CN109354064B - Preparation method of monodisperse monoclinic-phase zirconium dioxide nanoparticles and product thereof - Google Patents
Preparation method of monodisperse monoclinic-phase zirconium dioxide nanoparticles and product thereof Download PDFInfo
- Publication number
- CN109354064B CN109354064B CN201811534466.4A CN201811534466A CN109354064B CN 109354064 B CN109354064 B CN 109354064B CN 201811534466 A CN201811534466 A CN 201811534466A CN 109354064 B CN109354064 B CN 109354064B
- Authority
- CN
- China
- Prior art keywords
- zirconium
- zirconium dioxide
- monodisperse
- reaction
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- 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
Abstract
The invention discloses a preparation method of monodisperse monoclinic phase zirconium dioxide nano-particles and a product thereof, wherein the nano zirconium dioxide particles are prepared by a solvothermal method by using zirconium alcohol as a main raw material and glacial acetic acid and N, N-Dimethylformamide (DMF) as a mixed solvent in the absence of a surfactant. The method has the characteristics of rapidness, simplicity, good repeatability, high yield and operability, simple synthesis equipment, low cost, high efficiency and short reaction period, and the prepared product has the particle size of 1-10 nm, has the characteristics of monodispersity, high crystallinity (monoclinic phase) and the like, and has considerable market application prospect.
Description
Technical Field
The invention relates to a preparation method of zirconium dioxide nano-particles and products thereof, in particular to a preparation method of monodisperse monoclinic phase zirconium dioxide nano-particles and products thereof; belongs to the field of nanometer material preparation.
Background
Zirconium dioxide (ZrO)2) Is the main oxide of zirconium, which is generally a white odorless and tasteless crystal, and is poorly soluble in water, hydrochloric acid, and dilute sulfuric acid. Chemically inert and corrosion resistant, and has high melting point, high resistivity at normal temperature, high refractive indexThe property of low thermal expansion coefficient makes it an important high temperature resistant material, ceramic insulating material and ceramic opacifier, and in addition, the nano-grade zirconia can be used for making high temperature pigment, cosmetics, high-grade grinding material (polishing agent), high-tech ceramic, precision ceramic and for plasma nano-zirconia spraying, etc. and has extensive application value in national defense and civil fields (Song Ning, Hu Yi jadeite. research progress of nano-zirconia [ J]Guangzhou chemical 2009,37(05): 65-68; zhengwenyu, mother-of-pearl, Zhongzhu, and zirconium dioxide, their properties, uses and development direction [ J]Inorganic salt industry, 2000(01):18-20+ 1.).
Zirconium dioxide has three crystal forms, belongs to multi-mirror image transformation oxides, and has a crystal structure: the crystal is monoclinic system at low temperature, a tetragonal crystal form is formed at the temperature of more than 1100 ℃, and a cubic crystal form is formed at the temperature of more than 1900 ℃ (Yangjie, Luocing, Wulimna, Yeqing, Wanglimei, Yanjing, Tianchang' an, Yi Qi & Yi Qi & S.A. nanometer zirconium dioxide preparation and performance application research progress [ J ]. application chemical industry, 2014,43(09):1694 & 1696.). Among them, triclinic zirconia exists in nature as a raw baddeleyite, and baddeleyite is mainly found in basic matrix rock, carbonate rock and gangue rock of corresponding components, and coexists with nepheline, neon stone, apatite, fluorite, perovskite, zircon pyrochlore, and the like. The cryptocrystalline zircon seen in the nervus is a later-stage alteration product, which is symbiotic with zeolite and clay minerals. The baddeleyite has low grade in raw ore and can be used only after being subjected to mineral separation and purification. Based on this, the development of a method for preparing monodisperse monoclinic phase zirconium dioxide nanoparticles is particularly important. However, no report is found on the synthesis of high-purity, ultrafine, uniform and high-crystallinity monoclinic phase zirconium dioxide nano-particles in the absence of a surfactant through retrieval.
Disclosure of Invention
Aiming at the defects of the preparation method of zirconium dioxide in the prior art, the invention aims to provide a preparation method of a monodisperse monoclinic phase zirconium dioxide nano material and a product thereof.
