CN115448354A - Cerium oxide particles and method for preparing the same - Google Patents
Cerium oxide particles and method for preparing the same Download PDFInfo
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- CN115448354A CN115448354A CN202211127905.6A CN202211127905A CN115448354A CN 115448354 A CN115448354 A CN 115448354A CN 202211127905 A CN202211127905 A CN 202211127905A CN 115448354 A CN115448354 A CN 115448354A
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- 239000002245 particle Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910000420 cerium oxide Inorganic materials 0.000 title claims description 38
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims description 37
- 239000002243 precursor Substances 0.000 claims abstract description 46
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 28
- 238000000120 microwave digestion Methods 0.000 claims abstract description 24
- 150000000703 Cerium Chemical class 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 7
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 6
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 5
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- -1 cerium ions Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- SQKWGPOIVHMUNF-UHFFFAOYSA-K cerium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Ce+3] SQKWGPOIVHMUNF-UHFFFAOYSA-K 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-O tert-butylammonium Chemical compound CC(C)(C)[NH3+] YBRBMKDOPFTVDT-UHFFFAOYSA-O 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Analytical Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses cerium dioxide particles and a preparation method thereof, wherein the preparation method comprises the following steps: 1) Mixing water-soluble cerium salt and polyhydric alcohol in a molar ratio of 1; 2) Carrying out microwave treatment on the mixed solution in a microwave digestion instrument to obtain precursor reaction liquid; wherein the microwave treatment temperature is 120-200 ℃, and the time is 15-60 min; 3) Solid-liquid separation is carried out on the precursor reaction liquid, and the obtained solid is washed and dried to obtain a precursor; 4) Calcining the precursor to obtain cerium dioxide particles, wherein the cerium dioxide particles are spherical and have a particle size D 50 Is 100-300 nm. The cerium dioxide particles obtained by the method have good dispersibility.
Description
Technical Field
The present invention relates to cerium oxide particles and a method for preparing the same.
Background
The structural characteristics of the cerium oxide particles are one of the important indicators affecting the performance thereof. Ceria of different particle size, morphology, and particle size distribution may vary in use.
CN102020306A discloses a microwave rapid synthesis method of nano cerium dioxide, which takes a power continuous household microwave oven as a heat source, water as a solvent, organic amine (the organic amine comprises triethylene tetramine, tetraethylene pentamine, diethanol amine and ethanol amine) as an alkali source, and adopts microwave-assisted reflux without high temperature and high pressure and surfactant to obtain the nano cerium dioxide. The prepared cerium dioxide has a particle size of about 5nm.
CN101508456A discloses a microwave-assisted method for preparing nano cerium oxide with different morphologies, which comprises the following steps: preparing a cerous nitrate aqueous solution, and adding the cerous nitrate aqueous solution, ethylene glycol, oleic acid and tert-butylammonium into a high-temperature reaction kettle according to a specific volume ratio; sealing the high-temperature reaction kettle and then placing the high-temperature reaction kettle in a microwave environment for heating for 5-10 min; and after the reaction is finished, cooling the obtained mixture to room temperature, washing, centrifuging and drying to obtain the cerium oxide nano material. In this patent document, the spherical nano-cerium oxide has a particle size of less than 100nm. In addition, the patent document adds more reagents, which are not easy to recycle and have high cost.
CN109133140A discloses a method for preparing cerium dioxide nano-particles, firstly, cerium nitrate and pyridine-2,5-dicarboxylic acid are respectively dissolved in a mixed solvent of absolute ethyl alcohol and DMF, the volume ratio of the two solvents is 1:1, then the two solutions are mixed and stirred uniformly, and then ammonia water is added to adjust the pH value to 7.3-9.0; then placing the mixed solution into a round-bottom flask, reacting in a microwave oven reaction device in a laboratory for 10-40 min, cooling the reaction, centrifuging, washing, and drying to obtain cerium-based coordination polymer nano-ions; then calcining at 500-800 ℃ to obtain the cerium dioxide nano-particles. The ceria nanoparticles obtained in this patent document have an average particle diameter of about 35nm, and the reagents added in this patent document are not easily recycled and have a high cost.
