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CN-117902614-B - Nanometer spherical cerium dioxide and preparation method and application thereof

CN117902614BCN 117902614 BCN117902614 BCN 117902614BCN-117902614-B

Abstract

The invention provides a nano spherical cerium dioxide and a preparation method and application thereof. The preparation method comprises the following steps of adding a dispersing agent into cerium ion precursor slurry with the pH value of 0.1-4.0 to obtain a mixed solution, carrying out hydrothermal reaction on the mixed solution, and calcining to obtain the spherical cerium oxide. The spherical nano cerium dioxide prepared by the method has high sphericity, good particle-particle dispersibility, uniform and concentrated particle size distribution and controllable size of 30-500 nm.

Inventors

  • HU GUOPING
  • LI SIBIN
  • RAO FU
  • LIU ANYU
  • HUANG RENFENG
  • XIE XIAOFENG
  • QI TAO

Assignees

  • 中国科学院赣江创新研究院

Dates

Publication Date
20260508
Application Date
20240119

Claims (20)

  1. 1. A method for preparing nano-spherical cerium oxide, which is characterized by comprising the following steps: adding a dispersing agent into cerium ion precursor slurry with the pH value of 0.1-4.0 to obtain a mixed solution, performing hydrothermal reaction on the mixed solution, and calcining to obtain the nano spherical cerium oxide; the preparation method of the cerium ion precursor slurry comprises the following steps: adding a surfactant into the pretreated cerium ion solution, and mixing to obtain cerium ion precursor slurry; the pretreatment method comprises adding acid and water into the cerium ion solution for mixing; The surfactant comprises any one or a combination of at least two of diethylene diamine pentaacetic acid, hydroxyethyl ethylene diamine triacetic acid, ethylene diamine tetraacetic acid, ethylene diamine diacetic acid or ethylene diamine tetraoxalic acid; The volume ratio of the acid to the water is (1-2) to (1-4).
  2. 2. The preparation method of the cerium ion aqueous solution, the dispersing agent and the surfactant are in a mass ratio of (5-20): 30-100): 1-3.
  3. 3. The method of claim 1, wherein the method of mixing the surfactant with the cerium ion solution comprises ultrasonic mixing.
  4. 4. The method of claim 1, wherein the acid comprises any one or a combination of at least two of formic acid, acetic acid, propionic acid, oxalic acid, citric acid, or tartaric acid.
  5. 5. The method according to claim 4, wherein the acid is any one or a combination of at least two of acetic acid, propionic acid and oxalic acid.
  6. 6. The method according to claim 1, wherein the concentration of the acid is 0.1 to 15mol/L.
  7. 7. The method of claim 1, wherein the solute of the cerium ion solution is a cerium source.
  8. 8. The method according to claim 7, wherein the cerium source comprises any one or a combination of at least two of cerium chloride, cerium (III) nitrate, ceric (IV) nitrate, cerium (III) sulfate, ceric (IV) sulfate, ammonium cerium nitrate, or cerium hydroxide.
  9. 9. The method of claim 8, wherein the cerium source is cerium chloride and/or cerium (III) nitrate.
  10. 10. The method according to claim 1, wherein the concentration of the cerium ion solution is 0.1 to 9.0mol/L.
  11. 11. The method according to claim 1, wherein the surfactant is any one or a combination of at least two of diethylene diamine pentaacetic acid, ethylene diamine tetraacetic acid, or ethylene diamine tetraoxalic acid.
  12. 12. The method of claim 1, wherein the dispersant comprises any one or a combination of at least two of propylene glycol, polyethylene glycol, glycerol, ethylene glycol, or diethylene glycol monobutyl ether.
  13. 13. The method according to claim 1, wherein the hydrothermal reaction time is 0.1 to 72 hours.
  14. 14. The method of claim 13, wherein the hydrothermal reaction time is 0.5 to 5 hours.
  15. 15. The method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 20 to 300 ℃.
  16. 16. The method according to claim 15, wherein the hydrothermal reaction is performed at a temperature of 100 to 250 ℃.
  17. 17. The preparation method according to claim 1, wherein after the hydrothermal reaction, an intermediate product is obtained, and the intermediate product is sequentially separated and dried, and then the calcination is performed.
  18. 18. The method according to claim 17, wherein the separation method comprises subjecting the intermediate product to centrifugal separation treatment and washing the lower precipitate.
  19. 19. The method according to claim 18, wherein the centrifugal separation treatment is performed for 1 to 50 minutes.
  20. 20. The method according to claim 18, wherein the centrifugal separation treatment is performed at a speed of 300 to 20000r/min.

