CN113789090A - Graphene modified photocatalytic water-based paint and preparation method and application thereof - Google Patents

Graphene modified photocatalytic water-based paint and preparation method and application thereof Download PDF

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CN113789090A
CN113789090A CN202111087633.7A CN202111087633A CN113789090A CN 113789090 A CN113789090 A CN 113789090A CN 202111087633 A CN202111087633 A CN 202111087633A CN 113789090 A CN113789090 A CN 113789090A
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water
primer
based paint
bionic
paint
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CN113789090B (en
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杨波
倪进飞
张辉
何勃
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Guangzhou Special Equipment Testing And Research Institute Guangzhou Special Equipment Accident Investigation Technology Center Guangzhou Elevator Safety Operation Monitoring Center
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Guangzhou Special Pressure Equipment Inspection and Research Institute
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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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C09D5/002—Priming paints
    • 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
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The invention relates to a graphene modified photocatalytic water-based paint, a preparation method and an application thereof, wherein the paint comprises a finish paint and a primer, and the finish paint is prepared from the following components in percentage by weight: 10-25% of nano titanium dioxide, 10-25% of nano bismuth molybdate, 10-25% of bismuth oxyiodide, 20-30% of a film forming substance, 0.1-2% of graphene oxide, 0.1-2% of polyvinylpyrrolidone, 0.1-2% of hydroxypropyl methyl cellulose, 0.5-5% of dodecyl alcohol ester and 5-30% of water; the primer is prepared from the following components in percentage by weight: 10-25% of nano silicon dioxide, 10-35% of hollow glass beads, 20-30% of film forming substances, 0.5-5% of polydimethylsiloxane, 0.5-5% of diisopropanol adipate and 10-50% of water. The coating is coated on the bionic water lily, has strong adhesive force and can be used for degrading organic pollutants in black and odorous water.

Description

Graphene modified photocatalytic water-based paint and preparation method and application thereof
Technical Field
The invention relates to the technical field of water-based paint and environmental pollution treatment, in particular to graphene modified photocatalytic water-based paint and a preparation method and application thereof.
Background
The black and odorous water body is a water body which is black in color and emits odor. In recent years, as a large amount of exogenous pollutants such as domestic sewage, industrial wastewater and the like enter a water body, dissolved oxygen is consumed by the decomposition and metabolism of the pollutants, the water body is in an anoxic or anaerobic state, the water body smells due to the fact that organic matters in the water body decay to generate gases such as ammonia gas and hydrogen sulfide, and the water body is black due to the fact that ferrous sulfide and manganous sulfide are formed in the water body. The pollutants are fermented in an anaerobic way to generate methane and nitrogen to enable the bottom mud to float upwards, the pollutants such as nitrogen, phosphorus and the like in the bottom mud are released continuously to enter a water body, the water quality is gradually deteriorated, and the aquatic plants (submerged plants, floating-leaf plants and the like) and the aquatic animals (fish, shrimps and the like) are difficult to survive, the food chain is incomplete, the aquatic ecosystem is unbalanced and the like. The black and odorous water has many hazards, such as influencing the life of residents, harming human health, destroying the ecology of the water, damaging urban landscapes and the like. At present, the treatment of black and odorous water at home and abroad follows the concept of 'source control, purification and restoration'. The common purification methods include physical methods (such as sediment desilting, water diversion and dilution flushing, artificial aeration and the like), chemical methods (such as adding aluminum salt, nitrate, hydrogen peroxide and the like) and biological methods (such as aquatic plant purification, microorganism reinforced purification and the like). Although the method can improve the water quality of the black and odorous water body to a certain degree, a plurality of defects still exist. The physical method has the problems of high cost, low efficiency, secondary pollution and the like, for example, the desilted sediment needs to be further treated, and more pollutants are released from the sediment through manual aeration; toxic and harmful substances are easily brought in by a chemical method, for example, when aluminum salt is used for purification, the toxic substances are toxic to aquatic organisms, and the nitrate nitrogen concentration can be increased by adding nitrate; the biological method has the advantages of low cost, no secondary pollution and the like, but has the defects of long restoration period, low restoration effect sustainability and the like.
In recent years, some researches find that the photocatalysis technology has great application prospect in the field of black and odorous water treatment, the pollution control principle is to realize self-purification of water by utilizing visible light, sunlight is a light source of the photocatalysis technology, a power device is not needed, and chemical agents or biological strains are not needed to be added. However, the introduction and recovery of the photocatalyst is the bottleneck of applying the photocatalyst to sewage treatment at present. In the prior art, the photocatalysis net is generally formed by coating a photocatalyst on a polypropylene net, the firmness of the photocatalysis net is low, the photocatalyst is easy to wash and fall off when being placed in a water body, the polypropylene net is not beautiful enough when being placed in the water body, and the installation mode is complex.
Disclosure of Invention
Based on the above, the invention aims to provide the graphene modified photocatalytic water-based paint, which has good binding force with the bionic water lily, is coated on the bionic water lily, has strong adhesive force and good firmness, can not fall off when placed in a water body, can be conveniently used for degrading organic pollutants in a black and odorous water body when coated on the bionic water lily, is easy to recover, and can not generate secondary pollution. The technical scheme is as follows:
the graphene modified photocatalytic water-based paint comprises a finish paint and a primer, wherein the finish paint is prepared from the following components in percentage by weight: 10-25% of nano titanium dioxide, 10-25% of nano bismuth molybdate, 10-25% of bismuth oxyiodide, 18-30% of a film forming substance, 0.1-2% of graphene oxide, 0.1-2% of polyvinylpyrrolidone, 0.1-2% of hydroxypropyl methyl cellulose, 0.5-5% of dodecyl alcohol ester and 5-30% of water; the primer is prepared from the following components in percentage by weight: 10-25% of nano silicon dioxide, 10-35% of hollow glass beads, 20-30% of film forming substances, 0.5-5% of polydimethylsiloxane, 0.5-5% of diisopropanol adipate and 10-30% of water; the film forming matter is at least one of styrene-acrylic emulsion, silicone-acrylic emulsion and pure acrylic emulsion.
