CN111437857B - Photocatalytic film based on titanium nitride and titanium oxide and preparation method thereof - Google Patents
Photocatalytic film based on titanium nitride and titanium oxide and preparation method thereof Download PDFInfo
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 62
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002070 nanowire Substances 0.000 claims abstract description 50
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010936 titanium Substances 0.000 claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000002485 combustion reaction Methods 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004471 Glycine Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000002135 nanosheet Substances 0.000 claims description 5
- 238000003491 array Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 6
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 60
- 238000007146 photocatalysis Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 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 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 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
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- -1 titanium-hydrogen peroxide-melamine Chemical compound 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention discloses a photocatalytic film based on titanium nitride and titanium oxide and a preparation method thereof. The film is grown on a titanium substrate and made of TiN0.3/TiO0.89Nanowire array as trunk and anatase phase TiO wrapped on trunk2The nanometer sheet branches form a three-dimensional nanometer array. The main preparation process comprises the following steps: reacting the titanium sheet in a reaction solution containing hydrogen peroxide for a certain time within a certain temperature range, and performing high-temperature thermal treatment in an ammonia atmosphere to obtain TiN0.3/TiO0.89A nanowire array; and (3) placing the nanowire array in solution combustion precursor liquid for reaction for a certain time, and performing high-temperature heat treatment in a subsequent air atmosphere to finally obtain the titanium nitride/titanium oxide three-dimensional nanowire array film. The film has excellent photocatalytic activity under the irradiation of simulated sunlight.
Description
Technical Field
The invention relates to a titanium nitride and titanium oxide based photocatalytic film and a preparation method thereof, belongs to the technical field of photocatalysis, and can be used in the environmental protection fields of air purification, sewage treatment and the like.
Background
Semiconductor photocatalysis technology utilizes photons to excite electrons in a valence band of a semiconductor material to a conduction band to generate photon-generated carriers. The separated photon-generated carriers can initiate specific oxidation-reduction reaction to realize the degradation and removal of pollutants in the atmosphere or sewage. Nanostructured TiO2The photocatalyst has the advantages of low price, stable performance and environmental protection, and is the most ideal semiconductor photocatalyst in the current practical application. Numerous upgrading of TiO2In the photocatalysis efficiency technology, nanoparticles such as Au, Ag and the like are carried to generate surface plasmon effect and enhance the absorption of light, thereby effectively improving the efficiency. However, the expensive materials such as Au and Ag limit the scale application.
There have been some references to TiN/TiO2And (5) researching a composite photocatalyst. Chen et al react NH4F、TiO2And TiN as raw materials, and obtaining the TiN/F-TiO by utilizing a ball milling technology2Powder samples with photocatalytic activity higher than pure TiO2And F-doped TiO2(F-TiO2) Wherein the optimum content of TiN is 0.2 wt% (S.F. Chen, et al, Journal of Hazardous Materials,2011,186: 1560-. Fakhouri et al continuously perform TiN layer and TiO layer in the same vacuum environment by using radio frequency magnetron sputtering technology2Alternate deposition of layers, growth to form TiN/TiO2Laminated structure, TiO2Embedding a TiN layer in the film significantly improves the photocatalytic activity (H.Fakhouri, et al, Applied Catalysis A: General,2015,492: 83-92.). However, the powder photocatalyst has the problems of separation and recovery in application, and the magnetron sputtering and other techniques are complicated in equipment and low in production efficiency, so that the powder photocatalyst is not suitable for industrial application. The invention designs and realizes a photocatalytic film based on titanium nitride and titanium oxide, the preparation technology of the photocatalytic film is based on a titanium-hydrogen peroxide-melamine reaction system, one-dimensional titanium nitride/titanium oxide nanowire arrays prepared on a metal titanium substrate are taken as a skeleton trunk, and the subsequent liquid phase growth of TiO is combined2And (4) branching the nanosheets.
Disclosure of Invention
The invention aims to provide a photocatalytic film based on titanium nitride and titanium oxide and a preparation method thereof.
