CN109354064A - A kind of preparation method and products thereof of monodisperse and single monoclinic phase zirconium dioxide nanoparticles - Google Patents
A kind of preparation method and products thereof of monodisperse and single monoclinic phase zirconium dioxide nanoparticles Download PDFInfo
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- CN109354064A CN109354064A CN201811534466.4A CN201811534466A CN109354064A CN 109354064 A CN109354064 A CN 109354064A CN 201811534466 A CN201811534466 A CN 201811534466A CN 109354064 A CN109354064 A CN 109354064A
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- zirconium
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- C01G25/00—Compounds of zirconium
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- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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Abstract
The invention discloses a kind of preparation methods and products thereof of monodisperse and single monoclinic phase zirconium dioxide nanoparticles, the nano zirconium dioxide particle is under surfactant-free existence condition, it is primary raw material using zirconium alcohol, glacial acetic acid and N, dinethylformamide (DMF) is used as mixed solvent, is made by solvent-thermal method.This method has quick, succinctly, reproducible, yield and operability are high, and simultaneously synthesizing equipment is simple, it is at low cost, high-efficient, reaction time short feature, product particle obtained has monodispersity having a size of 1nm~10nm, the characteristics such as crystallinity height (monoclinic phase) have considerable market application prospect.
Description
Technical field
The present invention relates to preparation method of a kind of zirconium dioxide nanoparticles and products thereof more particularly to a kind of monodisperse and singles
The preparation method and products thereof of monoclinic phase zirconium dioxide nanoparticles；Belong to field of nano material preparation.
Background technique
Zirconium dioxide (ZrO2) be zirconium main oxides, be white odorless, tasteless crystal under usual condition, be insoluble in water,
Hydrochloric acid and dilute sulfuric acid.Chemical property torpescence is corrosion-resistant, and under high-melting-point, room temperature have high resistivity, high refractive index and
The property of low thermal coefficient of expansion makes it important heat-resisting material, ceramic insulating material and ceramic opacifier, in addition nanometer
Grade zirconium oxide can also manufacture hard fire colour, cosmetics, advanced grinding-material (polishing agent) and high-performance ceramics, high technology ceramics with
And be with a wide range of applications in national defence and people's livelihood field for plasma nano zircite spraying etc. (Song Ning, recklessly a jadelike stone
Progress [J] Chemical Industry in Guangzhou of nano zircite, 2009,37 (05): 65-68.；Zheng Wenyu, Chen Chao coin, Chen Zhongcong, dioxy
Change property, purposes and its developing direction [J] inorganic chemicals industry of zirconium, 2000 (01): 18-20+1.).
There are three types of crystal forms for zirconium dioxide tool, belong to more mirror image conversion oxides, crystal structure: it is monoclinic system when low temperature,
In 1100 DEG C of tetragonal structures formed above, in 1900 DEG C of cubics formed above, (sun is outstanding, Luo Xueting, Wu Liping, Ye Qing, Wang
Beautiful plum, Yang Jing, field Chang'an, the preparation of Yin Qiyi nano zirconium dioxide and performance applications progress [J] application chemical industry,
2014,43(09):1694-1696.).Wherein for anorthic system zirconium oxide, in nature in the form of baddeleyite raw ore
In the presence of, baddeleyite is mainly seen in the dyke rock of alkaline basic rock, carbonatite and corresponding ingredient, with nepheline, aegirine, apatite,
The symbiosis such as fluorite, perovskite, zircon pyrochlore.The cryptocrystalline zircon seen in iolite arteries and veins is paulopost alteration product, with boiling
Stone, clay mineral symbiosis.Grade of the baddeleyite in raw ore is very low, it is necessary to could use after purification by mineral.Based on this, single point
The exploitation of the preparation method of throwaway monoclinic phase zirconium dioxide nanoparticles is particularly important.However through retrieving, in no surface-active
High-purity, ultra-fine, uniform, high crystalline monoclinic phase zirconium dioxide nanoparticles are synthesized under agent existence condition to have not been reported.
Summary of the invention
For the deficiency of zirconium dioxide preparation method in the prior art, the problem to be solved in the present invention is to provide a kind of single point
The preparation method and products thereof of throwaway monoclinic phase Ions in nanocrystalline zirconia.