CN110194480B discloses a nano cerium oxide and a preparation method thereof, which comprises the steps of mixing cerium salt and carbonate or oxalate according to the molar ratio of 1:1-3, then adding an alcohol dispersant for full grinding reaction, washing and drying after the reaction to prepare a precursor; and then calcining the precursor. The particle size of the nano cerium oxide obtained in the patent document is less than 100nm; the obtained nano cerium oxide is not in the form of uniformly dispersed spheres.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing cerium oxide particles, which are substantially spherical and have a particle diameter D 50 Is 100-300 nm. The cerium dioxide particles prepared by the method have good dispersibility, basically have no adhesion and no agglomeration. It is another object of the present invention to provide cerium oxide particles obtained by the above method. The invention adopts the following technical scheme to achieve the purpose.
In one aspect, the present invention provides a method for preparing cerium oxide particles, comprising the steps of:
1) Mixing water-soluble cerium salt and polyhydric alcohol in a molar ratio of 1;
2) Carrying out microwave treatment on the mixed solution in a microwave digestion instrument to obtain precursor reaction liquid; wherein the microwave treatment temperature is 120-200 ℃, and the time is 15-60 min;
3) Solid-liquid separation is carried out on the precursor reaction liquid, and the obtained solid is washed and dried to obtain a precursor;
4) Calcining the precursor to obtain cerium dioxide particles;
wherein the oxidation is carried outThe cerium particles are spherical and have a particle diameter D 50 Is 100-300 nm.
According to the preparation method of the present invention, preferably, the water-soluble cerium salt is selected from one or more of cerous chloride, cerium sulfate, cerous nitrate and ceric ammonium nitrate.
According to the preparation method of the present invention, preferably, the water-soluble cerium salt is cerous chloride or cerous nitrate.
According to the preparation method of the present invention, preferably, in step 1), no surfactant or dispersant is added.
According to the preparation method provided by the invention, in the step 2), the power of the microwave digestion instrument is preferably 600-1000W.
According to the preparation method of the invention, preferably, in the step 3), solid-liquid separation is performed by centrifugal separation, and washing is performed by sequentially washing with ethanol and water.
According to the preparation method of the invention, in the step 3), the drying temperature is preferably 70-100 ℃, and the drying time is preferably 3-12 h.
According to the preparation method of the invention, preferably, in the step 4), the calcining temperature is 300-900 ℃ and the calcining time is 2-5 h.
According to the preparation method of the present invention, preferably, the polyol is glycerol.
In another aspect, the present invention provides cerium oxide particles obtained according to the preparation method of the present invention as described above.
The cerium oxide particles obtained according to the method for preparing cerium oxide particles of the present invention are substantially spherical, and the particle diameter D of the obtained cerium oxide 50 Is 100-300 nm. Furthermore, the cerium dioxide particles prepared by the method have good dispersibility, basically have no adhesion and no agglomeration. The preparation method of the invention uses less reagents, only adopts polyhydric alcohol (such as glycerol) during reaction, is easy to recycle and reduces the cost. The process of the present invention does not add any other surfactant or dispersant.
Drawings
FIG. 1 is an SEM image of a precursor obtained in example 1 of the present invention.
FIG. 2 is an SEM photograph of cerium oxide particles obtained in example 1 of the present invention.
Fig. 3 is an XRD pattern of the cerium oxide particles obtained in example 1 of the present invention.
FIG. 4 is a TEM image of cerium oxide particles obtained in example 2 of the present invention.
FIG. 5 is an SEM photograph of cerium oxide particles obtained in example 3 of the present invention.
FIG. 6 is an SEM photograph of cerium oxide particles obtained in comparative example 1 of the present invention.
FIG. 7 is an SEM photograph of cerium oxide particles obtained in comparative example 2 of the present invention.
FIG. 8 is an SEM photograph of cerium oxide particles obtained in comparative example 3 of the present invention.
FIG. 9 is an SEM photograph of cerium oxide particles obtained in comparative example 4 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
The method for preparing cerium oxide particles according to the present invention comprises the steps of: (1) a mixing step; (2) a microwave treatment step; (3) a post-treatment step; and (4) a calcining step. As described in detail below.
< mixing step >
Mixing water-soluble cerium salt and polyhydric alcohol to obtain a mixed solution.
In the present invention, the polyhydric alcohol may be an alcohol containing three or more hydroxyl groups. Preferably, the polyhydric alcohol is at least one selected from the group consisting of glycerol, pentaerythritol, trimethylolethane, xylitol, and sorbitol, more preferably one selected from the group consisting of glycerol, pentaerythritol, and trimethylolethane, and still more preferably glycerol.
In the present invention, the water-soluble cerium salt is selected from one or more of cerium chloride, cerium sulfate, cerium nitrate and cerium ammonium nitrate. Preferably, the water-soluble cerium salt is selected from one of cerium chloride, cerium sulfate, cerium nitrate and cerium ammonium nitrate. More preferably, the water-soluble cerium salt is cerous chloride or cerous nitrate.
In the present invention, the water-soluble cerium salts may be their corresponding hydrates.
The molar ratio of the water-soluble cerium salt to the polyol may be 1. Through a great deal of research and experiments, the method is found that cerium dioxide in a specific particle size range can be obtained and spherical cerium dioxide can be obtained only by mixing polyhydric alcohol as a solvent and a water-soluble cerium salt for post-treatment. Although the principle is not clear, we speculate that after the polyol is mixed with the water-soluble cerium salt and subjected to microwave treatment, the polyol can be complexed with cerium ions in the water-soluble cerium salt to form an organic complex, so that the cerium ions are uniformly dispersed at the molecular level, a stable, uniform and size-controllable precursor sphere is obtained, the agglomeration among particles is effectively prevented, and the precursor can obtain cerium dioxide microsphere powder with high purity, almost no adhesion and uniform particle size distribution after calcination.
Mixing water-soluble cerium salt and polyalcohol to obtain a mixed solution. No surfactant or dispersant was added during the mixing process.
According to one embodiment of the present invention, a water-soluble cerium salt and a polyhydric alcohol are uniformly mixed at a molar ratio of 1 to 5000 to obtain a mixed solution.
According to a preferred embodiment of the present invention, a water-soluble cerium salt and glycerol are uniformly mixed at a molar ratio of 1 to 5000 to obtain a mixed solution.
< microwave treatment step >
And carrying out microwave treatment on the mixed solution in a microwave digestion instrument to obtain a precursor reaction solution. This may be advantageous to obtain a uniform, dispersed and stable precursor. On the other hand, the reaction time can be shortened and the energy consumption can be reduced by microwave-assisted heating.
The microwave treatment temperature may be 120 to 200 deg.C, preferably 130 to 200 deg.C, and more preferably 140 to 180 deg.C. The time for the microwave treatment may be 15 to 60min, preferably 20 to 50min, and more preferably 20 to 40min.
The power of the microwave digestion instrument is 600-1000W, preferably 700-1000W, and more preferably 800-900W.
According to a specific embodiment of the invention, the mixed solution is transferred into a microwave digestion tank, the microwave digestion tank is sealed and then fixed in a microwave digestion instrument for microwave treatment for 20-40 min, the microwave treatment temperature is 130-200 ℃, and the precursor reaction solution is obtained after natural cooling to room temperature.
< post-treatment step >
And (3) carrying out solid-liquid separation on the precursor reaction liquid, and washing and drying the obtained solid to obtain the precursor.
The solid-liquid separation may be centrifugation or filtration, and is preferably centrifugation. After centrifugation, the upper layer solution was discarded to give a solid. The solid was washed with ethanol and water in this order. The number of washing times is 2 to 4. The resulting washed solid was then dried. The drying temperature may be 70 to 100 deg.C, preferably 80 to 100 deg.C, more preferably 80 to 90 deg.C. The drying time may be 3 to 12 hours, preferably 6 to 12 hours, more preferably 6 to 8 hours.