In some embodiments, the topcoat is prepared from the following components in percentage by weight: 15-20% of nano titanium dioxide, 15-20% of nano bismuth molybdate, 15-20% of bismuth oxyiodide, 20-25% of a film forming substance, 1.2-1.7% of graphene oxide, 1.2-1.7% of polyvinylpyrrolidone, 1.2-1.7% of hydroxypropyl methyl cellulose, 2.5-3.5% of dodecyl alcohol ester and 15-25% of water; the primer is prepared from the following components in percentage by weight: 13-17% of nano silicon dioxide, 22-28% of hollow glass beads, 23-27% of a film forming substance, 2-3% of polydimethylsiloxane, 2-3% of diisopropanol adipate and 25-30% of water.
In some embodiments, the topcoat is prepared from the following components in percentage by weight: 17% of nano titanium dioxide, 17% of nano bismuth molybdate, 17% of bismuth oxyiodide, 21.5% of a film-forming substance, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of film forming substance, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30% of water.
In some embodiments, the mass ratio of the nano titanium dioxide, the nano bismuth molybdate and the bismuth oxyiodide is 1:0.8-1.2: 0.8-1.2.
In some of these embodiments, the nano-titania and nano-bismuth molybdate each independently have a particle size of 5nm to 30 nm.
In some of these embodiments, the nano-titania has a particle size of 5nm to 8 nm.
In some of these embodiments, the nano bismuth molybdate has a particle size of 25nm to 30 nm.
In some of these embodiments, the bismuth oxyiodide has a particle size of 2 μm to 10 μm.
In some of these embodiments, the bismuth oxyiodide has a particle size of 8 μm to 10 μm.
In some of these embodiments, the film-forming material is a styrene-acrylic emulsion having a solids content of 40-50% and a viscosity of 200 to 2000mPa · s.
In some of these embodiments, the styrene-acrylic emulsion has a solids content of 43-47% and a viscosity of 1800 to 2000 mPas.
In some of these embodiments, the graphene oxide has a sheet diameter of 2um to 20 um.
In some of these embodiments, the graphene oxide has a platelet size of 8um to 12 um.
In some of these embodiments, the polyvinylpyrrolidone has a K value of 15 to 85.
In some of these embodiments, the polyvinylpyrrolidone has a K value of 25 to 35.
In some of these embodiments, the hydroxypropyl methylcellulose has a viscosity of 15 to 25 ten thousand mPa · s.
In some of these embodiments, the nanosilica has a particle size of 1nm to 30 nm.
In some of these embodiments, the nanosilica has a particle size of 15nm to 25 nm.
In some of these embodiments, the hollow glass microspheres have a true density of 0.1g/cc to 0.6 g/cc.
In some of these embodiments, the hollow glass microspheres have a true density of 0.1g/cc to 0.3 g/cc.
In some of these embodiments, the polydimethylsiloxane is Dow Corning DC 184.
The invention also provides a preparation method of the graphene modified photocatalytic water-based paint.
The specific technical scheme is as follows:
the preparation method of the graphene modified photocatalytic water-based paint comprises the following steps:
preparing a finish paint:
(1) mixing and stirring the graphene oxide and polyvinylpyrrolidone to obtain a mixture A;
(2) mixing and stirring the mixture A, the film forming substance and hydroxypropyl methyl cellulose to obtain a mixture B;
(3) mixing and stirring the mixture B with the nano titanium dioxide, the nano bismuth molybdate, the bismuth oxyiodide and the dodecyl alcohol ester to obtain a mixture C;
(4) mixing and stirring the mixture C and water to obtain a finish paint of the graphene modified photocatalytic water-based paint;
preparing a primer:
(1) mixing and stirring the nano silicon dioxide and the hollow glass beads to obtain a mixture D;
(2) mixing and stirring the mixture D and the film-forming substance to obtain a mixture E;
(3) mixing and stirring the mixture E, the polydimethylsiloxane and the diisopropanol adipic acid ester to obtain a mixture F;
(4) and mixing and stirring the mixture F and water to obtain the primer of the graphene modified photocatalytic water-based coating.
In some embodiments, the mixing and stirring in the step (1) are performed at a rotating speed of 500r/min-700r/min for 10min-30 min.
In some embodiments, the mixing and stirring in the step (2) are performed at a rotating speed of 600r/min-700r/min for 10min-20 min.
In some embodiments, the mixing and stirring in the step (3) are performed at a rotating speed of 500r/min-600r/min for 20min-30 min.
In some embodiments, the mixing and stirring in the step (4) is performed at a rotation speed of 550r/min-650r/min for 15min-25 min.
The invention also provides a photocatalytic water-based paint/bionic water lily composite material.
The specific technical scheme is as follows:
the photocatalytic water-based paint/bionic water lily composite material is composed of bionic water lily, a primer layer and a finish paint layer, wherein the primer layer is obtained by uniformly coating primer of graphene modified photocatalytic water-based paint on the surface of the bionic water lily, and the finish paint layer is obtained by uniformly coating finish paint of the graphene modified photocatalytic water-based paint on the surface of the primer layer.
In some embodiments, the bionic water lily is made of polylactic acid foam plastic, and the specific surface area of the bionic water lily is 0.5-20cm2/g。
In some embodiments, the bionic water lily has a specific surface area of 2-3cm2/g。
In some embodiments, the diameter of the bionic water lily is 5cm-500 cm.