The preparation method of monodisperse and single monoclinic phase zirconium dioxide nanoparticles of the present invention, step is:
(1) it is blended with solvent, zirconium alcohol is added sequentially in hydrothermal reaction kettle, and compactedness is controlled in reactor volume
50%~80%, and stir evenly；Then reaction kettle is sealed, is put it into insulating box, heating reaction；
(2) cooled to room temperature, product filter after rinsing, are dry after reaction, obtain monodisperse and single monoclinic phase dioxy
Change zirconium nano particle；
It is characterized by:
Step (1) described mixed organic solvents are the N,N-dimethylformamides (DMF) that volume ratio is 1:9~9:1: ice vinegar
The mixed liquor of sour (HAc)；The zirconium alcohol is zirconium iso-propoxide, zirconium-n-butylate or zirconium-n-propylate；Wherein, zirconium alcohol and mixed organic solvents
Volume ratio be 1:5~1:6；The condition of the heating reaction is: control solvent temperature at 180~200 DEG C, reaction 15h~
25h；
Step (2) the product purging method is: by products therefrom dehydrated alcohol repeated flushing to neutrality.
In the preparation method of above-mentioned monodisperse and single monoclinic phase zirconium dioxide nanoparticles: step (1) described mixed organic solvents
Preferably volume ratio be 5~7:3~5 N,N-dimethylformamide (DMF): the mixed liquor of glacial acetic acid (HAc)；The zirconium alcohol is excellent
Choosing is zirconium-n-butylate or zirconium-n-propylate；Wherein, the volume ratio of zirconium alcohol and mixed organic solvents is preferably 1:5；The heating reaction
Condition be preferably: control solvent temperature at 187~195 DEG C, reaction 18h~for 24 hours.
Further, in the preparation method of above-mentioned monodisperse and single monoclinic phase zirconium dioxide nanoparticles: step (1) described mixing
Organic solvent is the N,N-dimethylformamide (DMF) of the preferred 6:4 of volume ratio: the mixed liquor of glacial acetic acid (HAc)；The zirconium alcohol is excellent
Select zirconium-n-butylate；The condition of the heating reaction is preferably: controlling solvent temperature at 190 DEG C, reaction is for 24 hours.
The monodisperse and single monoclinic phase zirconium dioxide nanoparticles of the method for the invention preparation, it is characterised in that: the dioxy
Change zirconium particle size is 1nm~10nm, of uniform size, and monodispersity is high, is three monoclinic phase zirconium dioxide nanoparticles；Spacing of lattice
For 0.316nm, corresponding three monoclinic phase zirconium oxides (- 1,1,1) face, crystal form is monoclinic phase zirconium dioxide.
Wherein: above-mentioned zirconium dioxide particle is preferably dimensioned to be 3nm~8nm；Most preferably: the zirconium dioxide particle having a size of
5±1nm。
The invention discloses a kind of preparation methods and products thereof of monodisperse and single monoclinic phase zirconium dioxide nanoparticles.Its method
It is to use solvent-thermal method that zirconium alcohol is utilized as primary raw material, glacial acetic acid and n,N-Dimethylformamide (DMF) are used as mixed solvent,
Under the conditions of heat of solution, it is successfully prepared a kind of zirconium dioxide nanoparticles.This method is in surfactant-free existence condition
Under, successfully synthesize ultra-fine, uniform, high crystalline monoclinic phase Ions in nanocrystalline zirconia.Zirconium dioxide of the present invention
The preparation method of nano material is quick, succinctly, reproducible, and yield and operability are high, while the nanometer zirconium oxide
The features such as with purity is high, size is small, and particle is uniform, crystallinity height (monoclinic phase) has considerable market application prospect.
Detailed description of the invention
Fig. 1 is zirconium dioxide nanoparticles X-ray diffraction (XRD) map of preparation.
Fig. 2 is monoclinic phase zirconium dioxide nanoparticles transmission electron microscope (TEM) photo and its particle diameter distribution of preparation.
Fig. 3 is that the monodisperse and single monoclinic phase zirconium dioxide nanoparticles high resolution transmission electron microscopy (HRTEM) of preparation shines
Piece.
