CN110697773A - Preparation method of loose macroporous bismuth oxide nano material - Google Patents
Preparation method of loose macroporous bismuth oxide nano material Download PDFInfo
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- CN110697773A CN110697773A CN201911028449.8A CN201911028449A CN110697773A CN 110697773 A CN110697773 A CN 110697773A CN 201911028449 A CN201911028449 A CN 201911028449A CN 110697773 A CN110697773 A CN 110697773A
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- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 40
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- -1 bismuth salt compound Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- 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
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/651—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention relates to a preparation method of a loose macroporous bismuth oxide nano material, which comprises the steps of preparing a mixed solution containing sodium bismuthate and polyvinyl pyrrolidone, dripping concentrated nitric acid, stirring and uniformly mixing to obtain a reaction solution, sealing the reaction solution, carrying out ultrasonic heating treatment, purifying and separating after the reaction is finished to obtain a precursor product, and carrying out roasting heat treatment on the precursor product to obtain the loose macroporous bismuth oxide nano material. The technical scheme has the advantages of simple whole production process, simple and convenient operation, good repeatability, cheap and easily obtained raw materials and suitability for industrial production. The prepared bismuth oxide nano material has a massive spongy loose structure, contains a large number of pores, has the pore diameter of 100-300 nm, and belongs to a macroporous nano material.
Description
Technical Field
The invention relates to the field of preparation of semiconductor nano catalyst materials, in particular to a preparation method of a loose macroporous bismuth oxide nano material.
Background
The macroporous material as a catalyst has two main characteristics in structure: firstly, the pores are large, and can be used for macromolecule catalysis; and secondly, the opening of the holes is good, and each hole is communicated with each other to form a macroporous channel network, so that the transfer of macromolecules in the pore channel is facilitated. For macromolecular catalysis, diffusion of the reactant materials within the catalyst is often the controlling factor, and the macroporous material provides an ideal diffusion medium in structure. The application of bismuth oxide is very wide, and the bismuth oxide is not only a good organic synthesis catalyst, but also an important doped powder material in the electronic industry. At present, the research on the nano bismuth oxide material mainly focuses on the preparation of the superfine nano bismuth oxide material, and the preparation of the large-aperture nano bismuth oxide material is rarely reported.
The chinese patent document entitled "a process for producing bismuth oxide" (patent No. 200610118215.9) describes the following technical solutions: dissolving a bismuth salt compound in a small amount of organic solvent; the reaction is carried out in an instrument provided with a microwave emitting element, the reaction time is 3-60 minutes, and the reaction power is 180-900 watts; washing the obtained product with water and absolute ethyl alcohol respectively, drying at 70-100 ℃, and then roasting at 500-700 ℃ for 2-4 hours. Although the method can effectively prepare the nano bismuth oxide, the prepared nano material has limited aperture.
Disclosure of Invention
The invention aims to provide a preparation method of a loose macroporous bismuth oxide nano material, and the prepared bismuth oxide nano material has the advantages of large aperture, simple process and low cost.
The technical scheme adopted by the invention is as follows:
a preparation method of a loose macroporous bismuth oxide nano material is characterized by comprising the following operations:
preparing a mixed solution containing sodium bismuthate and polyvinyl pyrrolidone, dripping concentrated nitric acid, stirring and uniformly mixing to obtain a reaction solution, sealing the reaction solution, carrying out ultrasonic auxiliary heating treatment, carrying out purification and separation after the reaction is finished to obtain a precursor product, and carrying out heat treatment on the precursor product to obtain the loose macroporous bismuth oxide nano material.
The specific scheme is as follows:
transferring the reaction solution into a blue cap bottle for sealing, and then placing the blue cap bottle into an ultrasonic cleaner for ultrasonic water bath heating reaction.
The temperature of the water bath heating reaction is 25-60 ℃, and the time is 10-30 min.
And mixing the mixed solution according to the proportion that 1.0-1.2 g of polyvinylpyrrolidone is added into each 1mmol of sodium bismuthate.
And dropwise adding concentrated nitric acid according to the amount of 0.1-0.5 mL of concentrated nitric acid dropwise added to every 1mmol of sodium bismuthate in the reaction solution.
The mixed solution was mixed with 60mL of water per 1mmol of sodium bismuthate.
Dropwise adding concentrated nitric acid, stirring and uniformly mixing for 10-15 min, and then heating the reaction solution in a sealed water bath for reaction.
The temperature of the annealing treatment is 400-450 ℃, and the time is 1-3 h.
The detailed operation is as follows: the annealing treatment is carried out in a muffle furnace.
The purification separation comprises the filtration and recovery of the precipitate, followed by washing, drying and grinding of the dark brown precursor product.
