CN110255598A - A kind of preparation method of flower-like microsphere cerous carbonate and ceria - Google Patents
A kind of preparation method of flower-like microsphere cerous carbonate and ceria Download PDFInfo
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- CN110255598A CN110255598A CN201910572253.9A CN201910572253A CN110255598A CN 110255598 A CN110255598 A CN 110255598A CN 201910572253 A CN201910572253 A CN 201910572253A CN 110255598 A CN110255598 A CN 110255598A
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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
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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
- C01F17/247—Carbonates
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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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
Abstract
The invention belongs to technical field of powdered material preparation, disclose the preparation method of a kind of flower-like microsphere cerous carbonate and ceria.Compound concentration is 0.02~1.0mol/L, the precipitant solution that the cerium solution and concentration that pH value is 3.5~5.0 are 0.02~2.0mol/L, and it is cooled to the reaction temperature lower than 20 DEG C, then precipitant solution is added in cerium solution, it is stirred to react, reaction product is filtered, washed and drying and processing, obtains flower-like microsphere carbonic acid cerium precursor, then the calcination processing at 500~700 DEG C, obtains flower-like microsphere ceria.Preparation method of the invention does not add any additive, simple and easy, is not necessarily to high temperature, with short production cycle, low in cost；Product obtained has unique flower-like microsphere pattern, and partial size is 0.5~10 μm, can be applied to the fields such as fluorescent material, ultraviolet shielding material, catalyst carrier.
Description
Technical field
The invention belongs to technical field of powdered material preparation, and in particular to a kind of flower-like microsphere cerous carbonate and ceria
Preparation method.
Background technique
Cerous carbonate and ceria are important rare-earth products, and wherein ceria is because having a kind of unique electronics structure
Type, the excellent characteristics such as electricity, optics, magnetics make ceria be widely used in catalyst, high performance magnetic material, other
The fields such as functional material.Ceria large specific surface area with flower-like microsphere pattern, active site and chemical functional are abundant,
The three-dimensional hierarchical structure that nanostructure and micro nano structure cooperatively form will show uniqueness than two dimension or one-dimensional micro/nano structure
Performance and novel function, therefore prepare the floriform appearance micro-/ nano ball ceria with three-dimensional structure with great meaning
Justice.
Before the preparation of three-dimensional flower-shaped microballoon ceria obtains the cerous carbonate of flower-like microsphere pattern by distinct methods first
Body is driven, then using the heredity of calcining front and back pattern, calcining obtains the ceria of same pattern.Current many document reports
By changing hydro-thermal method condition, such as reaction dissolvent system, reaction time, additive, three-dimensional flower-shaped microballoon dioxy is prepared
Change cerium.
Ni etc. is using ammonium hydrogen carbonate as precipitating reagent, and hydro-thermal reaction 48h successfully prepares three-dimensional flower-shaped ceria at 120 DEG C.
(Ni JB,Gao J,Geng XY,Wei H.Facile hydrothermal synthesis of large-scale
monodisperse 3D flower-like CeO2nanospheres and their excellent magnetic
properties[J].Journal of Materials Science-Materials in Electronics,2017,28
(16): 12306-12311.) Zhong etc. is reported using cerium chloride and urea as reactant, tetrabutylammonium bromide
(tetrabutylammonium bromide, TBAB) is additive, and ethylene glycol is solvent, reacts 30min under the conditions of 180 DEG C
The method for preparing three-dimensional flower-shaped microballoon ceria.(Zhong LS,Hu JS,Cao AM,Liu Q,Song WG,Wan LJ.3D
flowerlike ceria micro/nanocomposite structure and its application for water
Treatment and CO removal [J] .Chemistry of Materials, 2007,19 (7): 1648-1655.) Li et al.