Specific embodiment
The content of present invention is described in detail combined with specific embodiments below.Example as described below be only it is of the invention compared with
Good embodiment, is not intended to limit the present invention in any form, according to the technical essence of the invention to implementation
Any simple modification that mode is made, equivalent variations and modification, belong in the range of technical solution of the present invention.
The present invention be using raw material or reagent be conventional commercial product.
Embodiment 1:
(1) by the mixed organic solvents of volume ratio DMF:HAc (n,N-Dimethylformamide: glacial acetic acid)=6:4, n-butanol
Zirconium is added sequentially in hydrothermal reaction kettle, and compactedness is controlled the 80% of reactor volume, and is stirred evenly；Then sealing reaction
Kettle is put it into drying box, makes hydrothermal temperature control at 180 ± 5 DEG C, the reaction time controls in 24 ± 0.5h.
(2) after reaction then cooled to room temperature, products therefrom dehydrated alcohol repeated flushing to neutrality are taken out
Filter, it is dry, obtain monodisperse and single monoclinic phase zirconium dioxide nanoparticles powder.
By the German Brooker D8 x-ray diffractometer analysis of resulting monodisperse and single monoclinic phase zirconium dioxide nanoparticles
(the result is shown in Figure 1).As seen in Figure 1, prepared nano particle XRD diffracting spectrum, corresponding PDF card number are 72-
1669, show that the Zirconium oxide nano grain crystal form is monoclinic phase, and good crystallinity；In addition, it can be seen that not from XRD spectrum
There are other miscellaneous peaks, illustrates sample purity height.
Resulting monodisperse and single monoclinic phase zirconium dioxide nanoparticles sample JEOL company of Japan is produced into JEM 2100F type
Transmission electron microscope is observed (result is shown in Fig. 2, Fig. 3).The data statistics shown by Fig. 2 transmission electron microscope photo and partial size
Size distribution is of uniform size as can be seen that the three monoclinic phases zirconium dioxide nanoparticles, and monodispersity is high, particle size 5 ±
1nm.It is clear to can be seen that the sample lattice fringe by Fig. 3 high-resolution-ration transmission electric-lens photo, hence it is evident that, show the zirconium dioxide
Crystallization Crystallization is good, while the spacing of lattice that statistics obtains is 0.316nm, and corresponding three monoclinic phase zirconium oxides (- 1,1,1) face is further
Show that the zirconium oxide crystal form is monoclinic phase zirconium dioxide.
Embodiment 2:
(1) by the mixed organic solvents of volume ratio DMF:HAc (n,N-Dimethylformamide: glacial acetic acid)=1:9, isopropanol
Zirconium is added sequentially in hydrothermal reaction kettle, and compactedness is controlled the 50% of reactor volume, and is stirred evenly；Then sealing reaction
Kettle is put it into drying box, makes hydrothermal temperature control at 190 ± 5 DEG C, the reaction time controls in 15.5 ± 0.5h.
(2) after reaction then cooled to room temperature, products therefrom dehydrated alcohol repeated flushing to neutrality are taken out
Filter, it is dry, obtain monodisperse and single monoclinic phase zirconium dioxide nanoparticles powder.
Embodiment 3:
(1) by the mixed organic solvents of volume ratio DMF:HAc (n,N-Dimethylformamide: glacial acetic acid)=9:1, normal propyl alcohol
Zirconium is added sequentially in hydrothermal reaction kettle, and compactedness is controlled the 70% of reactor volume, and is stirred evenly；Then sealing reaction
Kettle is put it into drying box, makes hydrothermal temperature control at 195 ± 5 DEG C, the reaction time controls in 20.5 ± 0.5h.
(2) after reaction then cooled to room temperature, products therefrom dehydrated alcohol repeated flushing to neutrality are taken out
Filter, it is dry, obtain monodisperse and single monoclinic phase zirconium dioxide nanoparticles powder.
Embodiment 4:
(1) by the mixed organic solvents of volume ratio DMF:HAc (n,N-Dimethylformamide: glacial acetic acid)=4:6, normal propyl alcohol
Zirconium is added sequentially in hydrothermal reaction kettle, and compactedness is controlled the 60% of reactor volume, and is stirred evenly；Then sealing reaction
Kettle is put it into drying box, makes hydrothermal temperature control at 185 ± 5 DEG C, the reaction time controls in 18.5 ± 0.5h.
