CN107469866B - Three-dimensional photocatalytic composite system and preparation method and application thereof - Google Patents
Three-dimensional photocatalytic composite system and preparation method and application thereof Download PDFInfo
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- CN107469866B CN107469866B CN201710740068.7A CN201710740068A CN107469866B CN 107469866 B CN107469866 B CN 107469866B CN 201710740068 A CN201710740068 A CN 201710740068A CN 107469866 B CN107469866 B CN 107469866B
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- 244000025254 Cannabis sativa Species 0.000 claims abstract description 87
- 239000002245 particle Substances 0.000 claims abstract description 30
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 61
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- 239000004202 carbamide Substances 0.000 claims description 6
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- 238000007865 diluting Methods 0.000 claims description 3
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- 230000008859 change Effects 0.000 description 5
- ZFUASHFORHAKBU-UHFFFAOYSA-N oxygen(2-) titanium(4+) trioxotungsten Chemical compound [W](=O)(=O)=O.[O-2].[O-2].[Ti+4] ZFUASHFORHAKBU-UHFFFAOYSA-N 0.000 description 5
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- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical class ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
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- HCXVRWNMKLEOKO-UHFFFAOYSA-N 2-benzofuran-1,3-dione;urea Chemical compound NC(N)=O.C1=CC=C2C(=O)OC(=O)C2=C1 HCXVRWNMKLEOKO-UHFFFAOYSA-N 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B01J35/19—
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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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- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a three-dimensional photocatalytic composite system, which comprises photocatalytic artificial grass and a photocatalytic fiber material compounded at the root of the photocatalytic artificial grass. The photocatalytic artificial grass and photocatalytic fiber material is prepared by coating photocatalytic coating on the surfaces of artificial grass and fiber materials, wherein the photocatalytic coating comprises a catalyst and sol, and the sol and the photocatalyst can form a self-assembled three-dimensional stacked structure on the surface of a base material, so that the contact area of organic pollutants and the photocatalyst can be increased, and the utilization efficiency of the photocatalyst is improved; and the addition of the sol enables an isolation layer to be formed between the photocatalyst and the base material, so that the phenomenon that the photocatalyst corrodes the base material is avoided, the acting force between the photocatalyst and the base material can be enhanced, and photocatalyst particles are not easy to fall off.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a three-dimensional photocatalysis composite system and a preparation method and application thereof.
Background
With the rapid development of modern science and technology, the contradiction between human and nature is increasingly sharp. The water resource is an essential part in life activities and daily life of people, but a large amount of emerging and artificial pollutants exist to cause serious pollution of the water resource, and the micro-pollutants which are difficult to biodegrade exist in water, so that the balance of ecological environment is destroyed, and the body health of people is seriously influenced.
The photocatalysis is a green, environment-friendly and environment-friendly method for removing organic pollutants, has good chemical stability and thermal stability, is nontoxic in the catalysis process, is environment-friendly, and has been widely concerned by people. The application of the photocatalytic technology to water environment treatment has been precedent, for example, the photocatalyst is loaded on the surfaces of some plastic carriers, and then the carriers are laid in water, but the method is not widely applied, mainly because the plastic carriers are high molecular materials, the photocatalyst attached to the surfaces can oxidize the carriers while oxidizing organic pollutants, so that the matrix materials are damaged, the color change and the deformation are easy, and the photocatalyst particles are easy to fall off, so that the photocatalytic effect is poor.
Disclosure of Invention
In view of the above, the present invention aims to provide a three-dimensional photocatalytic composite system, and a preparation method and an application thereof. The three-dimensional photocatalytic composite system provided by the invention has a good photocatalytic effect, catalyst particles are not easy to fall off, and the material of the matrix cannot be damaged in the photocatalytic process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a three-dimensional photocatalytic composite system, which comprises photocatalytic artificial grass and a photocatalytic fiber material compounded at the root of the artificial grass;
the photocatalytic artificial grass is prepared by coating photocatalytic coating on the surface of artificial grass;
the photocatalytic fiber material is prepared by coating a photocatalytic coating on the surface of a fiber material or is obtained by padding the fiber material in the photocatalytic coating;
the photocatalytic coating comprises a photocatalyst, sol and a solvent or comprises a photocatalyst dispersion liquid and a sol solution which are separately packaged;
the photocatalyst is one or a mixture of more of titanium dioxide, a titanium dioxide-graphene compound, a titanium dioxide-graphite-like phase carbon nitride-metal phthalocyanine compound, a titanium dioxide-tungsten trioxide compound, a graphite-like phase carbon nitride-metal phthalocyanine compound, a metal phthalocyanine-tungsten trioxide compound, a titanium dioxide-graphite-like phase carbon nitride-tungsten trioxide compound and a titanium dioxide-metal phthalocyanine-tungsten trioxide compound;
the sol is silica sol and/or aluminum sol.
Preferably, the pH value of the sol is 3-11;
the concentration of the sol is 2-50 wt%;
the particle size of the sol is 1-100 nm.
Preferably, the sol further comprises graphene; the mass content of graphene in the sol is 0.1-2% of the mass of the photocatalyst.
Preferably, when the photocatalytic coating comprises a photocatalyst, a sol and a solvent, the volume ratio of the mass of the photocatalyst to the volume of the solvent in the photocatalytic coating is 1-30 g: 1L, and the volume ratio of the mass of the sol to the volume of the solvent in the photocatalytic coating is 0.1-15 g: 1L;
preferably, when the photocatalytic coating comprises a photocatalyst dispersion liquid and a sol solution which are separately filled, the volume ratio of the mass of the photocatalyst to the volume of the solvent in the photocatalyst dispersion liquid is 1-30 g: 1L, and the volume ratio of the mass of the sol to the volume of the solvent in the sol solution is 0.1-15 g: 1L.
Preferably, the dry film loading capacity of the photocatalyst on the surface of the simulated grass is 0.1-12 g/m2；
The dry film loading capacity of the photocatalyst on the surface of the fiber material is 0.1-12 g/m2。
Preferably, the artificial grass is made of one or a mixture of polyethylene, polyester, polypropylene, polyvinyl chloride, polyamide, ethylene-vinyl acetate copolymer, polyacrylonitrile, polyurethane and cellulose;
the fiber material is made of one or a mixture of more of polyester, polyethylene, polyvinyl chloride, polypropylene, polyacrylonitrile, polyamide, polyurethane and cellulose.
The invention provides a preparation method of the three-dimensional photocatalytic composite system in the scheme, which comprises the following steps:
(1) when the photocatalytic coating comprises a photocatalyst, sol and a solvent, spraying the photocatalytic coating on the surface of the simulated grass to obtain the simulated grass coated with a wet film of the photocatalytic coating;
or when the photocatalytic coating comprises a photocatalyst dispersion liquid and a sol solution which are separately packaged, respectively spraying the photocatalytic dispersion liquid and the sol solution on the surface of the simulated grass to obtain the simulated grass coated with the wet film of the photocatalytic coating;
drying the simulated grass coated with the wet film of the photocatalytic coating to obtain photocatalytic simulated grass;
(2) when the photocatalytic coating comprises a photocatalyst, sol and a solvent, spraying the photocatalytic coating on the surface of the fiber material to obtain the fiber material coated with a wet film of the photocatalytic coating;
or when the photocatalyst dispersion liquid and the sol solution are separately packaged, respectively spraying the photocatalyst dispersion liquid and the sol solution on the surface of the fiber material to obtain the fiber material coated with a photocatalytic coating wet film;
or, when the photocatalytic coating comprises a photocatalyst, sol and a solvent, padding the composite fiber material in the photocatalytic coating to obtain the fiber material coated with the wet film of the photocatalytic coating;
or when the photocatalytic coating comprises a photocatalyst dispersion liquid and a sol solution which are separately packaged, padding the fiber material in the photocatalyst dispersion liquid and the sol solution respectively to obtain the fiber material coated with a wet film of the photocatalytic coating;
drying the fiber material coated with the wet photocatalytic coating film to obtain a photocatalytic fiber material;
(3) carrying out thermal bonding compounding on the photocatalytic simulation grass and the photocatalytic fiber material to obtain a three-dimensional photocatalytic composite system;
the step (1) and the step (2) have no time sequence limitation.
Preferably, the thermal bonding compounding is point-shaped pressure thermal compounding; the temperature of the punctiform pressurizing heat compounding is 80-200 ℃; the pressure of the punctiform pressurizing heat compounding is 1.5-10 MPa.
