CN107469869B - Preparation method of photocatalytic fiber web - Google Patents
Preparation method of photocatalytic fiber web Download PDFInfo
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- CN107469869B CN107469869B CN201710728063.2A CN201710728063A CN107469869B CN 107469869 B CN107469869 B CN 107469869B CN 201710728063 A CN201710728063 A CN 201710728063A CN 107469869 B CN107469869 B CN 107469869B
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- padding
- fiber material
- photocatalyst
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 116
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- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 149
- 239000002657 fibrous material Substances 0.000 claims abstract description 96
- 239000011941 photocatalyst Substances 0.000 claims abstract description 91
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- 238000000034 method Methods 0.000 claims abstract description 49
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- 239000010410 layer Substances 0.000 claims description 78
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 73
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 30
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- 239000004814 polyurethane Substances 0.000 claims description 26
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- 229920000742 Cotton Polymers 0.000 claims description 24
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- 238000006243 chemical reaction Methods 0.000 claims description 8
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 58
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 27
- 238000012360 testing method Methods 0.000 description 27
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- 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 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- 241001465754 Metazoa Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- B01J35/58—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention provides a preparation method of a photocatalytic fiber web, which is characterized in that a photocatalytic padding liquid containing a photocatalyst and sol is loaded on a composite fiber material through a padding method, a solvent in the composite fiber material is removed through drying, and finally a frame is used for reinforcing the photocatalytic composite fiber material to obtain the photocatalytic fiber web. The invention takes the composite fiber material as the matrix, and utilizes the characteristic of large specific surface area of the composite fiber material to improve the dispersion uniformity of photocatalyst particles on the surface of the composite fiber material, thereby improving the photocatalytic efficiency; the photocatalytic mangle liquid comprises sol, and the sol and the photocatalyst can form a self-assembled three-dimensional stacked structure on the surface of the composite fiber material, so that the contact area between organic pollutants in the air and the photocatalyst can be increased, and the utilization efficiency of the photocatalyst is further improved.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a preparation method of a photocatalytic fiber net.
Background
With the rapid development of human economic activities and production, a large amount of waste gas and smoke dust are discharged into the atmosphere while a large amount of energy is consumed, and the quality of the atmospheric environment is seriously influenced. In a range of atmospheres, organic pollutants, which were not originally present, are present in amounts and for durations that can be harmful and harmful to humans, animals and plants.
People spend about 80% of the day indoors and in vehicles, and therefore, air purifiers have been receiving attention in recent years. The existing air purifiers in the market mostly adopt methods such as adsorbent adsorption and chemical complexation for removing volatile organic pollutants. These methods have low organic pollutant removal rate and poor air purification effect.
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. However, new fields combining photocatalytic technology with air purification products are still under development.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a photocatalytic fiber web. The preparation method provided by the invention is simple and low in cost, and the prepared photocatalytic fiber net has a good photocatalytic effect, can efficiently degrade volatile organic pollutants in air, and is widely applied to air purification devices.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a photocatalytic fiber web, which comprises the following steps:
(1) padding the composite fiber material in a photocatalytic padding liquid to obtain a padded composite fiber material; the composite fiber material comprises a polyester gauze layer and a polyurethane cotton layer; the photocatalytic mangle liquid comprises a photocatalyst, sol and a solvent;
(2) drying the padded composite fiber material to obtain a photocatalytic composite fiber material;
(3) and reinforcing the photocatalytic composite fiber material by using a frame to obtain the photocatalytic fiber net.
Preferably, the step (1) is replaced by:
padding the composite fiber material in a photocatalyst dispersion liquid and a sol solution respectively to obtain a padded composite fiber material; the photocatalyst dispersion liquid comprises a photocatalyst and a solvent; the sol solution includes a sol and a solvent.
Preferably, the photocatalyst is one or a mixture of more of titanium dioxide, a titanium dioxide-graphene composite, a titanium dioxide-graphite-like phase carbon nitride-metal phthalocyanine composite, a titanium dioxide-tungsten trioxide composite, a graphite-like phase carbon nitride-metal phthalocyanine composite, a metal phthalocyanine-tungsten trioxide composite, a titanium dioxide-graphite-like phase carbon nitride-tungsten trioxide composite, and a titanium dioxide-metal phthalocyanine-tungsten trioxide composite.