The technical scheme of the invention is as follows:
a novel photocatalytic film based on titanium nitride and titanium oxide is prepared from TiN0.3And TiO0.89TiN consisting of mixed phases0.3/TiO0.89The nanowire array is taken as a main line, and TiO coated with anatase phase grows on the surface of the nanowire array2The nanometer sheet branches to form the three-dimensional nanometer array film.
The preparation method mainly comprises the following steps:
1) and (3) putting the cleaned titanium sheet into a hydrogen peroxide water solution with the mass concentration of 6-30%, adding 0.05-5% of nitric acid and melamine by mass, and reacting at 25-80 ℃ for 6-72 hours. After the reaction, taking out the sample, cleaning, completely drying, and performing heat treatment in air at 400-550 ℃ for 0.5-3 hours to obtain TiO grown on the titanium sheet substrate2A one-dimensional nanoarray film of nanowire arrays;
2) loading TiO on titanium sheet2The one-dimensional nano array film of the nano wire is subjected to heat treatment for 0.5 to 3 hours at the temperature of 750-900 ℃ in the ammonia atmosphere to obtain TiN0.3/TiO0.89A one-dimensional nanowire array film;
3) deionized water, glycine, nitric acid with the mass fraction of 63% and titanyl sulfate are added into the cleaned porcelain crucible, and the crucible is transferred into a heat treatment furnace to carry out solution combustion reaction to obtain fluffy black powder. Reacting black powder with 30% hydrogen peroxide solution at a mass ratio of 1:100 at 15 deg.C, and storing for 24-72 hr to obtain orange red solution combustion precursor solution;
4) mixing TiN0.3/TiO0.89And placing the one-dimensional nanowire array film in a solution combustion precursor solution to react for 10-60 minutes at 50-90 ℃, and then carrying out heat treatment for 0.5-3 hours in air at 400-550 ℃ to obtain the three-dimensional nanowire array film based on titanium nitride and titanium oxide.
In the technical scheme, the dosage ratio of the aqueous hydrogen peroxide solution, the nitric acid and the melamine in the step 1) is 50mL to 1mL to 10-100 mg.
The flow rate of the ammonia gas atmosphere in the step 2) is 100 mL/min.
The mass ratio of the deionized water, the glycine, the nitric acid with the mass fraction of 63% and the titanyl sulfate in the step 3) is 100:1.75:0.3: 1.25.
The temperature of the solution combustion reaction in the step 3) is 400 ℃.
The invention has the beneficial effects that:
different from the existing TiN/TiO2Powder or TiN/TiO2The invention relates to a laminated film, in particular to a three-dimensional nano array film based on titanium nitride and titanium oxide. The three-dimensional nano array arranged in a quasi-directional vertical mode to the substrate obtains a depth space of the film, so that the exposed area of the catalyst is increased, the active sites of the catalyst are increased, and photons and pollutant molecules can be ensured to be in contact with the active sites of the catalyst as much as possible; the heterojunction of titanium nitride and titanium oxide generates a built-in electric field, is beneficial to reducing the forbidden bandwidth, and superposes the surface plasmon effect caused by the interface of two heterogeneous phases, thereby further improving the photocatalysis effect; meanwhile, strong diffuse reflection action exists among the formed three-dimensional arrays, so that the full absorption and utilization of light are facilitated, and the photocatalysis effect is greatly improved.