The invention has the technical effects that: the technical scheme has the advantages of simple whole production process, simple and convenient operation, good repeatability, cheap and easily obtained raw materials and suitability for industrial production. The prepared bismuth oxide nano material has a massive spongy structure, is loose in structure, contains a large number of pores, has the pore diameter of 100-300 nm, and belongs to a macroporous nano material.
Drawings
FIG. 1 is a flow diagram of a process route for the macroporous bismuth oxide nanomaterial prepared in example 1;
FIG. 2 is an X-ray diffraction analysis (XRD) spectrum of the macroporous bismuth oxide nanomaterial prepared in example 1;
FIG. 3 is a field emission scanning electron microscope (FE-SEM) photomicrograph of the macroporous bismuth oxide nanomaterial prepared in example 1;
FIG. 4 is a field emission scanning electron microscope (FE-SEM) high magnification photograph of the macroporous bismuth oxide nanomaterial prepared in example 1.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the following description is given in conjunction with the accompanying examples. It is to be understood that the following text is merely illustrative of one or more specific embodiments of the invention and does not strictly limit the scope of the invention as specifically claimed.
Example 1
Weighing 1mmol sodium bismuthate pentahydrate NaBiO3·5H2Dissolving O and 1.1g polyvinylpyrrolidone (PVP) in 60mL of deionized water, dropwise adding 0.2mL of concentrated nitric acid (commercially available) into the reaction solution while stirring, and continuously stirring for 10 minutes; transferring the mixed reaction solution into a 100 mL blue cap bottle, sealing, placing the blue cap bottle into an ultrasonic cleaner, setting the temperature of ultrasonic water bath at 30 ℃, carrying out ultrasonic heating for 10 minutes, taking out the blue cap bottle after the reaction is finished, naturally cooling the blue cap bottle to room temperature, filtering, washing, drying and grinding the precipitate, and collecting a dark brown precursor; and (3) heating a proper amount of the dark brown precursor in a muffle furnace at the furnace temperature of 420 ℃ for 3 hours to obtain the loose macroporous bismuth oxide nano material.
Referring to the attached drawing 1, fig. 1 is a process technical route of the macroporous bismuth oxide nano material prepared by the method, and fig. 1 shows that the preparation process is simple and convenient, the equipment is simple, the repeatability is good, the raw materials are cheap and easy to obtain, and the method is suitable for industrial production.
Referring to the attached figure 2, figure 2 is an X-ray powder diffraction analysis (XRD) spectrogram of the macroporous bismuth oxide nano material prepared by the method. In FIG. 2, the diffraction peak has strong peak shape and sharp spectral line peak position corresponding to all diffraction peaks of JCPDF standard card (41-1449) one by one, and the index is monoclinic phase semiconductor Bi2O3The crystal, space group P21/c (14), lattice constant a = 5.85 Å, b =8.17 Å, c = 7.512 Å, α = γ =90 °, β =112.98 °. the diffraction peak in fig. 2 is very high in intensity, sharp in peak shape, indicating that the crystallinity of the crystal is very good.
Referring to fig. 3, fig. 3 is a Scanning Electron Microscope (SEM) image of the low power field of the macroporous bismuth oxide nano-material prepared as above. From FIG. 3, the semiconductor Bi can be seen2O3The crystal has a massive spongy structure, a loose structure, a large amount of pores, a large pore diameter and a uniform structure.
Referring to fig. 4, fig. 4 is a high power field Scanning Electron Microscope (SEM) photograph of the macroporous bismuth oxide nanomaterial prepared as described above. From FIG. 4, the semiconductor Bi can be seen2O3The crystal pore structures are mutually communicated to form a channel, the aperture reaches 100 ~ 300nm, and the crystal belongs to a macroporous nano material.
Example 2
Weighing 1mmol sodium bismuthate pentahydrate NaBiO3·5H2Dissolving O and 1.0g of polyvinylpyrrolidone (PVP) by using 60mL of deionized water, dripping 0.1mL of concentrated nitric acid into the reaction solution under the condition of stirring, and continuing to stir for 15 minutes; transferring the mixed reaction solution into a 100 mL blue cap bottle, sealing, placing the blue cap bottle into an ultrasonic cleaner, setting the temperature of ultrasonic water bath at 60 ℃, carrying out ultrasonic heating for 30 minutes, taking out the blue cap bottle after the reaction is finished, naturally cooling the blue cap bottle to room temperature, filtering, washing, drying and grinding the precipitate, and collecting a dark brown precursor; and (3) heating a proper amount of the dark brown precursor in a muffle furnace at 400 ℃ for 3 hours to obtain the loose macroporous bismuth oxide nano material.