Description

Nanometer spherical cerium dioxide and preparation method and application thereof Technical Field The invention belongs to the technical field related to preparation of nano rare earth materials, and particularly relates to nano spherical cerium dioxide and a preparation method and application thereof. Background Cerium oxide, which is a typical light rare earth oxide, has excellent oxidation-reduction performance due to its unique crystal structure, is widely applied to various functional materials, such as polishing materials, catalysts, lubricating materials, automobile exhaust purifying agents, ultraviolet absorbers, electronic ceramic materials and the like, and has very broad application and development prospects. At present, the morphology, the size and the functional application of the nanoscale cerium oxide material become hot spots for research. In recent years, researchers have synthesized ceria of different morphologies and sizes, such as submicron or nanoscale spheres, rods, cubes, petals, and the like, using different methods. The current preparation methods of nano cerium dioxide materials are quite mature and can be roughly divided into three categories, namely a gas phase method, a liquid phase method and a solid phase method. The gas phase method refers to chemical reaction among various simple substances or compounds under the gas phase condition, is a method for preparing nano-scale oxides, and has the advantages of low agglomeration, high purity, low preparation yield, high equipment cost and severe reaction condition. The liquid phase method is a method for preparing nano powder by controlling various reaction conditions to form a precursor in a liquid phase environment, drying and calcining. The method has the advantages of simple production equipment, high purity of the prepared powder, less agglomeration phenomenon, no need of harsh physical conditions such as high vacuum and the like, easy realization of industrial production, and is the most extensive method for preparing the nano particles. The liquid phase method mainly comprises precipitation method, solvothermal method, sol-gel method, microemulsion method, etc. The solid phase method is a method of obtaining nano powder through solid compounds or precursor formation through solid phase reaction and then high temperature decomposition. The equipment used is simple, the operation is convenient, but the purity of the obtained powder is often not high enough, the particle size distribution is also wider, and the method is suitable for occasions with lower requirements. CN114477264a discloses a nano cerium dioxide with the particle size of 50-150 nm prepared by a sol-gel method, the preparation method has simple process and low requirements on equipment, but the nano particles are seriously agglomerated, no fixed morphology exists, and the balling rate is low. CN113003601A discloses a preparation method of spherical nano cerium dioxide, which comprises the steps of using a high-speed shearing dispersing machine at 40-200 ℃ and introducing oxidizing gas to react to prepare the monodisperse spherical nano cerium dioxide with the particle size of 40-200 nm, wherein the method is complicated in process and high in operation requirement. CN101244837A discloses a preparation method of high-purity nano cerium dioxide, which is used for preparing nano cerium dioxide with uniform particles and higher purity by combining a hydrothermal method and a solid phase reaction, wherein the hydrothermal reaction is required to be carried out for 24-72 h at 150-180 ℃, the reaction time is longer, and the energy consumption is higher. CN111434379B discloses a preparation method of oil-soluble monodisperse nano cerium dioxide, which has the advantages of small particle size of cerium dioxide crystal, monodispersity, uniform particle size distribution, good dispersibility, high purity and high stability, and the disadvantage is that a large amount of organic solvents are used in the preparation process, the reaction conditions are severe, the operation requirement is high, and the preparation method is not suitable for industrial production. Therefore, how to develop a preparation method of nano cerium oxide powder with good dispersibility, controllable particle size and uniformity is an important research direction in the field. Disclosure of Invention The invention aims to provide a nano spherical cerium oxide with good dispersibility, controllable particle size and uniformity, and a preparation method and application thereof. In order to achieve the aim of the invention, the invention adopts the following technical scheme: The invention aims at providing a preparation method of nano spherical cerium dioxide, which comprises the following steps: And adding a dispersing agent into cerium ion precursor slurry with the pH value of 0.1-4.0 to obtain a mixed solution, performing hydrothermal reaction on the mixed solution, and calcining to obtain the nano