CN114700068B - Preparation method of tungsten trioxide single-layer nano sheet/titanium dioxide heterojunction composite material, obtained product and application - Google Patents
Preparation method of tungsten trioxide single-layer nano sheet/titanium dioxide heterojunction composite material, obtained product and application Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 40
- 239000002135 nanosheet Substances 0.000 title claims abstract description 37
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 6
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- 239000000243 solution Substances 0.000 claims description 13
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- 239000011976 maleic acid Substances 0.000 claims description 9
- 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 claims description 9
- 229940043267 rhodamine b Drugs 0.000 claims description 9
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
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- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
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- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- 238000007254 oxidation reaction Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a preparation method of a tungsten trioxide single-layer nano sheet/titanium dioxide heterojunction composite material, a product obtained by the preparation method and application thereof. According to the invention, the tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material can be obtained by taking the tungsten trioxide single-layer nano-sheet and titanium dioxide as raw materials through simple ultrasonic dispersion and calcination reactions, the operation is simple, the implementation is easy, the product yield is high, the obtained composite material has excellent photocatalytic degradation performance on organic dye, can be applied to the field of sewage treatment, and has the advantages of excellent catalytic performance, good stability, convenience and environmental protection.
Description
Technical Field
The invention relates to a preparation method of a heterojunction composite material, in particular to a preparation method of a tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material, the obtained composite material and application of the composite material in photocatalytic degradation of organic pollutants, and belongs to the technical fields of inorganic composite material preparation and photocatalysis.
Background
Toxic and harmful wastewater can be generated in the textile printing and dyeing process. Organic sewage has high stability and complex components, and causes great harm to the ecological system and human health. The treatment method of the printing and dyeing wastewater mainly comprises an adsorption method, an aerobic and anaerobic process, a catalytic oxidation process and the like. Considering that the adsorption cost of organic matters is high and the metabolism rate is slow, the photocatalysis technology has the advantages of high efficiency and more thorough degradation, so the photocatalysis technology is a promising strategy for treating the printing and dyeing wastewater.
Titanium dioxide is a typical semiconductor material, and has been widely used in the field of photocatalysis due to its advantages of environmental friendliness, good photochemical stability, no toxicity, low cost, and the like. Through continuous and intensive researches, the defects of wide band gap, small specific surface area, rapid photo-generated charge recombination and the like are gradually found to seriously obstruct the further development of titanium dioxide as a photocatalyst. Various strategies have been reported to improve the photocatalytic performance of titanium dioxide, such as ion doping, non-metal doping, noble metal deposition, and incorporation into semiconductors, which can significantly improve the photocatalytic activity. In particular, the heterojunction formed by the combination of two different semiconductors can improve the defects of a single semiconductor, prolong the spectral response, prevent the combination of photon-generated carriers and has very high development prospect.
The tungsten trioxide has a narrower band gap (about 2.7. 2.7 eV) and has a stronger visible light absorbing ability than a semiconductor such as titanium dioxide. However, the tungsten trioxide has a low conduction band potential, so that the light energy conversion is not ideal, and the photocatalytic application of the tungsten trioxide is limited. Subsequently, powerful solutions, such as Fe, have emerged 3+ /Fe 2+ The redox system assists in combining tungsten trioxide with other semiconductors and pairing them with heterogeneous structures, and noble metals are loaded and simultaneously exfoliated into tungsten trioxide single-layer nanoplatelets, all of which have shown good synergistic effects. Numerous studies have shown that 2D catalysts with atomic layer thickness have better catalytic activity than conventional (volume or thickness) particles due to their larger specific surface area and special electronic properties. Due to Ti 4+ And W is 6+ With similar characteristicsThe atomic radius, tungsten trioxide and titanium dioxide can be coupled through high temperature calcination to build a tungsten trioxide/titanium dioxide heterostructure that limits rapid synthesis of photoinduced charges.
However, the easily agglomerated tungsten trioxide single-layer nano-sheet has poor dispersibility, so that the tungsten trioxide single-layer nano-sheet and titanium dioxide cannot be uniformly mixed, and the composite product of the tungsten trioxide single-layer nano-sheet and the titanium dioxide is not easily separated and obtained, so that the successful composite of the tungsten trioxide single-layer nano-sheet and the titanium dioxide becomes a difficult problem.
Disclosure of Invention
Aiming at the problems of the compounding of titanium dioxide and tungsten trioxide single-layer nano sheets, the invention provides a preparation method of the tungsten trioxide single-layer nano sheet/titanium dioxide heterojunction composite material and an obtained product.
