CN114113268B - Preparation method of cobaltosic oxide cluster modified tin dioxide, product and application thereof - Google Patents
Preparation method of cobaltosic oxide cluster modified tin dioxide, product and application thereof Download PDFInfo
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 33
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical class O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000002086 nanomaterial Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 7
- 239000002114 nanocomposite Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 22
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 4
- 239000010457 zeolite Substances 0.000 abstract description 4
- -1 zeolite imidazolium salt Chemical class 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 20
- 230000004044 response Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Health & Medical Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of cobaltosic oxide cluster modified tin dioxide, a product and application thereof, wherein a Co and Zn complexed MOF structure is utilized and placed in a reaction precursor, after hydrothermal reaction, the MOF structure forms a large number of pores, and then Zn atoms in a sample are removed by acid etching to form a Co 3O4 cluster modified SnO 2 nano composite material. On one hand, a Zn complex zeolite imidazolium salt framework (ZIF-8) is used as a micropore template, and a large number of pores are formed in the nano material after acid etching; on the other hand, a Co complexing zeolite imidazole salt skeleton (ZIF-67) is utilized for heat treatment to form a Co 3O4 cluster modified SnO 2 nano composite structure; so that a large number of Sn 4+-O2 ‑· vacancies are provided in the system, the vacancies can greatly improve the sensitivity of the SnO 2 gas-sensitive material, and meanwhile, the Co 3O4/SnO2 heterojunction is constructed, so that the reactivity is improved.
Description
Technical Field
The invention relates to the technical field of gas sensors, in particular to a preparation method of cobaltosic oxide cluster modified tin dioxide, a product and application thereof.
Background
The metal oxide such as SnO 2、WO3 has the advantages of excellent performance, environmental friendliness, abundant resources, low price and the like, and is a gas-sensitive material with wider research. As a gas-sensitive material, a metal oxide has excellent response characteristics, but its response mechanism determines poor selectivity, and it is difficult to achieve effective discrimination of a target gas, and although the gas-sensitive performance of the material can be improved by processes such as surface modification of the metal oxide, metal/noble metal doping, etc., it is not satisfactory in terms of improvement of selectivity.
The invention provides a simple method for modifying SnO 2 nano material by Co 3O4 clusters, which utilizes nano material with ZIF structure to adjust pore structure in nano material, can generate a large number of pores with size of 3-5 nm on the surface and in nano material, the pore structure is conducive to adsorption of formaldehyde, the Co 3O4 clusters modify SnO 2 to construct heterojunction structure, promote catalytic reaction on the surface of material, greatly improve gas-sensitive performance, especially selectivity, of nano material, and has simple preparation process, low preparation cost and practical application value for further promoting development of semiconductor gas-sensitive devices.
Disclosure of Invention
The invention aims to provide a preparation method of cobaltosic oxide cluster modified tin dioxide.
Still another object of the present invention is: the cobaltosic oxide cluster modified tin dioxide product prepared by the method is provided.
Yet another object of the present invention is: there is provided the use of the above product.
The invention aims at realizing the following scheme: a preparation method of cobaltosic oxide cluster modified tin dioxide, which utilizes a Co and Zn complex MOF structure, is placed in a reaction precursor, a large number of pores are formed by the MOF structure after hydrothermal reaction, zn atoms in a sample are removed by acid etching, and a Co 3O4 cluster modified SnO 2 nano composite material is formed, and the preparation method comprises the following steps:
Step one: dissolving 1-2 g of triblock polymer F127 in 50mL of methanol, stirring to form a clear solution, dissolving 10-15 mmol of zinc nitrate hexahydrate and cobalt nitrate hexahydrate in 50mL of methanol, and stirring to form a solution A; dissolving 30-45 mmol of 2-methylimidazole in 50mL of methanol to form a solution B; rapidly pouring the B into the A, standing for 24 hours at room temperature, centrifuging, taking a precipitate, and vacuum drying at 60-70 ℃ for 4-12 hours to obtain a sample C;
Step two: placing 4-6 g of stannous chloride in 40-60 mL of a mixed solvent of deionized water and ethylene glycol, and stirring for 30min, wherein the volume ratio of the deionized water to the ethylene glycol is 2:3-3:2; then adding 4-6 mL of ethanolamine, stirring for 30min, adding 70-200 mg of the sample C obtained in the first step, stirring for 30min, placing in a hydrothermal kettle for sealing, reacting at 130-150 ℃ for 8-12 h, cooling to room temperature, centrifuging, and drying at 60-80 ℃ for 8-12 h to obtain a sample D;
Step three: and (3) placing the dried sample D in a muffle furnace, heating to a temperature of between 3 and 5 ℃/min, performing heat treatment for 1 to 2 hours at a temperature of between 450 and 650 ℃, cooling to room temperature, taking out the sample, placing the sample in a nitric acid solution with a concentration of 3.5M, sealing in a reaction kettle, performing hydrothermal reaction for 6 to 10 hours at a temperature of between 140 and 160 ℃, cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying to obtain the Co 3O4 cluster modified SnO 2 nano material.
The invention provides cobaltosic oxide cluster modified tin dioxide, which is prepared by the method.
The method of the invention uses Zn complex zeolite imidazole salt skeleton (ZIF-8) as a micropore template, then forms a large number of pores in the nano material after acid etching, and on the other hand, forms a Co3O4 cluster modified SnO2 nano composite structure by using the Co complex zeolite imidazole salt skeleton (ZIF-67) heat treatment process. According to the method, ZIF-8 and ZIF-67 are added into a precursor, after high-temperature treatment, zn elements introduced by the ZIF-8 are removed by an acid etching method, a large number of pores with the size of 3-5 nm can be formed in the nano material, the adsorption capacity of the material to formaldehyde can be improved, and the reaction sensitivity is improved by utilizing a Co 3O4/SnO2 heterostructure.
The invention also provides an application of the cobaltosic oxide cluster modified tin dioxide in toxic gas detection.
The method has the advantages of simple preparation process, low preparation cost, stable performance of the obtained product, wide application prospect and capability of controlling the pore structure of the material by controlling the amount of ZIF-8 when being used for target gas detection, improving the adsorption of the material to specific gas and improving the response selectivity.
Drawings
FIG. 1 is a graph of the sensitivity of Co 3O4 cluster modified SnO 2 nanomaterial of the present invention at 150℃to different gases at 10ppm concentration.
Detailed Description
Example 1:
The cobalt oxide cluster modified tin dioxide is prepared by placing a Co and Zn complexed MOF structure in a reaction precursor, forming a large number of pores by the MOF structure after hydrothermal reaction, and then removing Zn atoms in a sample by acid etching to form a Co 3O4 cluster modified SnO 2 nanocomposite material, wherein the preparation method comprises the following steps:
Step one: 1g of triblock polymer F127 is dissolved in 50mL of methanol and stirred to form a clear solution, then 3mmol of zinc nitrate hexahydrate and 7mmol of cobalt nitrate hexahydrate are dissolved in 50mL of methanol and stirred to form solution A; 30mmol of 2-methylimidazole is taken and dissolved in 50mL of methanol to form a solution B; pouring the B into the A rapidly, standing at room temperature for 24 hours, centrifuging to obtain a precipitate, and vacuum drying at 70 ℃ for 12 hours to obtain a sample C;
step two: placing 6g of stannous chloride in 60mL of a mixed solvent of deionized water and ethylene glycol, and stirring for 30min, wherein the volume ratio of the deionized water to the ethylene glycol is 2:3; then adding 4mL of ethanolamine, stirring for 30min, adding 100mg of the sample C obtained in the first step, stirring for 30min, placing in a hydrothermal kettle for sealing, reacting at 150 ℃ for 8 hours, cooling to room temperature, centrifuging, and drying at 80 ℃ for 12 hours to obtain a sample D;
Step three: and (3) placing the dried sample D in a muffle furnace, carrying out heat treatment at a heating rate of 3 ℃/min to 450 ℃ for 2 hours, cooling to room temperature, taking out the sample, placing the sample in a nitric acid solution with a concentration of 3.5M, sealing in a reaction kettle, carrying out hydrothermal reaction at 140 ℃ for 6 hours, cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying to obtain Co 3O4 cluster modified SnO 2 nano material powder.
The sensitivity of the Co 3O4 cluster modified SnO 2 nano material of the invention to different gases with the concentration of 10ppm at the working temperature of 150 ℃ is shown in figure 1, and the sensitivity to formaldehyde is the highest.
The powder prepared in the embodiment is dispersed and coated on a six-pin ceramic tube gas-sensitive test element, the response to formaldehyde gas is tested, the optimal corresponding temperature of the material is 150 ℃, and the response sensitivity to formaldehyde gas with the concentration of 10ppm is 28.9.
Example 2:
the cobaltosic oxide cluster modified tin dioxide was prepared in a similar manner to the procedure of example 1, as follows:
Step one, 2g of triblock polymer F127 is dissolved in 50mL of methanol and stirred to form a clear solution, then 5mmol of zinc nitrate hexahydrate and 5mmol of cobalt nitrate hexahydrate are dissolved in 50mL of methanol and stirred to form solution A; dissolving 40mmol of 2-methylimidazole in 50mL of methanol to form a solution B; pouring the B into the A rapidly, standing at room temperature for 24 hours, centrifuging, taking precipitate, and vacuum drying at 70 ℃ for 12 hours; obtaining a sample C;
Step two, placing 4g of stannous chloride in 60mL of mixed solvent of deionized water and ethylene glycol, and stirring for 30min, wherein the volume ratio of the deionized water to the ethylene glycol is 2:3; then adding 4mL of ethanolamine, stirring for 30min, adding 100mg of sample C, stirring for 30min, sealing in a hydrothermal kettle, reacting at 150 ℃ for 8 hours, cooling to room temperature, centrifuging to obtain a sample, and drying at 80 ℃ for 12 hours; obtaining a sample D;
and thirdly, placing the dried sample D in a muffle furnace, carrying out heat treatment for 2 hours at 450 ℃, heating up at a speed of 3 ℃/min, cooling to room temperature, taking out the sample, placing the sample in a nitric acid solution with a concentration of 3.5M, sealing in a reaction kettle, carrying out hydrothermal reaction for 6 hours at 140 ℃, cooling to room temperature, centrifuging, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying to obtain the Co 3O4 cluster modified SnO 2 nano material.
The powder prepared in the embodiment is dispersed and coated on a six-pin ceramic tube gas-sensitive test element, the response to formaldehyde gas is tested, the optimal corresponding temperature of the material is 150 ℃, and the response sensitivity to formaldehyde gas with the concentration of 10ppm is 33.8.
Example 3:
the cobaltosic oxide cluster modified tin dioxide was prepared in a similar manner to the procedure of example 1, as follows:
Step one, 1.5g of triblock polymer F127 is dissolved in 50mL of methanol and stirred to form a clear solution, then 10mmol of zinc nitrate hexahydrate and 5mmol of cobalt nitrate hexahydrate are dissolved in 50mL of methanol and stirred to form solution A; dissolving 35mmol of 2-methylimidazole in 50mL of methanol to form a solution B; pouring the B into the A rapidly, standing at room temperature for 24 hours, centrifuging, taking a precipitate, and vacuum drying the sample at 70 ℃ for 12 hours; obtaining a sample C;
step two, 5g of stannous chloride is placed in a mixed solvent of deionized water and ethylene glycol, stirring is carried out for 30min, wherein the volume ratio of the deionized water to the ethylene glycol is 2:3, the total amount of the deionized water to the ethylene glycol is 50mL, then 5mL of ethanolamine is added, stirring is carried out for 30min, 150mg of sample C is added, stirring is carried out for 30min, the mixture is placed in a hydrothermal kettle for sealing, the mixture is reacted for 10 h at 140 ℃, the mixture is cooled to room temperature, the mixture is centrifuged to obtain a sample, and then the sample is dried at 80 ℃ for 12 h; obtaining a sample D;
And thirdly, placing the dried sample D in a muffle furnace, carrying out heat treatment for 2 hours at 550 ℃, heating up at a speed of 3 ℃/min, cooling to room temperature, taking out the sample, placing the sample in a nitric acid solution with a concentration of 3.5M, sealing in a reaction kettle, carrying out hydrothermal reaction for 6 hours at 150 ℃, cooling to room temperature, centrifuging the sample, respectively cleaning for 3 times by using deionized water and absolute ethyl alcohol, and drying to obtain the Co 3O4 cluster modified SnO 2 nano material.
The powder prepared in the embodiment is dispersed and coated on a six-pin ceramic tube gas-sensitive test element, the response to formaldehyde gas is tested, the optimal corresponding temperature of the material is 150 ℃, and the response sensitivity to formaldehyde gas with the concentration of 10ppm is 32.5.
Claims (6)
1. A preparation method of cobaltosic oxide cluster modified tin dioxide is characterized in that a Co and Zn complex MOF structure is utilized and placed in a reaction precursor, a large number of pores are formed in the MOF structure after hydrothermal reaction, zn atoms in a sample are removed by acid etching, and a Co 3O4 cluster modified SnO 2 nano composite material is formed, and the preparation method comprises the following steps:
Step one: dissolving 1-2 g of triblock polymer F127 in 50mL of methanol, stirring to form a clear solution, dissolving 10-15 mmol of zinc nitrate hexahydrate and cobalt nitrate hexahydrate in 50mL of methanol, and stirring to form a solution A; dissolving 30-45 mmol of 2-methylimidazole in 50mL of methanol to form a solution B; rapidly pouring the B into the A, standing for 24 hours at room temperature, centrifuging, taking a precipitate, and vacuum drying at 60-70 ℃ for 4-12 hours to obtain a sample C;
Step two: placing 4-6 g of stannous chloride in 40-60 mL of a mixed solvent of deionized water and ethylene glycol, and stirring for 30min, wherein the volume ratio of the deionized water to the ethylene glycol is 2:3-3:2; then adding 4-6 mL of ethanolamine, stirring for 30min, adding 70-200 mg of the sample C obtained in the first step, stirring for 30min, placing in a hydrothermal kettle for sealing, reacting at 130-150 ℃ for 8-12 h, cooling to room temperature, centrifuging, and drying at 60-80 ℃ for 8-12 h to obtain a sample D;
Step three: and (3) placing the dried sample D in a muffle furnace, heating to a temperature of between 3 and 5 ℃/min, performing heat treatment for 1 to 2 hours at a temperature of between 450 and 650 ℃, cooling to room temperature, taking out the sample, placing the sample in a nitric acid solution with a concentration of 3.5M, sealing in a reaction kettle, performing hydrothermal reaction for 6 to 10 hours at a temperature of between 140 and 160 ℃, cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying to obtain the Co 3O4 cluster modified SnO 2 nano material.
2. The method for preparing the cobaltosic oxide cluster modified tin dioxide according to claim 1, which is characterized by comprising the following steps:
Step one: 1g of triblock polymer F127 is dissolved in 50mL of methanol and stirred to form a clear solution, then 3mmol of zinc nitrate hexahydrate and 7mmol of cobalt nitrate hexahydrate are dissolved in 50mL of methanol and stirred to form solution A; 30mmol of 2-methylimidazole is taken and dissolved in 50mL of methanol to form a solution B; pouring the B into the A rapidly, standing at room temperature for 24 hours, centrifuging to obtain a precipitate, and vacuum drying at 70 ℃ for 12 hours to obtain a sample C;
step two: placing 6g of stannous chloride in 60mL of a mixed solvent of deionized water and ethylene glycol, and stirring for 30min, wherein the volume ratio of the deionized water to the ethylene glycol is 2:3; then adding 4mL of ethanolamine, stirring for 30min, adding 100mg of the sample C obtained in the first step, stirring for 30min, placing in a hydrothermal kettle for sealing, reacting at 150 ℃ for 8 hours, cooling to room temperature, centrifuging, and drying at 80 ℃ for 12 hours to obtain a sample D;
Step three: and (3) placing the dried sample D in a muffle furnace, carrying out heat treatment at a heating rate of 3 ℃/min to 450 ℃ for 2 hours, cooling to room temperature, taking out the sample, placing the sample in a nitric acid solution with a concentration of 3.5M, sealing in a reaction kettle, carrying out hydrothermal reaction at 140 ℃ for 6 hours, cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying to obtain Co 3O4 cluster modified SnO 2 nano material powder.