The invention provides an application of the three-dimensional photocatalytic composite system or the three-dimensional photocatalytic composite system prepared by the preparation method in the scheme in photocatalysis.
The invention provides a three-dimensional photocatalytic composite system, which comprises photocatalytic artificial grass and a photocatalytic fiber material compounded at the root of the photocatalytic artificial grass. The photocatalytic artificial grass and photocatalytic fiber material is prepared by coating photocatalytic coating on the surfaces of the artificial grass and the fiber material,the photocatalytic coating comprises a catalyst and sol, wherein hydroxyl (-OH) exists on the surfaces of the catalyst and the sol, and a water molecule (H) is removed from the two substances in the contact process2O), forming a new chemical bond, spraying the coating on the surface of the simulated grass and fiber material, wherein the sol and the photocatalyst can form a self-assembled three-dimensional stacked structure on the surface of the substrate, and the contact area of the organic pollutant and the photocatalyst can be increased, so that the utilization efficiency of the photocatalyst is improved; and the addition of the sol enables an isolation layer to be formed between the photocatalyst and the base material, so that the phenomenon that the photocatalyst corrodes the base material is avoided, the acting force between the photocatalyst and the base material can be enhanced, and photocatalyst particles are not easy to fall off. The embodiment results show that the removal rate of the three-dimensional photocatalytic composite system provided by the invention to methylene blue can reach 99%, and the photocatalytic activity of the three-dimensional photocatalytic composite system subjected to a cyclic test after being washed has no obvious change, which indicates that the binding force between the photocatalyst and a base material is strong and the photocatalyst is not easy to fall off; and the material of the composite system can not be corroded in the photocatalysis process.
Drawings
FIG. 1 is a front view of a three-dimensional photocatalytic composite system prepared in an example of the present invention;
FIG. 2 is a side view of a three-dimensional photocatalytic composite system prepared in accordance with an embodiment of the present invention;
FIG. 3 shows the results of the photocatalytic degradation test in example 1 of the present invention;
FIG. 4 is a surface observation result of the polyester fiber mat in example 7 of the present invention.
Detailed Description
The invention provides a three-dimensional photocatalytic composite system, which comprises photocatalytic artificial grass and a photocatalytic fiber material compounded at the root of the artificial grass;
the photocatalytic artificial grass is prepared by coating photocatalytic coating on the surface of artificial grass;
the photocatalytic fiber material is prepared by coating a photocatalytic coating on the surface of a fiber material or is obtained by padding the fiber material in the photocatalytic coating;
the photocatalytic coating comprises a photocatalyst, sol and a solvent or comprises a photocatalyst dispersion liquid and a sol solution which are separately packaged;
the photocatalyst is one or a mixture of more of titanium dioxide, a titanium dioxide-graphene compound, a titanium dioxide-graphite-like phase carbon nitride-metal phthalocyanine compound, a titanium dioxide-tungsten trioxide compound, a graphite-like phase carbon nitride-metal phthalocyanine compound, a metal phthalocyanine-tungsten trioxide compound, a titanium dioxide-graphite-like phase carbon nitride-tungsten trioxide compound and a titanium dioxide-metal phthalocyanine-tungsten trioxide compound;
the sol is silica sol and/or aluminum sol.
In the present invention, when the photocatalyst comprises titanium dioxide; the titanium dioxide is preferably anatase crystal type titanium dioxide or mixed crystal type titanium dioxide; the particle size of the titanium dioxide is preferably 5-800 nm, more preferably 15-600 nm, and most preferably 50-500 nm; the source of the titanium dioxide is not particularly limited in the present invention, and titanium dioxide of a source well known to those skilled in the art, such as commercially available titanium dioxide, may be used.
In the present invention, when the photocatalyst includes a titanium dioxide-graphene composite, the mass ratio of titanium dioxide to graphene in the titanium dioxide-graphene composite is preferably 100: 0.1 to 2, more preferably 100: 0.2 to 1; the present invention has no particular requirement on the source of the titanium dioxide-graphene composite, and may be prepared using commercially available products or using methods well known to those skilled in the art. In a specific embodiment of the present invention, the titanium dioxide-graphene composite is preferably formed by directly mixing titanium dioxide and graphene; the invention has no special requirement on the type of the graphene, and preferably single-layer graphene, multi-layer graphene or a mixture of the single-layer graphene and the multi-layer graphene; the thickness of the multilayer graphene is preferably 0.3-50 nm, and more preferably 5-40 nm.
In the present invention, when the photocatalyst includes a titanium dioxide-graphite-like phase carbon nitride composite; the mass ratio of titanium dioxide to graphite-like phase carbon nitride in the titanium dioxide-graphite-like phase carbon nitride composite is preferably 100: 2-100, more preferably 100: 5-25; the invention has no special requirement on the source of the titanium dioxide-graphite-like phase carbon nitride compound, and can be prepared by using commercially available titanium dioxide-graphite-like phase carbon nitride compound products or by using a method well known to the technical personnel in the field; in particular embodiments of the present invention, the titanium dioxide and graphite-like phase carbon nitride are preferably directly mixed to provide a titanium dioxide-graphite-like phase carbon nitride composite.
The invention aims at the graphite-like phase carbon nitride (g-C)3N4) The type of (b) is not particularly required, and is preferably a single-layer graphite-like phase carbon nitride and/or a multilayer graphite-like phase carbon nitride; the thickness of the graphite-like phase carbon nitride is preferably 0.3-50 nm, and more preferably 5-40 nm; the source of the graphite-like phase carbon nitride is not particularly limited in the present invention, and the graphite-like phase carbon nitride can be produced using commercially available graphite-like phase carbon nitride products or by methods known to those skilled in the art.
In a specific embodiment of the invention, the graphite-like phase carbon nitride (g-C)3N4) The preparation method of (a) preferably comprises the steps of: and carrying out heat treatment on the urea to obtain the graphite-like phase carbon nitride. In the invention, the temperature of the heat treatment is preferably 300-650 ℃, more preferably 350-600 ℃, and most preferably 500-550 ℃; the time of the heat treatment is preferably 3-8 h, more preferably 4-7 h, and most preferably 5-6 h. According to the invention, the temperature is preferably raised from room temperature to the heat treatment temperature, and the heating rate of raising the temperature to the heat treatment temperature is preferably 1-6 ℃/min, and more preferably 2-4 ℃/min. The invention preferably carries out heat treatment under air atmosphere and normal pressure; the apparatus used for the heat treatment in the present invention is not particularly limited, and any apparatus known to those skilled in the art for performing heat treatment, such as a tube furnace or a box furnace, may be used.
In the present invention, when the photocatalyst includes a titanium dioxide-graphite-like phase carbon nitride-metal phthalocyanine complex; the mass ratio of titanium dioxide to graphite-like carbon nitride to metal phthalocyanine in the titanium dioxide-graphite-like carbon nitride-metal phthalocyanine compound is preferably 45-74: 25-50: 0.5-6, more preferably 55-65: 30-40: 1-4; the present invention does not require a particular source of the titanium dioxide-graphite-like phase carbonitride-metal phthalocyanine complex, and can be prepared using a commercially available titanium dioxide-graphite-like phase carbonitride-metal phthalocyanine complex or using methods well known to those skilled in the art. In a specific embodiment of the present invention, the preparation is preferably carried out according to the method of patent application No. 201610699773.2.
In the present invention, the raw material graphite-like carbon nitride and the kind and source of titanium dioxide for preparing the titanium dioxide-graphite-like carbon nitride-metal phthalocyanine compound are consistent with the above scheme, and are not described herein again.
In the present invention, the raw material metal phthalocyanine for preparing the titanium dioxide-graphite-like phase carbonitride-metal phthalocyanine complex has a structure represented by formula I:
in formula I, M is a transition metal ion, the type of the transition metal ion is not particularly limited in the present invention, and a transition metal ion capable of forming a complex with phthalocyanine, which is well known to those skilled in the art, may be used, and in a specific embodiment of the present invention, the transition metal ion preferably includes a zinc ion, an iron ion, a copper ion or a cobalt ion; r is-H, -NH2、-Cl、-F、-COOH、-NHCOCH3、-NHSO3H or-SO3The substitution site of H and R can be any one of 4 substitution sites on a benzene ring.
The source of the metal phthalocyanine is not particularly required in the invention, and the metal phthalocyanine can be prepared by using a commercial product of the metal phthalocyanine or a method well known to those skilled in the art; in a specific embodiment of the present invention, the preparation of the metal phthalocyanine is preferably performed by using a phthalodinitrile method or a phthalic anhydride urea method, and is preferably performed by a method in a specific reference (luwang. research on organic pollutants such as catalytic functional fiber degradation dyes, university of chekiang technology, 2010).