Example 3
Weighing 1mmol sodium bismuthate pentahydrate NaBiO3·5H2Dissolving O and 1.2g polyvinylpyrrolidone (PVP) by 60mL of deionized water, dripping 0.5mL of concentrated nitric acid into the reaction solution under the condition of stirring, and continuing to stir for 20 minutes; transferring the mixed reaction solution into a 100 mL blue cap bottle, sealing, placing the blue cap bottle into an ultrasonic cleaner, setting the temperature of ultrasonic water bath at 20 ℃, carrying out ultrasonic heating for 20 minutes, taking out the blue cap bottle after the reaction is finished, naturally cooling the blue cap bottle to room temperature, filtering, washing, drying and grinding the precipitate, and collecting a dark brown precursor; heating a proper amount of dark brown precursor in a muffle furnace at 450 ℃ for 1 hour to obtain the loose macroporous bismuth oxide nano materialAnd (5) feeding.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention. Structures, devices, and methods of operation not specifically described or illustrated herein are generally practiced in the art without specific recitation or limitation.
Claims (10)
1. A preparation method of a loose macroporous bismuth oxide nano material is characterized by comprising the following operations:
preparing a mixed solution containing sodium bismuthate and polyvinyl pyrrolidone, dripping concentrated nitric acid, stirring and uniformly mixing to obtain a reaction solution, sealing the reaction solution, carrying out ultrasonic auxiliary heating treatment, carrying out purification and separation after the reaction is finished to obtain a precursor product, and carrying out heat treatment on the precursor product to obtain the loose macroporous bismuth oxide nano material.
2. The method for preparing the bulk macroporous bismuth oxide nanomaterial of claim 1, wherein: transferring the reaction solution into a blue cap bottle for sealing, and then placing the blue cap bottle in an ultrasonic cleaner for ultrasonic-assisted heating reaction.
3. The method for preparing the bulk macroporous bismuth oxide nanomaterial according to claim 1 or 2, wherein: the temperature of the water bath for the ultrasonic-assisted heating reaction is 25-60 ℃, and the time is 10-30 min.
4. The method for preparing the bulk macroporous bismuth oxide nanomaterial of claim 1, wherein: and mixing the mixed solution according to the proportion that 1.0-1.2 g of polyvinylpyrrolidone is added into each 1mmol of sodium bismuthate.
5. The method for preparing the bulk macroporous bismuth oxide nanomaterial according to claim 1 or 4, wherein: and dropwise adding concentrated nitric acid according to the amount of 0.1-0.5 mL of concentrated nitric acid dropwise added to every 1mmol of sodium bismuthate in the reaction solution.
6. The method for preparing the bulk macroporous bismuth oxide nanomaterial of claim 5, wherein: the mixed solution was mixed with 60mL of water per 1mmol of sodium bismuthate.
7. The method for preparing the bulk macroporous bismuth oxide nanomaterial of claim 1, wherein: dropwise adding concentrated nitric acid, stirring and uniformly mixing for 10-15 min, and then heating the reaction solution in a sealed water bath for reaction.
8. The method for preparing the bulk macroporous bismuth oxide nanomaterial of claim 1, wherein: the temperature of the annealing treatment is 400-450 ℃, and the time is 1-3 h.
9. The method for preparing the bulk macroporous bismuth oxide nanomaterial of claim 8, wherein: the annealing treatment is carried out in a muffle furnace.
10. The method for preparing the bulk macroporous bismuth oxide nanomaterial of claim 8, wherein: the purification separation comprises the filtration and recovery of the precipitate, followed by washing, drying and grinding of the dark brown precursor product.
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|---|---|---|---|
| CN201911028449.8A CN110697773A (en) | 2019-10-28 | 2019-10-28 | Preparation method of loose macroporous bismuth oxide nano material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023143052A1 (en) * | 2022-01-25 | 2023-08-03 | 中科优品(天津)科技发展有限公司 | Application of bismuth trioxide as bactericide |
-
2019
- 2019-10-28 CN CN201911028449.8A patent/CN110697773A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| MING-GUO MA等: ""Microwave-assisted synthesis of hierarchical Bi2O3 spheres assembled from nanosheets with pore structure"", 《MATERIALS LETTERS》 * |
| YASHAR AZIZIAN-KALANDARAGH等: ""Ultrasound-assisted preparation and characterization of β--Bi2O3 nanostructures: Exploring the photocatalytic activity against rhodamine B"", 《SUPERLATTICES AND MICROSTRUCTURES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023143052A1 (en) * | 2022-01-25 | 2023-08-03 | 中科优品(天津)科技发展有限公司 | Application of bismuth trioxide as bactericide |
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