CN113649046A - Sandwich film and preparation method thereof - Google Patents
Sandwich film and preparation method thereof Download PDFInfo
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- CN113649046A CN113649046A CN202110951310.1A CN202110951310A CN113649046A CN 113649046 A CN113649046 A CN 113649046A CN 202110951310 A CN202110951310 A CN 202110951310A CN 113649046 A CN113649046 A CN 113649046A
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- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 238000005215 recombination Methods 0.000 claims abstract description 5
- 230000006798 recombination Effects 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011941 photocatalyst Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 239000012703 sol-gel precursor Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 229910002915 BiVO4 Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052961 molybdenite Inorganic materials 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 2
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- 238000011068 loading method Methods 0.000 abstract description 9
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- 239000010410 layer Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 11
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 9
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- 238000003795 desorption Methods 0.000 description 5
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- 231100000719 pollutant Toxicity 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical group N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
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- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 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
- 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
- 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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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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- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
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- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a sandwich film and a preparation method thereof. The film forms a multi-layer stable 'layer-layer' catalyst structure by loading a plurality of layers of catalysts with different components on a loading substrate. The catalyst material added as an additive in the layer-by-layer structure can generate a stable Z-shaped semiconductor structure with the original catalyst material, so that the electron-hole recombination rate of the material is greatly reduced, and the photocatalytic efficiency of the photocatalytic material under illumination is improved; meanwhile, the layer-layer structure can also improve the loading capacity of the catalyst material and prolong the service life of the material, and the loaded catalyst is firmly fixed on the surface of the base material by utilizing the intermolecular force of the loaded material, so that the loss of the catalyst in the use environment is reduced.
Description
Technical Field
The invention relates to the technical field of air and water purification, in particular to a sandwich film photocatalyst, a preparation method and application thereof.
Background
At present, a large amount of organic pollutants cannot be treated by the traditional physical and chemical methods, and the biochemical method is always in the way of being overwhelmed when organic pollutants with biological toxicity are treated. The advanced oxidation photocatalysis treatment method has an excellent treatment mode for toxic and harmful organic pollutants (such as volatile organic compounds, various disinfection byproducts, persistent organic pollutants, medicine pollutants and the like). The photocatalytic reaction is characterized in that light energy is used as an energy source for catalytic reaction, and when the light energy received by a semiconductor catalyst is larger than the forbidden bandwidth of the semiconductor catalyst, electrons are excited to jump from a valence band to a conduction band, so that photogenerated holes and photogenerated electrons are generated. Wherein the holes on the valence band have strong reducibility; the photo-generated electrons on the conduction band have strong oxidizing property; the surface of the semiconductor catalyst has extremely strong oxidation-reduction capability, and can carry out thorough oxidation-reduction on organic matters which cannot be thoroughly treated by various traditional treatment modes, such as heavy metal ions and the like. However, the photocatalysis has not been widely applied in the field of environmental treatment so far, and the reasons mainly include the following points: the light response wave band of the photocatalyst is narrow, and the light response wave band of the photocatalyst accounts for only 5% of sunlight by taking common catalyst titanium dioxide as an example; most of the traditional photocatalysts are powder photocatalysts, although the treatment effect on pollutants under illumination is good, the traditional photocatalysts are often difficult to recycle, so that the waste of the catalysts is caused, and secondary pollution to the environment is possibly caused due to the emission of catalyst materials; and thirdly, the traditional supported catalyst has poor weather resistance in extreme environments, and the loss of a large amount of catalyst can quickly deactivate the supported catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for forming a multi-layer stable 'layer-layer' catalyst structure by utilizing the photocatalytic performance of an enhanced supported photocatalyst and loading a plurality of layers of catalysts with different components on a load substrate. The catalyst material added as an additive phase in the layer-by-layer structure can generate a stable Z-shaped semiconductor structure with the original catalyst material, so that the electron-hole recombination rate of the material is greatly reduced, and the photocatalytic efficiency of the photocatalytic material under illumination is improved; meanwhile, the layer-layer structure can also improve the loading capacity of the catalyst material and prolong the service life of the material, and the loaded catalyst is firmly fixed on the surface of the base material by utilizing the intermolecular force of the loaded material, so that the loss of the catalyst in the use environment is reduced.
The invention is realized by the following technical scheme:
a sandwich film, the matrix of the film is uniformly loaded with the prepared sol-gel precursor on the surface of the matrix by a pulling method or a spraying method; wherein the substrate supports thereon a plurality of layers of catalysts having different compositions.