In some of these embodiments, the biomimetic water lily has a diameter of 5cm, 10cm, 20cm, 30cm, 50cm or 100 cm.
In some embodiments, the primer of the graphene modified photocatalytic water-based paint is 0.1-10g/cm2The dosage of the bionic water lily is uniformly coated on the surface of the bionic water lily; the finish paint of the graphene modified photocatalytic water-based paint is 0.2-20g/cm2The amount of the primer is uniformly coated on the surface of the primer layer.
In some embodiments, the primer of the graphene-modified photocatalytic water-based paint is 0.2g/cm2-4g/cm2The dosage of the bionic water lily is uniformly coated on the surface of the bionic water lily; the finish paint of the graphene modified photocatalytic water-based paint is 0.3g/cm2-5g/cm2The amount of the primer is uniformly coated on the surface of the primer layer.
In some embodiments, the primer of the graphene-modified photocatalytic water-based paint is 0.2g/cm2-0.4g/cm2The dosage of the bionic water lily is uniformly coated on the surface of the bionic water lily; the finish paint of the graphene modified photocatalytic water-based paint is 0.3g/cm2-0.5g/cm2The amount of the primer is uniformly coated on the surface of the primer layer.
The invention also provides a preparation method of the photocatalytic water-based paint/bionic water lily composite material.
The specific technical scheme is as follows:
the preparation method of the photocatalytic water-based paint/bionic water lily composite material comprises the following steps:
(1) dividing the primer of the graphene modified photocatalytic water-based paint into 1-3 times to be uniformly coated on the surface of the bionic water lily to form a primer layer;
(2) dividing the finish paint of the graphene modified photocatalytic water-based paint into 3-8 times to be uniformly coated on the surface of the primer layer; forming a finish paint layer to obtain the photocatalytic water-based paint/bionic water lily composite material.
In some embodiments, the preparation method of the photocatalytic water-based paint/bionic water lily composite material comprises the following steps:
(1) dividing the primer of the graphene modified photocatalytic water-based paint into 2 times to be uniformly coated on the surface of the bionic water lily to form a primer layer;
(2) dividing the finish paint of the graphene modified photocatalytic water-based paint into 4-5 times, and uniformly coating the finish paint on the surface of the primer layer to form a finish paint layer, thus obtaining the photocatalytic water-based paint/bionic water lily composite material.
In some of these embodiments, the subsequent application requires drying of the previously applied primer or topcoat.
In some of these embodiments, the drying is at a temperature of 45-55 ℃ for a period of 20-45 minutes.
The invention also provides a treatment method of the black and odorous water body.
The specific technical scheme is as follows:
a treatment method of black and odorous water comprises the following steps: and placing the photocatalytic water-based paint/bionic water lily composite material in the black and odorous water body to be treated so as to degrade pollutants in the black and odorous water body.
In some embodiments, the amount of the photocatalytic water-based paint/bionic water lily composite material is 40cm based on the area of the bionic water lily/the volume of the black and odorous water body2/L-150cm2/L。
In some embodiments, the amount of the photocatalytic water-based paint/bionic water lily composite material is 110cm based on the area of the bionic water lily/the volume of the black and odorous water body2/L-140cm2/L。
The invention provides a novel putting mode of a graphene oxide photocatalyst for black and odorous water treatment. Preparing graphene oxide, photocatalytic fillers (nano titanium dioxide, nano bismuth molybdate and bismuth oxyiodide), film forming substances (styrene-acrylic emulsion, silicone-acrylic emulsion and/or pure acrylic emulsion), polyvinylpyrrolidone, hydroxypropyl methyl cellulose and dodecyl alcohol ester into finish paint of the graphene modified photocatalytic water-based coating according to a certain proportion; preparing the primer of the graphene modified photocatalytic water-based coating from nano silicon dioxide, hollow glass beads, a film forming substance (styrene-acrylic emulsion, silicone-acrylic emulsion and/or pure acrylic emulsion), polydimethylsiloxane and diisopropanol adipate according to a certain proportion; the novel photocatalytic water-based paint/bionic water lily composite material can be formed by coating the primer on the bionic water lily and then coating the finish on the formed primer layer, and the composite material is used for treating black and odorous water and has an ideal treatment effect. The method has simple process, and the obtained composite material can be integrated with plants in the water body when being placed in the water body, thereby being very natural and beautiful.
The nano titanium dioxide, nano bismuth molybdate and bismuth oxyiodide catalysts in the finish paint are matched for use, so that the synergistic effect is achieved, the photocatalytic performance of the obtained graphene modified photocatalytic water-based paint and the composite material can be greatly improved, and the degradation effect of pollutants is improved; the graphene oxide can effectively inhibit the recombination probability of photo-generated electrons and photo-generated holes, and can be used together with the catalysts to further enhance the capability of the obtained graphene modified photocatalytic water-based paint and composite material in degrading organic pollutants. Wherein, TiO2The photocatalyst has a good photocatalytic effect, but can only absorb ultraviolet light. The bismuth oxyiodide has a small band gap (1.8eV), a wide light absorption range, a strong absorption capacity in a visible light region, an excellent visible light absorption capacity and an excellent organic matter photocatalytic oxidation degradation capacity, but the bismuth oxyiodide has a narrow forbidden band width, and photo-generated electrons and holes are easily compounded, so that the photocatalytic degradation capacity is reduced; bismuth molybdate has visible light photocatalytic performance, but has the problem that photo-generated electrons and holes are easy to recombine, so that the large-scale application of bismuth molybdate is limited; the p-type semiconductor bismuth oxyiodide and the n-type semiconductor bismuth molybdate are used for forming a bismuth oxyiodide/bismuth molybdate heterostructure, so that the photoproduction electron-hole separation can be effectively improved, and the photocatalysis performance can be improved; the graphene oxide has higher specific surface area and better electron transmission performance, and can be used in combination with the three photocatalysts to further improve the separation degree and photocatalytic performance of photoproduction electrons and holes; according to the invention, the nano titanium dioxide, the nano bismuth molybdate, the bismuth oxyiodide and the graphene oxide are combined, so that the modified photocatalytic aqueous property of the obtained graphene can be greatly improvedThe ability of coatings and composites to degrade organic contaminants. In addition, the non-bonded electrons of nitrogen and oxygen atoms in the long chain of the polyvinylpyrrolidone have strong action with the graphene, are easy to adsorb on two sides of a graphene sheet layer, have strong capability of dispersing graphene oxide, and are well dispersed in water, so that the compatibility between the graphene oxide and other components can be further improved, and the catalytic performance and the mechanical performance of the obtained graphene modified photocatalytic water-based coating are further improved; the problem of adhesion of the catalysts of nano titanium dioxide, nano bismuth molybdate and bismuth oxyiodide and the components of graphene oxide on the bionic water lily primer can be effectively solved by matching the styrene-acrylic emulsion, the dodecanol ester and the hydroxypropyl methyl cellulose, so that the graphene modified photocatalytic water-based paint has good adsorption performance.
