CN115739063B - Titanium oxide multistage array photocatalytic film and preparation method thereof - Google Patents
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 65
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 29
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 27
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 14
- 238000007146 photocatalysis Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002070 nanowire Substances 0.000 abstract description 16
- 239000004408 titanium dioxide Substances 0.000 abstract description 8
- 239000002057 nanoflower Substances 0.000 abstract description 6
- 239000002073 nanorod Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 150000007522 mineralic acids Chemical class 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 48
- 239000000047 product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 5
- 230000012010 growth Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002061 nanopillar Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention discloses a novel titanium oxide multistage array photocatalytic film and a preparation method thereof. The film grows on a titanium metal substrate and is made of TiO 2 The nanowire or the nanorod array is used as a trunk and TiO (titanium dioxide) wrapped on the top of the trunk 0.89 A multistage nano array formed by nano particles or nano flower branches. The main preparation process is as follows: in a certain temperature range, the titanium sheet reacts in a reaction solution containing hydrogen peroxide, tetraethylenepentamine and inorganic acid for a certain time, and the titanium sheet is subjected to high-temperature heat treatment in the air, so that the titanium oxide multi-stage array is finally obtained. The film has excellent photocatalytic activity under simulated sunlight irradiation.
Description
Technical Field
The invention relates to a titanium oxide multistage array photocatalytic film and a preparation method thereof, belongs to the technical field of photocatalysis, and can be used in the environmental protection fields of self-cleaning, sewage treatment, pollutant degradation, air purification and the like.
Background
With the progress of globalization, the problems of environmental pollution and high energy consumption are outstanding, and the effective way for treating pollution is found, and the mode of realizing clean sustainable development becomes the consensus of modern society. Electrons in the valence band of the semiconductor material are excited by photons to jump to the conduction band to generate photo-generated carriers, and a specific oxidation-reduction reaction occurs, so that the purpose of degrading pollutants is achieved. Titanium oxide is a wide forbidden band semiconductor with high stability, low cost, environmental protection and wide application, and has a plurality of applications in the fields of photocatalysis and the like. The titanium oxide nano powder has large specific surface area and good catalytic effect, but is easy to cause agglomeration and difficult to recycle, so that secondary pollution is formed; the titanium oxide array film can be recycled, so that secondary pollution is avoided, but the preparation process is difficult, the photocatalysis effect is inferior to that of nano powder, and the industrialization application of the titanium oxide array film is restricted. Therefore, the development of the titanium oxide array film with simple preparation process and excellent photocatalytic performance has important significance.
In order to improve the photocatalytic performance of the titanium oxide array film, a multistage array is constructed. Not only can the specific surface area of the oxidation state film be increased, but also a heterojunction can be formed, the separation of photon-generated carriers is promoted, and the photocatalysis efficiency is improved. There have been some studies on the structure of titanium oxide multi-stage arrays. The template method is the earliest mode applied to the preparation of titanium dioxide branched structure films. Li et al adopts a polystyrene alternating monolayer film as a template, and adopts laser pulse deposition to emit on the template to prepare the titanium dioxide nano-pillar. The nanopillar exhibits a good self-cleaning effect without ultraviolet rays. However, the equipment is difficult to realize industrialized mass production. Wang et al first deposited a titanium dioxide nanorod array on an FTO glass substrate by a hydrothermal method and then grown titanium dioxide nanobranches in a liquid phase deposition method using titanium tetrachloride as the titanium source. The branched structure exhibits a good photocatalytic effect. The preparation process is complex, the flow is multiple, the raw material consumption required by the preparation is large, and the preparation has challenges for realizing industrialization. Moreover, the current titanium oxide graded array films focus much on TiO 2 Growth of TiO on trunks 2 The branches, the trunk and the branches have small phase difference, and the constructed heterojunction effect is not obvious.
Disclosure of Invention
The invention designs and realizes a novel titanium oxide multi-stage array photocatalytic film, and the preparation technology thereofTitanium-hydrogen peroxide-tetraethylenepentamine-based reaction system for growing TiO on titanium metal substrate 2 The nanowire or the nanorod array is taken as a main body, and is combined with the secondary liquid phase growth of the stock solution, and the top of the nanowire or the nanorod array is coated with TiO 0.89 The nano particles or nano flower branches form a three-dimensional multi-stage nano array film with heterogeneous trunks and branches. The invention aims to provide a novel titanium oxide multi-stage array photocatalytic film and a preparation method thereof.
