CN114314521A - Method for controllable generation of oxygen vacancy in metal oxide - Google Patents
Method for controllable generation of oxygen vacancy in metal oxide Download PDFInfo
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- CN114314521A CN114314521A CN202210072497.2A CN202210072497A CN114314521A CN 114314521 A CN114314521 A CN 114314521A CN 202210072497 A CN202210072497 A CN 202210072497A CN 114314521 A CN114314521 A CN 114314521A
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- metal oxide
- oxygen vacancies
- powder
- quartz tube
- controlled generation
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 40
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000001301 oxygen Substances 0.000 title claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000010453 quartz Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 238000011049 filling Methods 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 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 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for controllable generation of oxygen vacancies in metal oxide, which comprises the following steps; step one, grinding and uniformly mixing metal oxide and sulfur powder, then filling the mixture into a customized quartz tube, and vacuumizing and sealing the quartz tube by using an oxyhydrogen flame tube sealing machine to isolate air; step two, calcining for one hour at the temperature of 150 ℃, 200 ℃, 300 ℃ and 400 ℃ respectively, cooling to room temperature, opening a sealed quartz tube, and taking out a powder mixture product; and step three, placing the powder mixture product obtained in the step two in a certain amount of chloroform solvent (50 ml), performing ultrasonic treatment and centrifugation, repeating the process for three times to remove redundant elemental sulfur, and then drying under a vacuum condition to finally obtain the metal oxide nanoparticles. The invention can precisely control the concentration of oxygen vacancy generation in the metal oxide by changing the sulfur powder content and the calcination temperature.
Description
Technical Field
The invention relates to the technical field of oxygen vacancy generation, in particular to a controllable generation method for oxygen vacancies in metal oxide.
Background
The generation of oxygen vacancy is accompanied by the generation of free electrons, and the existence of the free electrons can greatly improve the conductivity of the metal oxide, thereby promoting the application potential of the metal oxide in the field of energy storage. In addition, the existence of oxygen vacancy can reduce the rate of the combination of electrons and holes, thereby improving the photocatalytic performance of the metal oxide and leading the metal oxide to have wider application in the fields of photocatalysis and the like. At present, most methods for generating oxygen vacancies mainly adopt a post-treatment means of high-temperature calcination (more than or equal to 500 ℃) in a reducing atmosphere (including argon, hydrogen, vacuum and the like), the method mainly regulates and controls the concentration of the oxygen vacancies through the calcination temperature, the regulation and control parameters are single, and the concentration of the generated oxygen vacancies is not accurately controlled. Meanwhile, the high temperature condition may also cause the change of the morphology (including micro morphology, particle size, particle aggregation state, etc.) or the crystal structure of the metal oxide nanoparticles, thereby affecting the performance thereof. Therefore, it is urgent to find a technique for precisely controlling the generation of oxygen vacancy concentration without changing the morphology and crystal structure of the metal oxide under the condition of as low temperature as possible.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for the controllable generation of oxygen vacancies in metal oxides, which solves the problems in the prior art by changing the content of sulfur powder and the calcination temperature to achieve the purpose of accurately controlling the concentration of oxygen vacancies generated in the metal oxides based on the lower melting point and the reduction property of elemental sulfur.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for the controlled generation of oxygen vacancies in metal oxides comprising the steps of;
step one, grinding and uniformly mixing metal oxide and sulfur powder, then filling the mixture into a customized quartz tube, and vacuumizing and sealing the quartz tube by using an oxyhydrogen flame tube sealing machine to isolate air;
step two, calcining for one hour at the temperature of 150 ℃, 200 ℃, 300 ℃ and 400 ℃ respectively, cooling to room temperature, opening a sealed quartz tube, and taking out a powder mixture product;
and step three, placing the powder mixture product obtained in the step two in a certain amount of chloroform solvent (50 ml), performing ultrasonic treatment and centrifugation, repeating the process for three times to remove redundant elemental sulfur, and then drying under a vacuum condition to finally obtain the metal oxide nanoparticles.
The metal oxide in the step one is titanium oxide (TiO)2) Zinc oxide (ZnO), cerium oxide (CeO)2) Zirconium oxide (ZrO)2) Tin oxide (SnO)2) Or other metal oxide.
In the first step, the ratio of the metal oxide to the sulfur powder is 1:2(0.1g:0.2g), 1:1(0.1g:0.2g) and 1:0.5(0.1g:0.05 g).
The grain diameter after grinding in the step one is required to be less than 1 micron.
The conditions for customizing the quartz tube are as follows: the diameter is 1cm, the total length is 18cm, and the mouth is closed at the position of 10 cm.
The powder mixture product obtained in step two is a solid mixture of unreacted sulfur powder (light yellow) and partially reduced metal oxide (grey).
And in the third step, the product of the powder mixture is subjected to ultrasonic treatment for 10 minutes in a chloroform solvent, and is centrifuged for 5 minutes at 5000 revolutions.
And in the third step, drying is carried out for 12 hours at the temperature of 60 ℃ under the vacuum condition.
The metal oxide nano particles in the third step are gray solid powdery products with uniform color.
The invention has the beneficial effects that:
(1) the prepared metal oxide nanoparticles containing oxygen vacancies with different concentrations show improvement of conductivity of the nanoparticles to different degrees and reduction of electron hole combination probability, thereby showing improvement of electrochemical capacitance performance and photocatalytic performance of the nanoparticles;
(2) the invention introduces oxygen vacancy and possibly sulfur-related point defects, and the introduction of the defects can also influence the photocatalytic performance.