The obtained precursor has the characteristics of regular microspherical appearance, good dispersibility and uniform appearance.
< calcination step >
And calcining the precursor to obtain the cerium dioxide particles.
The calcination temperature may be 300 to 900 deg.C, preferably 400 to 800 deg.C, and more preferably 500 to 700 deg.C. The calcination time may be 2 to 5 hours, preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours. This is advantageous in obtaining the dispersed cerium oxide particles.
According to an embodiment of the present invention, the method for preparing cerium oxide particles comprises the following steps:
1) Mixing water-soluble cerium salt and glycerol in a molar ratio of 1;
2) Carrying out microwave treatment on the mixed solution in a microwave digestion instrument to obtain a precursor reaction solution; wherein the microwave treatment temperature is 120-200 ℃, and the time is 15-60 min;
3) Centrifugally separating the precursor reaction liquid, washing and drying the obtained solid to obtain a precursor;
4) Calcining the precursor at 300-900 ℃ for 2-5 h to obtain cerium dioxide particles;
wherein the cerium oxide particles obtained are substantially spherical and have a particle size D 50 Is 100-300 nm.
The cerium dioxide particles prepared by the method of the invention are basically spherical and have a particle size D 50 100-300 nm, good dispersity, basically no adhesion and no agglomeration.
The test methods of the following examples and comparative examples are illustrated below:
SEM: the test was performed using a ZEISS Sigma 500 field emission scanning electron microscope.
TEM: the test was performed using a Thermo Fisher Talos F200i transmission electron microscope.
Particle diameter D 50 : the test was carried out using a Mastersizer3000 laser particle sizer.
XRD: the test was performed using an X' Pert PRO X-ray diffractometer.
Example 1
Uniformly mixing cerous nitrate hexahydrate and glycerol according to a molar ratio of 1.
Transferring the prepared mixture into a microwave digestion tank, sealing and fixing the microwave digestion tank in a microwave digestion instrument, carrying out microwave treatment for 30min at 130 ℃, and naturally cooling to room temperature to obtain a precursor reaction liquid.
Centrifuging the obtained precursor reaction liquid for 10min at the rotation speed of 10000rpm, removing the upper layer solution, washing the obtained solid, and drying to obtain the precursor.
And calcining the precursor at 900 ℃ for 2h to obtain the cerium dioxide particles. It D 50 Is 180nm.
The SEM image of the precursor is shown in figure 1. The SEM image of the cerium oxide particles is shown in fig. 2, and the XRD analysis thereof is shown in fig. 3.
Example 2
Uniformly mixing cerium chloride hexahydrate and glycerol according to a molar ratio of 1.
Transferring the prepared mixture into a microwave digestion tank, sealing and fixing the microwave digestion tank in a microwave digestion instrument, carrying out microwave treatment for 30min at 180 ℃, and naturally cooling to room temperature to obtain a precursor reaction liquid.
Centrifuging the obtained precursor reaction liquid for 10min at the rotation speed of 10000rpm, removing the upper layer solution, washing the obtained solid, and drying to obtain the precursor.
And calcining the precursor at 700 ℃ for 2h to obtain the cerium dioxide particles. It D 50 Is 240nm. A TEM image of the cerium oxide particles is shown in fig. 4.
Example 3
And (2) uniformly mixing cerium sulfate and glycerol according to a molar ratio of 1.
Transferring the prepared mixture into a microwave digestion tank, sealing and fixing the microwave digestion tank in a microwave digestion instrument, carrying out microwave treatment for 30min at 200 ℃, and naturally cooling to room temperature to obtain a precursor reaction liquid.
Centrifuging the obtained precursor reaction liquid for 10min at the rotation speed of 10000rpm, removing the upper layer solution, washing the obtained solid, and drying to obtain the precursor.