In the composite photocatalyst comprising the metal phthalocyanine, the metal phthalocyanine can be loaded on the surfaces of other components (titanium dioxide, graphite-like phase carbon nitride and the like) so as to sensitize the components such as the titanium dioxide, the graphite-like phase carbon nitride and the like, thus widening the corresponding range of visible light of the photocatalyst and improving the utilization rate of light energy.
In the present invention, when the photocatalyst includes a titanium dioxide-tungsten trioxide complex; the mass ratio of titanium dioxide to tungsten trioxide in the titanium dioxide-tungsten trioxide composite is preferably 100: 2-1000, more preferably 100: 5-300; the present invention does not require a particular source of the titanium dioxide-tungsten trioxide complex, and can be produced using commercially available titanium dioxide-tungsten trioxide complexes or using methods well known to those skilled in the art. In a specific embodiment of the present invention, it is preferable to directly mix titanium dioxide and tungsten trioxide to obtain a titanium dioxide-tungsten trioxide composite; the type and source of the titanium dioxide are consistent with those of the scheme, and are not described again; the particle size of the tungsten trioxide is preferably 5-500 nm, more preferably 10-400 nm, and most preferably 50-300 nm.
In the present invention, when the photocatalyst includes a graphite-like phase carbon nitride-tungsten trioxide complex; the mass ratio of the graphite-like phase carbon nitride to the tungsten trioxide in the graphite-like phase carbon nitride-tungsten trioxide composite is preferably 100: 10-1000, more preferably 100: 20 to 500 parts by weight; the invention has no special requirement on the source of the graphite-like phase carbon nitride-tungsten trioxide compound, and can be prepared by using a commercial graphite-like phase carbon nitride-tungsten trioxide compound or a method well known by the technical personnel in the field; in a specific embodiment of the present invention, the graphite-like phase carbon nitride-tungsten trioxide composite is preferably obtained by directly mixing graphite-like phase carbon nitride and tungsten trioxide; the types and sources of the graphite-like phase carbon nitride and the tungsten trioxide are consistent with the scheme, and are not described again;
in the present invention, when the catalyst includes a graphite-like phase carbonitride-metal phthalocyanine complex, the mass ratio of the graphite-like phase carbonitride to the metal phthalocyanine in the graphite-like phase carbonitride-metal phthalocyanine complex is preferably 100: 0.05-10, more preferably 100: 0.1 to 5; the invention nitrifies the graphite-like phaseThe source of the carbon-metal phthalocyanine complex is not particularly limited, and may be prepared using commercially available graphite-like carbon nitride-metal phthalocyanine commercial products or using methods well known to those skilled in the art, and in particular embodiments of the invention, it is preferably prepared according to the references (L u Wangyang, Xu Tiefng, Wang Yu, et al. synthetic photonic properties and mechanism of g-C)3N4A coated with a zinc catalyst under visible light irradiation. Catal. B-environ.180(2016) 20-28).
In the present invention, when the photocatalyst includes a metal phthalocyanine-tungsten trioxide complex; the mass ratio of the metal phthalocyanine to the tungsten trioxide in the metal phthalocyanine-tungsten trioxide compound is preferably 0.05-10: 100, more preferably 0.1 to 5: 100, respectively; the metal phthalocyanine-tungsten trioxide composite is prepared by using a commercially available metal phthalocyanine-tungsten trioxide composite commodity or a method well known to those skilled in the art; the kind and source of the raw material metal phthalocyanine and tungsten trioxide for preparing the metal phthalocyanine-tungsten trioxide composite are consistent with the above scheme, and are not described in detail herein.
In the present invention, when the photocatalyst includes a titanium dioxide-graphite-like phase carbon nitride-tungsten trioxide complex; the mass ratio of titanium dioxide to graphite-like carbon nitride to tungsten trioxide in the titanium dioxide-graphite-like carbon nitride-tungsten trioxide composite is preferably 15-90: 2-50: 5-80, more preferably 30-90: 5-40: 10-70; the invention has no special requirement on the source of the titanium dioxide-graphite-like phase carbon nitride-tungsten trioxide compound, and can be prepared by using a commercially available titanium dioxide-graphite-like phase carbon nitride-tungsten trioxide compound commodity or a method well known by the technical personnel in the field; in a specific embodiment of the present invention, it is preferable to directly mix titanium dioxide, graphite-like phase carbon nitride and tungsten trioxide to prepare a titanium dioxide-graphite-like phase carbon nitride-tungsten trioxide composite; the types and sources of the raw materials of titanium dioxide, graphite-like phase carbon nitride and tungsten trioxide for preparing the titanium dioxide-graphite-like phase carbon nitride-tungsten trioxide compound are consistent with the scheme, and are not repeated herein.
In the present invention, when the photocatalyst includes a titanium dioxide-metal phthalocyanine-tungsten trioxide complex; the mass ratio of titanium dioxide to metal phthalocyanine to tungsten trioxide in the titanium dioxide-metal phthalocyanine-tungsten trioxide composite is preferably 10-90: 0.1-10: 5-90, more preferably 25-90: 0.2-5: 10-80 parts; the present invention has no particular requirement on the source of the titanium dioxide-metal phthalocyanine-tungsten trioxide complex, and can be prepared using commercially available titanium dioxide-metal phthalocyanine-tungsten trioxide complexes or using methods well known to those skilled in the art; in a specific embodiment of the present invention, the method for preparing the titanium dioxide-metal phthalocyanine-tungsten trioxide composite is similar to the method for preparing the titanium dioxide-graphite-like phase carbon nitride-metal phthalocyanine composite, and the graphite-like phase carbon nitride therein is replaced by tungsten trioxide; the types and sources of the raw materials of titanium dioxide, metal phthalocyanine and tungsten trioxide for preparing the titanium dioxide-metal phthalocyanine-tungsten trioxide composite are consistent with the scheme, and the description is omitted.
In the invention, the photocatalyst is a mixture of two or more of the above photocatalysts; when the photocatalyst is a mixture, the invention has no special requirements on the type and the mass ratio of the photocatalyst in the photocatalyst mixture, and any type of photocatalyst can be used for mixing in any mass ratio.
In the invention, the sol is silica sol and/or aluminum sol; the pH value of the sol is preferably 3-11, more preferably 6-10, and most preferably 7-9; the concentration of the sol is preferably 2 to 50 wt%, more preferably 10 to 30 wt%, most preferably 15 to 25 wt%, more preferably 20 wt%; the particle size of the sol is preferably 1 to 100nm, more preferably 5 to 50nm, and most preferably 8 to 20 nm. In the invention, when the sol is a mixture of silica sol and aluminum sol, the invention has no special requirement on the mass ratio of the silica sol to the aluminum sol in the mixture, and the mixture can be mixed by adopting any mass ratio. The source of the sol is not particularly limited in the present invention, and a sol having a source well known to those skilled in the art, such as a commercially available sol, may be used.
In the present invention, the sol preferably further contains graphene; the mass of the graphene in the sol is preferably 0.1-2% of that of the photocatalyst, and more preferably 0.5-1.5%; in a specific embodiment of the present invention, preferably, the graphene is directly mixed with the sol, so that the graphene is uniformly dispersed in the sol; the graphene is doped in the sol, so that the transmission of electrons is facilitated, and the catalytic activity of the photocatalyst can be improved.
The photocatalytic coating provided by the invention contains sol, and the sol and the photocatalyst can be dehydrated to form a new chemical bond in the contact process, so that a self-assembled three-dimensional stacked structure is formed on the surface of a base material, the contact area of an organic pollutant and the photocatalyst can be increased, and the utilization efficiency of the photocatalyst is improved; and the addition of the sol enables an isolation layer to be formed between the catalyst and the base material, so that the phenomenon that the composite base material is corroded by the catalyst is avoided, the acting force between the catalyst and the base material can be enhanced, and catalyst particles are not easy to fall off.
In the present invention, the solvent is preferably water or a mixture of water and ethanol; when the solvent comprises water and ethanol, the volume ratio of the water to the ethanol in the mixture of the water and the ethanol is preferably 19: 1-1: 19, more preferably 10: 1-1: 19, and most preferably 5: 1-1: 19.