The specific technical scheme of the invention is as follows:
the preparation method of the tungsten trioxide single-layer nano sheet/titanium dioxide heterojunction composite material comprises the following steps: adding the tungsten trioxide single-layer nano-sheet into a solvent, carrying out ultrasonic dispersion uniformly, then adding titanium dioxide and maleic acid aqueous solution, carrying out ultrasonic dispersion, continuously stirring the obtained mixed solution for reaction, centrifugally collecting a product, drying and calcining to obtain the tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material.
Further, the single-layer tungsten trioxide nano-sheet is also called a single-layer tungsten trioxide nano-sheet, which is called ML-WO for short 3 It can be prepared according to methods reported in the prior art, for example DOI: 10.1002/adfm.202009770.
Further, the titanium dioxide is in the form of powder and is commercially available.
Further, the solvent is absolute ethyl alcohol.
Further, the volume ratio of the solvent absolute ethyl alcohol to the maleic acid aqueous solution is 5-30:1.
Further, the molar quantity of the tungsten trioxide single-layer nano-sheet is 1-6% of the molar quantity of titanium dioxide.
Further, after the tungsten trioxide single-layer nano-sheet is added into the solvent, the ultrasonic dispersion is carried out for 40-50min; after adding titanium dioxide and maleic acid, performing ultrasonic dispersion for 30-40min, and then continuing mixing and stirring for 12-14h, so that the tungsten trioxide single-layer nano-sheet is fully compounded with the titanium dioxide.
Further, after the reaction was completed, the reaction solution was centrifuged at a rotation speed of 4000 to 4500 r/min.
Further, the calcination temperature is 300-350 ℃ and the calcination time is 3-4h.
Further, in the method of the invention, the mass ratio of the maleic acid to the tungsten trioxide single-layer nano-sheet is 1.2-1.6:1. The formation efficiency of the heterojunction of tungsten trioxide and titanium dioxide is improved by adding maleic acid, and the yield of the product is improved.
Furthermore, the invention also provides the tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material obtained by the method, and the composite material has excellent photocatalytic degradation performance, has good catalytic degradation effect on organic pollutants such as organic dye and the like, and can be used in the fields of sewage treatment and the like. Therefore, the invention also protects the application of the tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material in photocatalytic degradation of organic pollutants, and the composite material is used as a photocatalyst.
Further, the organic contaminant is an organic dye, and the organic dye comprises methylene blue, rhodamine B and the like.
The invention also provides a photocatalyst for catalyzing and degrading organic pollutants, and the photocatalyst comprises the tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material as an active ingredient.
The invention also provides a treatment method of the organic pollutant, which takes the tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material as a photocatalyst, and degrades the organic pollutant by a photocatalysis method, wherein the organic pollutant is an organic dye.
According to the invention, the tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material can be obtained by taking the tungsten trioxide single-layer nano-sheet and titanium dioxide as raw materials through simple ultrasonic dispersion and calcination reactions, the operation is simple, the implementation is easy, the product is easy to separate and the yield is high, the obtained composite material has excellent photocatalytic degradation performance on organic dye, can be applied to the field of sewage treatment, and has the advantages of excellent catalytic performance, good stability, convenience and environmental protection.
Drawings
FIG. 1 shows ML-WO obtained in example 1 3 /TiO 2 High Resolution Transmission Electron Microscope (HRTEM) image of the composite material.
FIG. 2 is the ML-WO obtained in comparative example 2 3 /TiO 2 High Resolution Transmission Electron Microscope (HRTEM) image of the composite material.
Detailed Description
The present invention will be described in further detail with reference to examples. It should be understood that the following description is illustrative only and is not limiting in any way.
In the following examples, ML-WO is used 3 The nano-sheet is prepared by DOI 10.1002/adfm.202009770, the thickness of the nano-sheet is 0.5-1.5 nm, and the size is 50-100 nm. The titanium dioxide used is a commercially available product.
Example 1
0.029g of ML-WO 3 (namely, tungsten trioxide single-layer nano-sheets) are added into a 100ML absolute ethanol solution, stirred and sonicated for 50min, then 1g titanium dioxide and 4ML of 0.1M maleic acid aqueous solution are added, the ultrasound is continued for 30min, then the mixed solution is stirred and mixed for 12h at room temperature, and then centrifuged at 4000r/min, the product is collected, dried at 60 ℃ for 12h, calcined at 320 ℃ for 3h in a muffle furnace after drying, and ground into powder, thus obtaining ML-WO 3 /TiO 2 1.13g of composite material.