3. The method for preparing the cobaltosic oxide cluster modified tin dioxide according to claim 1, which is characterized by comprising the following steps:
Step one, 2g of triblock polymer F127 is dissolved in 50mL of methanol and stirred to form a clear solution, then 5mmol of zinc nitrate hexahydrate and 5mmol of cobalt nitrate hexahydrate are dissolved in 50mL of methanol and stirred to form solution A; dissolving 40mmol of 2-methylimidazole in 50mL of methanol to form a solution B; pouring the B into the A rapidly, standing at room temperature for 24 hours, centrifuging, taking precipitate, and vacuum drying at 70 ℃ for 12 hours; obtaining a sample C;
Step two, placing 4g of stannous chloride in 60mL of mixed solvent of deionized water and ethylene glycol, and stirring for 30min, wherein the volume ratio of the deionized water to the ethylene glycol is 2:3; then adding 4mL of ethanolamine, stirring for 30min, adding 100mg of sample C, stirring for 30min, sealing in a hydrothermal kettle, reacting at 150 ℃ for 8 hours, cooling to room temperature, centrifuging to obtain a sample, and drying at 80 ℃ for 12 hours; obtaining a sample D;
and thirdly, placing the dried sample D in a muffle furnace, carrying out heat treatment for 2 hours at 450 ℃, heating up at a speed of 3 ℃/min, cooling to room temperature, taking out the sample, placing the sample in a nitric acid solution with a concentration of 3.5M, sealing in a reaction kettle, carrying out hydrothermal reaction for 6 hours at 140 ℃, cooling to room temperature, centrifuging, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying to obtain the Co 3O4 cluster modified SnO 2 nano material.
4. The method for preparing the cobaltosic oxide cluster modified tin dioxide according to claim 1, which is characterized by comprising the following steps:
Step one, 1.5g of triblock polymer F127 is dissolved in 50mL of methanol and stirred to form a clear solution, then 10mmol of zinc nitrate hexahydrate and 5mmol of cobalt nitrate hexahydrate are dissolved in 50mL of methanol and stirred to form solution A; dissolving 35mmol of 2-methylimidazole in 50mL of methanol to form a solution B; pouring the B into the A rapidly, standing at room temperature for 24 hours, centrifuging, taking a precipitate, and vacuum drying the sample at 70 ℃ for 12 hours; obtaining a sample C;
step two, 5g of stannous chloride is placed in a mixed solvent of deionized water and ethylene glycol, stirring is carried out for 30min, wherein the volume ratio of the deionized water to the ethylene glycol is 2:3, the total amount of the deionized water to the ethylene glycol is 50mL, then 5mL of ethanolamine is added, stirring is carried out for 30min, 150mg of sample C is added, stirring is carried out for 30min, the mixture is placed in a hydrothermal kettle for sealing, the mixture is reacted for 10 h at 140 ℃, the mixture is cooled to room temperature, the mixture is centrifuged to obtain a sample, and then the sample is dried at 80 ℃ for 12 h; obtaining a sample D;
And thirdly, placing the dried sample D in a muffle furnace, carrying out heat treatment for 2 hours at 550 ℃, heating up at a speed of 3 ℃/min, cooling to room temperature, taking out the sample, placing the sample in a nitric acid solution with a concentration of 3.5M, sealing in a reaction kettle, carrying out hydrothermal reaction for 6 hours at 150 ℃, cooling to room temperature, centrifuging the sample, respectively cleaning for 3 times by using deionized water and absolute ethyl alcohol, and drying to obtain the Co 3O4 cluster modified SnO 2 nano material.
5. A tricobalt tetraoxide cluster modified tin dioxide, characterized in that it is prepared according to the method of any one of claims 1 to 4.
6. Use of the cobaltosic oxide cluster modified tin dioxide according to claim 5 for formaldehyde detection.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111369175.6A CN114113268B (en) | 2021-11-18 | 2021-11-18 | Preparation method of cobaltosic oxide cluster modified tin dioxide, product and application thereof |
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| CN115849435A (en) * | 2022-12-26 | 2023-03-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tin dioxide nano material for gas detection, product and application thereof |
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