CN115448354B - Cerium oxide particles and method for preparing same - Google Patents
Cerium oxide particles and method for preparing same Download PDFInfo
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- CN115448354B CN115448354B CN202211127905.6A CN202211127905A CN115448354B CN 115448354 B CN115448354 B CN 115448354B CN 202211127905 A CN202211127905 A CN 202211127905A CN 115448354 B CN115448354 B CN 115448354B
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- 239000002245 particle Substances 0.000 title claims abstract description 66
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 48
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000120 microwave digestion Methods 0.000 claims abstract description 23
- 150000000703 Cerium Chemical class 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 45
- 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 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 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
- 239000004094 surface-active agent Substances 0.000 claims description 5
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 15
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 22
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 21
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture 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 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004005 microsphere 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
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 cerium ions Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 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
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 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
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 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
- 150000002500 ions Chemical class 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
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
Classifications
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- 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
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Analytical Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses cerium oxide particles and a preparation method thereof, wherein the preparation method comprises the following steps: 1) Mixing water-soluble cerium salt and polyalcohol in the molar ratio of 1:100-5000 to obtain mixed solution; 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) Performing solid-liquid separation on the precursor reaction liquid, and washing and drying the obtained solid to obtain a precursor; 4) Calcining the precursor to obtain cerium oxide particles, wherein the cerium oxide particles are spherical and have a particle diameter D 50 100-300 nm. The cerium oxide particles obtained by the method have good dispersibility.
Description
Technical Field
The invention relates to cerium oxide particles and a preparation method thereof.
Background
The structural characteristics of ceria particles are one of the important indicators affecting their performance. The ceria with different particle size, morphology and particle size distribution may vary in application.
CN102020306a discloses a microwave rapid synthesis method of nano cerium oxide, which uses a power continuous household microwave oven as a heat source, uses water as a solvent, uses organic amine (including triethylene tetramine, tetraethylene pentamine, diethanolamine and ethanolamine) as an alkali source, adopts microwave to assist in backflow, does not need high temperature and high pressure, and does not have a surfactant, thus obtaining the nano cerium oxide. The particle size of the prepared cerium oxide is about 5nm.
CN101508456a discloses a method for preparing nano cerium oxide with different morphologies by microwave assistance, which comprises the following steps: preparing a cerous nitrate aqueous solution, and adding the cerous nitrate aqueous solution, ethylene glycol, oleic acid and tertiary butyl ammonium 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. The particle size of the spherical nano cerium oxide in the patent document is less than 100nm. In addition, the patent document has a large amount of reagents, is difficult to recycle and has high cost.
CN109133140a discloses a method for preparing cerium dioxide nano particles, firstly, cerium nitrate, pyridine-2, 5-dicarboxylic acid are respectively dissolved in a mixed solvent of absolute ethanol 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 for 10-40 min in a laboratory microwave oven reaction device, cooling the reaction, centrifugally washing, and drying to obtain cerium-based coordination polymer nano ions; and then calcining at 500-800 ℃ to obtain the cerium oxide nano particles. The average particle diameter of the ceria nanoparticles obtained in this patent document is about 35nm, and the amount of the reagent added in this patent document is large, so that the ceria nanoparticles are not easily recycled and the cost is high.
CN110194480B discloses a nano cerium oxide and a preparation method thereof, comprising the steps of mixing cerium salt and carbonate or oxalate according to a molar ratio of 1:1-3, adding an alcohol dispersant for full grinding reaction, washing and drying after the reaction to prepare a precursor; and calcining the precursor. The particle size of the nano cerium oxide obtained in the patent document is smaller than 100nm; the resulting nano cerium oxide is not in a uniformly dispersed spherical shape.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a method for producing ceria particles, which method gives ceria particles having a substantially spherical shape and a particle diameter D of the obtained ceria particles 50 100-300 nm. The cerium oxide 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 the cerium oxide particles obtained by the above method. The invention adopts the following technical scheme to realize the aim.