The preparation method of the monodisperse monoclinic phase zirconium dioxide nano-particles comprises the following steps:
(1) sequentially adding a mixed organic solvent and zirconium alkoxide into a hydrothermal reaction kettle, controlling the filling degree to be 50-80% of the volume of the reaction kettle, and uniformly stirring; then sealing the reaction kettle, putting the reaction kettle into a thermostat, and heating for reaction;
(2) naturally cooling to room temperature after the reaction is finished, washing, filtering, and drying the product to obtain monodisperse monoclinic phase zirconium dioxide nanoparticles;
the method is characterized in that:
the mixed organic solvent in the step (1) is a mixed solution of N, N-Dimethylformamide (DMF) and glacial acetic acid (HAc) in a volume ratio of 1: 9-9: 1; the zirconium alkoxide is zirconium isopropoxide, zirconium n-butoxide or zirconium n-propoxide; wherein the volume ratio of the zirconium alkoxide to the mixed organic solvent is 1: 5-1: 6; the conditions of the heating reaction are as follows: controlling the temperature of the solvent at 180-200 ℃, and reacting for 15-25 h;
the product washing method in the step (2) comprises the following steps: the obtained product is repeatedly washed to be neutral by absolute ethyl alcohol.
The preparation method of the monodisperse monoclinic phase zirconium dioxide nano-particles comprises the following steps: the mixed organic solvent in the step (1) is preferably a mixed solution of N, N-Dimethylformamide (DMF) and glacial acetic acid (HAc) in a volume ratio of 5-7: 3-5; the zirconium alkoxide is preferably zirconium n-butoxide or zirconium n-propoxide; wherein, the volume ratio of the zirconium alkoxide to the mixed organic solvent is preferably 1: 5; the conditions for the heating reaction are preferably: controlling the temperature of the solvent at 187-195 ℃ and reacting for 18-24 h.
Further, in the preparation method of the monodisperse monoclinic phase zirconium dioxide nano-particles, the following steps are carried out: the mixed organic solvent in the step (1) is a mixed solution of N, N-Dimethylformamide (DMF) and glacial acetic acid (HAc) in a volume ratio of preferably 6: 4; the zirconium alkoxide is preferably zirconium n-butoxide; the conditions for the heating reaction are preferably: the temperature of the solvent is controlled at 190 ℃ and the reaction is carried out for 24 h.
The monodisperse monoclinic phase zirconium dioxide nano-particles prepared by the method are characterized in that: the zirconium dioxide particles are 1 nm-10 nm in size, uniform in size and high in monodispersity, and are triclinic-phase zirconium dioxide nanoparticles; the lattice spacing is 0.316nm, the crystal form is monoclinic phase zirconium dioxide corresponding to a triclinic phase zirconium oxide (-1, 1, 1) surface.
Wherein: the size of the zirconium dioxide particles is preferably 3 nm-8 nm; most preferably: the size of the zirconium dioxide particles is 5 +/-1 nm.
The invention discloses a preparation method of monodisperse monoclinic phase zirconium dioxide nano-particles and a product thereof. The method adopts a solvothermal method to successfully prepare the zirconium dioxide nano-particles by using zirconium alkoxide as a main raw material and glacial acetic acid and N, N-Dimethylformamide (DMF) as a mixed solvent under the condition of solution heat. The method successfully synthesizes the superfine, uniform and high-crystallinity monoclinic phase zirconium dioxide nano material under the condition of no surfactant. The preparation method of the zirconium dioxide nano material is rapid and simple, has good repeatability and high yield and operability, and meanwhile, the zirconium dioxide nano material has the characteristics of high purity, small size, uniform particles, high crystallinity (monoclinic phase) and the like, and has considerable market application prospect.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the prepared zirconium dioxide nanoparticles.
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the prepared monoclinic phase zirconium dioxide nanoparticles and the particle size distribution thereof.
Fig. 3 is a photograph of a High Resolution Transmission Electron Microscope (HRTEM) of the prepared monodisperse monoclinic phase zirconium dioxide nanoparticles.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples are merely illustrative of the preferred embodiments of the present invention and are not intended to limit the present invention in any way, and any simple modifications, equivalent changes and modifications made to the embodiments according to the technical spirit of the present invention fall within the scope of the technical solution of the present invention.