In the invention, when the photocatalytic coating comprises a photocatalyst, a sol and a solvent, the mass-to-solvent volume ratio of the photocatalyst in the photocatalytic coating is preferably 1-30 g: 1L, more preferably 3-20 g: 1L, and most preferably 5-15 g: 1L, and the mass-to-solvent volume ratio of the sol in the photocatalytic coating is preferably 0.1-15 g: 1L, more preferably 0.3-10 g: 1L, and most preferably 0.5-5 g: 1L.
In the present invention, when the photocatalytic coating includes a photocatalyst, a sol and a solvent, the preparation method of the photocatalytic coating preferably includes the steps of:
carrying out first ultrasonic mixing on a photocatalyst and a solvent to obtain photocatalyst dispersion liquid;
and carrying out second ultrasonic mixing on the photocatalyst dispersion liquid and the sol to obtain the photocatalytic coating.
According to the invention, a photocatalyst and a solvent are subjected to first ultrasonic mixing to obtain a photocatalyst dispersion liquid. In the invention, the power of the first ultrasonic mixing is preferably 200-500W, and more preferably 300-400W; the time of the first ultrasonic mixing is preferably 0.25-2 h, more preferably 0.4-1.5 h, and most preferably 0.5-1 h.
After the photocatalyst dispersion liquid is obtained, the photocatalyst dispersion liquid and the sol are subjected to second ultrasonic mixing to obtain the photocatalytic coating. In the invention, the power of the second ultrasonic mixing is preferably 200-500W, and more preferably 300-400W; the second ultrasonic mixing time is preferably 0.25-2 h, more preferably 0.4-1.5 h, and most preferably 0.5-1 h.
In the invention, when the photocatalytic coating comprises a photocatalyst dispersion liquid and a sol solution which are separately filled, the mass and the volume ratio of a photocatalyst in the photocatalyst dispersion liquid to a solvent is preferably 1-30 g: 1L, more preferably 3-20 g: 1L, and most preferably 5-15 g: 1L, and the mass and the volume ratio of the sol in the sol solution to the solvent is 0.1-15 g: 1L, more preferably 0.3-10 g: 1L, and most preferably 0.5-5 g: 1L.
In the present invention, when the photocatalytic coating includes a photocatalyst dispersion liquid and a sol solution which are separately packaged, the preparation method of the photocatalyst dispersion liquid is preferably the same as that of the above scheme, and is not described herein again.
In the present invention, the method for preparing the sol solution preferably includes the steps of: and mixing the sol and the solvent, and performing ultrasonic treatment to obtain a sol solution. In the invention, the power of the ultrasonic wave is preferably 200-500W, and more preferably 300-400W; the ultrasonic time is preferably 0.25-2 h, more preferably 0.4-1.5 h, and most preferably 0.5-1 h.
In the invention, the photocatalytic artificial grass is prepared by coating photocatalytic coating on the surface of artificial grass; the material of the simulated grass is preferably one or a mixture of more of polyethylene, polyester, polypropylene, polyvinyl chloride, polyamide, ethylene-vinyl acetate copolymer, polyacrylonitrile, polyurethane and cellulose; can be plastic product simulation grass and fiberThe dimension product is artificial grass or the plastic-fiber mixed product is artificial grass. In the invention, the dry film loading capacity of the photocatalyst on the surface of the simulated grass is preferably 0.1-12 g/m2More preferably 0.2 to 10g/m2Most preferably 0.5 to 8g/m2。
In the invention, the photocatalytic fiber material is prepared by coating a photocatalytic coating on the surface of a fiber material or is obtained by padding the fiber material in the photocatalytic coating; the material of the fiber material is preferably one or a mixture of more of polyester, polyethylene, polyvinyl chloride, polypropylene, polyacrylonitrile, polyamide, polyurethane and cellulose; the fiber felt, the fiber cloth, the non-woven fabric and the like can be concretely mentioned; the gram weight of the fiber material is preferably 20-300 g/m2More preferably 30 to 250g/m2Most preferably 50 to 200g/m2(ii) a The thickness of the fiber material is preferably 0.2-7 mm, more preferably 0.4-6 mm, and most preferably 0.5-5 mm. In the invention, the dry film loading capacity of the photocatalyst on the surface of the fiber material is preferably 0.1-12 g/m2More preferably 0.2 to 10g/m2Most preferably 0.5 to 8g/m2. The invention utilizes the characteristic of larger specific surface area of the fiber material to improve the distribution uniformity of the catalyst, thereby improving the photocatalytic efficiency of the composite system.
The invention provides a preparation method of the three-dimensional photocatalytic composite system in the scheme, which comprises the following steps:
(1) when the photocatalytic coating comprises a photocatalyst, sol and a solvent, spraying the photocatalytic coating on the surface of the simulated grass to obtain the simulated grass coated with a wet film of the photocatalytic coating;
or when the photocatalytic coating comprises a photocatalyst dispersion liquid and a sol solution which are separately packaged, respectively spraying the photocatalytic dispersion liquid and the sol solution on the surface of the simulated grass to obtain the simulated grass coated with the wet film of the photocatalytic coating;
drying the simulated grass coated with the wet film of the photocatalytic coating to obtain photocatalytic simulated grass;
(2) when the photocatalytic coating comprises a photocatalyst, sol and a solvent, spraying the photocatalytic coating on the surface of the fiber material to obtain the fiber material coated with a wet film of the photocatalytic coating;
or when the photocatalyst dispersion liquid and the sol solution are separately packaged, respectively spraying the photocatalyst dispersion liquid and the sol solution on the surface of the fiber material to obtain the fiber material coated with a photocatalytic coating wet film;
or, when the photocatalytic coating comprises a photocatalyst, sol and a solvent, padding the composite fiber material in the photocatalytic coating to obtain the fiber material coated with the wet film of the photocatalytic coating;
or when the photocatalytic coating comprises a photocatalyst dispersion liquid and a sol solution which are separately packaged, padding the fiber material in the photocatalyst dispersion liquid and the sol solution respectively to obtain the fiber material coated with a wet film of the photocatalytic coating;
drying the fiber material coated with the wet photocatalytic coating film to obtain a photocatalytic fiber material;
(3) carrying out thermal bonding compounding on the photocatalytic simulation grass and the photocatalytic fiber material to obtain a three-dimensional photocatalytic composite system;
the step (1) and the step (2) have no time sequence limitation.
In the invention, when the photocatalytic coating comprises a photocatalyst, a sol and a solvent, the photocatalytic coating is sprayed on the surface of the simulated grass to obtain the simulated grass coated with the wet film of the photocatalytic coating. In the invention, the spraying flow is preferably 50-300 ml/min, more preferably 60-250 ml/min, and most preferably 75-200 ml/min; the linear distance between the spray head and the surface of the simulated grass during spraying is preferably 5-25 cm, more preferably 7-20 cm, and most preferably 10-15 cm; the spraying amount of the photocatalytic coating on the surface of the simulated grass is preferably 50-1000 ml/m2More preferably 100 to 800ml/m2。
In the invention, when the photocatalytic coating comprises the photocatalyst dispersion liquid and the sol solution which are separately packaged, the photocatalytic dispersion liquid and the sol solution are respectively sprayed on the surface of the simulated grass to obtain the simulated grass coated with the wet film of the photocatalytic coating. The invention has no special requirement on the spraying sequence of the photocatalyst dispersion liquid and the sol solution, and the photocatalyst dispersion liquid can be sprayed firstly and then the sol solution can be sprayed, or the sol solution can be sprayed firstly and then the photocatalyst dispersion liquid can be sprayed. In the invention, the spraying flow rate of the photocatalytic dispersion liquid and the sol solution is preferably 50-300 ml/min, more preferably 60-250 ml/min, and most preferably 75-200 ml/min; the linear distance between the spray head and the surface of the simulated grass during spraying is preferably 5-25 cm, more preferably 7-20 cm, and most preferably 10-15 cm.
In the present invention, the thickness of the wet film of the photocatalytic coating on the surface of the artificial grass is preferably 50nm to 200 μm, and more preferably 200nm to 50 μm.
After the simulated grass coated with the wet film of the photocatalytic coating is obtained, the simulated grass coated with the wet film of the photocatalytic coating is dried to obtain the photocatalytic simulated grass. The method has no special requirements on the specific drying mode, and can completely remove the solvent on the surface of the simulated grass coated with the wet film of the photocatalytic coating; in a specific embodiment of the present invention, the drying is preferably airing or drying at room temperature; the drying temperature is preferably 80-200 ℃, and more preferably 100-150 ℃; the invention has no special requirement on the airing or drying time, and can completely remove the solvent. According to the invention, the solvent in the photocatalytic coating is removed through drying, and after the solvent is removed, the photocatalyst and the sol are loaded on the surface of the simulated grass in the form of catalyst particles and sol particles, and the catalyst particles and the sol particles can form a three-dimensional stacked structure.
