CN113694950B - graphene-TiO 2 Composite photocatalyst, preparation method thereof, air purification coating and display device - Google Patents

graphene-TiO 2 Composite photocatalyst, preparation method thereof, air purification coating and display device Download PDF

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CN113694950B
CN113694950B CN202110807315.7A CN202110807315A CN113694950B CN 113694950 B CN113694950 B CN 113694950B CN 202110807315 A CN202110807315 A CN 202110807315A CN 113694950 B CN113694950 B CN 113694950B
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tio
composite photocatalyst
air
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CN113694950A (en
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彭春燕
任娜娜
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New Line Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

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Abstract

The application provides a graphene-TiO 2 Composite photocatalyst, preparation method thereof, air purification paint and display device. The method comprises the steps of oxidizing and hydroxylating graphene to obtain a product A; carrying out amino modification and vinyl modification on the product A to obtain a product B; and compounding the product B with nitrogen-doped titanium dioxide to obtain the titanium dioxide. graphene-TiO prepared by the method 2 The composite photocatalyst can well integrate the advantages of the two materials, is beneficial to the separation of electron-hole pairs, is beneficial to the electron transfer effect, and further improves the photocatalytic efficiency. Wherein, graphene is subjected to oxidation, hydroxylation, amino modification and vinyl modification, and titanium dioxide is subjected to nitrogen doping. The modified graphene can effectively capture harmful substances in the air, so that the photocatalytic reaction speed is accelerated, and the air purifying effect is improved. The nitrogen doped modified titanium dioxide has large specific surface area, greatly increases the collision probability of the photocatalyst and air, and has good purifying effect.

Description

graphene-TiO 2 Composite photocatalyst, preparation method thereof, air purification coating and display device
Technical Field
The application belongs to the field of air purification, and in particular relates to graphene-TiO 2 Composite photocatalyst, preparation method thereof, air purification paint and display device.
Background
The touch screen is also called as a touch screen and a touch panel, is an induction type glass liquid crystal display device capable of receiving input signals such as a contact, is the simplest, convenient and natural man-machine interaction mode at present, and is widely applied to various industries and fields. The situation of utilizing the touch control integrated machine in indoor public places is visible everywhere, such as classrooms, meeting rooms, stations, banks, hospital guiding, office handling guidance and the like. These places are public places, and the flow of people is large and the air is poor. In addition, as interior decoration and the use of high-grade furniture are widely spread, a small amount of various organic solvents such as acetate, acetone, toluene and the like, and chemical substances such as formaldehyde, phthalate and the like are slowly released from adhesives, paints, insect repellents and the like of various building materials, artificial boards, wall paper, floor leather, carpets, floors, wooden furniture and the like, and are emitted into indoor air, so that acute discomfort such as dizziness, nausea and the like of residents or chronic allergic diseases such as asthma, dermatitis and the like are caused.
One of the solutions to the above problems is often to use an air cleaner. However, in public places, there are several problems in using the air purifier, the air purifier needs to be driven by electric energy, so that not only is the household electric quantity increased and the electric charge expenditure burden increased, but also in summer, the heat energy emitted by the air purifier can increase the indoor air conditioning load, thereby causing double electric energy consumption. In addition, the purifier occupies an indoor space when in use, so that an indoor space which is not originally abundant becomes more crowded.
As an air purifying agent, the photocatalyst has the characteristics of high treatment speed, no secondary pollution, good treatment effect and the like, and is considered as an ideal material for treating indoor air pollution at present. TiO (titanium dioxide) 2 Is a widely used photocatalyst. However, tiO 2 As a nano material, agglomeration easily occurs in the preparation process, and the size of formed particles is large, so that the specific surface area of nano particles is reduced, and the later application is not facilitated; in addition, the method has the defects of high photo-generated electron-hole pair recombination efficiency, insufficient visible light absorption capacity and the like, and influences the air purification effect.
Disclosure of Invention
In view of the deficiencies of the prior art, a first object of the present application is to provide a graphene-TiO 2 A preparation method of a composite photocatalyst. The method comprises the following steps:
oxidizing and hydroxylating graphene to obtain a product A;
carrying out amino modification and vinyl modification on the product A to obtain a product B;
compounding the product B with nitrogen-doped titanium dioxide to obtain the graphene-TiO 2 A composite photocatalyst.
In some embodiments of the present application, oxidizing and hydroxylating graphene to obtain product a comprises:
oxidizing the graphene by using an oxidant under a strong acid environment to obtain oxidized graphene;
and hydroxylating the graphene oxide by adopting hydrogen peroxide, and washing and drying the obtained first precipitate to obtain the product A.
In some embodiments of the present application, subjecting the product a to amino modification and vinyl modification, obtaining the product B comprises:
amino modifying the product A by adopting an amino modifier;
and carrying out vinyl modification on the amino modified product A by adopting a vinyl modifier to obtain the product B.
In some embodiments of the present application, the amino modification of product a with triethanolamine comprises:
amino modification of the product a with an amino modifier comprises:
dispersing the product A into a first dispersing agent, and then adding the amino modifier for uniform mixing;
adding methacryloyl chloride into the obtained mixed solution to cause complete precipitation, and obtaining a second precipitate;
carrying out vinyl modification on the amino modified product by adopting a vinyl modifier, wherein the step of obtaining the product B comprises the following steps:
dispersing the second precipitate into a second dispersing agent, and then adding the vinyl modifier and an initiator to react;
adding diethyl ether to separate out precipitate after the reaction is finished, and obtaining a third precipitate;
and washing and drying the third precipitate to obtain the product B.
In some embodiments of the present application, the above method further comprises the step of preparing nitrogen doped titanium dioxide:
and adopting one or more of urea aqueous solution, melamine and dicyandiamide as a nitrogen source, and carrying out nitrogen doping on the titanium dioxide to obtain the nitrogen doped titanium dioxide.
In some embodiments of the present application, the product B is composited with nitrogen doped titanium dioxide to obtain the graphene-TiO 2 The composite photocatalyst comprises:
uniformly mixing the product B with the nitrogen-doped titanium dioxide under the action of a surfactant;
the obtained mixed solution is treated for 1.5 to 2.5 hours at the high temperature of 750 to 850 ℃ after being sprayed and dried, and the graphene-TiO is obtained 2 A composite photocatalyst.
A second object of the present application is to provide a graphene-TiO 2 A composite photocatalyst prepared by the above method.
A third object of the present application is to provide an air purification paint comprising the above graphene-TiO 2 A composite photocatalyst.
In some embodiments of the present application, the air purification coating further comprises a dispersant, a binder, a film forming aid, a polymer emulsion, a surfactant, and an adhesion promoter;
wherein the graphene-TiO 2 The dosage ratio of the composite photocatalyst to the dispersant to the adhesive to the auxiliary film forming agent to the polymer emulsion to the surfactant to the adhesion promoter is (10-40): (1-10): (1-5): (1-10): (40-80): (0.5-5);
the polymer emulsion is an ester.
A fourth object of the present application is to provide a display device whose surface is the above air-purifying paint.
graphene-TiO prepared by the method 2 The composite photocatalyst combines graphene and titanium dioxide together well, can well integrate the advantages of the two materials, is beneficial to separation of electron-hole pairs and electron transfer effect, and further improves photocatalysis efficiency. Wherein, graphene is subjected to oxidation, hydroxylation, amino modification and vinyl modification, and titanium dioxide is subjected to nitrogen doping. The modified graphene can effectively capture harmful substances in the air, so that the photocatalytic reaction speed is accelerated, and the air purifying effect is improved.The nitrogen doped modified titanium dioxide has large specific surface area, greatly increases the collision probability of the photocatalyst and air, and has good purifying effect.
The photocatalyst technology is combined with the display screen, so that the problem of poor air quality in a using place can be effectively solved, the surface of the photocatalyst technology also has antibacterial activity, cross infection of operators can be avoided, and the photocatalyst technology has good economic benefit and application value. In addition, the modified titanium dioxide can enable the display to purify air under natural light conditions, and the purifying effect can be further improved by utilizing the light source of the display.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic illustration of a method for preparing graphene-TiO according to an embodiment of the present application 2 Schematic of the process flow of the composite photocatalyst.
Detailed Description
The following detailed description of specific embodiments of the invention is provided in connection with the accompanying drawings and examples in order to provide a better understanding of the aspects of the invention and advantages thereof. However, the following description of specific embodiments and examples is for illustrative purposes only and is not intended to be limiting of the invention.
It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
As shown in fig. 1, the graphene-TiO provided in the present application 2 The preparation method of the composite photocatalyst comprises the following steps:
s01: and oxidizing and hydroxylating the graphene to obtain a product A.
This step may include:
oxidizing graphene by using an oxidant under a strong acid environment to obtain oxidized graphene;
hydroxylating graphene oxide by hydrogen peroxide, washing and drying the obtained first precipitate to obtain a product A.
Of course, other raw materials may be used to oxidize and hydroxylate graphene. Alternatively, in the present application, the oxidizing agent may be potassium permanganate, potassium dichromate or potassium persulfate.
Specifically, this step may be:
at room temperature, adding graphene powder into concentrated sulfuric acid, stirring uniformly, adding sodium nitrate and potassium permanganate, diluting with deionized water, adding hydrogen peroxide, and finally washing and drying the obtained first precipitate to obtain a product A.
Optionally, the mass ratio of the graphene powder to the sodium nitrate to the potassium permanganate is (2-4): 1-3): 8-12.
Optionally, the dosage ratio of the graphene powder to the concentrated sulfuric acid is (1-2): (40-60) g/mL.
Optionally, adding sodium nitrate, stirring for 30-50 min, adding potassium permanganate, continuously stirring for 1.5-2 h at 30-50 ℃, and cooling in an ice bath.
Optionally, the hydrogen peroxide is present at a mass concentration of about 30%.
Optionally, diluting with deionized water, adding hydrogen peroxide, stopping adding hydrogen peroxide until the gas is completely separated out, and filtering the obtained suspension to obtain a first precipitate.
Alternatively, the first precipitate is washed with water and then dried at 50℃to 70℃for 24h to give the product A.
S02: and (3) carrying out amino modification and vinyl modification on the product A to obtain a product B.
This step may include:
amino modifying the product A by adopting an amino modifier;
and carrying out vinyl modification on the amino modified product A by adopting a vinyl modifier to obtain the product B.
Alternatively, the amino modifier may comprise one or more of triethanolamine, triethylenetetramine, 3-aminopropyl trimethoxysiloxane.
Alternatively, the vinyl modifier may include one or more of methacrylic acid, butyl methacrylate, 2- (trifluoromethyl) acrylic acid, sodium methacrylate, ethyl methacrylate, phenyl methacrylate.
Optionally, amino modifying product a with an amino modifier comprises:
dispersing the product A into a first dispersing agent, and then adding an amino modifier and uniformly mixing;
and adding methacryloyl chloride into the obtained mixed solution to cause complete precipitation, and obtaining a second precipitate. Alternatively, the methacryloyl chloride is dispersed in a dispersing agent and then added to the resulting mixed solution.
Optionally, the amino-modified product is vinyl-modified with a vinyl modifier, and obtaining the product B comprises:
dispersing the second precipitate into a second dispersing agent, and then adding a vinyl modifier and an initiator for reaction;
adding diethyl ether to separate out precipitate after the reaction is finished, and obtaining a third precipitate;
and washing and drying the third precipitate to obtain a product B.
Alternatively, the first dispersant and the second dispersant may be the same or different and may be N, N-dimethylacetamide, 2-amino-N, N-dimethylacetamide, 2-hydroxy-N, N-dimethylacetamide, N-dimethylformamide or the like.
Alternatively, the initiator is azobisisobutyronitrile.
Alternatively, the step may specifically be: and (3) uniformly mixing the product A with N, N-dimethylacetamide and triethanolamine, adding the mixture of the N, N-dimethylacetamide and methacryloyl chloride to cause complete precipitation, adding the obtained second precipitate into N, N-dimethylformamide to disperse, sequentially adding methacrylic acid, butyl methacrylate and azodiisobutyronitrile to react, adding diethyl ether to precipitate after the reaction is finished, and drying the obtained third precipitate to completely obtain the product B.
Optionally, the dosage ratio of the product A, N, N-dimethylacetamide and triethanolamine is (2-4): (5-7): (1400-1600) g/mL/mL.
Alternatively, the mass ratio of the N, N-dimethylacetamide to the methacryloyl chloride in the mixture of the N, N-dimethylacetamide and the methacryloyl chloride is (98-99): 2-1.
Optionally, a mixture of N, N-dimethylacetamide and methacryloyl chloride is slowly added in a titration mode, and stirred for 16 to 24 hours at room temperature, so that precipitation is complete, and a second precipitate is obtained.
Optionally, the dosage ratio of N, N-dimethylformamide, methacrylic acid, butyl methacrylate and azodiisobutyronitrile is (500-700): (2-3): (6-7): (60-80) mL/mL/mg.
Optionally, after methacrylic acid, butyl methacrylate and azodiisobutyronitrile are added, the mixture is reacted for 8 to 12 hours at the temperature of between 60 and 70 ℃ under the protection of inert gas, and after the reaction is finished and cooled to room temperature, diethyl ether is added to separate out a third precipitate.
Optionally, the third precipitate is washed with diethyl ether.
Optionally, the third precipitate is dried under vacuum at 50-70 ℃ to obtain the product B.
S03: compounding the product B with nitrogen-doped titanium dioxide to obtain graphene-TiO 2 A composite photocatalyst.
This step may include:
uniformly mixing the product B with nitrogen-doped titanium dioxide under the action of a surfactant;
the obtained mixed solution is treated for 1.5 to 2.5 hours at the high temperature of 750 to 850 ℃ after being sprayed and dried, and the graphene-TiO is obtained 2 A composite photocatalyst.
Optionally, the method further comprises the step of preparing nitrogen doped titanium dioxide:
and (3) carrying out nitrogen doping on the titanium dioxide to obtain the nitrogen doped titanium dioxide.
The steps can be as follows:
dispersing titanium sulfate in an n-propanol aqueous solution to obtain titanium dioxide;
and adopting urea aqueous solution as a nitrogen source, and carrying out nitrogen doping on the titanium dioxide to obtain the nitrogen doped titanium dioxide.
Alternatively, the titanium sulfate in the above step may be replaced with titanium tetrachloride, tetrabutyl titanate, titanium isopropoxide, titanium sulfate, titanyl sulfate, titanium difluorooxide, titanium flakes, or the like.
Optionally, the nitrogen-doped nitrogen source comprises one or more of an aqueous urea solution, melamine, and dicyandiamide.
Alternatively, the surfactant used herein is a mixture of sodium polypropylene glycol diacetate and sodium polypropylene glycol disulfate.
Optionally, the mass ratio of the sodium polypropylene glycol diacetate to the sodium polypropylene glycol disulfate to the water in the mixed solution of the sodium polypropylene glycol diacetate and the sodium polypropylene glycol disulfate is about 1:1:50.
Alternatively, the step may specifically be:
dispersing titanium sulfate in n-butanol aqueous solution, adding urea aqueous solution, adding product B and mixed solution of sodium polypropylene glycol diacetate and sodium polypropylene glycol disulfate, and drying the obtained mixed solution to obtain the graphene-TiO 2 A composite photocatalyst.
Optionally, the volume concentration of the n-butanol aqueous solution is 70-80%.
Optionally, the mass concentration of the urea aqueous solution is 25% -35%.
The volume concentration as used herein refers to the volume percent concentration, and the mass concentration (in wt% in the lower part) is the mass percent concentration.
Optionally, the dosage ratio of the titanium sulfate, the n-propanol water-soluble urea water solution, the product B, the polypropylene glycol sodium diacetate and the polypropylene glycol sodium disulfate is (7-8): (220-230): (55-65): (8-12): (25-35) g/mL/mL/g/mL.
Optionally, stirring titanium sulfate in n-butanol water solution at room temperature for 8-16 h, then carrying out ultrasonic treatment for 30-60 min, dropwise adding urea water solution by adopting a titration mode, and then adding the product B, sodium polypropylene glycol diacetate and sodium polypropylene glycol disulfateThe mixed solution is continuously treated by ultrasonic for 1.5 to 2.5 hours, and the obtained mixed solution is treated for 1.5 to 2.5 hours at the high temperature of 750 to 850 ℃ after being sprayed and dried to obtain the graphene-TiO 2 A composite photocatalyst.
graphene-TiO prepared by the method 2 The composite photocatalyst has the advantages that graphene and titanium dioxide are well compounded together, the advantages of the two materials can be well combined, the separation of electron-hole pairs is facilitated, the electron transfer effect is also facilitated, the photocatalytic efficiency is further improved, the titanium dioxide is modified by nitrogen doping, the specific surface area is large, the collision probability of the photocatalyst and air is greatly increased, and the purifying effect is very good. And the graphene can effectively capture harmful substances in the air, so that the photocatalytic reaction speed is accelerated, and the air purification effect is improved.
graphene-TiO prepared by the method 2 Composite photocatalyst improves TiO 2 The dispersibility of the catalyst, the agglomeration is avoided, and the photocatalysis effect is further improved.
Further, the application provides the graphene-TiO prepared by the method 2 A composite photocatalyst.
Further, the application provides an air purification coating, which comprises the graphene-TiO 2 A composite photocatalyst.
Optionally, the air cleaning coating further comprises a dispersant, a binder, a film forming aid, a polymer emulsion, a surfactant, and an adhesion promoter.
Alternatively, the dispersant is an aqueous solution of sodium polyacrylate salt at a concentration of about 40% by mass.
Alternatively, the binder is an alkoxysilane or an epoxy. The alkoxysilane can be well combined with the screen of the display.
Optionally, the film forming agent is one or more of propylene glycol monomethyl ether, tripropylene glycol n-butyl ether and propylene glycol methyl ether acetate.
In the present application, the polymer emulsion is an ester, and the polymer emulsion can improve the binding force and the fusion force of the coating and the matrix in the present application. Alternatively, the polymer emulsion comprises a mixture of vinyl acetate and acrylate or a mixture of polyvinyl acetate and acrylate. Optionally, the acrylate comprises one or more of methyl acrylate, ethyl acrylate, methyl 2-methacrylate, and ethyl 2-methacrylate. Wherein, the mass ratio of the vinyl acetate or the polyvinyl acetate to the acrylic ester can be (1-5) to (1-5).
Optionally, the surfactant used herein is one or more of organopolysiloxane defoamer, sodium polypropylene glycol diacetate, sodium polypropylene glycol disulfate, disodium salt of sulfonated dehydroabietic acid, gamma-aminopropyl triethoxysilane.
Alternatively, the adhesion promoter is an alkyd resin.
Optionally, graphene-TiO 2 The composite photocatalyst, dispersant, adhesive, filming assistant, polymer emulsion, surfactant and adhesion promoter in the weight ratio of 10-40 to 1-10 to 1-5 to 1-10 to 40-80 to 0.5-5.
Further, the present application provides a display device whose surface is the above air-purifying paint.
Specifically, after cleaning pretreatment is carried out on the protective glass, a certain amount of air purification paint is filled into a spraying machine and uniformly sprayed on the surface of the protective glass, and the protective glass with the air purification coating is obtained.
The photocatalyst technology is combined with the display screen, the problem of poor air quality in a display screen using place can be effectively solved, the surface of the photocatalyst technology also has antibacterial activity, cross infection of operators can be avoided, and the photocatalyst technology has good economic benefit and application value.
After the titanium dioxide is modified, the display can purify air under natural light conditions, and the purifying effect can be further improved by utilizing the light source of the display.
graphene-TiO of the present application 2 The composite photocatalyst has good dispersibility, and avoids TiO 2 The problem that the display is affected by the decrease of the photocatalytic activity and uneven distribution caused by agglomeration.
The invention will now be described with reference to specific examples. The values of the process conditions taken in the examples below are exemplary and can be obtained in the ranges indicated in the foregoing summary, and for process parameters not specifically identified, reference may be made to conventional techniques. The detection methods used in the examples below are all conventional in the industry. Reagents and apparatus used in the technical scheme provided by the invention are available from conventional channels or markets unless otherwise specified.
Example 1
The embodiment prepares a display with an air purifying effect, which comprises the following specific steps:
s1, preparing graphene-TiO 2 Composite photocatalyst
S11, adding 3.0g of graphene powder into 100mL of concentrated sulfuric acid at room temperature, uniformly stirring, adding 2.0g of sodium nitrate, stirring for 40min, adding 10g of potassium permanganate, continuously stirring at 30 ℃ for 1.5H, cooling in an ice bath, diluting with 600mL of deionized water, and adding a certain amount of H 2 O 2 Until the gas precipitation completely stops adding H 2 O 2 Finally, the resulting suspension was filtered, washed with water and dried at 60 ℃ for 24h to give product a.
S12, adding 0.3g of the product A and 0.6mL of triethanolamine into 150mL of N, N-dimethylacetamide, slowly dripping 60mL of N, N-dimethylacetamide (containing 1wt% of methacryloyl chloride) after uniformly mixing, stirring for 16 hours at room temperature to completely precipitate, dispersing the obtained precipitate into 60mL of N, N-dimethylformamide, sequentially adding 0.25mL of methacrylic acid, 0.5mL of butyl methacrylate and 7mg of azodiisobutyronitrile, stirring for 10 hours at 65 ℃ under the protection of inert gas, adding a certain amount of diethyl ether to precipitate after the reaction is finished and cooling to room temperature, filtering, washing with diethyl ether, and drying in a vacuum oven at 60 ℃ to obtain the target product B.
S13, 7.5g Ti (SO) was added to a mixture of 150ml n-propanol and 75ml deionized water 4 ) 2 Stirring at room temperature for 8h, and after sonication for 30min 60ml of 30wt% aqueous urea solution are added dropwise, followed by 10g of product B and 30ml of 0.1 to 54wt% 1:1 Polypropylene glycol sodium diacetate and Polypropylene glycolContinuously stirring the mixed solution of the sodium alcohol disulfate for 2 hours by ultrasonic, and treating the obtained mixed solution at a high temperature of 800 ℃ for 2.0 hours after spray drying treatment to obtain the graphene-TiO 2 A composite photocatalyst.
S2, preparing the air purifying paint
Calculated according to parts by weight, the prepared graphene-TiO 2 30 parts of composite photocatalyst, 2 parts of dispersing agent, 2 parts of adhesive, 5 parts of film forming assistant, 60 parts of polymer emulsion, 0.5 part of surfactant and 0.5 part of adhesion promoter.
Wherein the dispersing agent is 40wt% of sodium polyacrylate aqueous solution, the adhesive is alkoxy silane, the auxiliary film forming agent is propylene glycol monomethyl ether, the polymer emulsion is a mixture of vinyl acetate and 2-methyl methacrylate (the mass ratio is 1:1), the surfactant is organopolysiloxane defoamer, and the adhesion promoter is alkyd resin.
S3, preparing an air purification coating
After cleaning and preprocessing the screen glass of the display, a certain amount of air purification paint is filled into a spraying machine and mixed with high-pressure air in a nozzle, the distance between a spray gun and a matrix is 300mm, the moving speed of the spray gun is 250mm/s, and the pressure of the spray gun is 0.5MPa. In addition, the environment of spraying was controlled as follows: the normal temperature is 70% RH, the spray gun is perpendicular to the surface of the matrix at 90 degrees, the spraying sequence is from left to right and from top to bottom, in the spraying process, uniform speed, uniform spraying and overlapping of the pressure gun are 1/4 of each row of spraying, so that the contact surface of the sprayed matrix is completely sprayed in place, after the surface of the protective glass is completely wetted, the protective glass is solidified for 60 minutes at 150 ℃, and the display with the air purification coating is obtained after standing and cooling.
Example 2
The embodiment prepares a display with an air purifying effect, which comprises the following specific steps:
s1, preparing graphene-TiO 2 Composite photocatalyst
S11, the same as in the embodiment 1.
S12, adding 0.2g of the product A and 0.6mL of triethanolamine into 150mL of N, N-dimethylacetamide, slowly dripping 60mL of N, N-dimethylacetamide (containing 1wt% of methacryloyl chloride) after uniformly mixing, stirring for 16 hours at room temperature to completely precipitate, dispersing the obtained precipitate into 60mL of N, N-dimethylformamide, sequentially adding 0.25mL of methacrylic acid, 0.5mL of butyl methacrylate and 7mg of azodiisobutyronitrile, stirring for 10 hours at 65 ℃ under the protection of inert gas, adding a certain amount of diethyl ether to precipitate after the reaction is finished and cooling to room temperature, filtering, washing with diethyl ether, and drying in a vacuum oven at 60 ℃ to obtain the target product B.
S2 and S3 are the same as in example 1.
Example 3
The embodiment prepares a display with an air purifying effect, which comprises the following specific steps:
s1 is as in example 1.
S2, preparing the air purifying paint.
Calculated according to parts by weight, the prepared graphene-TiO 2 20 parts of composite photocatalyst, 2 parts of dispersing agent, 2 parts of adhesive, 5 parts of film forming assistant, 60 parts of polymer emulsion, 0.5 part of surfactant and 0.5 part of adhesion promoter.
S3 is the same as in example 1.
Comparative example 1
In comparative example 1, the preparation method of the air cleaning coating omits the step S12, and the product obtained in the step S11 is directly subjected to the treatment of the step S13, and the rest steps and the formulation ratio are the same as in example 1.
Comparative example 2
In comparative example 2, the aqueous urea solution in step S13 was replaced with deionized water, and the remaining steps and formulation ratios were the same as in example 1.
Effect detection
The antibacterial, antiviral and air purifying effects of the glass were examined by referring to methods in GB/T23763-2009 and QB/T2761-2006 using untreated glass as a control group and glass prepared in different examples as an experimental group, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the screen glass of the display manufactured by the method has very good antibacterial, antiviral and air purifying effects.
graphene-TiO of comparative example 1 2 The graphene of the composite photocatalyst is graphene subjected to oxidation and hydroxylation treatment only, and the graphene of comparative example 2 is graphene-TiO 2 TiO of composite photocatalyst 2 Without nitrogen doping modification. As can be seen from Table 1, the effects of the antibacterial, antiviral and air purifying effects are compared with those of the graphene-TiO prepared by the technical scheme of the application 2 Composite photocatalysts are much worse.
It is apparent that the above examples are only illustrative of the present invention and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (5)

1. graphene-TiO 2 The preparation method of the composite photocatalyst is characterized by comprising the following steps:
oxidizing graphene by using an oxidant under a strong acid environment to obtain oxidized graphene; hydroxylating the graphene oxide by adopting hydrogen peroxide, washing and drying the obtained first precipitate to obtain a product A;
dispersing the product A into a first dispersing agent, and then adding an amino modifier for uniform mixing; adding methacryloyl chloride into the obtained mixed solution to cause complete precipitation, and obtaining a second precipitate;
dispersing the second precipitate into a second dispersing agent, and then adding a vinyl modifier and an initiator to react; adding diethyl ether to separate out precipitate after the reaction is finished, and obtaining a third precipitate; washing and drying the third precipitate to obtain a product B;
dispersing titanium sulfate in n-butanol aqueous solution, adding urea aqueous solution, then adding product B, and mixing solution of sodium polypropylene glycol diacetate and sodium polypropylene glycol disulfate, spray drying the obtained mixed solution, and treating at 750-850 deg.C for 1.5-2.5 h to obtain the described graphene-TiO 2 A composite photocatalyst;
wherein the amino modifier comprises one or more of triethanolamine, triethylene tetramine and 3-aminopropyl trimethoxysilane;
the vinyl modifier comprises one or more of methacrylic acid, butyl methacrylate, 2- (trifluoromethyl) acrylic acid, sodium methacrylate, ethyl methacrylate and phenyl methacrylate; the initiator is azobisisobutyronitrile.
2. The graphene-TiO produced by the production method according to claim 1 2 A composite photocatalyst.
3. An air-purifying paint, characterized in that the air-purifying paint comprises the graphene-TiO according to claim 2 2 A composite photocatalyst.
4. The air cleaning paint of claim 3, further comprising a dispersant, a binder, a film forming aid, a polymer emulsion, a surfactant, and an adhesion promoter;
wherein, the graphene-TiO is calculated according to parts by weight 2 The composite photocatalyst, the dispersing agent, the adhesive, the film forming aid, the polymer emulsion, the surfactant and the adhesion promoter are in a weight ratio of (10-40): (1-10): (1-5): (1-10): (40-80): (0.5-5);
the polymer emulsion is an ester.
5. A display device, characterized in that a surface of the display device is coated with the air-purifying paint according to claim 3 or 4.
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CN106750054A (en) * 2017-03-16 2017-05-31 天津大学 Graphene of chemical bonding polypropylene long-chain and preparation method thereof
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CN101750657A (en) * 2008-12-17 2010-06-23 三星康宁精密琉璃株式会社 Display filter and display device removing indoor air pollutants
CN102040714A (en) * 2010-11-02 2011-05-04 浙江大学 Preparation method of polymer-grafted graphene
CN103949278A (en) * 2014-04-23 2014-07-30 上海荣富新型材料有限公司 Aluminum product coated with nitrogen-doped graphene/nitrogen-doped TiO2 photo-catalytic material
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