By differential responses system, including glucose/acrylic acid, fructose/acrylic acid, glucose/propionic acid, glucose/n-butylamine system,
Respectively in 180 DEG C and 200 DEG C reaction 72h, meso-pore Ce (OH) CO with flower-shaped three-dimensional structure has been synthesized3Microballoon is further forged
Burning obtains and Ce (OH) CO3The identical meso-pore Ce O of microballoon pattern2Microballoon.(Li HF,Lu GZ,Dai QG,Wang YQ,Guo Y,
Guo YL.Hierarchical Organization and Catalytic Activity of High-Surface-Area
Mesoporous Ceria Microspheres Prepared Via Hydrothermal Routes[J].Acs Applied
Materials&Interfaces,2010,2(3):838-846.)
However hydro-thermal method temperature is high, minimum 100 DEG C of flower-like microsphere ceria preparation temperature, the reaction time is longer, leads
Cause preparation cost high.In contrast, liquid-phase precipitation method temperature is low, is swift in response, and is more applicable for industrialized production, but at present
The ceria pattern that liquid-phase precipitation method prepares is single, mostly flat crystal, and not yet discovery report utilizes low-temperature precipitation method
Prepare the cerous carbonate and ceria of flower-like microsphere pattern.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the purpose of the present invention is to provide a kind of flower-like microspheres
The preparation method of cerous carbonate and ceria.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of flower-like microsphere cerous carbonate and ceria, including following preparation step:
(1) compound concentration is 0.02~1.0mol/L, and the cerium solution that pH value is 3.5~5.0, solvent is water or water and has
The mixed solvent of solvent；
(2) compound concentration is the precipitant solution of 0.02~2.0mol/L, and solvent is the mixing of water or water and organic solvent
Solvent；
(3) precipitant solution of the cerium solution of step (1) and step (2) is cooled to the reaction temperature lower than 20 DEG C,
Then precipitant solution is added in cerium solution, is stirred to react, reaction product is filtered, washed and drying and processing, obtains
Flower-like microsphere carbonic acid cerium precursor；
(4) by flower-like microsphere carbonic acid cerium precursor at 500~700 DEG C calcination processing, obtain flower-like microsphere ceria.
Preferably, cerium salt described in step (1) refers at least one of cerous nitrate, cerium chloride, cerous acetate and cerous sulfate.
Preferably, organic solvent described in step (1) and (2) refers to that water soluble alcohols organic solvent, water soluble alcohols have
Solvent volume fraction is no more than the 10% of mixed solvent；The water soluble alcohols organic solvent be preferably ethylene glycol, propylene glycol,
At least one of glycerine.
Preferably, precipitating reagent described in step (2) refers to soluble carbonate salt；The soluble carbonate salt is preferably carbonic acid
At least one of ammonium, ammonium hydrogen carbonate, sodium carbonate and sodium bicarbonate.
Preferably, the time being stirred to react described in step (3) is 10~60min.
Preferably, the time of calcination processing described in step (4) is 2~4h.
Preparation method of the invention have the following advantages that and the utility model has the advantages that
Preparation method of the invention does not add any additive, simple and easy, is not necessarily to high temperature, with short production cycle, low in cost,
It is expected to realize large-scale industrial production.Product cerous carbonate and ceria obtained have unique flower-like microsphere pattern,
Partial size is 0.5~10 μm, can be applied to the fields such as fluorescent material, ultraviolet shielding material, catalyst carrier.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of flower-like microsphere cerous carbonate prepared by embodiment 1；
Fig. 2 is the low magnification field emission scanning electron microscope figure of flower-like microsphere cerous carbonate prepared by embodiment 1；
Fig. 3 is the high-amplification-factor field emission scanning electron microscope figure of flower-like microsphere cerous carbonate prepared by embodiment 1；
Fig. 4 is the X-ray diffractogram of flower-like microsphere ceria prepared by embodiment 1；
Fig. 5 is the high-amplification-factor field emission scanning electron microscope figure of flower-like microsphere ceria prepared by embodiment 1；
The low magnification field emission scanning electron microscope figure of flower-like microsphere ceria prepared by Fig. 6 embodiment 3；
The high-amplification-factor field emission scanning electron microscope figure of flower-like microsphere ceria prepared by Fig. 7 embodiment 3.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) cerous nitrate solution is prepared, by 0.01mol cerous nitrate in 100mL deionized water, obtaining concentration is 0.10mol/
L cerous nitrate solution；
(2) sodium bicarbonate solution is prepared, by 0.03mol sodium bicarbonate in 100mL deionized water, obtaining concentration is
0.30mol/L sodium bicarbonate solution；
(3) precipitant solution of the cerium solution of step (1) and step (2) is cooled to 5 DEG C, and kept the temperature；Kept for 5 DEG C,
Precipitant solution is added in cerium solution, is stirred continuously in the process, 40min is reacted, sediment is successively filtered, is washed
It washs and drying and processing, obtains flower-like microsphere carbonic acid cerium precursor；
(4) flower-like microsphere carbonic acid cerium precursor is calcined 3 hours at 600 DEG C, obtains flower-like microsphere ceria.
Fig. 1 is the X-ray diffractogram of the flower-like microsphere cerous carbonate prepared, consistent with standard card PDF#38-0377, is lanthanum
Stone-type cerous carbonate Ce2(CO3)38H2O.Fig. 2 is the low magnification Flied emission scanning electrograph of the flower-like microsphere cerous carbonate of preparation, can
See that cerium carbonate product has flower-like microsphere pattern, pattern is uniform, and average grain diameter is at 0.5-10 μm.Fig. 3 be prepare it is flower-shaped micro-
The high-amplification-factor field emission scanning electron microscope figure of ball cerous carbonate, product has layered structure, by growing layer by layer on original thin slice
It forms, not sheet aggregate.Fig. 4 is the X-ray diffractogram of the flower-like microsphere ceria prepared, with standard card PDF#
34-0394 is consistent, is pure cubic fluorite CeO2.Fig. 5 is the high-amplification-factor field hair of the flower-like microsphere ceria prepared
Scanning electron microscope (SEM) photograph is penetrated, product morphology has heredity.It is identical as carbonic acid cerium precursor, there is layered structure, by original thin slice
On grow layer by layer.
Embodiment 2
(1) cerous nitrate solution is prepared, by 0.01mol cerous nitrate in 100mL deionized water, obtaining concentration is 0.10mol/
L cerous nitrate solution；
(2) sodium bicarbonate solution is prepared, by 0.03mol sodium bicarbonate in 100mL deionized water, obtaining concentration is
0.30mol/L sodium bicarbonate solution；
(3) precipitant solution of the cerium solution of step (1) and step (2) is cooled to 15 DEG C, and kept the temperature；Keep 15
DEG C, precipitant solution is added in cerium solution, is stirred continuously in the process, 40min is reacted, sediment was successively carried out
Filter, washing and drying and processing, obtain flower-like microsphere carbonic acid cerium precursor；
(4) flower-like microsphere carbonic acid cerium precursor is calcined 3 hours at 600 DEG C, obtains flower-like microsphere ceria.
Product structure and pattern are same as Example 1.
Embodiment 3
(1) cerous nitrate solution is prepared, by 0.01mol cerous nitrate in 100mL in the mixed solvent, mixed solvent is 2.5% body
The propylene glycol/water solution of fraction, obtaining concentration is 0.10mol/L cerous nitrate solution；
(2) sodium bicarbonate solution is prepared, by 0.03mol sodium bicarbonate in 100mL in the mixed solvent, mixed solvent is
The propylene glycol/water solution of 2.5% volume fraction, obtaining concentration is 0.30mol/L sodium bicarbonate solution；
(3) precipitant solution of the cerium solution of step (1) and step (2) is cooled to 1 DEG C, and kept the temperature；Kept for 1 DEG C,
Precipitant solution is added in cerium solution, is stirred continuously in the process, 40min is reacted, sediment is successively filtered, is washed
It washs and drying and processing, obtains flower-like microsphere carbonic acid cerium precursor；
(4) flower-like microsphere carbonic acid cerium precursor is calcined 3 hours at 600 DEG C, obtains flower-like microsphere ceria.