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 polyalcohol in the molar ratio of 1:100-5000 to obtain mixed solution;
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) Performing solid-liquid separation on the precursor reaction liquid, and washing and drying the obtained solid to obtain a precursor;
4) Calcining the precursor to obtain cerium oxide particles;
wherein the cerium oxide particles are spherical and have a particle diameter D 50 100-300 nm.
According to the preparation method of the present invention, preferably, the water-soluble cerium salt is selected from one or more of cerium chloride, cerium sulfate, cerium nitrate and ammonium cerium nitrate.
According to the preparation method of the present invention, preferably, the water-soluble cerium salt is cerium chloride or cerium 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 of the present invention, preferably, in the step 2), the power of the microwave digestion instrument is 600 to 1000W.
According to the preparation method of the invention, preferably, in the step 3), the solid-liquid separation adopts a centrifugal separation mode, and the washing adopts a sequential washing mode of ethanol and water.
According to the preparation method of the present invention, preferably, in the step 3), the drying temperature is 70 to 100 ℃ and the drying time is 3 to 12 hours.
According to the preparation method of the present invention, preferably, in the step 4), the calcination temperature is 300 to 900 ℃ and the calcination time is 2 to 5 hours.
According to the production method of the present invention, preferably, the polyol is glycerol.
In another aspect, the present invention provides a cerium oxide particle obtained according to the preparation method of the present invention as described above.
The ceria obtained by the method for producing ceria particles according to the invention is substantially spherical, and the particle diameter D of the obtained ceria 50 100-300 nm. Furthermore, the cerium dioxide particles prepared by the method have better dispersibility, basically have no adhesion and no agglomeration. The preparation method of the invention uses less reagent, only adopts polyol (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 of example 1 of the present invention.
Fig. 2 is an SEM image of cerium oxide particles obtained in example 1 of the present invention.
Fig. 3 is an XRD pattern of the ceria particles obtained in example 1 of the present invention.
Fig. 4 is a TEM image of the ceria particles obtained in example 2 of the present invention.
Fig. 5 is an SEM image of cerium oxide particles obtained in example 3 of the present invention.
FIG. 6 is an SEM image of cerium oxide particles obtained in comparative example 1 of the present invention.
FIG. 7 is an SEM image of cerium oxide particles obtained in comparative example 2 of the present invention.
FIG. 8 is an SEM image of cerium oxide particles obtained in comparative example 3 of the invention.
FIG. 9 is an SEM image of cerium oxide particles obtained in comparative example 4 of the invention.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
The preparation method of the cerium oxide particles comprises the following steps: (1) a mixing step; (2) a microwave treatment step; (3) a post-treatment step; (4) a calcination step. The following is a detailed description.
< mixing step >
Mixing water-soluble cerium salt and polyalcohol to obtain mixed solution.
In the present invention, the polyol may be an alcohol having three or more hydroxyl groups. Preferably, the polyhydric alcohol is at least one selected from glycerol, pentaerythritol, trimethylolethane, xylitol and sorbitol, more preferably one selected from glycerol, pentaerythritol and trimethylolethane, 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 ammonium cerium nitrate. Preferably, the water-soluble cerium salt is selected from one of cerium chloride, cerium sulfate, cerium nitrate and ammonium cerium nitrate. More preferably, the water-soluble cerium salt is cerium chloride or cerium 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 polyhydric alcohol may be 1:100 to 5000, preferably 1:200 to 2000, more preferably 300 to 1500, still more preferably 400 to 1200, still more preferably 400 to 1000. Through a great deal of research and experiments, it is found that cerium oxide in a specific particle size range can be obtained and spherical cerium oxide can be obtained by merely mixing and post-treating a water-soluble cerium salt with a polyhydric alcohol as a solvent. Although the principle is not clear, we speculate that after the polyol is mixed with the water-soluble cerium salt, the polyol can be complexed with cerium ions in the water-soluble cerium salt to form an organic complex after microwave treatment, so that cerium ions are uniformly dispersed at the molecular level to obtain precursor spheres with stable and uniform size and controllable size, agglomeration among particles is effectively prevented, and the precursor can obtain cerium dioxide microsphere powder with almost no adhesion and high purity, wherein the particle size of the precursor spheres is uniformly distributed without agglomeration after calcination.