The raw materials or reagents used in the invention are all conventional commercial products.
Example 1:
(1) sequentially adding a mixed organic solvent with the volume ratio of DMF to HAc (N, N-dimethylformamide to glacial acetic acid) to 6 to 4 and N-butyl zirconium into a hydrothermal reaction kettle, controlling the filling degree to be 80 percent of the volume of the reaction kettle, and uniformly stirring; then the reaction kettle is sealed and put into a drying box, the hydrothermal temperature is controlled at 180 +/-5 ℃, and the reaction time is controlled at 24 +/-0.5 h.
(2) And naturally cooling to room temperature after the reaction is finished, repeatedly washing the obtained product to be neutral by using absolute ethyl alcohol, and then carrying out suction filtration and drying to obtain the monodisperse monoclinic phase zirconium dioxide nano-particle powder.
The resulting monodisperse monoclinic phase zirconium dioxide nanoparticles were analyzed with a German Bruker D8X-ray diffractometer (see FIG. 1 for results). As can be seen from FIG. 1, the XRD diffraction pattern of the prepared nanoparticles corresponds to the PDF card number of 72-1669, and the crystal form of the zirconia nanoparticles is monoclinic phase and has good crystallinity; in addition, no other impurity peak can be seen from the XRD pattern, which indicates that the purity of the sample is high.
The obtained monodisperse monoclinic phase zirconium dioxide nanoparticle sample was observed by a transmission electron microscope of model JEM 2100F manufactured by JEOL (see FIGS. 2 and 3). As can be seen from data statistics and particle size distribution shown in a transmission electron microscope photograph of FIG. 2, the triclinic-phase zirconium dioxide nanoparticles have uniform size and high monodispersity, and the particle size is 5 +/-1 nm. As can be seen from the high-resolution transmission electron microscope photograph in FIG. 3, the lattice fringes of the sample are clear and obvious, which indicates that the crystallinity of the zirconium dioxide crystal is good, and the statistical lattice spacing is 0.316nm, and the corresponding triclinic-phase zirconium oxide (-1, 1, 1) surface further indicates that the crystal form of the zirconium oxide is monoclinic-phase zirconium dioxide.
Example 2:
(1) sequentially adding a mixed organic solvent with the volume ratio of DMF to HAc (N, N-dimethylformamide to glacial acetic acid) to 1 to 9 and zirconium isopropoxide into a hydrothermal reaction kettle, controlling the filling degree to be 50 percent of the volume of the reaction kettle, and uniformly stirring; then the reaction kettle is sealed and put into a drying box, the hydrothermal temperature is controlled at 190 +/-5 ℃, and the reaction time is controlled at 15.5 +/-0.5 h.
(2) And naturally cooling to room temperature after the reaction is finished, repeatedly washing the obtained product to be neutral by using absolute ethyl alcohol, and then carrying out suction filtration and drying to obtain the monodisperse monoclinic phase zirconium dioxide nano-particle powder.
Example 3:
(1) sequentially adding a mixed organic solvent with the volume ratio of DMF to HAc (N, N-dimethylformamide to glacial acetic acid) being 9:1 and zirconium N-propoxide into a hydrothermal reaction kettle, controlling the filling degree to be 70% of the volume of the reaction kettle, and uniformly stirring; then the reaction kettle is sealed and put into a drying box, the hydrothermal temperature is controlled at 195 +/-5 ℃, and the reaction time is controlled at 20.5 +/-0.5 h.
(2) And naturally cooling to room temperature after the reaction is finished, repeatedly washing the obtained product to be neutral by using absolute ethyl alcohol, and then carrying out suction filtration and drying to obtain the monodisperse monoclinic phase zirconium dioxide nano-particle powder.
Example 4:
(1) sequentially adding a mixed organic solvent with the volume ratio of DMF to HAc (N, N-dimethylformamide to glacial acetic acid) to 4 to 6 and zirconium N-propoxide into a hydrothermal reaction kettle, controlling the filling degree to be 60 percent of the volume of the reaction kettle, and uniformly stirring; then the reaction kettle is sealed and put into a drying box, the hydrothermal temperature is controlled at 185 +/-5 ℃, and the reaction time is controlled at 18.5 +/-0.5 h.