In addition, the photocatalyst has a degradation effect on organic matters, so that the photocatalyst also has a destruction effect on the bionic water lily. Therefore, the photocatalytic coating provided by the invention comprises the primer and the finish, wherein the primer is used for connecting the bionic water lily with the finish so as to protect the bionic water lily from being degraded by a photocatalyst in the finish, and the stability of the photocatalytic water-based coating/bionic water lily composite material is improved. The nano silicon dioxide can improve the anti-aging and chemical resistance of the bionic water lily, and is non-toxic, tasteless and pollution-free; the hollow glass beads and the nano silicon dioxide are compounded, so that the protection effect on the bionic water lily substrate is further improved; moreover, the hollow glass beads can also provide buoyancy, so that the reduction of the degradation effect of the photocatalytic water-based paint/bionic water lily composite material on pollutants in a water body due to the fact that the bionic water lily can not contact with sunlight due to gravity sedimentation is avoided; the adhesion problem of each component can be well solved through the matching of the styrene-acrylic emulsion, the polydimethylsiloxane and the diisopropanol adipate, the styrene-acrylic emulsion, the dodecanol ester and the hydroxypropyl methyl cellulose in the finish paint are matched, so that the obtained photocatalytic coating can be well adhered to the surface of the bionic water lily without falling off when being coated on the bionic water lily, the firmness is good, when the obtained photocatalytic water-based coating/bionic water lily composite material is placed in a water body, the coating cannot fall off, the degradation of pollutants in a black and odorous water body can be conveniently realized, the coating is easy to recover, and secondary pollution cannot be generated.
Through the mutual matching of the components, the photocatalytic water-based paint/bionic water lily composite material disclosed by the invention is good in stability, high in paint load, strong in adhesive force of the paint on the bionic water lily, firm and not easy to fall off; meanwhile, the bionic water lily has a larger specific surface area, and the area for receiving sunlight is much larger than other base materials such as aquatic weeds and the like; the composite material has high photocatalytic activity and good effect of purifying and degrading organic pollutants by the cooperation of multiple factors, and can efficiently treat various organic pollutants in black and odorous water. In addition, the graphene modified photocatalytic water-based paint disclosed by the invention is combined with the bionic water lily for sewage treatment, so that the paint attached to the bionic water lily can be moved and reused, the problem of recycling the paint is effectively solved, and the waste and secondary pollution caused by the fact that the paint falls off in a water body are avoided. In addition, the bionic water lily is used as a water plant and placed in water, is natural and attractive, is green and environment-friendly, and can also play a role in beautifying the landscape.
Drawings
FIG. 1 shows an embodiment of a bionic water lily.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The raw materials in the examples and comparative examples of the present invention are illustrated as follows:
the nano titanium dioxide has the particle size of 5nm and is purchased from Germany winning, creating, and solid match, Co.Ltd;
nano bismuth molybdate with the particle size of 30nm, which is purchased from Wuhanxing Zhongcheng science and technology Limited;
bismuth oxyiodide with a particle size of 10 μm, which is purchased from Jiangsu Xiancheng nano material science and technology Limited;
styrene-acrylic emulsion with a solid content of 45% and a viscosity of 2000mPa · s, available from Guangdong Baddofuko, Inc.;
graphene oxide, sheet diameter: 10um, available from Shandong Europlatin New materials, Inc.;
polyvinylpyrrolidone, K value: 30, available from national drug group chemical reagents ltd;
hydroxypropyl methylcellulose with a viscosity of 20 ten thousand mPa · s, available from Fuqiang Fine chemical Co., Ltd, Jinzhou;
dodecyl alcohol ester, available from Runzhong chemical Co., Ltd, Guangzhou;
nanometer silicon dioxide with particle size of 20nm is purchased from Technology of New material science and technology of Zong Tai, Qinghe county;
the hollow glass beads have the real density of 0.125g/cc and are purchased from Shanghai Kaiyn chemical Co., Ltd;
polydimethylsiloxane, dow corning DC184, available from south kyo danpei chemical ltd;
diisopropanol adipate, available from Hubei Xingsheng Hengye science and technology Limited;
the bionic water lily is made of polylactic acid foam plastic, and the specific surface area is 2.4cm2Per g, diameter5cm, purchased from Yiwubai search life department Co., Ltd, Jinhua, Zhejiang province.
The following are specific examples.