In the specific embodiment of the invention, in order to ensure that the catalyst loading capacity on the surface of the simulated grass meets the requirements, multiple times of spraying-drying can be carried out, namely, the simulated grass coated with the wet film of the photocatalytic coating is dried, then the obtained photocatalytic simulated grass is sprayed again on the surface, then the photocatalytic simulated grass is dried, and the like, until the photocatalyst loading capacity on the surface of the simulated grass meets the requirements; in the specific embodiment of the invention, the load of the photocatalyst on the surface of the dried simulated grass is detected, and the spraying-drying times are determined according to the load of the needed photocatalyst.
In the invention, the photocatalytic fiber material can be prepared by a spraying method or a padding method.
In the invention, when the photocatalytic coating comprises a photocatalyst, sol and a solvent, the photocatalytic coating is sprayed on the surface of the fiber material to obtain the fiber material coated with a wet film of the photocatalytic coating; the specific spraying conditions are consistent with the spraying conditions for preparing the photocatalytic simulation grass, and are not described again.
In the invention, when the photocatalytic coating comprises the photocatalyst dispersion liquid and the sol solution which are separately packaged, the photocatalytic dispersion liquid and the sol solution are respectively sprayed on the surface of the fiber material to obtain the fiber material coated with the wet film of the photocatalytic coating. In the present invention, the specific conditions of the spraying are consistent with the spraying conditions for preparing the photocatalytic simulation grass, and are not described herein again.
In the invention, the photocatalytic fiber material can also be prepared by a padding method, and when the photocatalytic coating comprises a photocatalyst, sol and a solvent, the composite fiber material is padded in the photocatalytic coating to obtain the fiber material coated with the photocatalytic coating wet film. In the invention, the dipping time in the padding is preferably 30-120 s, and more preferably 50-100 s; the padding speed is preferably 5-60 m/min, more preferably 10-50 m/min, and most preferably 15-40 m/min; the padding pressure is preferably 0.05-0.5 MPa, more preferably 0.07-0.4 MPa, and most preferably 0.1-0.3 MPa; the bath ratio of padding is preferably 1: 10-200, and more preferably 1: 15-100; the padding residual rate of padding is preferably 30-200%, more preferably 40-100%, and the method has no special requirements on the specific padding mode, and can be achieved by using a padding method well known to a person skilled in the art, such as one-padding, two-padding or three-padding; the invention does not require special equipment for said padding, and can be carried out using padding machines known to the person skilled in the art.
In the invention, when the photocatalytic coating comprises the separately-packaged photocatalyst dispersion liquid and sol solution, the fiber material is padded in the photocatalyst dispersion liquid and the sol solution respectively to obtain the fiber material coated with the wet film of the photocatalytic coating. In the present invention, the photocatalyst dispersion and sol solution are the same as those in the above scheme, and are not described herein again; the invention has no special requirements on the sequence of padding in the photocatalyst dispersion liquid and padding in the sol solution, and in the specific embodiment of the invention, the photocatalyst dispersion liquid can be padded firstly and then in the sol solution, or the photocatalyst dispersion liquid can be padded firstly and then in the sol solution; the specific conditions of padding are preferably consistent with the above scheme, and are not described herein again.
In the present invention, the thickness of the wet film of the photocatalytic coating on the surface of the fiber material is preferably 50nm to 200 μm, and more preferably 200nm to 50 μm.
After the fiber material coated with the photocatalytic coating wet film is obtained, the fiber material coated with the photocatalytic coating wet film is dried to obtain the photocatalytic fiber material. In the present invention, the drying is preferably airing or drying at room temperature; the drying temperature is preferably 80-130 ℃, and more preferably 100-120 ℃; the invention has no special requirement on the drying time, and can completely remove the solvent. According to the invention, the solvent in the photocatalytic coating is removed through drying, and after the solvent is removed, the photocatalyst and the sol are loaded on the surface of the fiber material in the form of catalyst particles and sol particles, and the catalyst particles and the sol particles can form a three-dimensional stacked structure.
In the specific embodiment of the invention, in order to ensure that the catalyst loading capacity on the surface of the fiber material meets the requirements, multiple times of spraying-drying or multiple times of padding can be carried out; in the specific embodiment of the invention, the photocatalyst loading on the surface of the dried fiber material is detected, and the number of spraying-drying or padding times is determined according to the required photocatalyst loading.
After the photocatalytic simulation grass and the photocatalytic fiber material are obtained, the photocatalytic simulation grass and the photocatalytic fiber material are thermally bonded and compounded to obtain a three-dimensional photocatalytic composite system. In the invention, the thermal bonding compounding is preferably point-shaped pressure thermal compounding; the temperature of the punctiform pressurizing heat compounding is 80-200 ℃, more preferably 100-180 ℃, and most preferably 130-150 ℃; the pressure of the punctiform pressurizing heat recombination is preferably 1.5-10 MPa, more preferably 2-8 MPa, and most preferably 3-6 MPa.
The invention provides an application of the three-dimensional photocatalytic composite system or the three-dimensional photocatalytic composite system prepared by the preparation method in the scheme in photocatalysis. In the invention, the three-dimensional photocatalysis composite system is preferably applied to water purification, and in a specific embodiment of the invention, the three-dimensional photocatalysis composite system is preferably applied to purification of landscape water or river water; in the invention, the water purification is mainly catalytic oxidation of organic pollutants, and the organic pollutants preferably comprise organic dyes, benzene ring compounds, naphthalene ring compounds or toxic aromatic compounds and the like in industrial or domestic wastewater; the invention has no special requirements on the specific application method of the three-dimensional photocatalysis composite system, and can be applied by using the application method known by the technical personnel in the field, specifically, the three-dimensional photocatalysis composite system is directly paved in landscape water or river water.
The three-dimensional photocatalytic composite system has no special requirements on a photocatalytic response light source, and can use any photocatalytic response light source known by persons skilled in the art, such as ultraviolet light, sunlight, fluorescent lamps, L ED lamps, xenon lamps, deuterium lamps and the like.
The preparation method and application of the three-dimensional photocatalytic composite system provided by the invention are described in detail below with reference to examples, but the preparation method and application are not to be construed as limiting the scope of the invention.
FIG. 1 is a front view of a three-dimensional photocatalytic composite system prepared in an example of the present invention; FIG. 2 is a side view of a three-dimensional composite system prepared according to an embodiment of the present invention.
Example 1
(1) 1g of anatase crystal TiO with the particle size of 300nm2Placing in a conical flask, adding 100ml of mixed solvent, and performing ultrasonic treatment at 400W for 0.5h to obtain photocatalyst dispersion; the volume ratio of the deionized water to the ethanol in the mixed solvent is 5: 3.
(2) Putting 0.5ml of silica sol into a conical flask, adding 99.5ml of mixed solvent, and performing ultrasonic treatment at 400W for 0.5h to obtain sol solution; the volume ratio of the deionized water to the ethanol in the mixed solvent is 5: 3; the concentration of the silica sol is 20 +/-1 wt%, the pH value is 7.5, and the particle size of the sol is 10-20 nm.
(3) 1g of anatase crystal TiO with the particle size of 300nm2Placing in a conical flask, adding 100ml of mixed solvent, and performing ultrasonic treatment at 400W for 0.5h to obtain TiO2A dispersion liquid; the volume ratio of the deionized water to the ethanol in the mixed solvent is 5: 3; in the TiO2Adding 0.5ml of silica sol into the dispersion liquid, and performing ultrasonic treatment at 400W for 0.5h to obtain a photocatalyst coating; the concentration of the silica sol is 20 +/-1 wt%, the pH value is 7.5, and the particle size of the sol is 10-20 nm.
Experiment 1: taking a polyvinyl chloride simulated eucalyptus plant with the height of 5cm, and putting the sol solution in the step (2) into a high-pressure electric spray gun for spraying, wherein the flow rate of the spray gun is set as 100ml/min, the spraying distance is 15cm, and the spraying amount is about 0.5 ml; and (3) putting the photocatalyst dispersion liquid in the step (1) into a high-pressure electric spray gun for spraying, wherein the flow rate of the spray gun is set to be 100ml/min, the spraying distance is 15cm, and the spraying amount is about 0.5 ml. Drying in an oven at 100 deg.C for 15min after spraying to obtain photocatalytic artificial grass (photocatalyst loading of 0.5 g/m)2) And is marked as photocatalytic artificial grass.