Preferably, the sol is silica sol and/or aluminum sol;
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 content of graphene in the sol is 0.1-2% of the mass of the photocatalyst.
Preferably, the mass ratio of the photocatalyst to the solvent in the photocatalytic mangle liquid is 1-30 g: 1L;
the mass of the sol in the photocatalytic mangling liquid and the volume ratio of the solvent are 0.1-15 g:1L of the compound.
Preferably, the mass ratio of the photocatalyst to the solvent in the photocatalyst dispersion liquid is 1-30 g: 1L;
the mass of the sol in the sol solution and the volume ratio of the solvent are 0.1-15 g:1L of the compound.
Preferably, the padding liquid speed of padding is independently 5-60 m/min; the padding liquid pressure of padding is independently 0.05-0.5 MPa.
Preferably, the drying temperature is 80-130 ℃.
Preferably, the surfaces of the polyester gauze layer and the polyurethane cotton layer independently further comprise a metal layer;
the metal layer is made of one or more of nickel, aluminum and copper.
The invention provides a preparation method of a photocatalytic fiber web, which is characterized in that a photocatalytic padding liquid containing a photocatalyst and sol is loaded on a composite fiber material through a padding method, a solvent in the composite fiber material is removed through drying, and finally a frame is used for reinforcing the photocatalytic composite fiber material to obtain the photocatalytic fiber web. The invention takes the composite fiber material as the matrix, and utilizes the characteristic of large specific surface area of the composite fiber material to improve the dispersion uniformity of photocatalyst particles on the surface of the composite fiber material, thereby improving the photocatalytic efficiency; and the photocatalyst of the present inventionThe chemical padding liquid comprises sol, wherein hydroxyl (-OH) exists on the surfaces of the sol and the photocatalyst, and one water molecule (H) is removed from the sol and the photocatalyst in the contact process2O), a new chemical bond (-O-), wherein the sol and the photocatalyst can form a self-assembled three-dimensional stacked structure on the surface of the composite fiber material after the padding liquid is dried, so that the contact area between organic pollutants in the air and the photocatalyst can be increased, and the utilization efficiency of the photocatalyst is further improved; the addition of the sol enables an isolation layer to be formed between the catalyst and the composite fiber material, so that the phenomenon that the composite fiber material is corroded by the catalyst is avoided, the acting force between the catalyst and the composite fiber material can be enhanced, and the catalyst is not easy to fall off; the preparation method provided by the invention is simple, low in cost and easy for industrial production. The embodiment result shows that the removal rate of formaldehyde by the photocatalytic fiber net obtained by the preparation method provided by the invention can reach 99%, and the photocatalytic activity of the photocatalytic fiber net subjected to a cyclic test after being washed by water has no obvious change, so that the photocatalytic fiber net prepared by the preparation method provided by the invention has strong binding force between the photocatalyst on the surface of the photocatalytic fiber net and the base material, is not easy to fall off, and does not corrode the material of the fiber net in the photocatalytic process.
Drawings
FIG. 1 shows the results of the photocatalytic degradation test in example 1 of the present invention;
FIG. 2 is a surface observation result of the polyester fiber mat in example 7 of the present invention.
Detailed Description
The invention provides a preparation method of a photocatalytic fiber web, which comprises the following steps:
(1) padding the composite fiber material in a photocatalytic padding liquid to obtain a padded composite fiber material; the composite fiber material comprises a polyester gauze layer and a polyurethane cotton layer; the photocatalytic mangle liquid comprises a photocatalyst, sol and a solvent;
(2) drying the padded composite fiber material to obtain a photocatalytic composite fiber material;
(3) and reinforcing the photocatalytic composite fiber material by using a frame to obtain the photocatalytic fiber net.