Drawings
FIG. 1 is TiO2Photograph after treatment at 300 ℃. (a) No sulfur powder is added; (b) adding sulfur powder.
FIG. 2 is TiO2X-ray powder diffraction pattern after heat treatment at 300 ℃. The black line is the diffraction pattern (marked as TiO) after heat treatment without adding sulfur powder2) The gray line is TiO containing oxygen vacancy after being thermally treated by adding sulfur powder2Powder (noted as TiO)2-x) The diffraction pattern of (a).
FIG. 3 shows the addition of sulfur powder and the TiO obtained after the addition of sulfur powder and the heat treatment2And (3) a decomposition scheme of the nano-particles to rhodamine B (RhB) under visible light.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1:
grinding and mixing 1g of titanium dioxide powder and 1g of sulfur powder for 10 minutes, placing the mixture in the customized quartz tube and sealing the tube to isolate air, then calcining the mixture for 1 hour under the conditions that the set temperature is 300 ℃ and the heating rate is 10 ℃/min, cooling the mixture to room temperature, carrying out ultrasonic treatment on the mixed powder in chloroform for 10 minutes, then centrifuging the mixture for 5 minutes, and finally carrying out vacuum drying at 60 ℃ for 12 hours to obtain dry gray solid powder (a physical photograph shown in the right diagram in fig. 1).
For comparison, 2g of titanium dioxide powder (without added sulfur powder) was charged into the above-mentioned custom-made quartz tube, and after the same calcination conditions, the color of the powder was white, and the heat treatment did not change the color thereof, and the color of titanium dioxide itself, i.e., white, was still exhibited. (photograph of the real object as shown in the left image of FIG. 1).
As shown in fig. 2: the powder samples of fig. 1 were each tableted and passed through an X-ray powder diffractometer to determine whether the structure of the titanium dioxide after calcination at 300 c was changed after the addition of sulfur powder. As shown in the figure, the black line is a diffraction pattern (marked as TiO) after heat treatment without adding sulfur powder2) And grey is the diffraction pattern (recorded as TiO) measured after heat treatment with sulfur powder2-x). From the comparison result of diffraction pattern, the TiO is not changed by adding the sulfur powder2The crystal structure of (1).
As shown in fig. 3: for TiO treated at 300 DEG C2-xSample, which had a decomposition rate of RhB of 71.2% under visible light, and TiO before treatment2The RhB decomposition rate of the sample at 25 ℃ in visible light was 69.3%. The presence of oxygen vacancies traps electrons to facilitate the separation of photo-generated electrons and holes. The photocatalytic activity of the sample is improved.
When the content of the elemental sulfur and the calcination temperature are different, the obtained final metal oxide powder presents different shades of gray, that is, by adjusting the two parameters, the metal oxide containing oxygen vacancies with different concentrations can be obtained, and the purpose of controlling the concentration of the generated oxygen vacancies is achieved.
Claims (9)
1. A method for the controlled generation of oxygen vacancies in metal oxides, comprising the steps of;
step one, grinding and uniformly mixing metal oxide and sulfur powder, then filling the mixture into a customized quartz tube, and vacuumizing and sealing the quartz tube by using an oxyhydrogen flame tube sealing machine to isolate air;
step two, calcining for one hour at the temperature of 150 ℃, 200 ℃, 300 ℃ and 400 ℃ respectively, cooling to room temperature, opening a sealed quartz tube, and taking out a powder mixture product;
and step three, placing the powder mixture product obtained in the step two in a certain amount of chloroform solvent for ultrasonic treatment and centrifugation, repeating the process for three times to remove redundant elemental sulfur, and then drying under a vacuum condition to finally obtain the metal oxide nanoparticles.
2. The method for the controlled generation of oxygen vacancies in metal oxide according to claim 1, wherein the metal oxide in the first step is titanium oxide (TiO)2) Zinc oxide (ZnO), cerium oxide (CeO)2) Zirconium oxide (ZrO)2) Tin oxide (SnO)2) Or other metal oxide.
3. The method for the controlled generation of oxygen vacancies in metal oxide according to claim 1, wherein the ratio of metal oxide to sulfur powder in the first step is 1:2(0.1g:0.2g), 1:1(0.1g:0.2g), 1:0.5(0.1g:0.05 g).
4. The method for the controlled generation of oxygen vacancies in metal oxides according to claim 1, wherein the particle size after grinding in the first step is required to be less than 1 micron.
5. The method of claim 1, wherein the conditions for the quartz tube in step one are: the diameter is 1cm, the total length is 18cm, and the mouth is closed at the position of 10 cm.
6. The process of claim 1, wherein the powder mixture product of step two is a solid mixture of unreacted sulfur powder (light yellow) and partially reduced metal oxide (gray).
7. The method for the controlled generation of oxygen vacancies in metal oxide according to claim 1, wherein the powder mixture product of step three is subjected to ultrasonic treatment for 10 minutes and then centrifuged at 5000 rpm for 5 minutes in chloroform solvent.
8. The method for the controlled generation of oxygen vacancies in metal oxides according to claim 1, wherein the drying step three is carried out under vacuum at 60 ℃ for 12 hours.
9. The method for the controlled generation of oxygen vacancies in metal oxide according to claim 1, wherein the metal oxide nanoparticles in step three are a gray solid powdery product with uniform color.
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| CN114774980A (en) * | 2022-05-10 | 2022-07-22 | 浙江工业大学 | Vanadium oxide catalyst containing different valence states formed by controlling different calcination conditions, and synthesis method and application thereof |
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Application publication date: 20220412 |