Taking a 3 cm-by-3 cm polyester fiber felt, soaking the polyester fiber felt in the sol solution in the step (2), and after the soaking is finished, padding the fiber felt on a padding machine; and (3) soaking the fiber felt in the photocatalyst dispersion liquid in the step (1), and padding the fiber felt on a padding machine after the soaking is finished. After padding, drying in a baking oven at 100 ℃ for 30min to obtain the photocatalytic fiber felt (the loading of the photocatalyst is 0.5 g/m)2). In the padding process, the speed of the padding machine is set to be 15m/min, and the pressure is set to be 0.2 MPa. The gram weight of the fiber felt is 70g/m2The thickness is 0.5 mm.
And thermally bonding and compounding the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system, wherein the thermal compounding temperature is 100 ℃, the pressure is 2MPa, and the three-dimensional photocatalytic composite system is marked as a photocatalytic composite system A.
Experiment 2: taking a polyvinyl chloride simulated eucalyptus plant with the height of 5cm, and putting the sol solution in the step (2) into a high-pressure electric spray gun for spraying, wherein the flow rate of the spray gun is set as 100ml/min, the spraying distance is 15cm, and the spraying amount is about 0.5 ml; then (1) is mixed) The photocatalyst dispersion liquid in the high-pressure electric spray gun is filled in the high-pressure electric spray gun for spraying, the flow rate of the spray gun is set as 100ml/min, the spraying distance is 15cm, and the spraying amount is about 0.5 ml; and after the spraying is finished, drying in a drying oven at 100 ℃ for 15 min. Repeating the steps of spraying and drying once to obtain the photocatalytic simulation grass (the loading capacity of the photocatalyst is 1 g/m)2)。
Taking a 3 cm-by-3 cm polyester fiber felt, soaking the polyester fiber felt in the sol solution in the step (2), and after the soaking is finished, padding the fiber felt on a padding machine; and (3) soaking the fiber felt in the photocatalyst dispersion liquid in the step (1), and padding the fiber felt on a padding machine after the soaking is finished. Drying in a 100 deg.C oven for 30min after padding, repeating the above padding and drying steps to obtain the photocatalytic fiber felt (photocatalyst loading is 1 g/m)2). In the padding process, the speed of a padding machine is set to be 15m/min, and the pressure is set to be 0.2 MPa; the gram weight of the fiber felt is 70g/m2The thickness is 0.5 mm.
Carrying out hot sticking compounding on the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system; the thermal compounding temperature is 100 ℃, and the pressure is 2 MPa. Is marked as a photocatalytic composite system B.
Experiment 3: and (3) taking a polyvinyl chloride simulated eucalyptus plant with the height of 5cm, and filling the photocatalyst coating in the step (3) into a high-pressure electric spray gun for spraying. The flow rate of the spray gun was set at 100ml/min, the spray distance was 15cm, and the spray amount was about 0.5 ml. Drying in an oven at 100 deg.C for 15min after spraying to obtain photocatalytic artificial grass (photocatalyst loading of 0.5 g/m)2)。
And (3) soaking a 3 cm-by-3 cm polyester fiber felt in the photocatalytic coating in the step (3), and padding the fiber felt on a padding machine after the soaking is finished. After padding, drying in a baking oven at 100 ℃ for 30min to obtain the photocatalytic fiber felt (the loading of the photocatalyst is 0.5 g/m)2) (ii) a In the padding process, the speed of the padding machine is set to be 15m/min, and the pressure is set to be 0.2 MPa. The gram weight of the fiber felt is 70g/m2The thickness is 0.5 mm.
Carrying out hot sticking compounding on the obtained photocatalytic simulation grass and the photocatalytic fiber to obtain a three-dimensional photocatalytic composite system; the thermal compounding temperature is 100 ℃, and the pressure is 2 MPa. Is marked as a photocatalytic composite system C.
Experiment 4: and (3) taking a polyvinyl chloride simulated eucalyptus plant with the height of 5cm, and filling the photocatalytic coating in the step (3) into a high-pressure electric spray gun for spraying. The flow rate of the spray gun was set at 100ml/min, the spray distance was 15cm, and the spray amount was about 0.5 ml. And after the spraying is finished, drying in a drying oven at 100 ℃ for 15 min. Repeating the steps of spraying and drying once to obtain the photocatalytic simulation grass (the loading capacity of the photocatalyst is 1 g/m)2)。
And (3) soaking a 3 cm-by-3 cm polyester fiber felt in the photocatalytic coating in the step (3), and padding the fiber felt on a padding machine after the soaking is finished. Drying in a 100 deg.C oven for 30min after padding, repeating the above padding and drying steps to obtain the photocatalytic polyester fiber felt (photocatalyst loading is 1 g/m)2). In the padding process, the speed of the padding machine is set to be 15m/min, and the pressure is set to be 0.2 MPa. The gram weight of the fiber felt is 70g/m2The thickness is 0.5 mm.
And thermally sticking and compounding the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system. The thermal compounding temperature is 100 ℃, and the pressure is 2 MPa. Is marked as a photocatalytic composite system D.
Control experiment: taking a polyvinyl chloride simulated eucalyptus plant with the height of 5cm, putting the photocatalyst dispersion liquid prepared in the step (1) into a high-pressure electric spray gun for spraying, and then drying; the spraying flow, spraying distance, spraying amount, drying temperature and time were all the same as those in experiment 1, and photocatalytic artificial grass (photocatalyst loading amount was 0.5 g/m) was obtained2)。
Soaking a 3 cm-by-3 cm polyester fiber felt in the photocatalyst dispersion liquid in the step (1), and padding the fiber felt on a padding machine after the soaking is finished; padding conditions are consistent with experiment 1, and the photocatalytic fiber felt (the loading amount of the photocatalyst is 0.5 g/m) is obtained2)。
Carrying out hot sticking compounding on the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system; the thermal compounding temperature is 100 ℃, and the pressure is 2 MPa. And marking as a control group of the photocatalytic composite system.
Photocatalytic degradation test: under simulated sunlight, carrying out a photocatalytic degradation experiment on the prepared photocatalytic composite system A, the photocatalytic composite system B, the photocatalytic composite system C, the photocatalytic composite system D and a control group of the photocatalytic composite system, wherein the photocatalytic degradation experiment comprises the following steps:
taking methylene blue as a substrate, carrying out a reaction in a xenon lamp aging test box, taking a sample every 5min, and testing the change of the absorbance by using an ultraviolet-visible spectrophotometer to calculate the change of the methylene blue concentration in the solution along with the reaction time, wherein the initial concentration of the methylene blue is 5 × 10-5mol/L, 25 ℃ reaction temperature, total reaction time 30min, results are shown in FIG. 3.
As can be seen from FIG. 3, the removal rate of the composite system obtained by the method provided by the invention for methylene blue is higher, the removal rate at 10min is up to 94%, and at 30min, the photocatalytic composite system provided by the invention can substantially completely remove the methylene blue, while the removal rate of a control group is only 77%.
Photocatalytic degradation cycle test: and washing the photocatalytic composite system D which completes one photocatalytic degradation experiment with deionized water for three times, drying at 60 ℃, performing the photocatalytic degradation experiment according to the steps, then performing the washing, drying and photocatalytic degradation experiments on the photocatalytic composite system, and repeating the steps for 6 times. The experimental result shows that after 6 times of cycle tests, the photocatalytic composite system can still remove methylene blue basically and completely within 30min, which shows that the catalytic activity is basically unchanged, and shows that the photocatalyst in the photocatalytic coating has strong binding force with a base material and is not easy to fall off.
Example 2
(1) 1g of anatase crystal TiO with the particle size of 25nm2Placing in a conical flask, adding 100ml of mixed solvent, and performing ultrasonic treatment at 400W for 0.5h to obtain TiO2A dispersion liquid; the volume ratio of the deionized water to the ethanol in the mixed solvent is 3: 2; in the TiO2Adding 0.5ml of silica sol into the dispersion liquid, and performing ultrasonic treatment at 400W for 0.5h to obtain the photocatalytic coating; the silica sol has a pH of 7.5 and a concentration20 +/-1 wt% and the sol has a particle size of 10-20 nm.