The technical scheme of the invention is as follows:
a novel titanium oxide multi-stage array photocatalysis film is prepared from TiO 2 The nanowire or the nanorod array is taken as a main body, and TiO is coated on the top of the nanowire or the nanorod array 0.89 The nano particles or nano flower branches form a three-dimensional multi-stage nano array film with heterogeneous trunks and branches.
The invention provides a titanium oxide multistage array photocatalytic film, which comprises the following components: a titanium metal substrate, a trunk array growing on the surface of the titanium metal substrate, wherein the trunk array consists of a rod-shaped trunk and branches growing on the top of the rod-shaped trunk; the rod-shaped trunk is made of TiO 2 Crystal structure, tiO 2 The crystal form of the crystal is anatase, and the TiO is 2 The length of the crystal ranges from 20nm to 100nm; the branches are made of granular TiO 0.89 Crystal structure of the granular TiO 0.89 The grain diameter of the crystal ranges from 2nm to 500nm.
The invention also provides a preparation method of the titanium oxide multi-stage array photocatalytic film, which comprises the following steps:
placing the cleaned titanium metal substrate in a hydrogen peroxide water solution with the mass concentration of 3-30%, adding a preset amount of inorganic dilute acid and tetraethylenepentamine into the titanium metal substrate, and reacting for 3-48 hours at 20-90 ℃;
step (2), the whole reaction system is kept stand in a water bath environment with the temperature of 1-4 ℃ for 1 hour;
step (3), the whole reaction system is placed in a temperature of 60-90 ℃ to react for 24-72 hours;
and (4) taking out the sample, cleaning, completely drying, and performing heat treatment for 0.5-3 hours in the air at 400-600 ℃ to obtain the titanium oxide multi-stage array film grown on the titanium metal substrate.
Preferably, in the step (1), the titanium metal substrate is any one of a titanium foil, a titanium sheet, a titanium plate, and a titanium mesh.
Preferably, in the step (1), the dosage ratio of the aqueous hydrogen peroxide solution, the inorganic dilute acid and the tetraethylenepentamine is 50 mL/1 to 10mg; the inorganic dilute acid is any one of nitric acid, sulfuric acid and hydrochloric acid with the mass fraction of 0.01% -5%.
The beneficial effects of the invention are as follows:
compared with the currently reported TiO 2 /TiO 2 The powder or array film is different, and the invention is based on TiO 0.89 And TiO 2 Two heterogeneous titanium oxide multi-level nano array films. TiO perpendicular to metallic titanium substrate 0.89 /TiO 2 The multilevel array is arranged in a quasi-directional mode, the specific surface area of the catalyst is increased due to the increase of the depth space, active sites for capturing light are increased, the contact probability of pollutants and the active sites is increased, and the photocatalysis efficiency is improved; tiO (titanium dioxide) 0.89 And TiO 2 The heterostructure is established to generate a built-in electric field, which is beneficial to reducing the forbidden bandwidth of the array film and further improving the photocatalysis effect; the multi-stage array forms a three-dimensional space, and rich diffuse reflection exists between the multi-planes, so that photon absorption and utilization are facilitated, and further photocatalysis performance is greatly improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, a brief description of the drawings is provided below, and some specific examples of the present invention will be described in detail below by way of example and not by way of limitation with reference to the accompanying drawings. The same reference numbers will be used throughout the drawings to refer to the same or like parts or portions. It will be appreciated by those skilled in the art that the drawings are not necessarily drawn to scale. In the accompanying drawings:
FIG. 1 is a TiO prepared in example 1 2 A field emission scanning electron micrograph of the nanowire array film;
FIG. 2 is a preparation of example 1TiO of (C) 0.89 /TiO 2 A field emission scanning electron micrograph of the multi-level array film;
FIG. 3 is a TiO prepared in example 1 2 Nanowire array thin film, tiO 0.89 /TiO 2 X-ray diffraction pattern of multi-stage array film;
FIG. 4 is a TiO film prepared in example 2 0.89 /TiO 2 A field emission scanning electron micrograph of the multi-level array film;
FIG. 5 is a TiO film prepared in example 3 0.89 /TiO 2 A field emission scanning electron micrograph of the multi-level array film;
FIG. 6 is a TiO prepared in example 4 0.89 /TiO 2 A field emission scanning electron micrograph of the multi-level array film;
FIG. 7 is a graph showing the photocatalytic degradation of rhodamine B in the titanium oxide array films prepared in examples 1 to 4.
Detailed Description
The present invention is further illustrated below with reference to examples, but the present invention is not limited to the following examples.