The invention padding the composite fiber material in the photocatalysis padding liquid to obtain the padded composite fiber material. In the present invention, the composite fiber material comprises a polyester gauze layer and a polyurethane cotton layer, and in some specific embodiments of the present invention, the composite fiber material preferably comprises a polyester gauze layer and a polyurethane cotton layer which are laminated at intervals; more preferably a polyester gauze layer and a polyurethane cotton layer; the thickness of the polyester gauze layer is preferably 0.2-1 mm, and more preferably 0.3-0.8 mm; the thickness of the polyurethane foam layer is preferably 0.8-3 mm, and more preferably 1-2.5 mm; in another embodiment of the present invention, the composite fiber material is preferably a sandwich structure; the sandwich structure preferably comprises a core layer, an upper surface layer and a lower surface layer; the core layer is preferably a polyurethane foam layer; the upper surface layer and the lower surface layer are preferably polyester gauze layers; the thicknesses of the polyurethane cotton layer and the polyester gauze layers of the upper and lower surface layers are preferably consistent with the scheme, and are not described again.
In the present invention, the polyester gauze layer and the polyurethane cotton layer preferably independently further comprise a metal layer on the surface; the material of the metal layer is preferably one or more of nickel, aluminum and copper; the thickness of the metal layer is preferably 50-5000 nm, more preferably 100-4500 nm, and most preferably 500-4000 nm; the invention selects the composite fiber material comprising the metal layer, can avoid the direct contact of photocatalyst particles and a polyester gauze layer or a polyurethane cotton layer, and avoids the corrosion phenomenon of the catalyst to a carrier.
In the invention, the pore diameter of the composite fiber material is preferably 5-200 PPI, and more preferably 20-150 PPI; the area of the composite fiber material is not particularly required in the invention, and in the specific embodiment of the invention, the area of the composite fiber material is preferably determined according to actual requirements. The source of the composite fiber material is not particularly limited in the present invention, and a composite fiber material having a source known to those skilled in the art and meeting the above requirements, such as a commercially available composite fiber material, may be used.
In the present invention, the photocatalytic mangle includes a photocatalyst, a sol, and a solvent. In the present invention, the photocatalyst is preferably one or a mixture of several of titanium dioxide, a titanium dioxide-graphene composite, a titanium dioxide-graphite-like phase carbon nitride-metal phthalocyanine composite, a titanium dioxide-tungsten trioxide composite, a graphite-like phase carbon nitride-metal phthalocyanine composite, a metal phthalocyanine-tungsten trioxide composite, a graphite-like phase carbon nitride-metal phthalocyanine composite, a titanium dioxide-graphite-like phase carbon nitride-tungsten trioxide composite, and a titanium dioxide-metal phthalocyanine-tungsten trioxide composite.
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 has no special requirement on the source of the graphite-like phase carbon nitride-metal phthalocyanine compound, and uses the commercial graphite-like phase carbon nitride-metal phthalocyanine or uses the fieldThe preparation can be carried out by methods well known to the skilled person; in a particular embodiment of the invention, preference is given to using the reference (Lu Wangyang, Xu Tiefeng, Wang Yu, et al. synthetic photocatalytic 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 present invention has no particular requirement for the source of the metal phthalocyanine-tungsten trioxide complex, and can be prepared using commercially available commercial metal phthalocyanine-tungsten trioxide complexes or using methods 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 mass of the photocatalyst in the photocatalytic mangle liquid and the volume ratio of the solvent are preferably 1-30 g:1L, more preferably 3-20 g:1L, and still more preferably 5-15 g: 1L.
In the invention, the sol is silica sol and/or aluminum sol; the mass of the sol in the photocatalytic mangling liquid and the volume ratio of the solvent are preferably 0.1-15 g:1L, more preferably 0.3-10 g:1L, most preferably 0.5-5 g: 1L; 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 2-50 wt%, more preferably 10-30 wt%, and most preferably 15-25 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 padding liquid 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 the composite fiber 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 composite fiber material, so that the phenomenon that the composite fiber material is corroded by the catalyst is avoided, the acting force between the catalyst and the composite fiber 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 present invention, the preparation method of the photocatalytic mangle preferably comprises the following steps:
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 mangle liquid.