Mixing water-soluble cerium salt and polyalcohol to obtain mixed solution. No surfactant or dispersant is added during the mixing process.
According to one embodiment of the invention, the water-soluble cerium salt and the polyalcohol are uniformly mixed in a molar ratio of 1:100-5000 to obtain a mixed solution.
According to a preferred embodiment of the present invention, the water-soluble cerium salt and glycerol are uniformly mixed in a molar ratio of 1:100-5000 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 for obtaining a uniform, dispersed and stable precursor. On the other hand, the microwave auxiliary heating can shorten the reaction time and reduce the energy consumption.
The microwave treatment temperature may be 120 to 200 ℃, preferably 130 to 200 ℃, more preferably 140 to 180 ℃. The time of the microwave treatment may be 15 to 60 minutes, preferably 20 to 50 minutes, more preferably 20 to 40 minutes.
The power of the microwave digestion instrument is 600 to 1000W, preferably 700 to 1000W, and more preferably 800 to 900W.
According to one 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, preferably centrifugation. After centrifugation, the upper layer solution was discarded to obtain a solid. The solid was washed sequentially with ethanol and water. The washing times are 2-4 times. The resulting washed solid was then dried. The drying temperature may be 70 to 100 ℃, preferably 80 to 100 ℃, more preferably 80 to 90 ℃. The drying time may be 3 to 12 hours, preferably 6 to 12 hours, more preferably 6 to 8 hours.
The obtained precursor has regular microsphere morphology, and has the characteristics of good dispersibility and uniform morphology.
< calcination step >
And calcining the precursor to obtain the cerium oxide particles.
The calcination temperature may be 300 to 900 ℃, preferably 400 to 800 ℃, more preferably 500 to 700 ℃. 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 dispersible ceria particles.
According to one embodiment of the present invention, the preparation method of cerium oxide particles comprises the following specific steps:
1) Mixing water-soluble cerium salt and glycerol in a molar ratio of 1:100-5000 to obtain a mixed solution;
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 oxide particles;
wherein the obtained ceria particles are substantially spherical and have a particle diameter D 50 100-300 nm.
The cerium oxide particles prepared by the method of the invention are basically spherical and have the particle diameter D 50 100-300 nm, good dispersibility, basically no adhesion and no agglomeration.
The test methods of the following examples and comparative examples are described 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 : testing was performed using a Mastersizer3000 laser particle sizer.
XRD: the test was performed using an X' Pert PRO X-ray diffractometer.
Example 1
Cerium nitrate hexahydrate and glycerol are uniformly mixed according to the molar ratio of 1:1000 to obtain a mixture.
Transferring the prepared mixture into a microwave digestion tank, sealing and fixing the microwave digestion tank in a microwave digestion instrument, performing microwave treatment at 130 ℃ for 30min, and naturally cooling to room temperature to obtain a precursor reaction solution.
Centrifuging the obtained precursor reaction solution for 10min at a rotation speed of 10000rpm, removing the upper layer solution, washing the obtained solid, and drying to obtain the precursor.
The precursor is calcined at 900 ℃ for 2 hours to obtain the cerium oxide particles. Its D 50 180nm.
SEM images of the precursors are shown in fig. 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
Cerium chloride hexahydrate and glycerol are uniformly mixed according to the molar ratio of 1:100 to obtain a mixture.
Transferring the prepared mixture into a microwave digestion tank, sealing and fixing the microwave digestion tank in a microwave digestion instrument, performing microwave treatment at 180 ℃ for 30min, and naturally cooling to room temperature to obtain a precursor reaction solution.
Centrifuging the obtained precursor reaction solution for 10min at a rotation speed of 10000rpm, removing the upper layer solution, washing the obtained solid, and drying to obtain the precursor.
The precursor is calcined at 700 ℃ for 2 hours to obtain cerium oxide particles. Its D 50 240nm. A TEM image of the ceria particles is shown in fig. 4.
Example 3
Cerium sulfate and glycerol are uniformly mixed according to the molar ratio of 1:1000 to obtain a mixture.
Transferring the prepared mixture into a microwave digestion tank, sealing and fixing the microwave digestion tank in a microwave digestion instrument, performing microwave treatment at 200 ℃ for 30min, and naturally cooling to room temperature to obtain a precursor reaction solution.
Centrifuging the obtained precursor reaction solution for 10min at a rotation speed of 10000rpm, removing the upper layer solution, washing the obtained solid, and drying to obtain the precursor.
The precursor is calcined at 300 ℃ for 2 hours to obtain cerium oxide particles. Its D 50 280nm. SEM images of the ceria particles are shown in fig. 5.
Example 4
Cerium nitrate hexahydrate and glycerol are uniformly mixed according to the mol ratio of 1:822 to obtain a mixture.
Transferring the prepared mixture into a microwave digestion tank, sealing and fixing the microwave digestion tank in a microwave digestion instrument, performing microwave treatment at 130 ℃ for 30min, and naturally cooling to room temperature to obtain a precursor reaction solution.
Centrifuging the obtained precursor reaction solution for 10min at a rotation speed of 10000rpm, removing the upper layer solution, washing the obtained solid, and drying to obtain the precursor.
The precursor is calcined at 700 ℃ for 2 hours to obtain cerium oxide particles. Its D 50 260nm.
Comparative examples 1 to 4
The procedure was as in example 1, except that the process parameters shown in Table 1 were followed.
SEM images of cerium oxide 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 measured effectively 50 。
As can be seen from FIG. 3, the present invention obtains a face-centered cubic structured ceria (CeO) 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 uniform-sized cerium oxide microspheres, D 50 Is basically 100-300 nm.
As is clear from comparison of example 1 and comparative examples 1 and 2, the control of the molar ratio of glycerol to cerium nitrate hexahydrate within the scope of the present invention is advantageous in obtaining the cerium oxide particles of the present invention having good dispersibility; otherwise, agglomeration is easy or spherical particles cannot be obtained.
As is clear from a comparison between example 1 and comparative example 3, the cerium oxide particles of the present invention having good dispersibility could not be obtained by using propylene glycol instead of glycerol.
As is clear from a comparison between example 1 and comparative example 4, the use of ethylene glycol instead of glycerol is disadvantageous in obtaining the ceria particles of the present invention having good dispersibility.
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (9)
1. A method for preparing cerium oxide particles, comprising the steps of:
1) Mixing water-soluble cerium salt and polyalcohol in the molar ratio of 1:100-5000 to obtain mixed solution;
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) Performing solid-liquid separation on the precursor reaction liquid, and washing and drying the obtained solid to obtain a precursor;
4) Calcining the precursor to obtain cerium oxide particles;
wherein the cerium oxide particles are spherical and have a particle diameter D 50 100-300 nm;
the polyol is an alcohol containing three or more hydroxyl groups.
2. The method of claim 1, wherein the water-soluble cerium salt is selected from one or more of cerium chloride, cerium sulfate, cerium nitrate, and ammonium cerium nitrate.
3. The method of claim 1, wherein the water-soluble cerium salt is cerium chloride or cerium nitrate.
4. The method of claim 1, wherein in step 1), no surfactant or dispersant is added.
5. The method according to claim 1, wherein in the step 2), the power of the microwave digestion instrument is 600 to 1000W.
6. The method according to claim 3, wherein in the step 3), the solid-liquid separation is performed by centrifugation, and the washing is performed by sequential washing with ethanol and water.
7. The method according to claim 1, wherein in step 3), the drying temperature is 70 to 100 ℃ and the drying time is 3 to 12 hours.
8. The method according to claim 1, wherein in step 4), the calcination temperature is 300 to 900 ℃ and the calcination time is 2 to 5 hours.
9. The method of claim 1, wherein the polyol is glycerol.
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