Drawings
FIG. 1 shows TiO prepared in example 12A field emission scanning electron microscope photograph of the one-dimensional nanowire film;
FIG. 2 is TiN prepared in example 10.3/TiO0.89A field emission scanning electron microscope photograph of the one-dimensional nanowire film;
FIG. 3 is TiN prepared in example 10.3/TiO0.89An X-ray diffraction pattern of the one-dimensional nanowire film;
FIG. 4 is a SEM photograph of the three-dimensional nano-array film of titanium nitride/titanium oxide prepared in example 1;
FIG. 5 is a SEM photograph of the three-dimensional nano-array film of titanium nitride/titanium oxide prepared in example 2;
FIG. 6 is a SEM photograph of the three-dimensional nano-array film of titanium nitride/titanium oxide prepared in example 3;
FIG. 7 is an X-ray diffraction pattern of the three-dimensional nano-array film of titanium nitride/titanium oxide prepared in example 3;
FIG. 8 is a graph of a photocatalytic degradation rhodamine B of the three-dimensional nano-array film prepared in examples 1-3;
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
step 2, loading TiO on the titanium sheet2The nanowire sample is thermally treated for 3 hours at 750 ℃ in the ammonia gas atmosphere with the flow of 100mL/min to obtain TiN0.3/TiO0.89A one-dimensional nanowire film;
and step 3, adding 100mL of deionized water, 1.75g of glycine, 0.6mL of nitric acid with the mass fraction of 63% and 1.25g of titanyl sulfate into the ceramic crucible. And transferring the crucible to a heat treatment furnace at 400 ℃ for solution combustion reaction to obtain fluffy black powder. Adding 0.5g of black powder into 50mL of hydrogen peroxide solution with the mass concentration of 30%, and preserving at 15 ℃ for 72 hours to obtain orange-red solution combustion precursor solution;
step 4, setting the area to be 2.5 multiplied by 2.5cm2Of (3) TiN0.3/TiO0.89And (3) placing the one-dimensional nanowire array film into 15mL of solution combustion precursor solution to react for 60 minutes at 50 ℃, and finally performing heat treatment for 3 hours in an air atmosphere at 400 ℃ to obtain the titanium nitride/titanium oxide three-dimensional nanowire array film.
FIG. 1 shows the TiO obtained in step 12The field emission scanning electron microscope photo of the nanowire array film can show that the nanowire array film has a one-dimensional nanowire array structure. FIG. 2 shows TiN obtained in step 20.3/TiO0.89The field emission scanning electron microscope picture of the one-dimensional nanowire film shows that the nanowire array structure is basicallyRemain unchanged. FIG. 3 shows TiN obtained by step 20.3/TiO0.89The X-ray diffraction pattern of the one-dimensional nanowire film is compared with a standard card to obtain a product with TiN phase0.3、TiO0.89And Ti from the substrate. Fig. 4 is a scanning electron microscope photograph of the titanium nitride/titanium oxide three-dimensional nano-array film obtained in step 4, and it can be seen that the product has a three-dimensional multilevel array structure arranged in a quasi-orientation vertical to the substrate and is composed of nano-sheets uniformly coated on the surface of the nano-wire framework.
Example 2
step 2, loading TiO on the titanium sheet2The nanowire sample is thermally treated for 3 hours at 900 ℃ in the ammonia gas atmosphere with the flow of 100mL/min to obtain TiN0.3/TiO0.89A one-dimensional nanowire film;
and step 3, adding 100mL of deionized water, 1.75g of glycine, 0.6mL of nitric acid with the mass fraction of 63% and 1.25g of titanyl sulfate into the ceramic crucible. And transferring the crucible to a heat treatment furnace at 400 ℃ for solution combustion reaction to obtain fluffy black powder. Adding 1g of black powder into 100mL of hydrogen peroxide solution with the mass concentration of 30%, and storing at 15 ℃ for 24 hours to obtain orange-red solution combustion precursor solution;
step 4, setting the area to be 2.5 multiplied by 2.5cm2Of (3) TiN0.3/TiO0.89And (3) placing the one-dimensional nanowire array film into 15mL solution combustion precursor solution to react for 60 minutes at 90 ℃, and finally performing heat treatment for 3 hours in an air atmosphere at 550 ℃ to obtain the titanium nitride/titanium oxide three-dimensional nanowire array film.
Fig. 5 is a scanning electron microscope photograph of the titanium nitride/titanium oxide three-dimensional nano-array film obtained in this example, and it can be seen that the product also has a three-dimensional multi-level array structure aligned quasi-directionally perpendicular to the substrate, compared with fig. 4, the nano-sheet size is larger, and the formed branch structure has a distinct three-dimensional multi-level structure.