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 mangle liquid. 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.
After the photocatalytic padding liquid is obtained, the composite fiber material is padded in the photocatalytic padding liquid to obtain the padded composite fiber material. In the invention, the dipping time in the padding is preferably 30-120 s, and more preferably 50-100 s; the padding liquid speed of padding is preferably 5-60 m/min, more preferably 10-50 m/min, and most preferably 15-40 m/min; the padding liquid pressure of padding 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 the padding is preferably 1: 10-200, and more preferably 1: 15-100; the padding residual rate of padding is preferably 30-200%, and more preferably 40-100%; the invention has no special requirements on the specific padding mode, and the padding method known by the technicians in the field can be used, such as one-dipping one-padding, two-dipping two-padding or three-dipping 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 present invention, the step (1) may be replaced by: and padding the composite fiber material in the photocatalyst dispersion liquid and the sol solution to obtain the padded composite fiber material.
In the present invention, the photocatalyst dispersion liquid includes a photocatalyst and a solvent; the mass of the photocatalyst in the photocatalytic dispersion liquid and the volume ratio of the solvent are preferably 1-30 g:1L, more preferably 3-20 g:1L, and most preferably 5-15 g: 1L; the types of the photocatalyst and the solvent are consistent with the scheme, and are not described again; the preparation method of the photocatalyst dispersion liquid is consistent with the scheme, and the details are not repeated.
In the present invention, the sol solution includes a sol and a solvent; the mass of the sol in the sol solution and the volume ratio of the solvent are 0.1-15 g:1L, more preferably 0.3-10 g:1L, most preferably 0.5-5 g: 1L; the kind of the sol and the solvent is preferably the same as in the above scheme, and will not be described herein.
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.
And (3) padding the composite fiber material in the photocatalyst dispersion liquid and the sol solution respectively to obtain the padded composite fiber material. 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 invention, when the composite fiber material is a sandwich structure, because the composite fiber material has a net structure, in the padding process, padding liquid can penetrate into the composite fiber material, so that catalyst particles and sol particles can be attached to a core layer (polyurethane cotton layer) of the sandwich structure.
After the padded composite fiber material is obtained, the padded composite fiber material is dried to obtain the photocatalytic composite fiber material. In the present invention, the drying is preferably oven drying; 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 mangle liquid is removed through drying, and after the solvent is removed, the photocatalyst and the sol are loaded on the surface of the composite 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.
After the photocatalytic composite fiber material is obtained, the photocatalytic composite fiber material is reinforced by a frame to obtain the photocatalytic fiber net. The present invention does not require any particular method for said reinforcement, and may be implemented using reinforcement methods known to those skilled in the art.
The photocatalyst and the sol are loaded on the surface of the composite fiber material through padding and drying, and the dry film loading capacity of the photocatalyst on the surface of the composite fiber material is preferably 1-20 g/m2More preferably 2 to 17g/m2Most preferably 5 to 15g/m2。
The photocatalytic fiber net prepared by the preparation method has a photocatalytic function, and can perform photocatalytic oxidation on organic pollutants in the air to degrade the organic pollutants into small molecular substances; in the embodiment of the invention, the air purifier can be applied to air purification, such as air purifiers and other devices; in the invention, the air purification is mainly catalytic oxidation of volatile organic pollutants, and the volatile organic pollutants preferably comprise indoor volatile organic pollutants or compounds such as formaldehyde, mercaptoethanol, toluene, hydrocarbons or benzene series.
The photocatalytic fiber net obtained by the preparation method has no special requirements on a photocatalytic response light source, and can be prepared by using photocatalytic response light sources well known by persons skilled in the art, such as ultraviolet light, sunlight, fluorescent lamps, LED lamps, xenon lamps, deuterium lamps and the like.
The following examples are provided to illustrate the preparation and application of the photocatalytic fiber web of the present invention in detail, but they should not be construed as limiting the scope 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) Taking a 330 x 420mm composite fiber material (the upper surface layer and the lower surface layer are polyester gauze layers, the thickness is 0.5mm, the sandwich layer is a polyurethane cotton layer, the thickness is 1mm, the surfaces of the polyester gauze layer and the polyurethane cotton layer are both plated with 100nm nickel metal layers), soaking the composite fiber material in the sol solution obtained in the step (2) for 30s, then padding the composite fiber material on a padding machine, then soaking the composite fiber material in the catalyst dispersion liquid obtained in the step (1) after padding is finished, and padding the composite fiber material on the padding machine after 30s of padding. In the padding process, the speed of the padding machine is set to be 15m/min, and the pressure is set to be 0.1 MPa. Repeating the steps of dipping and padding once, namely dipping and padding twice. After padding, drying in an oven at 80 ℃ for 30min to obtain the photocatalyst with the load of 1g/m2The photocatalytic composite fiber material of (1).
(4) And (4) reinforcing the photocatalytic composite material obtained in the step (3) by using a polyester frame to obtain the photocatalytic air purification fiber net.
Photocatalytic degradation test: under an ultraviolet lamp, the photocatalytic fiber net prepared by the embodiment is placed in a sealed box body to carry out a photocatalytic degradation experiment on formaldehyde, a formaldehyde detector is arranged in the box body to carry out real-time monitoring on the formaldehyde concentration, and data are read and recorded every 15 min. Wherein the initial concentration of formaldehyde is 0.8mg/m3The reaction temperature is 25 ℃, and the size of a test sealing box body is 1m3The ultraviolet lamp was set at 30W, the reaction time was 1h, and the results are shown in FIG. 1.
As can be seen from figure 1, the removal rate of the photocatalytic fiber net to formaldehyde is more than 70% at 30 min; the removal rate of formaldehyde reaches more than 90 percent in 1 hour. The photocatalytic fiber net prepared by the preparation method provided by the invention has high light utilization rate, can effectively perform catalytic oxidation on volatile organic compounds in air, and has good application prospect in air purification.
Photocatalytic degradation cycle test: washing the photocatalytic fiber net subjected to one-time photocatalytic degradation experiment with deionized water for three times, drying at 60 ℃, performing the photocatalytic degradation experiment according to the steps, then performing the water washing, drying and photocatalytic degradation experiments on the photocatalytic fiber net, and repeating the steps for 6 times. The experimental result shows that after 6 times of cycle tests, the removal rate of the formaldehyde by the photocatalytic fiber web can still reach more than 90%, which shows that the catalytic activity is basically unchanged, and shows that the binding force between the photocatalyst particles and the fiber web is strong and the photocatalyst particles are 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 a photocatalytic mangle liquid; 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.
(2) And (2) taking a 330 x 420mm composite fiber material (the upper surface layer and the lower surface layer are polyester gauze layers, the thickness of the composite fiber material is 1mm, the sandwich layer is a polyurethane cotton layer, and the thickness of the sandwich layer is 1.5mm), soaking the composite fiber material in the photocatalytic padding liquid in the step (1), and padding the composite fiber material on a padding machine after soaking for 50s, namely, padding one time. In the padding process, the speed of the padding machine is set to be 20m/min, and the pressure is set to be 0.15 MPa. After padding, drying in an oven at 80 ℃ for 30min to obtain the catalyst with the loading of 0.5g/m2The photocatalytic composite fiber material of (1).
(3) And (3) reinforcing the photocatalytic composite material obtained in the step (2) by using a polyester frame to obtain the photocatalytic air purification fiber net.
The photocatalytic degradation test was carried out on the obtained photocatalytic fiber web according to the photocatalytic degradation test method in example 1, in which the initial concentration of formaldehyde was 0.8mg/m3The reaction temperature is 25 ℃, and the size of a test sealing box body is 1m3The ultraviolet lamp is 30W, the reaction time is 1h, and the removal rate of the photocatalytic fiber net to formaldehyde is over 80 percent in 30 min.
The photocatalytic degradation cycle test was performed according to the method of example 1, and after 6 cycles of the cycle test, the removal rate of the photocatalytic fiber web to formaldehyde still reached more than 80%.
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 photocatalyst 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 mangle liquid; the pH value of the silica sol is 10, the concentration is 20 +/-1 wt%, and the particle size of the silica sol is 10-20 nm.
(3) And (3) taking a 330 x 420mm composite fiber material (the upper surface layer and the lower surface layer are polyester gauze layers, the thickness of each composite fiber material is 1mm, the sandwich layer is a polyurethane cotton layer, the thickness of each composite fiber material is 1.5mm, the surfaces of the polyester gauze layers and the polyurethane cotton layers are both plated with 100nm copper metal layers), soaking the composite fiber material in the photocatalytic mangle liquid obtained in the step (2), and after soaking for 100 seconds, padding the composite material on a padding machine, namely, one-padding and one-padding. 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. After padding, drying in a drying oven at 100 ℃ for 30min to obtain the catalyst with the loading capacity of 0.45g/m2The photocatalytic composite fiber material of (1).
(4) And (4) reinforcing the photocatalytic composite material obtained in the step (3) by using a polyester frame to obtain the photocatalytic air purification fiber net.
The photocatalytic degradation test was carried out on the obtained photocatalytic fiber web according to the photocatalytic degradation test method in example 1, in which the initial concentration of formaldehyde was 0.8mg/m3The reaction temperature is 25 ℃, and the size of a test sealing box body is 1m3The ultraviolet lamp is 30W, the reaction time is 1h, and the removal rate of the photocatalytic fiber net to formaldehyde is more than 90% in 1 h.
The photocatalytic degradation cycle test was performed according to the method of example 1, and after 6 cycles of the cycle test, the removal rate of the photocatalytic fiber web to formaldehyde still reached 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 6h to obtain g-C3N4。
G to C3N41.0g of the mixture was mixed with 100ml of N-dimethylformamide and sonicated at 500W for 5h to give g-C3N4A dispersion liquid; anatase type TiO with the particle size of 50nm22.0g of the mixture is mixed with 100mL of N, N-dimethylformamide and 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 50mLN, N-dimethylformamide, and performing ultrasonic treatment at 200W for 30h to obtain an unsubstituted iron phthalocyanine solution;
dropwise adding the mixed dispersion liquid into the unsubstituted iron phthalocyanine solution at the speed of 50mL/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 0.2mol/L NaOH solution and 0.1mol/L H2SO4Respectively 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) Taking a composite fiber material with the size of 330 x 420mm (the upper surface layer and the lower surface layer are polyester gauze layers, the thickness is 1mm,and (3) the sandwich layer is a polyurethane cotton layer, the thickness of the sandwich layer is 1.5mm, the surfaces of the polyester gauze layer and the polyurethane cotton layer are both plated with 100nm aluminum metal layers, the polyurethane gauze layer and the polyurethane cotton layer are firstly soaked in the sol solution in the step (2) for 50s, then the composite material is padded on a padding machine, after padding is finished, the composite material is soaked in the photocatalyst dispersion liquid in the step (2), and after 50s of soaking, the composite material is padded on the padding machine, namely, one padding is carried out. In the padding process, the speed of the padding machine is set to be 25m/min, and the pressure is set to be 0.25 MPa. After padding, drying in a 110 ℃ oven for 30min to obtain the photocatalyst with the loading capacity of 0.4g/m2The photocatalytic composite fiber material of (1).
(4) And (4) reinforcing the photocatalytic composite material obtained in the step (3) by using a polyester frame to obtain the photocatalytic air purification fiber net.
The photocatalytic degradation test was carried out on the obtained photocatalytic fiber web according to the photocatalytic degradation test method in example 1, in which the initial concentration of formaldehyde was 0.8mg/m3The reaction temperature is 25 ℃, and the size of a test sealing box body is 1m3The ultraviolet lamp is 30W, the reaction time is 1h, and the removal rate of the formaldehyde by the photocatalytic fiber net reaches more than 90% in 45 min.
The photocatalytic degradation cycle test was performed according to the method of example 1, and after 6 cycles of the cycle test, the removal rate of the photocatalytic fiber web to formaldehyde still reached more than 90%.