And calcining the precursor at 300 ℃ for 2h to obtain the cerium dioxide particles. It D 50 Is 280nm. The SEM image of the cerium oxide particles is shown in fig. 5.
Example 4
Uniformly mixing cerous nitrate hexahydrate and glycerol according to a molar ratio of 1.
Transferring the prepared mixture into a microwave digestion tank, sealing the microwave digestion tank, fixing the microwave digestion tank in a microwave digestion instrument, carrying out microwave treatment for 30min at 130 ℃, and naturally cooling to room temperature to obtain a precursor reaction liquid.
Centrifuging the obtained precursor reaction liquid for 10min at the rotation speed of 10000rpm, removing the upper layer solution, washing the obtained solid, and drying to obtain the precursor.
And calcining the precursor at 700 ℃ for 2h to obtain the cerium dioxide particles. It D 50 Was 260nm.
Comparative examples 1 to 4
The procedure was as in example 1 except for the process parameters shown in Table 1.
SEM images of the ceric oxides obtained in comparative examples 1, 2, 3 and 4 are shown in fig. 6, 7, 8 and 9, respectively.
TABLE 1
In Table 1, "- -" indicates that the particle diameter D could not be effectively measured 50 。
As can be seen from FIG. 3, the present invention obtained cerium oxide (CeO) having a face centered cubic structure 2 ). As can be seen from FIG. 1, the precursor of the present invention is spherical particles with uniform size, good dispersibility and no adhesion. As can be seen from FIGS. 2, 4 and 5, the method of the present invention can obtain cerium dioxide microspheres with uniform size, D 50 Basically between 100 and 300nm.
As is clear from comparison between example 1 and comparative examples 1 and 2, it is advantageous to obtain the cerium oxide particles having good dispersibility according to the present invention by controlling the molar ratio of glycerin to cerous nitrate hexahydrate within the range of the present invention; otherwise, agglomeration is easy or spherical particles cannot be obtained.
As can be seen from comparison between example 1 and comparative example 3, the cerium oxide particles having good dispersibility according to the present invention could not be obtained by using propylene glycol instead of glycerin.
As is clear from comparison between example 1 and comparative example 4, the use of ethylene glycol instead of glycerin is not favorable for obtaining the cerium oxide particles having good dispersibility according to the present invention.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and alterations that may occur to those skilled in the art may fall within the scope of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A method for preparing cerium dioxide particles, which is characterized by comprising the following steps:
1) Mixing water-soluble cerium salt and polyhydric alcohol in a molar ratio of 1;
2) Carrying out microwave treatment on the mixed solution in a microwave digestion instrument to obtain precursor reaction liquid; wherein the microwave treatment temperature is 120-200 ℃, and the time is 15-60 min;
3) Solid-liquid separation is carried out on the precursor reaction liquid, and the obtained solid is washed and dried to obtain a precursor;
4) Calcining the precursor to obtain cerium dioxide particles;
wherein the cerium dioxide particles are spherical and have a particle size D 50 Is 100-300 nm.
2. The method according to claim 1, wherein the water-soluble cerium salt is selected from one or more of cerous chloride, cerium sulfate, cerous nitrate and ceric ammonium nitrate.
3. The method according to claim 1, wherein the water-soluble cerium salt is cerous chloride or cerous nitrate.
4. The method according to claim 1, wherein no surfactant or dispersant is added in step 1).
5. The preparation method according to claim 1, wherein in the step 2), the power of the microwave digestion instrument is 600-1000W.
6. The process according to claim 3, wherein in the step 3), the solid-liquid separation is performed by centrifugal separation, and the washing is performed by washing with ethanol and water sequentially.
7. The method according to claim 1, wherein the drying temperature in step 3) is 70 to 100 ℃ and the drying time is 3 to 12 hours.
8. The preparation method according to claim 1, wherein in the step 4), the calcination temperature is 300 to 900 ℃ and the calcination time is 2 to 5 hours.
9. The method according to claim 1, wherein the polyol is glycerol.
10. Cerium oxide particles obtained by the production method according to any one of claims 1 to 9.
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