In the present invention, unless otherwise specified, the materials and equipment used are commercially available or are commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
1) Placing the cleaned titanium sheet into 50mL of hydrogen peroxide water solution with the mass concentration of 3%, adding 1mL of nitric acid with the mass fraction of 0.01% and 1mg of tetraethylenepentamine, and reacting at 20 ℃ for 48 hours;
2) The whole reaction system is kept stand in a low-temperature water bath environment with the temperature of 4 ℃ for 1 hour;
3) Then the whole reaction system is placed at 90 ℃ to react for 24 hours;
4) Taking out a sample, cleaning, completely drying, and performing heat treatment for 3 hours in the air at 400 ℃ to obtain a titanium oxide multi-stage array film growing on a titanium sheet;
FIG. 1 shows that after step 2), the sample is taken out, washed and dried completely to obtain TiO 2 Field emission scanning of nanowire array filmsElectron micrograph, it can be seen that it has a one-dimensional nanowire array structure. FIG. 2 shows the TiO obtained in step 4) 0.89 /TiO 2 The appearance of the product can be seen by a field emission scanning electron microscope photograph of the multi-stage array film, namely a nano flower structure grown on the top of the nanowire, and the multi-stage three-dimensional depth array characteristic is achieved. FIG. 3 shows the TiO obtained after washing and drying the sample obtained after step 2) 2 Nanowire array film, tiO obtained by step 4) 0.89 /TiO 2 The X-ray diffraction pattern of the multi-stage array film is compared with a standard card to obtain products which respectively correspond to metallic titanium and TiO from a substrate 2 And TiO 0.89 . Compared with TiO 2 Nanowire array film, tiO 0.89 /TiO 2 The multi-stage array film is provided with TiO 0.89 The peak of the titanium oxide multi-stage array film is shown to be prepared by secondary growth of stock solution in the embodiment.
Example 2
1) Placing the cleaned titanium plate in 50mL of 30% hydrogen peroxide aqueous solution, adding 5% nitric acid and 10mg tetraethylenepentamine into 1mL of the solution, and reacting for 3 hours at 90 ℃;
2) The whole reaction system is kept stand in a low-temperature water bath environment with the temperature of 1 ℃ for 1 hour;
3) Then the whole reaction system is placed at 60 ℃ to react for 72 hours;
4) Taking out a sample, cleaning, completely drying, and performing heat treatment for 0.5 hour in the air at 600 ℃ to obtain a titanium oxide multi-stage array film growing on a titanium plate;
FIG. 4 shows the TiO obtained in this example 0.89 /TiO 2 The product can be seen to be a three-dimensional multi-stage array morphology as well from a scanning electron micrograph of the multi-stage array film. Compared with fig. 2, the nanowire is thicker, the nanoflower at the top is thicker, the flower shape is larger, and the nanowire has an obvious branch structure.
Example 3
1) Placing the cleaned titanium foil into 50mL of hydrogen peroxide water solution with the mass concentration of 20%, adding 2% sulfuric acid and 7mg tetraethylenepentamine into 1mL at the same time, and reacting for 24 hours at 60 ℃;
2) The whole reaction system is kept stand in a low-temperature water bath environment with the temperature of 1 ℃ for 1 hour;
3) Then the whole reaction system is placed at 80 ℃ to react for 48 hours;
4) Taking out a sample, cleaning, completely drying, and performing heat treatment for 1 hour in the air at 500 ℃ to obtain a titanium oxide multi-stage array film growing on the titanium foil;
FIG. 5 shows the TiO obtained in this example 0.89 /TiO 2 The scanning electron microscope photograph of the multi-stage array film can see that the morphology of the product is different from that of the product shown in fig. 2 and 4, and the top is nano granular TiO 0.89 It is suggested that different mineral acids may induce morphological growth tendencies of nanoparticles or nanoflower.
Example 4
1) Placing the cleaned titanium wire mesh in 50mL of hydrogen peroxide water solution with the mass concentration of 30%, adding 3% hydrochloric acid and 9mg of tetraethylenepentamine with the mass fraction of 1mL, and reacting at 60 ℃ for 48 hours;
2) The whole reaction system is kept stand in a low-temperature water bath environment with the temperature of 3 ℃ for 1 hour;
3) Then the whole reaction system is placed at 60 ℃ to react for 48 hours;
4) Taking out a sample, cleaning, completely drying, and performing heat treatment for 2 hours in the air at 450 ℃ to obtain a titanium oxide multi-stage array film grown on a titanium wire mesh;
FIG. 6 shows the TiO obtained in this example 0.89 /TiO 2 Scanning electron micrographs of multi-stage array films revealed the morphology of the product, which is different from that of FIGS. 2 and 4 and FIG. 5, tiO 0.89 In the shape of nano particles, grown on TiO 2 The side surfaces of the nanowire trunk are integrally formed into tree branch shapes instead of being coated with TiO as shown in figures 2, 4 and 5 2 The top of the trunk, further indicating that different mineral acids affect TiO 0.89 Deposition growth location and morphology.