In one of the layers the catalyst is TiO2，WO3，Ag3PO4，BiVO4，Bi2WO6，MoS2And ZnO.
In another of the layers the catalyst is CdS, g-C3N4，ZnGaO，V2O5One kind of (1).
The catalyst and the sol-gel precursor are subjected to high-temperature treatment to generate the catalyst, so that the Z-shaped photocatalytic semiconductor is formed.
The Z-type photocatalytic semiconductor enables photo-generated electrons to be concentrated on a relatively negative conduction band, and photo-generated holes to be concentrated on a relatively positive valence band, so that the recombination of the photo-generated electrons and the photo-generated holes is limited.
The material of the substrate is one of ceramic, graphite, zeolite, stainless steel, nickel and nickel-based alloy, titanium and titanium-based alloy. The shape of the matrix is one of spherical shape, sheet shape, reticular shape, fibrous shape, foam shape and sponge shape.
A preparation method of a sandwich film comprises the following steps: 1) uniformly covering the sol without the additive phase on the surface of the substrate, and after vacuum drying treatment, placing the treated substrate in a muffle furnace for sintering to form a first layer of film; 2) uniformly covering the sol added with the additive phase on the surface of the substrate, and after vacuum drying treatment, placing the treated substrate in a muffle furnace for sintering to form a second layer of film; 3) repeating the step 1) and the step 2) to prepare the sandwich film photocatalyst; 4) the sol used in step 1) and step 2) may be exchanged. In the step 1) and the step 2), atomized liquid drops can be thinned or completely immersed by adopting a hydraulic spray nozzle, and then the substrate is pulled upwards at a constant speed to form a coating. The sandwich film can be applied to air and water purification.
Compared with the prior art, the invention has the beneficial effects that:
1. the film structure is a multilayer film structure, and the components of catalysts of all layers are different and are respectively formed by alternately forming TiO2 and g-C3N4, so that a Z-shaped semiconductor structure beneficial to charge transfer can be formed, photo-generated carriers (charges) are efficiently separated, the photocatalytic efficiency is higher, and the film structure has a catalytic effect on wide spectrum ranges of visible light and ultraviolet light.
2. The present application forms a multi-layer stable "layer-to-layer" catalyst structure by loading multiple layers of catalysts of different compositions on a supporting substrate. The catalyst material added as an additive in the layer-by-layer structure can generate a stable Z-shaped semiconductor structure with the original catalyst material, so that the electron-hole recombination rate of the material is greatly reduced, and the photocatalytic efficiency of the photocatalytic material under illumination is improved; meanwhile, the layer-layer structure can also improve the loading capacity of the catalyst material and prolong the service life of the material, and the loaded catalyst is firmly fixed on the surface of the base material by utilizing the intermolecular force of the loaded material, so that the loss of the catalyst in the use environment is reduced.
3. The Z-type photocatalytic material enables photoproduction electrons to be concentrated on a negative conduction band, and photoproduction holes to be concentrated on a positive valence band, so that the combination of the photoproduction electrons and the photoproduction holes is limited, the oxidation reduction capability of the material is improved, and the absorption range of sunlight spectrum is also improved. The thickness of a single layer of the catalyst film generated by sintering the sol-gel precursor solution or the sol-gel precursor solution added with the additive phase at high temperature is nano-scale to micron-scale; the mass ratio of the addition phase in the sol-gel precursor solution is 0-10% wt.
4. The sandwich film has a Z-shaped semiconductor structure beneficial to charge transfer, can be effectively excited in a partial visible light wave band and an ultraviolet full wave band range below 400nm, and generates photocatalysis efficiency to degrade sewage and purify air.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a SEM illustration (1000X) of a sandwich film;
FIG. 2 is a SEM illustration (2000X) of a sandwich film;
FIG. 3 is a schematic diagram of a TiO2/g-C3N4/TiO2 supported photocatalytic film prepared on a ceramic carrier;
FIG. 4 is a comparison of XRD diffraction patterns of a TiO2 film, g-C3N4, sandwich (TiO 2g-C3N4/TiO 2) film;
FIG. 5 is a graph of the response of the photogenerated voltage to the UV excitation light source (λ max =254 nm) for a sandwich film;
FIG. 6 is a graph of the response of the photo-generated current to the UV excitation light source for a sandwich film (λ max =254 nm);
fig. 7 is a graph comparing the photocatalytic degradation performance of a model contaminant, Methylene Blue (MB).