The low magnification field emission scanning electron microscope figure and high-amplification-factor of flower-like microsphere ceria obtained by the present embodiment
Field emission scanning electron microscope figure is shown in that Fig. 6 and Fig. 7, petal-shaped thin slice are closer respectively.
Embodiment 4
(1) cerous nitrate solution is prepared, by 0.01mol cerous nitrate in 100mL in the mixed solvent, mixed solvent is 5% volume
The glycol/water solution of score, obtaining concentration is 0.10mol/L cerous nitrate solution；
(2) sodium bicarbonate solution is prepared, by 0.03mol sodium bicarbonate in 100mL in the mixed solvent, mixed solvent 5%
The glycol/water solution of volume fraction, obtaining concentration is 0.30mol/L sodium bicarbonate solution；
(3) precipitant solution of the cerium solution of step (1) and step (2) is cooled to 1 DEG C, and kept the temperature；Kept for 1 DEG C,
Precipitant solution is added in cerium solution, is stirred continuously in the process, 40min is reacted, sediment is successively filtered, is washed
It washs and drying and processing, obtains flower-like microsphere carbonic acid cerium precursor；
(4) flower-like microsphere carbonic acid cerium precursor is calcined 3 hours at 600 DEG C, obtains flower-like microsphere ceria.
Product structure and pattern are same as Example 3.
Embodiment 5
(1) cerous nitrate solution is prepared, by 0.01mol cerous nitrate in 100mL in the mixed solvent, mixed solvent is 5% volume
Glycerine/aqueous solution of score, obtaining concentration is 0.10mol/L cerous nitrate solution；
(2) sodium bicarbonate solution is prepared, by 0.03mol sodium bicarbonate in 100mL in the mixed solvent, mixed solvent 5%
Glycerine/aqueous solution of volume fraction, obtaining concentration is 0.30mol/L sodium bicarbonate solution；
(3) precipitant solution of the cerium solution of step (1) and step (2) is cooled to 1 DEG C, and kept the temperature；Kept for 1 DEG C,
Precipitant solution is added in cerium solution, is stirred continuously in the process, 40min is reacted, sediment is successively filtered, is washed
It washs and drying and processing, obtains flower-like microsphere carbonic acid cerium precursor；
(4) flower-like microsphere carbonic acid cerium precursor is calcined 3 hours at 600 DEG C, obtains flower-like microsphere ceria.
Product structure and pattern are same as Example 3.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of flower-like microsphere cerous carbonate and ceria, it is characterised in that including following preparation step:
(1) compound concentration is 0.02~1.0mol/L, the cerium solution that pH value is 3.5~5.0, and solvent is water or water and organic molten
The mixed solvent of agent；
(2) compound concentration is the precipitant solution of 0.02~2.0mol/L, and solvent is the mixed solvent of water or water and organic solvent；
(3) precipitant solution of the cerium solution of step (1) and step (2) is cooled to the reaction temperature lower than 20 DEG C, then
Precipitant solution is added in cerium solution, is stirred to react, reaction product is filtered, washed and drying and processing, obtains flower-shaped
Microballoon carbonic acid cerium precursor；
(4) by flower-like microsphere carbonic acid cerium precursor at 500~700 DEG C calcination processing, obtain flower-like microsphere ceria.
2. the preparation method of a kind of flower-like microsphere cerous carbonate and ceria according to claim 1, it is characterised in that: step
Suddenly cerium salt described in (1) refers at least one of cerous nitrate, cerium chloride, cerous acetate and cerous sulfate.