Comparative test examples 1 to 4 titanium oxide TiO 0.89 /TiO 2 Effect of photocatalytic degradation of rhodamine B molecules in water by multistage array film sampleThe specific method is as follows:
(1) Simulating the photocatalytic performance of sunlight: by 2X 2cm 2 The light intensity of the film in the visible light part is 140mW/cm 2 The light intensity of the ultraviolet part is 4.0mW/cm 2 25mL of the catalytic degradation rate of 0.005mmol/L rhodamine B was characterized under irradiation with a xenon lamp.
(2) The photocatalysis test comprises dark adsorption for 30 minutes and photocatalysis for 120 minutes, and magnetic stirring is continuously carried out in the degradation process, and samples are taken every 30 minutes.
The change in the concentration of the target degradation product was measured by a change in absorbance value at its main absorption wavelength with a UV-1800PC type ultraviolet-visible spectrophotometer, and a photocatalytic degradation curve was drawn as shown in fig. 7. It can be seen that all TiO under simulated sunlight 0.89 /TiO 2 The efficiency of photocatalytic degradation of rhodamine B of the multistage array film sample is higher than that of pure one-dimensional TiO 2 Nanowire array films, which can be attributed to: 1) The titanium dioxide has a plasmon effect under the irradiation of visible light, and can exert the photocatalytic activity; 2) TiO (titanium dioxide) 0.89 /TiO 2 The interface heterojunction formed by the multi-stage array film can promote the separation of photo-generated carriers and improve the photocatalysis efficiency. TiO as obtained in comparative examples 1 to 4 0.89 /TiO 2 The sample prepared in example 4 has a larger surface area and has significant advantages in contact with contaminants and photons. In the present invention, it is shown that the inorganic acid preferably used as the reaction liquid can obtain better photocatalytic performance.
From FIGS. 1, 2, 4, 5 and 6, the products obtained in the examples, tiO 2 The length of the crystal ranges from 20nm to 100nm, and TiO 0.89 The grain diameter of the crystal ranges from 2nm to 500nm.
While the invention has been described with respect to certain preferred embodiments, it will be apparent to those skilled in the art that various changes and substitutions can be made herein without departing from the scope of the invention as defined by the appended claims.
Claims (4)
1. A titanium oxide multi-stage array photocatalysis film is characterized in that,
comprising the following steps: a titanium metal substrate, a trunk array growing on the surface of the titanium metal substrate, wherein the trunk array consists of a rod-shaped trunk and branches growing on the top of the rod-shaped trunk;
the rod-shaped trunk is made of TiO 2 Crystal structure, tiO 2 The crystal form of the crystal is anatase, and the TiO is 2 The length of the crystal ranges from 20nm to 100nm;
the branches are made of granular TiO 0.89 Crystal structure of the granular TiO 0.89 The grain diameter of the crystal ranges from 2nm to 500nm.
2. A method for preparing the titanium oxide multi-stage array photocatalytic film according to claim 1, comprising the steps of:
placing the cleaned titanium metal substrate in a hydrogen peroxide water solution with the mass concentration of 3-30%, adding a preset amount of inorganic dilute acid and tetraethylenepentamine into the titanium metal substrate, and reacting for 3-48 hours at 20-90 ℃;
step (2), the whole reaction system is kept stand in a water bath environment with the temperature of 1-4 ℃ for 1 hour;
step (3), the whole reaction system is placed in a temperature of 60-90 ℃ to react for 24-72 hours;
and (4) taking out the sample, cleaning, completely drying, and performing heat treatment for 0.5-3 hours in the air at 400-600 ℃ to obtain the titanium oxide multi-stage array film grown on the titanium metal substrate.
3. The method for preparing a titanium oxide multi-stage array photocatalytic film according to claim 2, wherein in the step (1), the titanium metal substrate is any one of a titanium foil, a titanium sheet, a titanium plate and a titanium mesh.
4. The method for preparing a titanium oxide multi-stage array photocatalytic film according to claim 2, wherein the dosage ratio of the aqueous hydrogen peroxide solution, the inorganic dilute acid and the tetraethylenepentamine in the step (1) is 50 ml:1-10 mg; the inorganic dilute acid is any one of nitric acid, sulfuric acid and hydrochloric acid with the mass fraction of 0.01% -5%.
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