(2) And (3) taking a polyvinyl chloride simulated eucalyptus plant with the height of 5cm, and filling the photocatalytic coating in the step (1) into a high-pressure electric spray gun for spraying. The flow rate of the spray gun was set at 100ml/min, the spray distance was 15cm, and the spray amount was about 0.5 ml. Drying in a 50 deg.C oven for 30min after spraying to obtain photocatalytic artificial grass (photocatalyst loading is 0.5 g/m)2)。
(3) And (3) taking a 3 cm-by-3 cm polyester fiber felt, soaking the polyester fiber felt in the photocatalytic coating in the step (1), and after the soaking is finished, padding the fiber felt on a padding machine. Drying in a 100 deg.C oven for 30min after padding, repeating the above padding and drying steps to obtain the photocatalytic fiber felt (photocatalyst loading is 1 g/m)2). In the padding process, the speed of the padding machine is set to be 15m/min, and the pressure is set to be 0.15 MPa. The gram weight of the fiber felt is 100g/m2The thickness is 0.6 mm.
(4) And thermally sticking and compounding the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system. The thermal compounding temperature is 100 ℃, and the pressure is 2 MPa.
The photocatalytic degradation test was carried out on the obtained photocatalytic composite system according to the photocatalytic degradation test method in example 1, wherein the concentration of methylene blue was 5 × 10-5mol/L, the reaction temperature is 25 ℃, the reaction time is 30min, and the removal rate at 20min reaches more than 90%.
The photocatalytic degradation cycle test is carried out according to the method in the embodiment 1, and after 6 times of cycle tests, the removal rate of the photocatalytic composite system to formaldehyde can still reach more than 90%.
Example 3
(1) Placing 15g of urea in a semi-closed alumina crucible with a cover, heating to 550 ℃ in a tube furnace at a heating rate of 2 ℃/min and maintaining for 5h to obtain g-C3N4。
(2) 0.5g of anatase crystal TiO with the particle size of 50nm2And 0.5g of g-C in step (1)3N4Placing in a conical flask, adding 100ml of mixed solvent, and performing ultrasonic treatment at 400W for 0.5h to obtain the photocatalysisThe agent dispersion liquid. The volume ratio of the deionized water to the ethanol in the mixed solvent is 5: 1; adding 1.25ml of silica sol into the photocatalyst dispersion liquid, and performing ultrasonic treatment at 400W for 0.5h to obtain a photocatalytic coating; the pH value of the silica sol is 7.5, the concentration is 20 +/-1 wt%, and the particle size of the silica sol is 10-20 nm.
(3) And (3) taking a polyvinyl chloride simulated eucalyptus plant with the height of 5cm, and filling the photocatalytic coating in the step (2) into a high-pressure electric spray gun for spraying. The flow rate of the spray gun was 175ml/min, the spray distance was 15cm, and the spray amount was about 0.5 ml. Drying in a 60 deg.C oven for 30min after spraying to obtain photocatalytic artificial grass (photocatalyst loading is 0.5 g/m)2)。
(4) And (3) taking a 3 cm-by-3 cm polyester fiber felt, and putting the photocatalytic coating in the step (2) into a high-pressure electric spray gun for spraying. The flow rate of the spray gun was 175ml/min, the spray distance was 15cm, and the spray amount was about 0.5 ml. Drying in an oven at 80 deg.C for 30min after spraying to obtain photocatalytic fiber felt (photocatalyst loading amount of 0.5 g/m)2)。
(5) And thermally sticking and compounding the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system. The thermal compounding temperature is 100 ℃, and the pressure is 2 MPa.
The photocatalytic degradation test was carried out on the obtained photocatalytic composite system according to the photocatalytic degradation test method in example 1, wherein the concentration of methylene blue was 5 × 10-5mol/L, the reaction temperature is 25 ℃, the reaction time is 30min, and the removal rate reaches over 90 percent at 10 min.
The photocatalytic degradation cycle test is carried out according to the method in the embodiment 1, and after 6 times of cycle tests, the removal rate of the photocatalytic composite system to formaldehyde can still reach more than 90%.
Example 4
(1) Placing 15g of urea in a semi-closed alumina crucible with a cover, heating to 530 ℃ in a tube furnace at a heating rate of 1 ℃/min and maintaining for 5h to obtain g-C3N4。
G to C3N41.0g of the mixture was mixed with 100m L N, N-dimethylformamide and sonicated at 500WFor 5h, to give g-C3N4A dispersion liquid; anatase type TiO with the particle size of 50nm22.0g of the mixture is mixed with 100m L N, N-dimethylformamide and is subjected to ultrasonic treatment for 8 hours at 200W to obtain TiO2A dispersion liquid; subjecting said g-C to3N4Dispersion and TiO2Mixing the dispersion liquid, and stirring for 2 hours at 500rpm to obtain a mixed dispersion liquid;
mixing 40mg of unsubstituted iron phthalocyanine (FePc) with 50m L N, N-dimethylformamide, and performing ultrasonic treatment at 200W for 30h to obtain an unsubstituted iron phthalocyanine solution;
dropwise adding the mixed dispersion liquid into an unsubstituted iron phthalocyanine solution at the speed of 50m L/H, reacting for 8H at the temperature of 45 ℃, filtering the material obtained after the reaction by using a G6 sand core funnel, washing by using N, N-dimethylformamide for 3 times, and using 0.2 mol/L NaOH solution and 0.1 mol/L H solution2SO4Respectively washing for 2 times, finally washing with ultrapure water to neutrality, and freeze-drying at-60 deg.C for 16h to obtain titanium dioxide and graphite-like phase carbon nitride and iron phthalocyanine composite photocatalyst (g-C)3N4/FePc/TiO2)。
(2) Mixing 1g of g-C in step (1)3N4/FePc/TiO2Placing the mixture into a conical flask, adding 100ml of mixed solvent, and performing ultrasonic treatment at 400W for 0.5h to obtain photocatalyst dispersion liquid, wherein the volume ratio of deionized water to ethanol in the mixed solvent is 5: 3;
taking 2ml of silica sol, and diluting the silica sol by 100 times with deionized water to obtain a sol solution, wherein the concentration of the silica sol is 20 +/-1 wt%, the pH value is 7.5, and the particle size of the sol is 5-8 nm.
(3) And (3) taking a polyvinyl chloride simulated eucalyptus plant with the height of 5cm, putting the photocatalyst dispersion liquid obtained in the step (2) into a high-pressure electric spray gun for spraying, then pouring out the residual photocatalyst dispersion liquid, and putting the sol solution obtained in the step (2) into the high-pressure electric spray gun for spraying. The flow rate of the spray gun was set at 200ml/min, the spraying distance was 15cm, and the amount sprayed was about 0.5ml per time. Drying in a 60 deg.C oven for 30min after spraying, repeating the above spraying steps once, and drying in a 80 deg.C oven for 30min to obtain photocatalytic artificial grass (photocatalyst loading is 1 g/m)2)。
(4) And (3) taking a 3 cm-by-3 cm polyester fiber felt, soaking the polyester fiber felt in the sol solution obtained in the step (2), padding the fiber felt on a padding machine after the soaking is finished, soaking the fiber felt in the photocatalyst dispersion liquid obtained in the step (2), and padding the fiber felt on the padding machine after the soaking is finished. Drying in a 100 deg.C oven for 30min after padding, repeating the above padding and drying steps to obtain the photocatalytic fiber felt (photocatalyst loading is 1 g/m)2). In the padding process, the speed of the padding machine is set to be 20m/min, and the pressure is set to be 0.2 MPa. The gram weight of the fiber felt is 100g/m2The thickness is 0.6 mm.
(5) And thermally sticking and compounding the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system. The thermal compounding temperature is 100 ℃, and the pressure is 2 MPa.
The photocatalytic degradation test was carried out on the obtained photocatalytic composite system according to the photocatalytic degradation test method in example 1, wherein the concentration of methylene blue was 5 × 10-5mol/L, the reaction temperature is 25 ℃, the reaction time is 30min, and the removal rate at 10min reaches more than 95%.
The photocatalytic degradation cycle test is carried out according to the method in the embodiment 1, and after 6 times of cycle tests, the removal rate of the photocatalytic composite system to formaldehyde can still reach more than 95%.
Example 5
(1) Placing 15g of urea in a semi-closed alumina crucible with a cover, heating to 525 deg.C at a heating rate of 1 deg.C/min in a tube furnace and maintaining for 6h to obtain g-C3N4；
(2) Mixing 0.1g of tungsten trioxide and 0.9g of g-C in step (1)3N4Placing in a conical flask, adding 100ml of mixed solvent, and performing ultrasonic treatment at 400W for 0.5h to obtain photocatalyst dispersion; the volume ratio of the deionized water to the ethanol in the mixed solvent is 1: 1; adding 1.5ml of silica sol into the photocatalyst dispersion liquid, and performing ultrasonic treatment at 400W for 0.5h to obtain a photocatalytic coating; the pH value of the silica sol is 7.5, the concentration is 20 +/-1 wt%, and the particle size of the silica sol is 10-20 nm.