3. the preparation method of a kind of flower-like microsphere cerous carbonate and ceria according to claim 1, it is characterised in that: step
Suddenly organic solvent described in (1) and (2) refers to that water soluble alcohols organic solvent, water soluble alcohols organic solvent volume score do not surpass
Cross the 10% of mixed solvent.
4. the preparation method of a kind of flower-like microsphere cerous carbonate and ceria according to claim 3, it is characterised in that: institute
Stating water soluble alcohols organic solvent is at least one of ethylene glycol, propylene glycol, glycerine.
5. the preparation method of a kind of flower-like microsphere cerous carbonate and ceria according to claim 1, it is characterised in that: step
Suddenly precipitating reagent described in (2) refers to soluble carbonate salt.
6. the preparation method of a kind of flower-like microsphere cerous carbonate and ceria according to claim 5, it is characterised in that: institute
Stating soluble carbonate salt is at least one of ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate and sodium bicarbonate.
7. the preparation method of a kind of flower-like microsphere cerous carbonate and ceria according to claim 1, it is characterised in that: step
Suddenly the time being stirred to react described in (3) is 10~60min.
8. the preparation method of a kind of flower-like microsphere cerous carbonate and ceria according to claim 1, it is characterised in that: step
Suddenly the time of calcination processing described in (4) is 2~4h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299469A (en) * | 2020-09-22 | 2021-02-02 | 江汉大学 | Cerium dioxide and preparation method and application thereof |
| CN113120940A (en) * | 2019-12-30 | 2021-07-16 | 安集微电子科技（上海）股份有限公司 | Spherical cerium carbonate and synthesis method of cerium oxide |
| CN114425334A (en) * | 2020-10-15 | 2022-05-03 | 南京大学 | CeO2Micron flower-loaded Ru nano-particle compound and preparation method thereof |
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| CN1903731A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院物理研究所 | Flower shape structured nano-cerium oxide and its preparation method and use |
| CN103180248A (en) * | 2010-08-12 | 2013-06-26 | 大东化成工业株式会社 | Sheet-shaped cerium oxide and petal-shaped cerium oxide powder as aggregate of the sheet-shaped cerium oxide, process for production of the sheet-shaped cerium oxide and the petal-shaped cerium oxide powder, coated sheet-shaped cerium oxide and petal-shaped cerium oxide powder as aggregate of the coated sheet-shaped cerium oxide, and cosmetic |
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2019
- 2019-06-28 CN CN201910572253.9A patent/CN110255598B/en active Active
Patent Citations (2)
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| CN1903731A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院物理研究所 | Flower shape structured nano-cerium oxide and its preparation method and use |
| CN103180248A (en) * | 2010-08-12 | 2013-06-26 | 大东化成工业株式会社 | Sheet-shaped cerium oxide and petal-shaped cerium oxide powder as aggregate of the sheet-shaped cerium oxide, process for production of the sheet-shaped cerium oxide and the petal-shaped cerium oxide powder, coated sheet-shaped cerium oxide and petal-shaped cerium oxide powder as aggregate of the coated sheet-shaped cerium oxide, and cosmetic |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113120940A (en) * | 2019-12-30 | 2021-07-16 | 安集微电子科技（上海）股份有限公司 | Spherical cerium carbonate and synthesis method of cerium oxide |
| CN112299469A (en) * | 2020-09-22 | 2021-02-02 | 江汉大学 | Cerium dioxide and preparation method and application thereof |
| CN112299469B (en) * | 2020-09-22 | 2023-03-14 | 江汉大学 | Cerium dioxide and preparation method and application thereof |
| CN114425334A (en) * | 2020-10-15 | 2022-05-03 | 南京大学 | CeO2Micron flower-loaded Ru nano-particle compound and preparation method thereof |
| CN114425334B (en) * | 2020-10-15 | 2024-02-02 | 南京大学 | CeO 2 Ru nano particle compound loaded by micron flower and preparation method thereof |
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