Example 5
(1) Placing 15g of urea in a semi-closed alumina crucible with a cover, heating to 545 deg.C at a heating rate of 1 deg.C/min in a tube furnace, and maintaining for 6h to obtain g-C3N4；
(2) 0.5g of tungsten trioxide and 0.7g 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 mangle liquid; 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) 330 x 420mm in sizeAnd (3) soaking the small composite fiber material (the upper surface layer and the lower surface layer are polyester gauze layers, the thickness of each of the polyester gauze layers is 1mm, the sandwich layer is a polyurethane cotton layer, the thickness of each of the polyurethane gauze layers is 1.5mm, the surfaces of the polyester gauze layers and the polyurethane cotton layers are both plated with 100nm of aluminum metal layers) in the photocatalyst padding liquid obtained in the step (2) for 120s, padding the composite material on a padding machine, and repeating the processes of padding and soaking once, namely, two times of padding and two times of padding. In the padding process, the speed of the padding machine is set to be 25m/min, and the pressure is set to be 0.2 MPa. And after padding, drying in a 100 ℃ oven for 30 min. The loading of the photocatalyst is 1g/m2The photocatalytic composite fiber material of (1).
(4) And (4) reinforcing the photocatalytic composite material obtained in the step (3) by using a polyester frame to obtain the photocatalytic air purification fiber net.
The photocatalytic degradation test was carried out on the obtained photocatalytic fiber web according to the photocatalytic degradation test method in example 1, in which the initial concentration of formaldehyde was 0.8mg/m3The reaction temperature is 25 ℃, and the size of a test sealing box body is 1m3The ultraviolet lamp is 30W, the reaction time is 1h, and the removal rate of the photocatalytic fiber net to formaldehyde is over 85 percent in 30 min.
The photocatalytic degradation cycle test was performed according to the method of example 1, and after 6 cycles of the cycle test, the removal rate of the photocatalytic fiber web to formaldehyde still reached more than 85%.
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) Take 330 x 420The composite fiber material (the upper surface layer and the lower surface layer are polyester gauze layers, the thickness is 1mm, the sandwich layer is a polyurethane cotton layer, the thickness is 1.5mm, the surfaces of the polyester gauze layer and the polyurethane cotton layer are both plated with 100nm aluminum metal layers) with the size of mm is firstly soaked in the catalyst dispersion liquid in the step (2), after 60 seconds of soaking, the composite material is padded on a padding machine, after the padding is finished, the composite material is firstly soaked in the sol solution in the step (2), and after 60 seconds of soaking, the composite material is padded on the padding machine. In the padding process, the speed of the padding machine is set to be 25m/min, and the pressure is set to be 0.2 MPa. Repeating the processes of dipping and padding twice, namely three times of dipping and three times of padding. After padding, drying in a drying oven at 150 ℃ for 13min to obtain the photocatalyst with the loading capacity of 1.5g/m2The photocatalytic composite fiber material of (1).
(4) And (4) reinforcing the photocatalytic composite material obtained in the step (3) by using a polyester frame to obtain the photocatalytic air purification fiber net.
The photocatalytic degradation test was carried out on the obtained photocatalytic fiber web according to the photocatalytic degradation test method in example 1, in which the initial concentration of formaldehyde was 0.8mg/m3The reaction temperature is 25 ℃, and the size of a test sealing box body is 1m3The ultraviolet lamp is 30W, the reaction time is 1h, and the removal rate of the photocatalytic fiber net to formaldehyde is more than 90% in 30 min.
The photocatalytic degradation cycle test was performed according to the method of example 1, and after 6 cycles of the cycle test, the removal rate of the photocatalytic fiber web to formaldehyde still reached more than 90%.
