CN110560022A - Method for preparing oxygen vacancy type metal oxide semiconductor - Google Patents
Method for preparing oxygen vacancy type metal oxide semiconductor Download PDFInfo
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- CN110560022A CN110560022A CN201910705688.6A CN201910705688A CN110560022A CN 110560022 A CN110560022 A CN 110560022A CN 201910705688 A CN201910705688 A CN 201910705688A CN 110560022 A CN110560022 A CN 110560022A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000001301 oxygen Substances 0.000 title claims abstract description 64
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 64
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 38
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 38
- 239000004065 semiconductor Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000000843 powder Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 150000003254 radicals Chemical class 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 230000005855 radiation Effects 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 description 22
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 10
- -1 hydroxyl radicals Chemical class 0.000 description 9
- 238000001237 Raman spectrum Methods 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 230000001699 photocatalysis Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
- 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
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The embodiment of the invention provides a preparation method of an oxygen vacancy type metal oxide semiconductor, which solves the problems that in the prior art, the requirement on equipment is high, potential safety hazards exist when an oxygen vacancy type semiconductor material is prepared, impurity elements which are difficult to eliminate are introduced in the preparation process, the safety and reliability are high, the requirement on the equipment is low, reagents are easy to obtain, the process flow is simple, and the popularization is easy.
Description
Technical Field
The invention belongs to the technical field of semiconductor preparation, and particularly relates to a preparation method of an oxygen vacancy type metal oxide semiconductor.
background
The photocatalysis technology can utilize sunlight to obtain clean energy and degrade pollutants, and is a green technology with important application prospect in the field of energy and environment. In the photocatalytic technology, the preparation of high-efficiency photocatalyst is important. The metal oxide semiconductor has wide application prospect in the aspects of photolysis of water, photochromism, photodegradation and solar cells because of easy preparation, no toxicity, low price and good stability.
Due to the problems of low spectral utilization rate, small specific surface area, easy recombination of photo-generated carriers and the like of the photocatalyst, a variety of methods for modifying and modifying the photocatalyst, such as noble metal doping, semiconductor recombination, dye sensitization and the like, have been developed. However, these methods have complicated processes and high costs, and are not suitable for mass production of photocatalysts.
In the prior art, methods for preparing oxygen vacancy type semiconductor materials are a high-temperature high-pressure pure hydrogen reduction method, a displacement reaction method and a laser synthesis method. In the process of implementing the embodiment of the application, the inventor of the application finds that the method has high requirements on equipment, high cost in the preparation process and certain potential safety hazard on one hand; on the other hand, impurity elements which are difficult to eliminate are also introduced. Therefore, there is still a need to develop a new oxygen vacancy type semiconductor manufacturing method.
disclosure of Invention
In order to solve the problems that in the prior art, the requirement on equipment is high, potential safety hazards exist and impurity elements which are difficult to eliminate are introduced in the preparation process when an oxygen vacancy type semiconductor material is prepared, the embodiment of the invention aims to provide a preparation method of an oxygen vacancy type metal oxide semiconductor.
In order to achieve the purpose, the embodiment of the invention adopts the following technical scheme:
A method for producing an oxygen-vacancy type metal oxide semiconductor, comprising the steps of:
S1: dispersing metal oxide powder in a free radical quencher to form a metal oxide dispersion system;
S2: removing oxygen in the metal oxide dispersion system to obtain a suspension;
s3: performing high-energy ray irradiation treatment on the suspension of step S2;
S4: and (5) performing solid-liquid separation on the product obtained in the step S3, and cleaning and drying the solid product to obtain the oxygen vacancy type metal oxide semiconductor.
in the above process, the metal oxide powder is dispersed in a radical quencher, mainly a hydroxyl radical quencher, in order to consume the oxidizing hydroxyl radicals and leave only the reducing radicals, thereby generating oxygen vacancies during irradiation. Because the suspension can generate reducing free radicals, mainly hydrated ions, after being irradiated by high-energy rays; at the same time, oxidative radicals, mainly hydroxyl radicals, are also produced.
Preferably, the metal oxide comprises TiO2、WO3、Fe2O3And ZnO.
Preferably, the free radical quencher comprises ethanol.
further preferably, the radical quencher comprises at least one of isopropanol, ethylene glycol and formic acid.
Ethanol, isopropanol, ethylene glycol and formic acid all act as quenching hydroxyl radicals, with ethanol being preferred for cost reasons.
