CN106629842A - Preparation method of nanocrystalline material with hollow structure of barium zirconate - Google Patents
Preparation method of nanocrystalline material with hollow structure of barium zirconate Download PDFInfo
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- CN106629842A CN106629842A CN201611208054.2A CN201611208054A CN106629842A CN 106629842 A CN106629842 A CN 106629842A CN 201611208054 A CN201611208054 A CN 201611208054A CN 106629842 A CN106629842 A CN 106629842A
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
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- 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
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- 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
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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
- C01P2004/34—Spheres hollow
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- 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
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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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The invention discloses a preparation method of a barium zirconate hollow structure nanocrystalline material. The method comprises the steps of dissolving zirconium oxychloride into water, mixing uniformly and adding ammonium hydroxide by dropping, thus acquiring zirconic oxyhydroxide white sediment; adding ethidene diamine into the zirconic oxyhydroxide white sediment, adding barium salt while stirring, adding KOH, keeping the concentration of 0.8-10mol/L, stirring uniformly, thus acquiring turbid liquid, and putting the turbid liquid into a reaction still; putting the reaction still into solvent at the temperature of 150-220 DEG C to thermally react for 6-36h, and then washing, drying and grinding, thus acquiring the BaZrO3 hollow structure nanocrystalline material. According to the method provided by the invention, the BaZrO3 hollow structure nanocrystalline material is synthesized by using a one-step solvent thermal reaction method. The synthesized BaZrO3 hollow structure nanocrystalline material is simple in preparation technology, low in cost, easy to control, large in specific surface area and high in productivity.
Description
Technical field
The present invention relates to perovskite field of functional materials, and in particular to a kind of system of barium zirconate hollow structure nanocrystalline material
Preparation Method.
Background technology
Perovskite functional material BaZrO3It is a kind of important infusibility multivariant oxide, because thermal coefficient of expansion is little, heat conduction
Property poor, satisfactory mechanical property, heat endurance and good chemical stability, high-temperature superconductor, fuel cell, dielectric material,
The aspects such as sensor, heat insulating coat have latent effect widely.It is well known that performance of the microstructure of material to material
There is important impact.Therefore, BaZrO is regulated and controled by suitable technique3The microstructure of material, for the optimization of performance
It is significant.
The performance that three-dimensional material does not much possess under the nanocrystalline yardstick with Conventional nano of hollow material, such as skin effect
With small-size effect etc..Because hollow material is nanocrystalline with big specific surface area, the characteristic such as carrier transfer time is short, its thing
Physicochemical performance is very sensitive to interfacial reaction and external environment, is with a wide range of applications at the aspect such as optically and electrically.
In sum, BaZrO3Hollow structure nanocrystalline material has important Research Prospects and using value.And according to
Document report, BaZrO3The synthesis technique of hollow structure nanocrystalline material mainly has hydro-thermal method, circumfluence method, sol-gal process, and this is several
Kind.These methods are generally limited by aspects such as complex process, high cost, the wastings of resources, can not be obtained in actual production
To large-scale application.Therefore, in order to overcome these shortcomings, just seem very promising using the method for a step solvent heat.
Solvent-thermal method is easy to operate, and by factors such as the reaction temperatures and temperature retention time of adjusting solvent heat crystal growth can be controlled.Cause
This, the present invention synthesizes BaZrO using the method for a step solvent heat3Hollow structure nanocrystalline material.The BaZrO of synthesis3Hollow structure
Nanocrystalline material process is simple, with low cost, it is easy to control, specific surface area is big, and products collection efficiency is high.
The content of the invention
It is an object of the invention to provide a kind of process is simple, with low cost, it is easy to control, specific surface area is big, and product is produced
The high BaZrO of rate3The preparation method of hollow structure nanocrystalline material.