Example 1
The graphene modified photocatalytic water-based coating provided by the embodiment comprises a finish and a primer, wherein the finish is prepared from the following components in percentage by weight: 17% of nano titanium dioxide, 17% of nano bismuth molybdate, 17% of bismuth oxyiodide, 21.5% of styrene-acrylic emulsion, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of styrene-acrylic emulsion, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30% of water.
The preparation method of the finish paint comprises the following steps:
(1) mixing and stirring the graphene oxide and the polyvinylpyrrolidone at the rotating speed of 600r/min for 20min to obtain a mixture A;
(2) mixing and stirring the mixture A, the styrene-acrylic emulsion and the hydroxypropyl methyl cellulose for 15min at the rotating speed of 650r/min to obtain a mixture B;
(3) mixing and stirring the mixture B, the nano titanium dioxide, the nano bismuth molybdate, the bismuth oxyiodide and the dodecyl alcohol ester at the rotating speed of 550r/min for 25min to obtain a mixture C;
(4) and mixing and stirring the mixture C and water at the rotating speed of 600r/min for 20min to obtain the finish paint of the graphene modified photocatalytic water-based coating.
The preparation method of the primer comprises the following steps:
(1) mixing and stirring the nano silicon dioxide and the hollow glass beads for 20min at the rotating speed of 600r/min to obtain a mixture D;
(2) mixing and stirring the mixture D and the styrene-acrylic emulsion for 15min at the rotating speed of 650r/min to obtain a mixture E;
(3) mixing and stirring the mixture E, polydimethylsiloxane and diisopropanol adipate for 20min at the rotating speed of 600r/min to obtain a mixture F;
(4) and mixing and stirring the mixture F and water at the rotating speed of 650r/min for 15min, and adjusting the viscosity of the coating to obtain the primer of the graphene modified photocatalytic water-based coating.
Example 2
The graphene modified photocatalytic water-based coating provided by the embodiment comprises a finish and a primer, wherein the finish is prepared from the following components in percentage by weight: 10% of nano titanium dioxide, 10% of nano bismuth molybdate, 10% of bismuth oxyiodide, 30% of styrene-acrylic emulsion, 2% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 5% of dodecyl alcohol ester and 30% of water; the primer is prepared from the following components in percentage by weight: 25% of nano silicon dioxide, 35% of hollow glass beads, 20% of styrene-acrylic emulsion, 5% of polydimethylsiloxane, 5% of diisopropanol adipate and 10% of water.
The preparation method is the same as example 1.
Example 3
The graphene modified photocatalytic water-based coating provided by the embodiment comprises a finish and a primer, wherein the finish is prepared from the following components in percentage by weight: 24.8% of nano titanium dioxide, 24.8% of nano bismuth molybdate, 24.6% of bismuth oxyiodide, 20% of styrene-acrylic emulsion, 0.1% of graphene oxide, 0.1% of polyvinylpyrrolidone, 0.1% of hydroxypropyl methylcellulose, 0.5% of dodecyl alcohol ester and 5% of water; the primer is prepared from the following components in percentage by weight: 10% of nano silicon dioxide, 10% of hollow glass beads, 30% of styrene-acrylic emulsion, 0.5% of polydimethylsiloxane, 0.5% of diisopropanol adipate and 49% of water.
The preparation method is the same as example 1.
Example 4
The graphene modified photocatalytic water-based coating provided by the embodiment comprises a finish and a primer, wherein the finish is prepared from the following components in percentage by weight: 10% of nano titanium dioxide, 16% of nano bismuth molybdate, 25% of bismuth oxyiodide, 21.5% of styrene-acrylic emulsion, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of styrene-acrylic emulsion, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30% of water.
The preparation method is the same as example 1.
Example 5
The graphene modified photocatalytic water-based coating provided by the embodiment comprises a finish and a primer, wherein the finish is prepared from the following components in percentage by weight: 25% of nano titanium dioxide, 13% of nano bismuth molybdate, 13% of bismuth oxyiodide, 21.5% of styrene-acrylic emulsion, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of styrene-acrylic emulsion, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30% of water.
The preparation method is the same as example 1.
Comparative example 1
The graphene modified photocatalytic water-based paint provided by the comparative example consists of a finish paint and a primer, wherein the finish paint is prepared from the following components in percentage by weight: 51% of nano titanium dioxide, 21.5% of styrene-acrylic emulsion, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of styrene-acrylic emulsion, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30% of water.
The preparation method is the same as example 1.
Comparative example 2
The graphene modified photocatalytic water-based paint provided by the comparative example consists of a finish paint and a primer, wherein the finish paint is prepared from the following components in percentage by weight: 25% of nano titanium dioxide, 26% of nano bismuth molybdate, 21.5% of styrene-acrylic emulsion, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of styrene-acrylic emulsion, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30% of water.
The preparation method is the same as example 1.
Comparative example 3
The graphene modified photocatalytic water-based paint provided by the comparative example consists of a finish paint and a primer, wherein the finish paint is prepared from the following components in percentage by weight: 25% of nano titanium dioxide, 26% of bismuth oxyiodide, 21.5% of styrene-acrylic emulsion, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of styrene-acrylic emulsion, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30% of water.
Comparative example 4
The graphene modified photocatalytic water-based paint provided by the comparative example consists of a finish paint and a primer, wherein the finish paint is prepared from the following components in percentage by weight: 17% of nano titanium dioxide, 17% of nano bismuth molybdate, 17% of bismuth oxyiodide, 21.5% of styrene-acrylic emulsion, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 21.5% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of styrene-acrylic emulsion, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30.3% of water.
The preparation method is the same as example 1.