Preferably, in step S1, the mass ratio of the metal oxide powder to the radical quencher is (0.1 to 10): 100.
preferably, the particle size of the metal oxide powder is less than 200 nm.
Preferably, the high-energy radiation is60co-gamma rays.
Preferably, the irradiation dose is 10-100 kGy.
Preferably, the irradiation dose is 30-60 kGy.
The optimal radiation dose of the embodiment of the invention is 50kGy, and less than 50kGy is difficult to generate enough oxygen vacancies; the photoelectric performance is obviously reduced when the voltage exceeds 50 kGy.
The embodiment of the invention has the beneficial effects
1. The preparation method of the oxygen vacancy type metal oxide semiconductor solves the problems that in the prior art, the requirement on equipment is high, potential safety hazards exist when an oxygen vacancy type semiconductor material is prepared, impurity elements which are difficult to eliminate are introduced in the preparation process, the safety and reliability are high, the requirement on the equipment is low, reagents are easy to obtain, the process flow is simple, and the popularization is easy;
2. The photoelectrochemical activity of the oxygen vacancy type semiconductor material prepared by the method of the embodiment of the invention is higher than that of the same material prepared by the prior art;
3. The preparation method provided by the embodiment of the invention has quantitative controllability in preparation of the oxygen vacancy, and the semiconductor catalyst with different oxygen vacancies can be obtained by controlling the radiation dose.
Drawings
FIG. 1 is a rhodamine B degradation curve under visible light of titanium dioxide powder containing oxygen vacancies in example 2.
FIG. 2 is a transmission electron micrograph of an oxygen vacancy-containing titanium dioxide powder according to example 2.
FIG. 3 is a Raman spectrum of titanium dioxide powder containing oxygen vacancies according to example 2.
FIG. 4 is a light absorption property spectrum of the oxygen vacancy-containing titanium dioxide powder of example 2.
FIG. 5 is a graph showing the photoelectrochemical properties of the oxygen vacancy-containing titanium dioxide powder of example 2.
FIG. 6 is a rhodamine B degradation curve under visible light of the titanium dioxide powder containing oxygen vacancies in example 3.
FIG. 7 is a transmission electron micrograph of an oxygen vacancy-containing titanium dioxide powder of example 3.
FIG. 8 is a Raman spectrum of titanium dioxide powder containing oxygen vacancies according to example 3.
FIG. 9 is a light absorption property spectrum of titanium dioxide powder containing oxygen vacancies in example 3.
FIG. 10 is a graph showing the photoelectrochemical properties of the oxygen vacancy-containing titanium dioxide powder of example 3.
FIG. 11 is a rhodamine B degradation curve under visible light for the titanium dioxide powder containing oxygen vacancies in example 4.
FIG. 12 is a transmission electron micrograph of an oxygen vacancy-containing titanium dioxide powder of example 4.
FIG. 13 is a Raman spectrum of titanium dioxide powder containing oxygen vacancies according to example 4.
FIG. 14 is an electron paramagnetic resonance spectrum of the oxygen vacancy-containing titanium dioxide powder of example 4.
FIG. 15 is a light absorption property spectrum of the oxygen vacancy-containing titanium dioxide powder of example 4.
FIG. 16 is a graph showing the photoelectrochemical properties of the oxygen vacancy-containing titanium dioxide powder of example 4.
FIG. 17 shows Raman spectra of three titanium dioxide powders.
Detailed Description
The embodiment of the invention provides a preparation method of an oxygen vacancy type metal oxide semiconductor.
In order to better understand the above technical solutions, the above technical solutions will be described in detail with reference to specific embodiments.
Example 1
a method for producing an oxygen-vacancy type metal oxide semiconductor, comprising the steps of:
s1: dispersing metal oxide powder in a free radical quencher to form a metal oxide dispersion system;
S2: removing oxygen in the metal oxide dispersion system to obtain a suspension;
S3: performing high-energy ray irradiation treatment on the suspension of step S2;
S4: and (5) performing solid-liquid separation on the product obtained in the step S3, and cleaning and drying the solid product to obtain the oxygen vacancy type metal oxide semiconductor.
In the above process, the metal oxide powder is dispersed in a radical quencher, which is a hydroxyl radical quencher, in order to consume the oxidizing hydroxyl radicals and leave only the reducing radicals, thereby generating oxygen vacancies during irradiation. Because the suspension can generate reducing free radicals, mainly hydrated ions, after being irradiated by high-energy rays; at the same time, oxidative radicals, mainly hydroxyl radicals, are also produced.
The metal oxide comprises TiO2、WO3、Fe2O3And ZnO, the radical quencher comprising at least one of ethanol, isopropanol, ethylene glycol, and formic acid. Ethanol is preferred.
in step S1, the mass ratio of the metal oxide powder to the radical quencher is (0.1-10): 100.
The particle size of the metal oxide powder is less than 200 nm.
Preferably, the high-energy radiation is60Co-gamma rays.
The irradiation dose is 10-100 kGy, preferably 30-60 kGy.
The optimal radiation dose of the embodiment of the invention is 50kGy, and less than 50kGy is difficult to generate enough oxygen vacancies; the photoelectric performance is obviously reduced when the voltage exceeds 50 kGy.
Example 2
This example actually produced an oxygen vacancy type metal oxide semiconductor photocatalyst TiO2-XThe method specifically comprises the following steps:
Weighing 0.2g nanometer titanium dioxide (99.8%, 10-25nm, anatase, hydrophilic, manufacturer: Aladdin) into 40ml ethanol, and performing ultrasonic treatment for 30min, N2After oxygen discharge and sealing, the tube is placed in a radiation field and irradiated with 31.4kGy dose. After irradiation, repeatedly cleaning with ethanol and deionized water, and vacuum drying to obtain a sample for later use.
The titanium dioxide suspension before irradiation is milky white, and after irradiation, the color of the suspension becomes blue gray, which indicates that oxygen vacancy is generated, the light absorption wavelength range is widened, and the visible light is strongly absorbed to cause the color of the suspension to become dark.
TiO because an intermediate energy level is formed and reaction active sites are increased when oxygen vacancies are introduced2-XThe photocatalytic performance of the powder is enhanced, and the rate of degrading rhodamine B under visible light is enhanced, as shown in figure 1. Fig. 2 is a transmission electron micrograph of a material, and it can be seen from fig. 2 that the crystal lattice of the semiconductor is partially destroyed due to the introduction of oxygen vacancies, and thus partial folding and fracture occur. FIG. 3 shows the TiO prepared2-XThe Raman characterization spectrum of the powder is characterized in that the loss of oxygen causes the blue shift of a Raman curve (Delta s is 2 cm)-1) The presence of oxygen vacancies is further illustrated by the raman spectrum. Fig. 4 is a light absorption property diagram of a material illustrating that the formation of oxygen vacancies enhances the absorption of sunlight by the semiconductor material. FIG. 5 is a diagram of the photoelectrochemical properties of an oxygen vacancy type semiconductor material, from which it can be seen that the defect structure of oxygen vacancies significantly improves the photoelectrocatalysis properties of the material.
Example 3
this example actually produced an oxygen vacancy type metal oxide semiconductor photocatalyst TiO2-XThe method specifically comprises the following steps:
Weighing 0.2g nanometer titanium dioxide (99.8%, 10-25nm, anatase, hydrophilic, manufacturer: Aladdin) into 40ml ethanol, and performing ultrasonic treatment for 30min, N2After oxygen discharge and sealing, the tube is put into a radiation field and irradiated with 41.8kGy dose. After irradiation, repeatedly cleaning with ethanol and deionized water, and vacuum drying to obtain a sample for later use.
FIG. 6 is TiO2-XThe rhodamine B curve is degraded through photocatalysis, oxygen vacancies are generated through irradiation treatment, and the degradation rate is obviously superior to that of a contrast. To TiO 22-xthe transmission electron microscopy test showed that the presence of wrinkles in the lattice fringes indicated the formation of oxygen vacancies, as shown in FIG. 7. The raman test results are shown in fig. 8; the light absorption properties and the photoelectrochemical properties are shown in fig. 9 and 10, respectively.
Example 4
This example actually produced an oxygen vacancy type metal oxide semiconductor photocatalyst TiO2-XThe method specifically comprises the following steps:
Weighing 0.2g nanometer titanium dioxide (99.8%, 10-25nm, anatase, hydrophilic, manufacturer: Aladdin) into 40ml ethanol, and performing ultrasonic treatment for 30min, N2After oxygen discharge and sealing, the tube is placed in a radiation field and irradiated to 49.5 kGy. After irradiation, repeatedly cleaning with ethanol and deionized water, and vacuum drying to obtain a sample for later use.