(2) And naturally cooling to room temperature after the reaction is finished, repeatedly washing the obtained product to be neutral by using absolute ethyl alcohol, and then carrying out suction filtration and drying to obtain the monodisperse monoclinic phase zirconium dioxide nano-particle powder.
Claims (6)
1. A method for preparing monodisperse monoclinic phase zirconium dioxide nano-particles comprises the following steps:
(1) sequentially adding a mixed organic solvent and zirconium alkoxide into a hydrothermal reaction kettle, controlling the filling degree to be 50-80% of the volume of the reaction kettle, and uniformly stirring; then sealing the reaction kettle, putting the reaction kettle into a thermostat, and heating for reaction;
(2) naturally cooling to room temperature after the reaction is finished, washing, filtering, and drying the product to obtain monodisperse monoclinic phase zirconium dioxide nanoparticles;
the method is characterized in that:
the mixed organic solvent in the step (1) is a mixed solution of N, N-dimethylformamide and glacial acetic acid in a volume ratio of 1: 9-9: 1; the zirconium alkoxide is zirconium isopropoxide, zirconium n-butoxide or zirconium n-propoxide; wherein the volume ratio of the zirconium alkoxide to the mixed organic solvent is 1: 5-1: 6; the conditions of the heating reaction are as follows: controlling the temperature of the solvent at 180-200 ℃, and reacting for 15-25 h;
the product washing method in the step (2) comprises the following steps: the obtained product is repeatedly washed to be neutral by absolute ethyl alcohol.
2. The method of claim 1, wherein the method comprises the steps of: the mixed organic solvent in the step (1) is a mixed solution of N, N-dimethylformamide and glacial acetic acid in a volume ratio of 5-7: 3-5; the zirconium alkoxide is n-butyl zirconium or n-propyl zirconium; wherein the volume ratio of the zirconium alkoxide to the mixed organic solvent is 1: 5; the conditions of the heating reaction are as follows: controlling the temperature of the solvent at 187-195 ℃ and reacting for 18-24 h.
3. The method of claim 2, wherein the method comprises the steps of: the mixed organic solvent in the step (1) is a mixed solution of N, N-dimethylformamide and glacial acetic acid in a volume ratio of 6: 4; the zirconium alkoxide is n-butyl zirconium; the conditions of the heating reaction are as follows: the temperature of the solvent is controlled at 190 ℃ and the reaction is carried out for 24 h.
4. Monodisperse monoclinic zirconium dioxide nanoparticles prepared by the process of any of claims 1 to 3, characterized in that: the zirconium dioxide particles are 1 nm-10 nm in size, uniform in size and high in monodispersity, and are triclinic-phase zirconium dioxide nanoparticles; the lattice spacing is 0.316nm, the crystal form is monoclinic phase zirconium dioxide corresponding to a triclinic phase zirconium oxide (-1, 1, 1) surface.
5. Monodisperse monoclinic phase zirconium dioxide nanoparticles according to claim 4, characterized in that: the size of the zirconium dioxide particles is 3 nm-8 nm.
