CN109942204A - A kind of dirt-resistant self-cleaning material and the preparation method and application thereof - Google Patents
A kind of dirt-resistant self-cleaning material and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention provides a kind of dirt-resistant self-cleaning material and the preparation method and application thereof.The material includes that the silica of hydrophilic has the titanium dioxide of oleophobic, graphene oxide and tin oxide with conductive capability, and the lamella g-C with visible light catalytic ability3N4；The graphene oxide, lamella g-C3N4, silica, tin oxide, titanium dioxide mass ratio be 1:(1~50): (0.5~10): (10~500): (10~500).Dirt-resistant self-cleaning material of the invention, raw material used are easy to get, cheap；Hydrophily with higher and photo-catalysis capability can play the role of dirt-resistant self-cleaning；Production method is simple, does not need heavy mechanical equipment and manpower and material resources, can be mass-produced.
Description
Technical field
The invention belongs to self-cleaning material fields, and in particular to a kind of material for glass material surface dirt-resistant self-cleaning.
Background technique
With the development of economy, various novel buildings come into being, and the building of many high levels is increasingly favored in use
Glass curtain wall.Due to being influenced by atmospheric haze, grieshoch, nitrogen oxides and oxysulfide and acid rain etc., glass curtain wall surface
A large amount of pollutants can be gathered, lead to the reduction of its permeability, influence the beauty of building.China is for the main of glass curtain wall at present
Cleaning mode is manual cleaning, and this method needs to consume a large amount of manpower and financial resources, and the safety that additionally, there may be cleanup crew is asked
Topic.And the glass durability against pollution after cleaning is poor, and glass curtain wall will be contaminated again in a relatively short period of time.Therefore, it grinds
Sending out a kind of can make glass curtain wall have biggish meaning with the coating of anti-fouling and self-cleaning ability.
Anti-fouling material mainly has hydrophobicity, ultra-hydrophilic type, photocatalyst-type etc. at present.It hydrophobic material surface can only be to hydrophily
Pollutant has preferable antifouling effect.And hydrophobic material is liable to stick to for motor vehicle exhaust emission bring lipophilicity pollutant
Surface.
Summary of the invention
The present invention provides one for the existing problem to the pollutants such as greasy dirt stain resistance deficiency of existing hydrophobic material
The hydrophilic and oleophobic and Photosensitive that kind is simple and efficient can be used for the new coating material of glass material surface dirt-resistant self-cleaning；And it is a kind of
The preparation method of the dirt-resistant self-cleaning new coating material easy to operate that can largely prepare；A kind of the new of above-mentioned dirt-resistant self-cleaning is also provided
Type coating material is applied to the method for glass.
A kind of dirt-resistant self-cleaning material, the material include that the silica of hydrophilic has the titanium dioxide of oleophobic, have and lead
The graphene oxide and tin oxide of electric energy power, and the lamella g-C with visible light catalytic ability3N4；The graphene oxide,
Lamella g-C3N4, silica, tin oxide, titanium dioxide mass ratio be 1:(1~50): (0.5~10): (10~500): (10~
500).Preferably, the graphene oxide, lamella g-C3N4, silica, tin oxide, titanium dioxide mass ratio be 1:(10~
50): (1~6): (50~250): (50~250).
Wherein, in above-mentioned dirt-resistant self-cleaning material, the material further includes ethyl alcohol, the dosage of the ethyl alcohol and the oxidation stone
The volume mass ratio (mL/g) of black alkene can be (80-120): 1.
The present invention also provides the preparation methods of above-mentioned dirt-resistant self-cleaning material, and described method includes following steps:
By the graphene oxide, lamella g-C3N4, silica, tin oxide, titanium dioxide according to mass ratio be 1:(1~50):
(0.5~10): (10~500): (10~500) are added in ethyl alcohol, and obtained mixture is agitated, ultrasonic disperse, obtain institute
State dirt-resistant self-cleaning material.
Wherein, in above-mentioned preparation method, the preparation process of the graphene oxide includes the following steps: that by mass ratio be 1:
(0.5~2): graphite powder, the K of (0.5~2)2S2O8And P2O5It is added to the concentrated sulfuric acid that 5~40 mL mass concentrations are 95~99%
In, it is reacted 2~6 hours at 60~100 DEG C, is subsequently cooled to 10~50 DEG C, 500~1500 mL ultrapure waters are added, placed
6~24 hours, pre-oxidation graphite was obtained after dry at 20~90 DEG C after product is washed to neutrality；By the pre-oxidation
Graphite is added in the concentrated sulfuric acid that 100~500 mL mass concentrations are 95~99%, and adding mass ratio is 1:(1~50)
NaNO3And KMnO4, it is reacted 1~5 hour at 0~10 DEG C, is warming up at 20~50 DEG C and reacts 1~5 hour, addition 100~
1000 mL ultrapure waters react 0.5~5 hour under the conditions of 80~100 DEG C, 500~1500 mL ultrapure waters and 10 are then added
The H that~50 mL mass concentrations are 20~30%2O2, the reaction was continued 1~5 hour, by obtained product mass concentration be 1~
20% HCl solution washing, is washed with massive laundering to neutrality, and ultrasonic disperse 1~5 hour at 20~50 DEG C is aoxidized
Graphene aqueous suspensions are freeze-dried to obtain graphene oxide.
Wherein, in above-mentioned preparation method, the lamella g-C3N4Preparation process include the following steps: 1~100 g tri-
Poly cyanamid is placed in crucible, is heated to 300~600 DEG C with 1~10 DEG C/min of heating rate, and keep 1 at such a temperature
~10 hours, then obtain yellow bulk g-C3N4, by the g-C3N4Grind into powder, and being added in crucible, with 1~8 DEG C/
The heating rate of minute is heated to 300~600 DEG C, and reacts 1~10 hour, obtains lamella g-C3N4。
Wherein, in above-mentioned preparation method, the stirring is to stir 100-500 minutes at 10-50 DEG C.
Wherein, in above-mentioned preparation method, the ultrasonic disperse is ultrasonic disperse 10-200 minutes at 10-50 DEG C.
The present invention also provides the methods that above-mentioned dirt-resistant self-cleaning material is applied to glass surface, comprising the following steps: uses glass
Grinding agent removes the greasy dirt of glass surface to be applied, is cleaned glass surface 1~5 time using ethyl alcohol, natural air drying 1~5 hour, will
The dirt-resistant self-cleaning material is uniformly applied to glass surface with glass scraper, and natural air drying 1~50 hour.
Beneficial effects of the present invention:
The present invention provides the new coating materials that a kind of efficient hydrophilic and Photosensitive can be used for glass material surface dirt-resistant self-cleaning
Material, the new coating material include hydrophilic material oxidation silicon, graphene oxide and titanium dioxide, the titanium dioxide with oleophobic
Titanium, graphene oxide and tin oxide with conductive capability, and the lamella g-C with visible light catalytic ability3N4.The present invention is logical
It crosses photochemical catalyst and removes it organic pollutant, catalysis material utilizes the energy of sunlight, can be by the electron transition in valence band
A hole is generated to conduction band, while in valence band, it is right to form photoproduction " electron-hole ", and it is with redox ability, can incite somebody to action
It is attached to the contaminant degradation on its surface, is achieved the purpose that self-cleaning.
1, dirt-resistant self-cleaning material of the invention, raw material used are easy to get, cheap；
2, the material of dirt-resistant self-cleaning of the invention hydrophily with higher and photo-catalysis capability, can play the role of dirt-resistant self-cleaning；
3, dirt-resistant self-cleaning coating material production method of the invention is simple, does not need heavy mechanical equipment and manpower and material resources, can
Produce in enormous quantities.
Detailed description of the invention
Fig. 1 is the surface hydrophilic effect picture of the glass in embodiment 2 :(a) before the spraying antifouling self-cleaning material of embodiment 1,
(b) after spraying the antifouling self-cleaning material of embodiment 1.
Specific embodiment
Further detailed description is done to technical solution of the present invention below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
Embodiment 1
The preparation method of dirt-resistant self-cleaning coating material, the specific steps are as follows:
(1) graphite powder, the K for being 1:0.8:0.8 by mass ratio2S2O8And P2O5It is added to the dense sulphur that 24 mL mass concentrations are 98%
It in acid, is reacted 4 hours at 85 DEG C, is subsequently cooled to 30 DEG C, 1000 mL ultrapure waters are added, placed 12 hours, product is washed
Obtain pre-oxidation graphite after washing to neutrality after drying at 50 DEG C；The pre-oxidation graphite is added to 240 mL mass concentrations
In 98% concentrated sulfuric acid, to add the NaNO that mass ratio is 1:63And KMnO4, react 3 hours, be warming up at 35 DEG C at 0 DEG C
Reaction 2 hours is added 500 mL ultrapure waters, reacts 1 hour under the conditions of 95 DEG C, 1000 mL ultrapure waters and 40 are then added
The H that mL mass concentration is 30%2O2, the reaction was continued 2 hours, and obtained product is washed with the HCl solution that mass concentration is 10%
It washs, is washed with massive laundering to neutrality, and ultrasonic disperse 3 hours at 50 DEG C obtain graphene oxide aqueous suspensions, freezed dry
It is dry to obtain graphene oxide；
(2) 10 g melamines are placed in crucible, are heated to 500 DEG C with 5 DEG C/min of heating rate, and at such a temperature
It is kept for 4 hours, then obtains yellow bulk g-C3N4, by the g-C3N4Grind into powder, and being added in crucible, with 2.5 DEG C/
The heating rate of minute is heated to 500 DEG C, and reacts 2 hours, obtains lamella g-C3N4；
(3) by the resulting graphene oxide of step (1), the resulting lamella g-C of step (2)3N4, silica, tin oxide, titanium dioxide
Titanium is added in 100 mL ethyl alcohol, the graphene oxide, lamella g-C3N4, silica, tin oxide, titanium dioxide mass ratio
For 1:10:2:200:10, mixture is stirred 30 minutes at 30 DEG C with magnetic rotor, is divided in 30 degrees Celsius of lower ultrasonic disperses 30
Clock obtains the material of the dirt-resistant self-cleaning.
Embodiment 2
The preparation method of dirt-resistant self-cleaning coating material, the specific steps are as follows:
(1) graphite powder, the K for being 1:0.8:0.8 by mass ratio2S2O8And P2O5It is added to the dense sulphur that 24 mL mass concentrations are 98%
It in acid, is reacted 4 hours at 85 DEG C, is subsequently cooled to 30 DEG C, 1000 mL ultrapure waters are added, placed 12 hours, product is washed
Obtain pre-oxidation graphite after washing to neutrality after drying at 50 DEG C；The pre-oxidation graphite is added to 240 mL mass concentrations
In 98% concentrated sulfuric acid, to add the NaNO that mass ratio is 1:63And KMnO4, react 3 hours, be warming up at 35 DEG C at 0 DEG C
Reaction 2 hours is added 500 mL ultrapure waters, reacts 5 hours under the conditions of 90 DEG C, 1000 mL ultrapure waters and 40 are then added
The H that mL mass concentration is 30%2O2, the reaction was continued 2 hours, and obtained product is washed with the HCl solution that mass concentration is 10%
It washs, is washed with massive laundering to neutrality, and ultrasonic disperse 3 hours at 50 DEG C obtain graphene oxide aqueous suspensions, freezed dry
It is dry to obtain graphene oxide；
(2) 10 g melamines are placed in crucible, are heated to 600 DEG C with 5 DEG C/min of heating rate, and at such a temperature
It is kept for 2 hours, then obtains yellow bulk g-C3N4, by the g-C3N4Grind into powder, and being added in crucible, with 2.5 DEG C/
The heating rate of minute is heated to 500 DEG C, and reacts 3 hours, obtains lamella g-C3N4；
(3) by the resulting graphene oxide of step (1), the resulting lamella g-C of step (2)3N4, silica, tin oxide, titanium dioxide
Titanium is added in 100 mL ethyl alcohol, the graphene oxide, lamella g-C3N4, silica, tin oxide, titanium dioxide mass ratio
For 1:1:2:10:2, mixture is stirred 60 minutes at 30 DEG C with magnetic rotor, 30 degrees Celsius lower ultrasonic disperse 60 minutes,
Obtain the material of the dirt-resistant self-cleaning.
Embodiment 3
1 dirt-resistant self-cleaning material of embodiment is applied to the method for glass surface, comprising the following steps: is removed with glass grinding agent to be coated
The greasy dirt for smearing glass surface, using ethyl alcohol clean glass surface 3 times, natural air drying 2 hours, by the dirt-resistant self-cleaning material glass
Glass is scraped and is uniformly applied to glass surface, and natural air drying 24 hours.
The result shows that water droplet contact angle is less than 5 degree, cleaning effect such as Fig. 1 in the spraying present invention after anti-pollution self-cleaning material
It is shown.
Claims (9)
1. a kind of dirt-resistant self-cleaning material, which is characterized in that the material includes that the silica of hydrophilic has the titanium dioxide of oleophobic
Titanium, graphene oxide and tin oxide with conductive capability, and the lamella g-C with visible light catalytic ability3N4；The oxygen
Graphite alkene, lamella g-C3N4, silica, tin oxide, titanium dioxide mass ratio be 1:(1~50): (0.5~10): (10~
500): (10~500).
2. dirt-resistant self-cleaning material according to claim 1, which is characterized in that the graphene oxide, lamella g-C3N4, oxygen
SiClx, tin oxide, titanium dioxide mass ratio be 1:(10~50): (1~6): (50~250): (50~250).
3. dirt-resistant self-cleaning material according to claim 1 or 2, which is characterized in that the material further includes ethyl alcohol, the second
The volume mass ratio (mL/g) of the dosage of alcohol and the graphene oxide is (80-120): 1.
4. the preparation method of any one of the claim 1-3 dirt-resistant self-cleaning material, which is characterized in that the method includes as follows
Step:
By the graphene oxide, lamella g-C3N4, silica, tin oxide, titanium dioxide according to mass ratio be 1:(1~50):
(0.5~10): (10~500): (10~500) are added in ethyl alcohol, and obtained mixture is agitated, ultrasonic disperse, obtain institute
State dirt-resistant self-cleaning material.
5. the preparation method according to claim 4, which is characterized in that the preparation process of the graphene oxide includes as follows
Step: being 1:(0.5~2 by mass ratio): graphite powder, the K of (0.5~2)2S2O8And P2O5Being added to 5~40 mL mass concentrations is
It in 95~99% concentrated sulfuric acid, is reacted 2~6 hours at 60~100 DEG C, is subsequently cooled to 10~50 DEG C, it is added 500~
1500 mL ultrapure waters are placed 6~24 hours, obtain pre-oxidation stone after dry at 20~90 DEG C after product is washed to neutrality
Ink；The pre-oxidation graphite is added in the concentrated sulfuric acid that 100~500 mL mass concentrations are 95~99%, adds quality
Than for 1:(1~50) NaNO3And KMnO4, reacted 1~5 hour at 0~10 DEG C, be warming up at 20~50 DEG C and react 1~5
Hour, 100~1000 mL ultrapure waters are added, reacts 0.5~5 hour under the conditions of 80~100 DEG C, then addition 500~
The H that 1500 mL ultrapure waters and 10~50 mL mass concentrations are 20~30%2O2, the reaction was continued 1~5 hour, the product that will be obtained
It is washed, is washed with massive laundering to neutrality, and the ultrasonic disperse 1 at 20~50 DEG C with the HCl solution that mass concentration is 1~20%
It obtains graphene oxide aqueous suspensions within~5 hours, is freeze-dried to obtain graphene oxide.
6. the preparation method according to claim 4, which is characterized in that the lamella g-C3N4Preparation process include it is as follows
Step: 1~100 g melamine is placed in crucible, is heated to 300~600 DEG C with 1~10 DEG C/min of heating rate,
And keep at such a temperature 1~10 hour, then obtain yellow bulk g-C3N4, by the g-C3N4Grind into powder, and be added
In crucible, 300~600 DEG C is heated to 1~8 DEG C/min of heating rate, and react 1~10 hour, obtains lamella g-
C3N4。
7. the preparation method according to claim 4, which is characterized in that the stirring is to stir 100-500 at 10-50 DEG C
Minute.
8. the preparation method according to claim 4, which is characterized in that the ultrasonic disperse is the ultrasound point at 10-50 DEG C
It dissipates 10-200 minutes.
9. any one of claim 1-3 dirt-resistant self-cleaning material is applied to the method for glass surface, which is characterized in that the method packet
It includes following steps: removing the greasy dirt of glass surface to be applied with glass grinding agent, cleaned glass surface 1~5 time using ethyl alcohol, from
It so air-dries 1~5 hour, the dirt-resistant self-cleaning material is uniformly applied to glass surface with glass scraper, natural air drying 1~50 is small
When.
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Cited By (3)
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| CN114832803A (en) * | 2022-04-08 | 2022-08-02 | 重庆城市综合交通枢纽（集团）有限公司 | Film-forming composition, preparation method thereof and application of composite photocatalyst |
| CN115029028A (en) * | 2022-06-16 | 2022-09-09 | 大连理工大学 | Application of novel photocatalytic antifouling agent |
| CN115594998A (en) * | 2022-11-02 | 2023-01-13 | 中南林业科技大学（Cn） | Composite coating with photocatalytic self-cleaning capability, and preparation method and application thereof |
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Application publication date: 20190628 |