Comparative example 5
The graphene modified photocatalytic water-based paint provided by the comparative example consists of a finish paint and a primer, wherein the finish paint is prepared from the following components in percentage by weight: 17% of nano titanium dioxide, 17% of nano bismuth molybdate, 17% of bismuth oxyiodide, 21.5% of styrene-acrylic emulsion, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water; the primer is prepared from the following components in percentage by weight: 40% of nano silicon dioxide, 25% of styrene-acrylic emulsion, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30% of water.
The preparation method is the same as example 1.
Comparative example 6
The graphene modified photocatalytic water-based paint provided by the comparative example consists of a finish paint and a primer, wherein the finish paint is prepared from the following components in percentage by weight: 17% of nano titanium dioxide, 17% of nano bismuth molybdate, 17% of bismuth oxyiodide, 21.5% of styrene-acrylic emulsion, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose and 23% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of styrene-acrylic emulsion, 2.5% of polydimethylsiloxane and 32.5% of water.
Comparative example 7
The graphene modified photocatalytic water-based coating provided by the comparative example only consists of a finish, and the finish is prepared from the following components in percentage by weight: 17% of nano titanium dioxide, 17% of nano bismuth molybdate, 17% of bismuth oxyiodide, 21.5% of styrene-acrylic emulsion, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water.
Example 6
The graphene modified photocatalytic water-based paint prepared in examples 1-5 and comparative examples 1-6 is combined with the bionic water lily to prepare a photocatalytic water-based paint/bionic water lily composite material (respectively marked as composite materials 1-5 and comparative materials 1-6), and the preparation method is as follows:
(1) dividing 4g of the primer of the graphene modified photocatalytic water-based paint into 2 times to be uniformly coated on 12.6cm2After the 1 st coating, drying the coated primer, then coating the primer for the 2 nd time, and drying to form a primer layer; the temperature for each drying was 50 ℃ for 30 minutes.
(2) Dividing 4g of finish paint of the graphene modified photocatalytic water-based paint into 5 times to be uniformly coated on the surface of the primer layer formed in the step (1), drying the finish paint coated at the previous time and then performing the subsequent coating, and naturally airing at room temperature for 48 hours to form a finish paint layer, thus obtaining the photocatalytic water-based paint/bionic water lily composite material; the temperature for each drying was 55 ℃ for 20 minutes.
The graphene modified photocatalytic water-based paint prepared in the comparative example 7 is combined with the bionic water lily to prepare the photocatalytic water-based paint/bionic water lily composite material (marked as the comparative material 7), and the preparation method comprises the following steps:
dividing 4g of finish paint of the graphene modified photocatalytic water-based paint into 5 times to be uniformly coated on 12.6cm2The surface of the bionic water lily is coated for the next time, the finish paint coated for the previous time is dried and then is naturally dried for 48 hours at room temperature to form a finish paint layer, and the photocatalytic water paint/bionic water lily composite material is obtained; the temperature for each drying was 55 ℃ for 20 minutes.
Example 7
In the embodiment, the photocatalytic water-based paint/bionic water lily composite material prepared in the embodiment 6 is used for treating black and odorous water.
The polluted bottom mud used in the experiment is collected on a downstream riverbed of a polluted water body in the Guangzhou Zhujiang river basin. 2000g of collected bottom mud is surface layer bottom mud in a downstream riverbed, the depth is 0-20cm of riverbed sampling depth, and the collected bottom mud is placed in a plastic barrel, shielded from light and dark and sealed for storage.
Pretreating the sample bottom mud: a100 mL beaker is used as a reaction device to simulate the photocatalysis process of static water. The experimental operation steps for sub-packaging the bottom mud are as follows:
the method comprises the following steps of picking out impurities in the bottom mud such as solid matters such as waterweeds, stones, garbage and the like, firstly weighing 500g of bottom mud samples, uniformly mixing in a 1000mL beaker, and then injecting deionized water as overlying water until the volume of the bottom mud and the water is 1000 mL.
Taking 12 parts of 10mL black and odorous water from a 1000mL beaker filled with bottom mud and water, respectively filling the black and odorous water into a 100mL beaker, and then injecting deionized water into the beaker to 100mL to serve as black and odorous water for experiments, wherein the number of the black and odorous water is 1-12 #. Taking the product prepared in example 612.6cm of each photocatalytic water-based paint/bionic water lily composite material2And (3) putting the material into 100ml of black and odorous water body for degradation experiment, wherein the degradation experiment is carried out for 12 hours, and the light source is a long-arc xenon lamp light source (Guangzhou star Chuang electronic Co., Ltd.) with the power of 400 w.
Analyzing and measuring related indexes: ammonia nitrogen (Nashin reagent photometry), oxidation-reduction potential (electrode method) and dissolved oxygen (electrochemical method) are detected according to the urban black and odorous water body treatment working guideline (No. 2015 130) issued by the urban and rural construction department of housing and environmental protection department. The degradation test results are shown in table 1:
TABLE 1
Figure BDA0003266353380000151
Figure BDA0003266353380000161
As can be seen from the data in Table 1: the photocatalytic water-based paint/bionic water lily composite material prepared by the invention has good effect of treating black and odorous water, can effectively reduce the ammonia nitrogen value in the water, and improves the dissolved oxygen content and the oxidation-reduction potential. The photocatalytic water-based paint/bionic water lily composite material prepared in the embodiment 1 has the best effect due to proper mixture ratio of the raw materials.
Comparative example 1 compared to example 1, the photocatalyst had only nano-titania; comparative example 2 compared to example 1, the photocatalyst had only nano titanium dioxide and nano bismuth molybdate, no bismuth oxyiodide was added; comparative example 3 compared to example 1, the photocatalyst had only nano titanium dioxide and bismuth oxyiodide, and no nano bismuth molybdate was added; the photocatalytic water-based paint/bionic water lily composite material prepared in the comparative examples 1-3 has a far worse effect on treatment of black and odorous water than that of the example 1, so that the nano titanium dioxide, the nano bismuth molybdate and the bismuth oxyiodide have a synergistic effect when being used as a photocatalyst in a compounding way, and the degradation effect on pollutants is far better than that of one or two effects when the nano titanium dioxide, the nano bismuth molybdate and the bismuth oxyiodide act together.
Compared with the example 1, in the comparative example 4, no graphene oxide is added, so that the photo-generated electrons and photo-generated holes are easily compounded, and therefore, the capacity (the effect of treating black and odorous water) of the photocatalytic water-based paint/bionic water lily composite material prepared in the comparative example 4 for degrading organic pollutants is poorer than that of the example 1.
Compared with the example 1, the comparative example 5 is not added with the hollow glass microspheres, and the prepared photocatalytic water-based paint/bionic water lily composite material is easy to sink to the water bottom, so that the irradiation of a light source is reduced, the photocatalytic activity of the material is reduced, and the pollutant degradation effect is reduced, so that the capacity of degrading organic pollutants (the black and odorous water treatment effect) of the photocatalytic water-based paint/bionic water lily composite material prepared in the comparative example 5 is poorer than that of the example 1.
Compared with the example 1, in the comparative example 6, the film-forming aids of dodecanol ester and diisopropanol adipate are not added, so that the adhesiveness of the primer and the finish on the bionic water lily is poor, part of the primer and the finish fall off in a water body, the dispersibility is poor, and even the primer and the finish sink to the water bottom, so that the photocatalyst in the finish is influenced to be irradiated by a light source, the photocatalytic activity of the photocatalyst is reduced, and the pollutant degradation effect is reduced, therefore, the capacity (the black and odorous water body treatment effect) of the photocatalytic water-based paint/bionic water lily composite material prepared in the comparative example 6 for degrading organic pollutants is poorer than that of the example 1.
The comparative example 7 only contains finish paint, and after the finish paint is combined with the bionic water lily, the oxidation effect of the photocatalyst can destroy the bionic water lily substrate to a certain extent, so that the capacity (the effect of treating black and odorous water bodies) of the photocatalytic water-based paint/bionic water lily composite material prepared in the comparative example 7 for degrading organic pollutants is poorer than that of the example 1.
In addition, the photocatalytic water-based paint/bionic water lily composite materials prepared in examples 1-5 and comparative examples 1-7 are dried and weighed after degradation experiments, and compared with the weight before the experiments, the weight difference before and after the experiments is calculated. The results show that the weight difference of the photocatalytic water-based paint/bionic water lily composite materials prepared in examples 1-5 and comparative examples 1-5 before and after the degradation experiment is not more than 0.2g, and the error is within 5%. The weight difference of the photocatalytic water-based paint/bionic water lily composite material prepared in the comparative example 6 before and after the degradation experiment is 1.5g, and the error range is large, which further indicates that the adhesion of the paint on the bionic water lily in the photocatalytic water-based paint/bionic water lily composite material prepared in the comparative example 6 is poor, and the paint can fall off in a water body. The weight difference of the photocatalytic water-based paint/bionic water lily composite material prepared in the comparative example 7 before and after the degradation experiment is 1.3g, and the error is large, which is probably because the comparative example 7 only has finish paint, the oxidation effect of the photocatalyst can destroy the bionic water lily substrate to a certain extent, so that the paint can fall off to a certain extent, and the weight of the composite material is reduced.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The graphene modified photocatalytic water-based paint is characterized by comprising a finish paint and a primer, wherein the finish paint is prepared from the following components in percentage by weight: 10-25% of nano titanium dioxide, 10-25% of nano bismuth molybdate, 10-25% of bismuth oxyiodide, 18-30% of a film forming substance, 0.1-2% of graphene oxide, 0.1-2% of polyvinylpyrrolidone, 0.1-2% of hydroxypropyl methyl cellulose, 0.5-5% of dodecyl alcohol ester and 5-30% of water; the primer is prepared from the following components in percentage by weight: 10-25% of nano silicon dioxide, 10-35% of hollow glass beads, 20-30% of film forming substances, 0.5-5% of polydimethylsiloxane, 0.5-5% of diisopropanol adipate and 10-50% of water; the film forming matter is at least one of styrene-acrylic emulsion, silicone-acrylic emulsion and pure acrylic emulsion.
2. The graphene-modified photocatalytic water-based paint according to claim 1, wherein the finish paint is prepared from the following components in percentage by weight: 15-20% of nano titanium dioxide, 15-20% of nano bismuth molybdate, 15-20% of bismuth oxyiodide, 20-25% of a film forming substance, 1.2-1.7% of graphene oxide, 1.2-1.7% of polyvinylpyrrolidone, 1.2-1.7% of hydroxypropyl methyl cellulose, 2.5-3.5% of dodecyl alcohol ester and 15-25% of water; the primer is prepared from the following components in percentage by weight: 13-17% of nano silicon dioxide, 22-28% of hollow glass beads, 23-27% of a film forming substance, 2-3% of polydimethylsiloxane, 2-3% of diisopropanol adipate and 25-35% of water;
preferably, the finishing paint is prepared from the following components in percentage by weight: 17% of nano titanium dioxide, 17% of nano bismuth molybdate, 17% of bismuth oxyiodide, 21.5% of a film-forming substance, 1.5% of graphene oxide, 1.5% of polyvinylpyrrolidone, 1.5% of hydroxypropyl methyl cellulose, 3% of dodecyl alcohol ester and 20% of water; the primer is prepared from the following components in percentage by weight: 15% of nano silicon dioxide, 25% of hollow glass beads, 25% of film forming substance, 2.5% of polydimethylsiloxane, 2.5% of diisopropanol adipate and 30% of water;
preferably, the mass ratio of the nano titanium dioxide to the nano bismuth molybdate to the nano bismuth oxyiodide is 1:0.8-1.2: 0.8-1.2.
3. The graphene-modified photocatalytic water-based paint as claimed in claim 1 or 2, wherein the nano titanium dioxide and the nano bismuth molybdate have a particle size of 5nm to 30nm respectively and independently; and/or the presence of a gas in the gas,
the particle size of the bismuth oxyiodide is 2-10 μm; and/or the presence of a gas in the gas,
the film forming material is styrene-acrylic emulsion, the solid content of the film forming material is 40-50%, and the viscosity of the film forming material is 200-2000 mPa & s; and/or the presence of a gas in the gas,
the sheet diameter of the graphene oxide is 2-20 um; and/or the presence of a gas in the gas,
the K value of the polyvinylpyrrolidone is 15-85; and/or the presence of a gas in the gas,
the viscosity of the hydroxypropyl methyl cellulose is 15-25 ten thousand mPa.s; and/or the presence of a gas in the gas,
the particle size of the nano silicon dioxide is 1nm-30 nm; and/or the presence of a gas in the gas,
the true density of the hollow glass beads is 0.1g/cc-0.6 g/cc; and/or the presence of a gas in the gas,
the polydimethylsiloxane is Dow Corning DC 184.
4. The preparation method of the graphene modified photocatalytic water-based paint according to any one of claims 1 to 3, characterized by comprising the following steps:
preparing a finish paint:
(1) mixing and stirring the graphene oxide and polyvinylpyrrolidone to obtain a mixture A;
(2) mixing and stirring the mixture A, the film forming substance and hydroxypropyl methyl cellulose to obtain a mixture B;
(3) mixing and stirring the mixture B with the nano titanium dioxide, the nano bismuth molybdate, the bismuth oxyiodide and the dodecyl alcohol ester to obtain a mixture C;
(4) mixing and stirring the mixture C and water to obtain a finish paint of the graphene modified photocatalytic water-based paint;
preparing a primer:
(1) mixing and stirring the nano silicon dioxide and the hollow glass beads to obtain a mixture D;
(2) mixing and stirring the mixture D and the film-forming substance to obtain a mixture E;
(3) mixing and stirring the mixture E, the polydimethylsiloxane and the diisopropanol adipic acid ester to obtain a mixture F;
(4) and mixing and stirring the mixture F and water to obtain the primer of the graphene modified photocatalytic water-based coating.
5. The photocatalytic water-based paint/bionic water lily composite material is characterized by comprising bionic water lily, a primer layer and a finish paint layer, wherein the primer layer is obtained by uniformly coating the primer of the graphene modified photocatalytic water-based paint according to any one of claims 1 to 3 on the surface of the bionic water lily, and the finish paint layer is obtained by uniformly coating the finish paint of the graphene modified photocatalytic water-based paint according to any one of claims 1 to 3 on the surface of the primer layer.
6. The photocatalytic water-based paint/bionic water lily composite material as claimed in claim 5, wherein the bionic water lily is made of polylactic acid foam plastic, and the specific surface area of the material is 0.5-20cm2(ii)/g; and/or the presence of a gas in the gas,
the diameter of the bionic water lily is 5cm-500 cm.
7. The photocatalytic water-based paint/bionic water lily composite material as claimed in claim 5 or 6, wherein the primer of the graphene modified photocatalytic water-based paint is 0.1g/cm2-10g/cm2The dosage of the bionic water lily is uniformly coated on the surface of the bionic water lily; the finish paint of the graphene modified photocatalytic water-based paint is 0.2g/cm2-20g/cm2The dosage of the primer layer is uniformly coated on the surface of the primer layer;
preferably, the primer of the graphene modified photocatalytic water-based paint is 0.2g/cm2-0.4g/cm2The dosage of the bionic water lily is uniformly coated on the surface of the bionic water lily; the finish paint of the graphene modified photocatalytic water-based paint is 0.3g/cm2-0.5g/cm2The amount of the primer is uniformly coated on the surface of the primer layer.
8. The preparation method of the photocatalytic water-based paint/bionic water lily composite material as claimed in any one of claims 5 to 7 is characterized by comprising the following steps:
(1) dividing the primer of the graphene modified photocatalytic water-based paint into 1-3 times to be uniformly coated on the surface of the bionic water lily to form a primer layer;
(2) dividing the finish paint of the graphene modified photocatalytic water-based paint into 3-8 times, and uniformly coating the finish paint on the surface of the primer layer to form a finish paint layer, thus obtaining the photocatalytic water-based paint/bionic water lily composite material.
9. The preparation method of the photocatalytic water-based paint/bionic water lily composite material as claimed in claim 8, is characterized by comprising the following steps:
(1) dividing the primer of the graphene modified photocatalytic water-based paint into 2 times to be uniformly coated on the surface of the bionic water lily to form a primer layer;
(2) dividing the finish paint of the graphene modified photocatalytic water-based paint into 4-5 times to be uniformly coated on the surface of the primer layer; forming a finish paint layer to obtain the photocatalytic water-based paint/bionic water lily composite material;
preferably, the latter coating is carried out after the primer or the top coat which is coated in the former coating is dried;
preferably, the drying temperature is 45-55 ℃ and the drying time is 20-45 minutes.
10. A treatment method of black and odorous water is characterized by comprising the following steps: placing the photocatalytic water-based paint/bionic water lily composite material of any one of claims 5-7 in a black and odorous water body to be treated so as to degrade pollutants in the black and odorous water body; preferably, the dosage of the photocatalytic water-based paint/bionic water lily composite material is 40cm based on the area of the bionic water lily/the volume of the black and odorous water body2/L-150cm2/L。
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