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
The invention will now be described in further detail by way of specific examples in conjunction with figures 1-6.
Example 1
Step one, preparing sol containing an additive phase: adding 10 wt% of g-C3N4 into a sol taking tetrabutyl titanate as a main effective component, sequentially stirring for 1h under the condition of sealing by using a magnetic stirrer at 550rpm, and performing ultrasonic dispersion for 30min to obtain a uniform and stable sol containing an addition phase.
Step two, loading a film on the substrate: and (3) refining the sol containing the additive phase prepared in the step one by using a hydraulic spray nozzle, uniformly spraying the refined sol on the surface of a pre-treated titanium alloy film (300 mm multiplied by 900mm multiplied by 0.1 mm), and drying for 2 hours in an oven at 70 ℃.
Step three, firing a matrix load film: placing the film prepared in the step two in a muffle furnace for sintering; heating to 450 ℃ at a speed of 10 ℃/min, preserving heat for 1h, cooling the film along with the furnace, and taking out.
Step four, loading a film on a substrate: and (3) refining the sol using tetrabutyl titanate as a main effective component in the step one by using a hydraulic spray nozzle, uniformly spraying the refined sol on the surface of the film prepared in the step three, and drying the film in an oven at 70 ℃ for 2 hours.
Step five, firing a matrix load film: placing the film prepared in the fourth step into a muffle furnace for sintering; heating to 450 ℃ at a speed of 10 ℃/min, preserving heat for 1h, cooling the film along with the furnace, and taking out.
The prepared catalytic material is characterized by using a scanning electron microscope, after the film is sintered twice, the roughness of the surface of the material is obviously increased, the material on the surface of the catalytic film is in cross-linked distribution and has no obvious cracks, carbon nitride parts at each part of the surface are distributed in an isolated island manner, films in other areas are mutually cross-linked to show extremely high integrity, and the surface compactness of the material without a substrate exposed is excellent.
The TiO2/C3N4/TiO2 sandwich film can effectively act in the ultraviolet full-wave band range and partial visible light range of < =500nm, and the structural arrangement of the sandwich film is improved by combining experimental data and relevant schematic diagrams.
The material is obtained by XRD analysis of pure g-C3N4, pure TiO2 and a sandwich film, the crystal structure of the surface material of the sandwich film is the same as that of a pure TiO2 film, so the material has excellent response capability under an ultraviolet band, in addition, the maximum absorption peak of the g-C3N4 material obtained by an ultraviolet visible absorption spectrum is 386nm, the light absorption capability is strong in a range of 386nm to 500nm, and the fluorescence excitation spectrum shows that the fluorescence excitation intensity is strongest under 454 nm. The catalyst system is proved to be capable of carrying out effective photocatalytic reaction in the ultraviolet full-wave band and partial visible light range.
Example 2
The photogeneration voltage and photogeneration current performance of the catalytic material prepared in example 1 are measured. The test was performed using the Shanghai Chenghua CHI700E electrochemical workstation three-electrode system. The catalytic material was used as the working electrode, the electrode area was 1809.56 mm 2. A3.5 wt% sodium chloride solution is used as a test environment, a cold cathode ultraviolet lamp with the dominant wavelength =254nm and the rated power of 1w is placed at a position 0.5 cm away from a working electrode in parallel, and the cold cathode ultraviolet lamp is controlled to be switched on and off to determine the change situation of the voltage and the current of the surface of the electrode under the conditions of light excitation and no light. The test results are shown in FIGS. 5-6: the following table shows that the prepared material shows excellent photoelectric response performance expansion under optical excitation.
| Kind of photocatalytic film | She reference electrode excitation light wavelength λ =254nm (× 10) at a photo-generated current vs-5A） |
| Sandwich film | 11.236 |
| Pure TiO2 film | 4.864 |
| Pure g-C3N4 film | 0.025 |
Example 3
The catalytic performance was determined using the catalytic material prepared in example 1 with methylene blue as the model contaminant. Cutting a catalytic membrane loaded with 50mg of catalytic material into a wafer with the diameter of 1mm, putting 50 mL of methylene blue trihydrate solution with the concentration of 25 mg/L into a quartz reactor with the effective volume of 100 mL together for dark adsorption and desorption balance for 2h, adjusting a xenon lamp to 300w, placing a 420nm cut-off filter for test, sampling respectively when the adsorption and desorption balance is 0min, the adsorption and desorption balance is 120 min, and photocatalysis is carried out for 10, 20, 30, 45 and 60min, and scanning at the wave band of 500nm-700nm under an ultraviolet spectrophotometer. Wherein the absorbance at 664 nm can be used to linearly characterize the presence of methylene blue in a body of water. In the embodiment, the band below 420nm (including the ultraviolet full-spectrum band) in the xenon lamp simulating the sun is shielded by adding the 420nm cut-off filter, so that the high-efficiency photocatalytic degradation performance of the catalytic material in the visible light band is completely embodied. The following table shows the degradation effect of the sandwich film system on Methylene Blue (MB).