FIG. 1 shows the ML-WO obtained 3 /TiO 2 High Resolution Transmission Electron Microscopy (HRTEM) image of selected regions simultaneously appearing as ML-WO as shown in FIG. 1 3 Crystal face and TiO 2 The crystal planes and the transition regions marked with dashed lines show the formation of heterojunction.
Example 2
Preparation of ML-WO according to the method of example 1 3 /TiO 2 A composite material, except that: ML-WO 3 0.0897g,10ml 0.1M in the amount of the aqueous maleic acid solution to obtain ML-WO 3 /TiO 2 The composite was 1.25g.
Example 3
Preparation of ML-WO according to the method of example 1 3 /TiO 2 A composite material, except that: ML-WO 3 0.1527g,17ml 0.1M in the amount of the aqueous maleic acid solution to obtain ML-WO 3 /TiO 2 The composite was 1.81g.
Comparative example 1
0.029g of ML-WO 3 (namely, tungsten trioxide single-layer nano-sheets) are added into 100ml of absolute ethanol solution, stirred and sonicated for 50min, then 1g of titanium dioxide is added, the sonication is continued for 30min, then the mixed solution is stirred and mixed for 12h at room temperature, and then centrifuged at 4000r/min, and no precipitate is precipitated after centrifugation.
Comparative example 2
0.029g of ML-WO 3 (namely, tungsten trioxide single-layer nano-sheets) and 1g of titanium dioxide are mixed, added into a ball milling tank for ball milling and mixing for 30min, and then calcined for 3h at 320 ℃ to obtain ML-WO 3 /TiO 2 A composite material.
The High Resolution Transmission Electron Microscope (HRTEM) image of the obtained product is shown in FIG. 2, from which it can be seen that the obtained material is obtained as TiO 2 The crystal face form exists, and no heterogeneous structure is formed.
Application example 1
ML-WO obtained in examples 1-3 and comparative example 2 3 /TiO 2 The composite material was a photocatalyst, 20mg of the photocatalyst was added to 100ml of 50 μm concentration methylene blue solution (ph=7), and the mixture was stirred and adsorbed for 30min in the dark. The photocatalytic reaction was then carried out under ultraviolet light (365 nm), sampled every 2min, for 10min. Extracting the supernatant from the obtained sample with 0.22 nanofiltration membrane, and measuring lambda with ultraviolet-visible spectrophotometer max Absorbance was measured at 664nm, and the degradation rate of the composite material to methylene blue dye was calculated as follows:
the test results are shown in table 1 below:
application example 2
ML-WO obtained in examples 1-3 and comparative example 2 3 /TiO 2 The composite material was a photocatalyst, 20mg of the photocatalyst was taken, and each of them was added to 100ml of rhodamine B solution (ph=7) at a concentration of 15 μm, and the mixture was stirred and adsorbed for 30min in darkness. Then in sunlight (350W/m) 2 ) The photocatalytic reaction is carried out, sampling is carried out every 4min, and the reaction is carried out for 20min. Extracting the supernatant from the obtained sample with 0.22 nanofiltration membrane, and measuring lambda with ultraviolet-visible spectrophotometer max Absorbance at 552nm was measured, and the degradation rate of the composite material to rhodamine B dye was calculated as follows:
the test results are shown in table 2 below:
application example 3
20mg of ML-WO of example 1 and comparative example 2 3 /TiO 2 The composite material was put into 100ml of rhodamine B solution (ph=7) at 15 μm concentration, and after the mixture was stirred and adsorbed for 30min in the dark, 300 μl of peroxodisulfate PDS was added, followed by sun light (350W-m 2 ) The photocatalytic reaction is carried out, sampling is carried out every 2min, and the reaction is carried out for 12min. Extracting the supernatant from the obtained sample with 0.22 nanofiltration membrane, and measuring lambda with ultraviolet-visible spectrophotometer max Absorbance was measured at 552nm, and the degradation rate of the composite material to rhodamine B dye was calculated in the same manner as in application example 2.
The test results are shown in table 3 below:
application example 4
20mg of ML-WO of example 1 and comparative example 2 3 /TiO 2 The composite material was put into 100ml of rhodamine B solution (ph=7) at a concentration of 15 μm, and after the mixture was stirred and adsorbed for 30min in the dark, 300 μl of peroxomonosulfate PMS was added, followed by sun light (350W/M 2 ) The photocatalytic reaction is carried out, sampling is carried out every 2min, and the reaction is carried out for 12min. Extracting the supernatant from the obtained sample with 0.22 nanofiltration membrane, and measuring lambda with ultraviolet-visible spectrophotometer max Absorbance was measured at 552nm, and the degradation rate of the composite material to rhodamine B dye was calculated in the same manner as in application example 2.
The test results are shown in table 4 below:
application example 5
20mg of ML-WO of example 1 and comparative example 2 3 /TiO 2 The composite was put into 100ml of methylene blue solution (ph=7) at a concentration of 50 μm, and the mixture was stirred and adsorbed for 30min in the dark. The photocatalytic reaction was carried out under ultraviolet light (365 nm), and after 10 minutes, sampling was carried out. Extracting the supernatant from the obtained sample with 0.22 nanofiltration membrane, and measuring lambda with ultraviolet-visible spectrophotometer max Absorbance was measured at 664nm, and the degradation rate of the composite material to methylene blue dye was calculated in the same manner as in application example 1.
And then filtering, washing and drying the composite material, recovering, and repeating the photocatalysis experiment to verify the catalytic stability of the composite material for multiple recycling.
The test results are shown in table 5 below:
as can be seen from the above experimental results, the ML-WO obtained by the present invention 3 /TiO 2 The composite material has excellent photocatalytic performance, can realize the rapid degradation of the organic dye in a short time, and has the advantages of no obvious degradation rate reduction after 5 times of circulation and good stability.
Claims (1)
1. The application of the tungsten trioxide single-layer nano sheet/titanium dioxide heterojunction composite material in photocatalytic degradation of rhodamine B is characterized in that: 20mg of tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material is put into 100mL of rhodamine B solution with the concentration of 15 mu M, pH =7, the mixture is stirred and absorbed for 30min in darkness, 300 mu L of peroxomonosulfate PMS is added, and then the mixture is stirred and absorbed for 30min in darkness at the concentration of 350W/m 2 Performing photocatalytic reaction in the sunlight, sampling every 2min, and reacting for 12min; the preparation method of the tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material comprises the following steps: adding 0.029g tungsten trioxide single-layer nano-sheets into 100mL absolute ethanol solution, stirring and carrying out ultrasonic treatment for 50min, then adding 1g titanium dioxide and 4mL of 0.1M maleic acid aqueous solution, continuing ultrasonic treatment for 30min, then stirring and mixing the mixed solution at room temperature for 12h, centrifuging at 4000r/min, collecting the product, drying at 60 ℃ for 12h, calcining at 320 ℃ for 3h in a muffle furnace after drying, and grinding into powder to obtain 1.13g of tungsten trioxide single-layer nano-sheet/titanium dioxide heterojunction composite material.
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| JP2012140255A (en) * | 2010-12-28 | 2012-07-26 | Shinshu Univ | 2d bronze type tungsten oxide nanosheet, method for production thereof, and photocatalyst and photochromic device using the nanosheet |
| CN107715864A (en) * | 2017-10-31 | 2018-02-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tungsten oxide/titanium dioxide hetero-junctions compounded visible light photocatalyst and products thereof and application |
| CN108465475A (en) * | 2018-04-04 | 2018-08-31 | 东莞市石鼓污水处理有限公司 | A kind of preparation method of WO3-ZrO2 photocatalysis sewages processing composite membrane |
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2022
- 2022-03-30 CN CN202210324011.XA patent/CN114700068B/en active Active
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|---|---|---|---|---|
| JP2012140255A (en) * | 2010-12-28 | 2012-07-26 | Shinshu Univ | 2d bronze type tungsten oxide nanosheet, method for production thereof, and photocatalyst and photochromic device using the nanosheet |
| CN107715864A (en) * | 2017-10-31 | 2018-02-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tungsten oxide/titanium dioxide hetero-junctions compounded visible light photocatalyst and products thereof and application |
| CN108465475A (en) * | 2018-04-04 | 2018-08-31 | 东莞市石鼓污水处理有限公司 | A kind of preparation method of WO3-ZrO2 photocatalysis sewages processing composite membrane |
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| "Efficient Decomposition of Organic Pollutants Over In2O3/TiO2 Nanocomposite Photocatalyst Under Visible Light Irradiation";Ashok Kumar et al.;《J Clust Sci》;第23卷;第247-257页 * |
| Bilal Ahmed et al.."Facile and controlled synthesis of aligned WO3 nanorods and nanosheets as an efficient photocatalyst material".《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》.2016,第175卷第250-261页. * |
| Hayat Khan et al.."Spray dried TiO2/WO3 heterostructure for photocatalytic applications with residual activity in the dark".《Applied Catalysis B: Environmental》.2017,第226卷第311-323页. * |
| Yong Joo Kim et al.."Heterojunction of FeTiO3 Nanodisc and TiO2 Nanoparticle for a Novel Visible Light Photocatalyst".《J. Phys. Chem. C》.2009,第113卷(第44期),第19179-19184页. * |
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