(3) Taking a polyvinyl chloride simulated eucalyptus plant with the height of 5cm, and the step (a)2) The photocatalytic coating is arranged in a high-pressure electric spray gun for spraying. The flow rate of the spray gun was set at 150ml/min, the spray distance was 15cm, and the spray amount was about 0.5 ml. Drying in oven at 125 deg.C for 30min to obtain photocatalytic artificial grass (photocatalyst loading of 0.5 g/m)2)。
(4) And (3) taking a 3 cm-by-3 cm polyester fiber felt, soaking the polyester fiber felt in the photocatalytic coating in the step (2), and after the soaking is finished, padding the fiber felt on a padding machine. Drying in a 100 deg.C oven for 30min after padding, repeating the above padding and drying steps once to obtain the photocatalytic fiber felt (photocatalyst loading is 1 g/m)2). In the padding process, the speed of the padding machine is set to be 10m/min, and the pressure is set to be 0.1 MPa. The gram weight of the fiber felt is 100g/m2The thickness is 0.6 mm.
(5) And thermally sticking and compounding the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system. The thermal compounding temperature is 100 ℃, and the pressure is 2 MPa.
The photocatalytic degradation test was carried out on the obtained photocatalytic composite system according to the photocatalytic degradation test method in example 1, wherein the concentration of methylene blue was 5 × 10-5mol/L, the reaction temperature is 25 ℃, the reaction time is 15min, and the removal rate at 10min reaches more than 95%.
The photocatalytic degradation cycle test is carried out according to the method in the embodiment 1, and after 6 times of cycle tests, the removal rate of the photocatalytic composite system to formaldehyde can still reach more than 95%.
Example 6
(1) Placing 15g of urea in a semi-closed alumina crucible with a cover, heating to 550 ℃ in a tube furnace at a heating rate of 1 ℃/min and maintaining for 5h to obtain g-C3N4。
(2) 0.3g of tungsten trioxide and 0.7g of g-C in step (1)3N4Placing in a conical flask, adding 100ml of deionized water, and performing ultrasonic treatment at 400W for 0.5h to obtain photocatalyst dispersion; the volume ratio of the deionized water to the ethanol in the mixed solvent is 3: 2;
taking 2.5ml of silica sol, and diluting by 100 times with deionized water to obtain a sol solution; the concentration of the silica sol is 20 +/-1 wt%, the pH value is 7.5, and the particle size of the sol is 5-8 nm.
(3) And (3) taking a polyester simulated eucalyptus with the height of 5cm, putting the sol solution obtained in the step (2) into a high-pressure electric spray gun for spraying, then pouring out the residual solution, and putting the photocatalyst dispersion liquid obtained in the step (2) into the high-pressure electric spray gun for spraying. The flow rate of the spray gun was set at 150ml/min, the spray distance was 15cm, and the spray amount was about 0.5 ml. Drying in an oven at 115 deg.C for 30min after spraying to obtain photocatalytic artificial grass (photocatalyst loading of 0.5 g/m)2)。
(4) And (3) taking a 3 cm-by-3 cm polyester fiber felt, putting the sol solution obtained in the step (2) into a high-pressure electric spray gun for spraying, then pouring out the residual solution, and putting the photocatalyst dispersion liquid obtained in the step (2) into the high-pressure electric spray gun for spraying. The flow rate of the spray gun was 175ml/min, the spray distance was 15cm, and the spray amount was about 0.5 ml. Drying in a 100 deg.C oven for 30min after finishing spraying to obtain photocatalytic fiber felt (photocatalyst loading amount is 0.5 g/m)2)。
(5) And thermally sticking and compounding the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system. The thermal compounding temperature is 100 ℃, and the pressure is 2 MPa.
The photocatalytic degradation test was carried out on the obtained photocatalytic composite system according to the photocatalytic degradation test method in example 1, wherein the concentration of methylene blue was 5 × 10-5mol/L, the reaction temperature is 25 ℃, the reaction time is 15min, and the removal rate at 15min reaches more than 99%.
The photocatalytic degradation cycle test is carried out according to the method in the embodiment 1, and after 6 times of cycle tests, the removal rate of the photocatalytic composite system to formaldehyde can still reach more than 99%.
Example 7
In order to more easily observe whether the base material of the photocatalytic composite system is easily corroded in the photocatalytic process, in this example, a white polyester fiber felt surface with the same quality as the fiber web material is used for a photocatalytic experiment, and the observation phenomenon specifically includes the following steps:
(1) spraying the photocatalytic coating prepared in the step (3) in the embodiment 1 on the surface of a polyester fiber felt, setting the flow rate of a spray gun to be 100ml/min, the spraying distance to be 15cm and the spraying amount to be about 0.5ml, drying the coated photocatalytic coating in a drying oven at 100 ℃ for 15min, and repeating the spraying and drying steps once to obtain an experimental group;
(2) the TiO prepared in step (1) of example 12Spraying the dispersion (i.e. the photocatalytic coating without the sol) on the surface of the polyester fiber felt, wherein the spraying conditions are consistent with those in the step (1), and obtaining a control group;
and (3) irradiating the control group and the experimental group under a 400W ultraviolet lamp, wherein the irradiation distance is 30cm, the irradiation time is 8h, observing the surface change of the polyester fiber felt after the irradiation is finished, and the observation result is shown in figure 4, wherein the polyester fiber felt of the control group turns yellow according to figure 2, while the color of the polyester fiber felt of the experimental group is basically unchanged, which indicates that the polyester fiber felt of the control group is seriously corroded, and the polyester fiber felt of the experimental group is basically not corroded. The test result shows that the photocatalytic complex system does not corrode the material of the base material in the photocatalytic process and cannot damage the performance of the base material.
From the above examples, it is understood that the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A preparation method of a three-dimensional photocatalytic composite system comprises the following steps:
(1) placing 15g of urea in a semi-closed alumina crucible with a cover, heating to 550 ℃ in a tube furnace at a heating rate of 1 ℃/min and maintaining for 5h to obtain g-C3N4；
(2) 0.3g of tungsten trioxide and 0.7g of g-C in step (1)3N4Placing in a conical flask, adding 100ml of deionized water, and performing ultrasonic treatment at 400W for 0.5h to obtain photocatalyst dispersion;
taking 2.5ml of silica sol, and diluting by 100 times with deionized water to obtain a sol solution; the concentration of the silica sol is 20 +/-1 wt%, the pH is 7.5, and the particle size of the silica sol is 5-8 nm;
(3) taking a polyester simulation eucalyptus with the height of 5cm, putting the sol solution in the step (2) into a high-pressure electric spray gun for spraying, then pouring out the residual solution, and putting the photocatalyst dispersion liquid in the step (2) into the high-pressure electric spray gun for spraying; the flow rate of the spray gun is set to be 150ml/min, the spraying distance is 15cm, and the spraying amount is 0.5 ml; drying in an oven at 115 ℃ for 30min after the spraying is finished to obtain the photocatalytic simulation grass; the photocatalyst loading capacity of the photocatalytic simulation grass is 0.5g/m2；
(4) Taking a polyester fiber felt of 3cm × 3cm, putting the sol solution obtained in the step (2) into a high-pressure electric spray gun for spraying, then pouring out the residual solution, putting the photocatalyst dispersion liquid obtained in the step (2) into the high-pressure electric spray gun for spraying, setting the flow rate of the spray gun to be 175ml/min, the spraying distance to be 15cm and the spraying amount to be 0.5ml, drying in a drying oven at 100 ℃ for 30min after the spraying is finished to obtain the photocatalytic fiber felt, wherein the photocatalyst loading amount of the photocatalytic fiber felt is 0.5g/m2；
(5) Carrying out hot sticking compounding on the obtained photocatalytic simulation grass and the photocatalytic fiber felt to obtain a three-dimensional photocatalytic composite system; the temperature of the hot bonding and compounding is 100 ℃, and the pressure is 2 MPa.
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| CN106824248A (en) * | 2017-03-02 | 2017-06-13 | 安徽工业大学 | A kind of pattern and the controllable WO of composition3Nanometer sheet/g C3N4The preparation method of nano composite material |
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