Example 3
step 2, loading TiO on the titanium sheet2The nanowire sample is thermally treated for 2 hours at 800 ℃ in the ammonia gas atmosphere with the flow of 100mL/min to obtain TiN0.3/TiO0.89A one-dimensional nanowire film;
and step 3, adding 100mL of deionized water, 1.75g of glycine, 0.6mL of nitric acid with the mass fraction of 63% and 1.25g of titanyl sulfate into the ceramic crucible. And transferring the crucible to a heat treatment furnace at 400 ℃ for solution combustion reaction to obtain fluffy black powder. Adding 0.5g of black powder into 50mL of hydrogen peroxide solution with the mass concentration of 30%, and preserving at 15 ℃ for 48 hours to obtain orange-red solution combustion precursor solution;
step 4, setting the area to be 2.5 multiplied by 2.5cm2Of (3) TiN0.3/TiO0.89And (3) placing the one-dimensional nanowire array film into 15mL of solution combustion precursor solution to react for 30 minutes at 80 ℃, and finally performing heat treatment for 1 hour in an air atmosphere at 450 ℃ to obtain the titanium nitride/titanium oxide three-dimensional nanowire array film.
FIG. 6 is a scanning electron microscope photograph of the three-dimensional nano-array film of titanium nitride/titanium oxide obtained in this example, which shows that the morphology of the product is similar to that of FIG. 5, indicating that the branch structure coated on the trunk is nearly saturated after the deposition time is longer than 30 minutes. FIG. 7 is the X-ray diffraction pattern of the three-dimensional nano-array film of titanium nitride/titanium oxide obtained in this example, which is compared with a standard card to show that the phase of the obtained product is TiN0.3Anatase TiO2And Ti from the substrate.
The efficiency of photocatalytic degradation of rhodamine B molecules in water by the samples prepared in examples 1-3 is tested in a comparative way, and the specific method is as follows:
(1) ultraviolet light catalysis performance: using 2.5X 2.5cm2The light intensity of the film is 5.0mW/cm2And (3) characterizing the catalytic degradation rate of 25mL of 0.005mmol/L rhodamine B under ultraviolet irradiation.
(2) Simulation of solar photocatalytic performance: using 2.5X 2.5cm2The light intensity of the film in the visible light part is 140mW/cm2The light intensity of the ultraviolet part is 4.0mW/cm2The catalytic degradation rate of 25mL of 0.005mmol/L rhodamine B is characterized under the irradiation of a xenon lamp.
(3) The photocatalysis test comprises dark adsorption for 30 minutes and photocatalysis for 120 minutes, magnetic stirring is continuously carried out in the degradation process, and sampling is carried out once every 30 minutes.
The change of the concentration of the target degradation product was measured by the change of the absorbance value corresponding to the main absorption wavelength of a UV-1800PC type UV-vis spectrophotometer, and a photocatalytic degradation curve was drawn, as shown in fig. 8. Compared with the pure ultraviolet illumination, the photocatalytic degradation efficiency of the titanium nitride/titanium oxide three-dimensional nano array film sample on rhodamine B under the simulated sunlight illumination is higher, and is obviously higher than that of pure TiO under the same illumination condition2And TiN0.3/TiO0.89The photocatalytic activity of one-dimensional nanoarray films can be attributed to: 1) TiO 22Composite TiN0.3Surface plasmon effect under the irradiation of the subsequently introduced visible light; 2) the interface heterojunction structure of the titanium nitride/titanium oxide three-dimensional nano array film promotes the separation of photon-generated carriers. The photocatalytic activity of the titanium nitride/titanium oxide three-dimensional nano array film samples obtained in examples 2 and 3 is close to that of the titanium nitride/titanium oxide three-dimensional nano array film sample obtained in example 1, which shows that the TiN in the invention0.3/TiO0.89Anatase phase TiO coated on surface of one-dimensional nanowire array framework2The deposition time required for the nanosheet branches is preferably no less than 30 minutes.
Example 4
step 2, loading TiO on the titanium sheet2Carrying out heat treatment on the nanowire sample at 800 ℃ for 2 hours in an ammonia gas atmosphere with the flow of 100mL/min to obtain a TiN one-dimensional nanowire film;
and step 3, adding 100mL of deionized water, 1.75g of glycine, 0.6mL of nitric acid with the mass fraction of 63% and 1.25g of titanyl sulfate into the ceramic crucible. And transferring the crucible to a heat treatment furnace at 400 ℃ for solution combustion reaction to obtain fluffy black powder. Adding 0.5g of black powder into 50mL of hydrogen peroxide solution with the mass concentration of 30%, and preserving at 15 ℃ for 48 hours to obtain orange-red solution combustion precursor solution;
step 4, setting the area to be 2.5 multiplied by 2.5cm2The TiN one-dimensional nanowire array film is placed in 15mL solution combustion precursor solution to react for 30 minutes at 80 ℃, and finally is subjected to heat treatment for 1 hour in air atmosphere at 450 ℃ to obtain TiO taking titanium nitride as a main body and titanium dioxide nanowires as branches2A TiN nanometer tree array film.
Comparison of the TiO obtained in step 1 of this example2As can be seen from the X-ray diffraction pattern of TiN obtained in step 2 of this example, TiN was not obtained without the titanium dioxide production method of the present invention0.3/TiO0.89One-dimensional nanowire array thin film. In combination with the TiO obtained in this example2Scanning electron micrograph of/TiN nanotree film and TiO obtained in this example2The TEM image of TiN nanotree film clearly shows that the thin film of nanotree structure obtained in example 4 is used as an array film, and the TiO obtained in this example is used2Comparing the scanning electron microscope photo of the TiN nanometer tree film with the graphs of FIG. 4, FIG. 5 and FIG. 6, it can be clearly seen that the branches of the titanium nitride/titanium oxide-based three-dimensional nanometer array photocatalytic film prepared by the invention are flaky and have larger surface area compared with the linear branches of the nanometer tree,there are significant advantages in contact with contaminants and photons.
Claims (5)
1. A photocatalytic film based on titanium nitride and titanium oxide, characterized in that: with TiN0.3And TiO0.89TiN consisting of mixed phases0.3/TiO0.89The nanowire array is taken as a main line, and TiO coated with anatase phase grows on the surface of the nanowire array2The nano sheets are branched to form a three-dimensional nano array film; the preparation method comprises the following steps:
1) putting the cleaned titanium sheet into a hydrogen peroxide aqueous solution with the mass concentration of 6-30%, adding 0.05-5% of nitric acid and melamine by mass at the same time, and reacting at 25-80 ℃ for 6-72 hours; after the reaction, taking out the sample, cleaning, completely drying, and performing heat treatment in air at 400-550 ℃ for 0.5-3 hours to obtain TiO grown on the titanium sheet substrate2A one-dimensional nanoarray film of nanowire arrays;
2) loading TiO on titanium sheet2The one-dimensional nano array film of the nano wire is subjected to heat treatment for 0.5 to 3 hours at the temperature of 750-900 ℃ in the ammonia atmosphere to obtain TiN0.3/TiO0.89A one-dimensional nanowire array film;
3) adding deionized water, glycine, nitric acid with the mass fraction of 63% and titanyl sulfate into a cleaned porcelain crucible, transferring the crucible into a heat treatment furnace to perform solution combustion reaction to obtain fluffy black powder, reacting the black powder with a hydrogen peroxide solution with the mass concentration of 30% at the temperature of 15 ℃ in a mass ratio of 1:100, and storing for 24-72 hours to obtain an orange-red solution combustion precursor solution;
4) mixing TiN0.3/TiO0.89And placing the one-dimensional nanowire array film in a solution combustion precursor solution to react for 10-60 minutes at 50-90 ℃, and then carrying out heat treatment for 0.5-3 hours in air at 400-550 ℃ to obtain the three-dimensional nanowire array film based on titanium nitride and titanium oxide.
2. The photocatalytic film based on titanium nitride and titanium oxide according to claim 1, characterized in that the ratio of the amount of the aqueous hydrogen peroxide solution, nitric acid and melamine used in step 1) is 50mL:1mL:10-100 mg.
3. The titanium nitride and titanium oxide-based photocatalytic film according to claim 1, characterized in that the flow rate of the ammonia gas atmosphere in step 2) is 100 mL/min.
4. The photocatalytic film based on titanium nitride and titanium oxide according to claim 1, wherein the mass ratio of deionized water, glycine, nitric acid with a mass fraction of 63% and titanyl sulfate in step 3) is 100:1.75:0.3: 1.25.
5. The photocatalytic film based on titanium nitride and titanium oxide according to claim 1, characterized in that the temperature of the solution combustion reaction in step 3) is 400 ℃.
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