To TiO 22-Xthe powder was subjected to photocatalytic performance test, and the results are shown in fig. 11. Transmission electron microscopy testing as in fig. 12; the Raman spectrum is shown in FIG. 13; the EPR detection result is shown in FIG. 14, and a characteristic peak (Ov) corresponding to an oxygen vacancy can be observed in the EPR diagram of the material; the light absorption properties and photoelectrochemical properties are shown in fig. 15 and 16, respectively.
fig. 17 is a schematic diagram showing a comparison of raman spectra of the titanium dioxide powders containing oxygen vacancies of example 2, example 3 and example 4, and it can be found from the figure that the raman spectra increase with the increase of irradiation dose and the blue shift increases, which indicates that the content of oxygen vacancies in the semiconductor catalyst increases, and further indicates that the preparation of oxygen vacancies has quantitative controllability.
Example 5
This example actually prepares an oxygen vacancy type metal oxide semiconductor photocatalyst WO3-XThe method specifically comprises the following steps:
Weighing 0.2g of nano tungsten trioxide, putting the nano tungsten trioxide into 40ml of ethanol, and carrying out ultrasonic treatment for 30min, wherein N is2After oxygen discharge and sealing, the tube is placed in a radiation field and irradiated to 49.5 kGy. After irradiation, repeatedly cleaning with ethanol and deionized water, and vacuum drying to obtain a sample for later use.
The tungsten trioxide suspension before irradiation is light yellow, and after irradiation, the tungsten trioxide suspension becomes dark blue, which indicates that oxygen vacancies are generated, the light absorption wavelength range is widened, and the visible light is strongly absorbed to cause the suspension to become dark.
Claims (9)
1. A method for producing an oxygen-vacancy type metal oxide semiconductor, characterized by comprising the steps of:
S1: dispersing metal oxide powder in a free radical quencher to form a metal oxide dispersion system;
s2: removing oxygen in the metal oxide dispersion system to obtain a suspension;
S3: performing high-energy ray irradiation treatment on the suspension of step S2;
s4: and (5) performing solid-liquid separation on the product obtained in the step S3, and cleaning and drying the solid product to obtain the oxygen vacancy type metal oxide semiconductor.
2. the method of claim 1, wherein the metal oxide comprises TiO2、WO3、Fe2O3And ZnO.
3. The method of claim 1, wherein the radical quencher comprises ethanol.
4. The method of claim 3, wherein the radical quencher comprises at least one of isopropanol, ethylene glycol, and formic acid.
5. The method according to claim 1, wherein in step S1, the mass ratio of the metal oxide powder to the radical quencher is (0.1-10): 100.
6. the method of claim 1, wherein the metal oxide powder has a particle size of less than 200 nm.
7. The method of claim 1, wherein the high energy radiation comprises60Co-gamma rays.
8. The method according to claim 1, wherein the irradiation dose is 10 to 100 kGy.
9. The method according to claim 8, wherein the irradiation dose is 30 to 60 kGy.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113877555A (en) * | 2021-10-11 | 2022-01-04 | 湖南省核农学与航天育种研究所 | Preparation method and application of titanium-oxygen material |
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| CN101024253A (en) * | 2007-03-29 | 2007-08-29 | 上海大学 | Method for making nana copper-tin alloy by electronic beam irridation |
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| CN101024253A (en) * | 2007-03-29 | 2007-08-29 | 上海大学 | Method for making nana copper-tin alloy by electronic beam irridation |
| CN108375601A (en) * | 2018-01-03 | 2018-08-07 | 中国工程物理研究院电子工程研究所 | The measurement method of oxygen vacancy concentration in a kind of silicon oxide film |
Non-Patent Citations (1)
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| YONG HU等: "Room-Temperature Irradiation Route To Synthesize a Large-Scale Single-Crystalline ZnO Hexangular Prism", 《INORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113877555A (en) * | 2021-10-11 | 2022-01-04 | 湖南省核农学与航天育种研究所 | Preparation method and application of titanium-oxygen material |
| CN113877555B (en) * | 2021-10-11 | 2024-03-22 | 湖南省核农学与航天育种研究所 | Preparation method and application of titanium-oxygen material |
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Application publication date: 20191213 |