(2) after reaction then cooled to room temperature, products therefrom dehydrated alcohol repeated flushing to neutrality are taken out
Filter, it is dry, obtain monodisperse and single monoclinic phase zirconium dioxide nanoparticles powder.
Claims (6)
1. a kind of preparation method of monodisperse and single monoclinic phase zirconium dioxide nanoparticles, step is:
(1) it is blended with solvent, zirconium alcohol is added sequentially in hydrothermal reaction kettle, and compactedness is controlled the 50% of reactor volume
~80%, and stir evenly；Then reaction kettle is sealed, is put it into insulating box, heating reaction；
(2) cooled to room temperature, product filter after rinsing, are dry after reaction, obtain monodisperse and single monoclinic phase zirconium dioxide
Nano particle；
It is characterized by:
Step (1) described mixed organic solvents are the N,N-dimethylformamides (DMF) that volume ratio is 1:9~9:1: glacial acetic acid
(HAc) mixed liquor；The zirconium alcohol is zirconium iso-propoxide, zirconium-n-butylate or zirconium-n-propylate；Wherein, zirconium alcohol and mixed organic solvents
Volume ratio is 1:5~1:6；The condition of the heating reaction is: control solvent temperature at 180~200 DEG C, reaction 15h~
25h；
Step (2) the product purging method is: by products therefrom dehydrated alcohol repeated flushing to neutrality.
2. the preparation method of monodisperse and single monoclinic phase zirconium dioxide nanoparticles according to claim 1, it is characterised in that: step
(1) mixed organic solvents are the N,N-dimethylformamides (DMF) that volume ratio is 5~7:3~5: glacial acetic acid (HAc) mixes
Close liquid；The zirconium alcohol is zirconium-n-butylate or zirconium-n-propylate；Wherein, the volume ratio of zirconium alcohol and mixed organic solvents is 1:5；It is described to add
The condition of thermal response is: make solvent temperature control at 187~195 DEG C, reaction 18h~for 24 hours.
3. the preparation method of monodisperse and single monoclinic phase zirconium dioxide nanoparticles according to claim 2, it is characterised in that: step
(1) mixed organic solvents are the N,N-dimethylformamides (DMF) that volume ratio is 6:4: the mixed liquor of glacial acetic acid (HAc)；
The zirconium alcohol is zirconium-n-butylate；The condition of the heating reaction is: controlling solvent temperature at 190 DEG C, reaction is for 24 hours.
4. the monodisperse and single monoclinic phase zirconium dioxide nanoparticles of one of claims 1 to 3 the method preparation, it is characterised in that:
The zirconium dioxide particle is having a size of 1nm~10nm, and of uniform size, monodispersity is high, is three monoclinic phase zirconium dioxide nanoparticles；
Spacing of lattice is 0.316nm, and corresponding three monoclinic phase zirconium oxides (- 1,1,1) face, crystal form is monoclinic phase zirconium dioxide.
5. monodisperse and single monoclinic phase zirconium dioxide nanoparticles according to claim 4, it is characterised in that: the zirconium dioxide
Particle size is 3nm~8nm.
6. monodisperse and single monoclinic phase zirconium dioxide nanoparticles according to claim 5, it is characterised in that: the zirconium dioxide
Particle size is 5 ± 1nm.
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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 |
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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 |
|---|
| KEJING WU ET AL.: "Carbon Promoted ZrO2 Catalysts for Aqueous-Phase Ketonization of Acetic Acid", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| WENZHI HUANG ET AL.: "Effect of the organic additions on crystal growth behavior of ZrO2 nanocrystals prepared via sol–gel process", 《CHEMICAL ENGINEERING JOURNAL》 * |
| XIAOLIANG YAN ET AL.: "Synthesis of mesoporous and tetragonal zirconia with inherited morphology from metal–organic frameworks", 《CRYSTENGCOMM》 * |
| 程凤梅等: "新型纳米ＺｒＯ２／聚酰亚胺复合超薄膜的制备表征", 《复合材料学报》 * |
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