6. Monodisperse monoclinic phase zirconium dioxide nanoparticles according to claim 5, characterized in that: the size of the zirconium dioxide particles is 5 +/-1 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811534466.4A CN109354064B (en) | 2018-12-14 | 2018-12-14 | Preparation method of monodisperse monoclinic-phase zirconium dioxide nanoparticles and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811534466.4A CN109354064B (en) | 2018-12-14 | 2018-12-14 | Preparation method of monodisperse monoclinic-phase zirconium dioxide nanoparticles and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109354064A CN109354064A (en) | 2019-02-19 |
| CN109354064B true CN109354064B (en) | 2020-10-09 |
Family
ID=65329780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811534466.4A Active CN109354064B (en) | 2018-12-14 | 2018-12-14 | Preparation method of monodisperse monoclinic-phase zirconium dioxide nanoparticles and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109354064B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765755A (en) * | 2012-07-23 | 2012-11-07 | 天津大学 | Preparation method of blocky zirconium oxide aerogel |
| CN103274465A (en) * | 2013-05-30 | 2013-09-04 | 太原理工大学 | Nano zirconium dioxide with high specific surface area and synthesis method thereof |
-
2018
- 2018-12-14 CN CN201811534466.4A patent/CN109354064B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765755A (en) * | 2012-07-23 | 2012-11-07 | 天津大学 | Preparation method of blocky zirconium oxide aerogel |
| CN103274465A (en) * | 2013-05-30 | 2013-09-04 | 太原理工大学 | Nano zirconium dioxide with high specific surface area and synthesis method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Carbon Promoted ZrO2 Catalysts for Aqueous-Phase Ketonization of Acetic Acid;Kejing Wu et al.;《ACS Sustainable Chem. Eng.》;20170308;第5卷;第3509-3516页 * |
| Effect of the organic additions on crystal growth behavior of ZrO2 nanocrystals prepared via sol–gel process;Wenzhi Huang et al.;《Chemical Engineering Journal》;20111231;第168卷;第1360-1368页 * |
| Synthesis of mesoporous and tetragonal zirconia with inherited morphology from metal–organic frameworks;Xiaoliang Yan et al.;《CrystEngComm》;20150714;第17卷;第6426–6433页 * |
| 新型纳米ＺｒＯ２／聚酰亚胺复合超薄膜的制备表征;程凤梅等;《复合材料学报》;20180731;第35卷(第7期);第1725-1730页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109354064A (en) | 2019-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7867463B2 (en) | Process for producing cerium oxide nanocrystals | |
| KR20080078864A (en) | Methods for production of metal oxide nano particles, and nano particles and preparations produced thereby | |
| CN107954623B (en) | Preparation method for in-situ growth of nano particles on surface of solid waste | |
| CN112357955B (en) | Method for preparing titanium dioxide powder with different morphologies by solid phase method | |
| US20080311031A1 (en) | Methods For Production of Metal Oxide Nano Particles With Controlled Properties, and Nano Particles and Preparations Produced Thereby | |
| CN104556176A (en) | Preparation method for aluminum oxide nano-particles | |
| CN108483474A (en) | A kind of preparation method of nano-level sphere aluminium oxide | |
| CN108975378A (en) | A kind of dysprosia raw powder's production technology | |
| CN103570049B (en) | Method for preparing completely dispersed alpha aluminum oxide nano particles | |
| CN111057399B (en) | Preparation method of rare earth doped clay mineral-based bismuth yellow hybrid pigment with adjustable fluorescence and color | |
| CN1123551C (en) | Nanometer grade tetragonal-phase barium titanate powder and its prepn. | |
| CN111675238A (en) | Method for preparing multi-morphology nano zinc oxide by solid phase method | |
| CN102502848A (en) | Solvothermal preparation method for alkali manganese oxide nanowires | |
| CN109354064B (en) | Preparation method of monodisperse monoclinic-phase zirconium dioxide nanoparticles and product thereof | |
| CN105727922A (en) | Li-doped SrTiO3 octadecahedron nano-particles and preparation method thereof | |
| CN112645366A (en) | Preparation method of nano magnesium oxide | |
| US7943116B1 (en) | High-yield synthesis of brookite TiO2 nanoparticles | |
| Anzlovar et al. | Sub micrometer and nano-ZnO as filler in PMMA materials | |
| CN109502643B (en) | Boron-magnesium co-doped VO2Powder and preparation method and application thereof | |
| CN111747441A (en) | Method for solid-phase synthesis of nano zinc oxide by utilizing alcohol amine compound | |
| Chitan et al. | Synthesis of γ-alumina nano powder from Nepheline syenite | |
| CN112047383A (en) | Method for preparing nano iron oxide by solid phase method and iron oxide material | |
| CN106564947A (en) | Method for preparing near infrared reflection titanium dioxide material through continuous grinding and grading | |
| Chen et al. | Facile synthesis and characterisation of dandelion-like V2O3 core–shell microspheres | |
| CN113371756B (en) | La-Sc-ZrO2 nano crystal material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |