratio of solution A and solution B is 1:2, after stirring 2h under normal temperature, forms even colloidal sol C; Even colloidal sol at room temperature obtains colloidal sol needed for plated film without ageing.
4) substrate to be coated is put into the deionized water that volume ratio is 1:0.5 and alcohol mixed solution ultrasonic cleaning 15min, by dry at cleaned substrate to be coated 80 DEG C, obtain the substrate cleaned up.
5) 60s is left standstill by the ceramic substrate immersion precipitation C cleaned up, then plated film is repeatedly vertically at the uniform velocity lifted until obtain the film that thickness is 8 μm with the speed of 3cm/min, by the film plating substrate that obtains in 120 DEG C of dry 12h, then at 600 DEG C, calcine 3h, obtain nitrogen-doped titanium dioxide self-cleaning film.
The degradation rate of the present embodiment is the results detailed in accompanying drawing 1, and hydrophily is the results detailed in Table 1.
The hydrophily table with test results of table 1 embodiment titanium deoxid film
| Film type | Contact angle before illumination | Contact angle after illumination |
| Ordinary titanium dioxide film | 52 | 45 |
| Embodiment 1 | 48 | 15 |
| Embodiment 2 | 50 | 23 |
| Embodiment 3 | 56 | 27 |
| Embodiment 4 | 52 | 31 |
| Embodiment 5 | 49 | 25 |
Claims (10)
1. a preparation method for nitrogen-doped titanium dioxide self-cleaning film, is characterized in that comprising the steps:
1) butyl titanate, absolute ethyl alcohol, acetylacetone,2,4-pentanedione are mixed acquisition solution A; Controlling the volume fraction of acetylacetone,2,4-pentanedione in solution A is 2%-4%;
2) deionized water, hydrochloric acid, absolute ethyl alcohol, polyvinylpyrrolidone are mixed acquisition solution B; Controlling the mass percent of polyvinylpyrrolidone in solution B is 1%-5%;
3) described solution A is dripped enter in solution B, stir, ageing or without ageing, obtain colloidal sol C;
4) vertically at the uniform velocity lift in the substrate immersion colloidal sol C to be coated cleaned up with plated film, then through super-dry, calcining, obtain the nitrogen-doped titanium dioxide self-cleaning film that thickness is 0.2-10 μm.
2. the preparation method of nitrogen-doped titanium dioxide self-cleaning film according to claim 1, is characterized in that: in solution A, and described butyl titanate and absolute ethyl alcohol volume ratio are 1:(2-5); In solution B, the volume ratio of described ionized water, hydrochloric acid, absolute ethyl alcohol is 1:(0.2-0.5): (5-15).
3. the preparation method of nitrogen-doped titanium dioxide self-cleaning film according to claim 1, is characterized in that: described solution A and solution B volume ratio are 1:(0.5-2).
4. the preparation method of nitrogen-doped titanium dioxide self-cleaning film according to claim 1, is characterized in that: described digestion time is 0-36h.
5. the preparation method of nitrogen-doped titanium dioxide self-cleaning film according to claim 1, is characterized in that: the temperature of described drying is 80-150 DEG C, and the time is 2-12h.
6. the preparation method of nitrogen-doped titanium dioxide self-cleaning film according to claim 1, is characterized in that: the described speed at the uniform velocity lifted is 1cm/min-10cm/min.
7. the preparation method of nitrogen-doped titanium dioxide self-cleaning film according to claim 1, is characterized in that: the temperature of described calcining is 200-700 DEG C, and the time is 1-5h.
8. the preparation method of nitrogen-doped titanium dioxide self-cleaning film according to claim 1, is characterized in that: described substrate to be coated adopts ceramic substrate.
9. a nitrogen-doped titanium dioxide self-cleaning film, is characterized in that, it is obtained by the preparation method in claim 1-8 described in any one.
10. the application of nitrogen-doped titanium dioxide self-cleaning film according to claim 9 in photocatalysis to degrade organic matter and exterior wall tile automatically cleaning.
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| CN107126944A (en) * | 2017-05-11 | 2017-09-05 | 大连理工大学 | A kind of many doping titanium dioxide nano particles of many defects with high visible light catalytic activity and preparation method |
| CN107552080A (en) * | 2017-08-31 | 2018-01-09 | 河海大学 | A kind of support type N TiO2Photochemical catalyst and its preparation method and application |
| CN107670681A (en) * | 2017-10-11 | 2018-02-09 | 辽宁工程技术大学 | A kind of N doping TiO2The preparation method of powder |
| CN108503388A (en) * | 2018-04-18 | 2018-09-07 | 广西欧神诺陶瓷有限公司 | A kind of self-cleaning ceramic brick and preparation method thereof |
| CN114471193A (en) * | 2022-03-07 | 2022-05-13 | 四川轻化工大学 | Filtering membrane with ultraviolet-resistant self-cleaning function and application thereof |
| WO2022116005A1 (en) * | 2020-12-01 | 2022-06-09 | 莱恩创科（北京）科技有限公司 | Titanium dioxide sterilization and disinfection film |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107126944A (en) * | 2017-05-11 | 2017-09-05 | 大连理工大学 | A kind of many doping titanium dioxide nano particles of many defects with high visible light catalytic activity and preparation method |
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| CN107552080A (en) * | 2017-08-31 | 2018-01-09 | 河海大学 | A kind of support type N TiO2Photochemical catalyst and its preparation method and application |
| CN107670681A (en) * | 2017-10-11 | 2018-02-09 | 辽宁工程技术大学 | A kind of N doping TiO2The preparation method of powder |
| CN107670681B (en) * | 2017-10-11 | 2020-01-14 | 辽宁工程技术大学 | Nitrogen-doped TiO2Method for preparing powder |
| CN108503388A (en) * | 2018-04-18 | 2018-09-07 | 广西欧神诺陶瓷有限公司 | A kind of self-cleaning ceramic brick and preparation method thereof |
| WO2022116005A1 (en) * | 2020-12-01 | 2022-06-09 | 莱恩创科（北京）科技有限公司 | Titanium dioxide sterilization and disinfection film |
| CN114471193A (en) * | 2022-03-07 | 2022-05-13 | 四川轻化工大学 | Filtering membrane with ultraviolet-resistant self-cleaning function and application thereof |
| CN114471193B (en) * | 2022-03-07 | 2022-11-25 | 四川轻化工大学 | Filtering membrane with ultraviolet-resistant self-cleaning function and application thereof |
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