Example 7
In order to more easily observe whether the fiber web substrate is easily corroded in the photocatalysis process, the white polyester fiber felt with the same quality as the fiber web is used for carrying out the photocatalysis experiment, and the observation phenomenon comprises the following specific steps:
(1) the polyester fiber felt is soaked in the sol solution prepared in the step (2) of the embodiment 1 for 30 seconds, the composite fiber material is padded on a padding machine, the composite fiber material is soaked in the catalyst dispersion liquid in the step (1) after the padding is finished, and the composite fiber material is padded on the padding machine after the composite fiber material is soaked for 30 seconds. In the padding process, the speed of the padding machine is set to be 15m/min, and the pressure is set to be 0.1 MPa. Repeating the steps of dipping and padding once, namely dipping and padding twice. After padding, drying in an oven at 80 ℃ for 30min to obtain an experimental group;
(2) padding a polyester fiber felt in the catalyst dispersion liquid prepared in the step (1) in the embodiment 1, and then drying, wherein padding and drying conditions are consistent with those in the step (1), so as to obtain 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 2, wherein the polyester fiber felt of the control group turns yellow according to the 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 fiber web prepared by the preparation method provided by the invention does not corrode the material of the fiber web in the photocatalytic process.
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 method of making a photocatalytic web, comprising the steps of:
(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 6h to obtain g-C3N4；
G to C3N41.0g of the mixture was mixed with 100ml of N-dimethylformamide and sonicated at 500W for 5h to give g-C3N4A dispersion liquid; anatase type TiO with the particle size of 50nm22.0g of the mixture is mixed with 100mLN, N-dimethylformamide and treated with ultrasound for 8 hours under 200W to obtain TiO2A dispersion liquid; subjecting said g-C to3N4Dispersion and TiO2Mixing the dispersions, stirring at 500rpm for 2h to obtain a mixtureMixing the dispersion liquid;
mixing 40mg of unsubstituted iron phthalocyanine with 50mLN, N-dimethylformamide, and performing ultrasonic treatment at 200W for 30h to obtain an unsubstituted iron phthalocyanine solution;
dropwise adding the mixed dispersion liquid into the unsubstituted iron phthalocyanine solution at the speed of 50mL/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 0.2mol/L NaOH solution and 0.1mol/L H2SO4Respectively washing for 2 times, finally washing with ultrapure water to be neutral, and freeze-drying at-60 ℃ for 16h to obtain the titanium dioxide and graphite-like phase carbon nitride and iron phthalocyanine composite photocatalyst;
(2) placing 1g of the titanium dioxide, graphite-like phase carbon nitride and iron phthalocyanine composite photocatalyst in the step (1) 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) taking a 330 x 420mm composite fiber material, soaking the composite fiber material in the sol solution in the step (2) for 50s, then padding the composite material on a padding machine, soaking the composite fiber material in the photocatalyst dispersion liquid in the step (2) after padding is finished, and padding the composite fiber material on the padding machine after 50s of soaking, namely, one-padding; in the padding process, the speed of a padding machine is set to be 25m/min, and the pressure is set to be 0.25 MPa; after padding, drying in a 110 ℃ oven for 30min to obtain the photocatalyst with the loading capacity of 0.4g/m2The photocatalytic composite fiber material of (1); the upper surface layer and the lower surface layer of the composite fiber material are polyester gauze layers with the thickness of 1mm, the sandwich layer is a polyurethane cotton layer with the thickness of 1.5mm, and the surfaces of the polyester gauze layer and the polyurethane cotton layer are both plated with 100nm aluminum metal layers;
(4) and (4) reinforcing the photocatalytic composite material obtained in the step (3) by using a polyester frame to obtain the photocatalytic fiber net.
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| CN102631910A (en) * | 2012-03-20 | 2012-08-15 | 中国海洋石油总公司 | Stable graphene/titanium oxide composite nanosol and preparation method thereof |
| CN105451882A (en) * | 2013-03-12 | 2016-03-30 | 株式会社东芝 | Photocatalyst and photocatalyst dispersion using same, photocatalyst coating, photocatalyst film, and product |
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| CN101485974A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Method for supporting nano titanic oxide on surface of carrier material |
| CN102631910A (en) * | 2012-03-20 | 2012-08-15 | 中国海洋石油总公司 | Stable graphene/titanium oxide composite nanosol and preparation method thereof |
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