| Reaction time | Absorbance (Abs) at 664 nm of the solution | Methylene blue removal (%) |
| Adsorption and desorption balance for 0min | 3.905 | 0 |
| Adsorption and desorption balance for 120 min | 3.69 | 5.505761844 |
| Photocatalysis for 10 min | 1.654 | 57.64404609 |
| Photocatalysis for 20 min | 1.073 | 72.52240717 |
| Photocatalysis for 30min | 0.291 | 92.54801536 |
| Photocatalysis for 45 min | 0.09 | 97.69526248 |
| Photocatalysis for 60min | 0.097 | 97.51600512 |
As can be seen from FIG. 7, the catalytic material prepared by the invention has excellent photocatalytic performance, and the sandwich film can remove more than 90% of methylene blue in the solution for 30min under the irradiation of visible light to the model pollutant, namely the methylene blue. The first-order reaction rate constant K value of the degradation is K in three systemsSandwich film=0.0845；Kg-C3N4=0.0079；KTiO2 film= 0.0371; as can be seen, the photocatalytic degradation capability of the sandwich structure film is far higher than that of a pure TiO2 film system and a g-C3N4 system, which are respectively about 10.69 times and 2.77 times.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent variations and modifications made to the above embodiments according to the technical spirit of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A sandwich film, comprising: the prepared sol-gel precursor is uniformly loaded on the surface of a matrix of the film by a pulling method or a spraying method; wherein the substrate is loaded with a plurality of layers of catalysts with different components to form a sandwich film.
2. The sandwich film of claim 1, wherein: in one of the layers the catalyst is TiO2，WO3，Ag3PO4，BiVO4，Bi2WO6，MoS2And ZnO.
3. The sandwich film of claim 1, wherein: in another of the layers the catalyst is CdS, g-C3N4，ZnGaO，V2O5One kind of (1).
4. The sandwich film of claim 3, wherein: the catalyst and the sol-gel precursor are subjected to high-temperature treatment to generate the catalyst which forms the components of the Z-type photocatalytic semiconductor and effectively acts in the ultraviolet full-wave range and partial visible light range of < =500 nm.
5. The sandwich film of claim 4, wherein: the Z-type photocatalytic semiconductor enables photo-generated electrons to be concentrated on a relatively negative conduction band, and photo-generated holes to be concentrated on a relatively positive valence band, so that the recombination of the photo-generated electrons and the photo-generated holes is limited.
6. The sandwich film of claim 1, wherein: the material of the substrate is one of ceramic, graphite, zeolite, stainless steel, nickel and nickel-based alloy, titanium and titanium-based alloy.
7. The sandwich film of claim 1, wherein: the shape of the matrix is one of spherical shape, sheet shape, reticular shape, fibrous shape, foam shape and sponge shape.
8. The method of making a sandwich film of any one of claims 1-7, wherein: the method comprises the following steps: 1) uniformly covering the sol without the additive phase on the surface of the substrate, and after vacuum drying treatment, placing the treated substrate in a muffle furnace for sintering to form a first layer of film; 2) uniformly covering the sol added with the additive phase on the surface of the substrate, and after vacuum drying treatment, placing the treated substrate in a muffle furnace for sintering to form a second layer of film; 3) repeating the step 1) and the step 2) to prepare the sandwich film photocatalyst; 4) the sol used in step 1) and step 2) may be exchanged.
9. The method of manufacturing a sandwich film of claim 8, wherein: in the step 1) and the step 2), atomized liquid drops can be thinned or completely immersed by adopting a hydraulic spray nozzle, and then the substrate is pulled upwards at a constant speed to form a coating.
10. Use of the sandwich film of any of claims 1-7 for air and water purification.
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