A kind of barium zirconate (BaZrO3) hollow structure nanocrystalline material preparation method, comprise the following steps：
1) it is zirconium oxychloride is soluble in water, it is well mixed, then ammoniacal liquor is added dropwise, obtain the oxyhydroxide white precipitate of zirconium；
2) ethylenediamine is added in the oxyhydroxide white precipitate of zirconium, barium salt is added in stirring, add KOH, KOH's is dense
Degree maintains 0.8mol/L～10mol/L, stirs, and obtains suspension, then suspension is loaded into reactor；
3) at a temperature of reactor being put into into 150 DEG C -220 DEG C after solvent thermal reaction 6h～36h, it is scrubbed afterwards, drying and
After grinding, BaZrO is obtained3Hollow structure nanocrystalline material, is white powder.
Step 1) in, the amount of the material of described zirconium oxychloride is 2～8mol with the ratio of the volume of water：5～15L, enters one
The amount of material and the ratio of the volume of water for walking preferred, described zirconium oxychloride is 4～6mol：8～12L, it is further preferred that described oxygen
The amount of the material of zirconium chloride is 5mol with the ratio of the volume of water：10L.
The mass percent of described ammoniacal liquor is 20%～40%, more preferably 30%.
Step 2) in, described ethylenediamine and step 1) in the ratio of volume of water be 2～4:1, it is further preferably, described
Ethylenediamine and step 1) in the ratio of volume of water be 3:1.
Barium and the mol ratio of zirconium in zirconium oxychloride are 0.95～1.2 in described barium salt：1, further preferably, described barium
Barium and the mol ratio of zirconium in zirconium oxychloride are 1～1.2 in salt：1.
The concentration of KOH maintains 0.8mol/L～4mol/L, further preferably, the concentration of KOH maintain 1mol/L～
3mol/L。
Step 3) in, solvent thermal reaction 6h～24h at a temperature of reactor is put into into 180 DEG C -210 DEG C.
Described washing is using water and ethanol cyclic washing.
Reactor is put in baking oven, solvent thermal reaction is carried out in the closed environment of reactor.
It is pure that above-mentioned zirconium oxychloride, barium salt, KOH, ethylenediamine, absolute ethyl alcohol are chemistry.
Compared with prior art, the invention has the advantages that：
The present invention prepares BaZrO by the method for a step solvent heat3Hollow structure is nanocrystalline.The present invention is formed in the first step
The oxyhydroxide white precipitate of zirconium, is BaZrO3Synthesis provide zirconium source.Second step is added after barium source, in KOH mineralizers
Stir with ethylenediamine solvent, be well mixed, be to prepare BaZrO3The nanocrystalline offer presoma of hollow structure.Finally control reaction
Temperature and time, and then maturing process is controlled, synthesize BaZrO3Hollow structure nanocrystalline material.The preparation method is easy to control
System, with low cost, process is simple, it is possible to achieve large-scale production.
The present invention synthesizes BaZrO using the method for a step solvent heat3Hollow structure nanocrystalline material.The BaZrO of synthesis3In
Hollow structure nanocrystalline material process is simple, with low cost, it is easy to control, specific surface area is big, and products collection efficiency is high.
Description of the drawings
Fig. 1 is BaZrO prepared by embodiment 13The nanocrystalline SEM photograph of hollow structure；
Fig. 2 is BaZrO prepared by embodiment 13The nanocrystalline TEM photos of hollow structure；
Fig. 3 is BaZrO prepared by embodiment 13The nanocrystalline STEM photos of hollow structure.
Specific embodiment
The inventive method is further illustrated with reference to embodiments.
Embodiment 1
1) zirconium oxychloride 5mmol is dissolved in 10mL deionized waters, stirring and dissolving, concentration is added dropwise in resulting solution is
The ammonia spirit of 30% (mass percent), obtains the oxyhydroxide white precipitate of zirconium；
2) ethylenediamine 30mL is added in the oxyhydroxide white precipitate of zirconium, barium salt is separately added in stirring, keep Ba:
Zr mol ratios are 1:1, KOH concentration maintains 1M, after stirring certain hour, above-mentioned suspension is loaded into reactor；
3) closed reactor is put into into baking oven, after the solvent thermal reaction 12h at a temperature of 200 DEG C, after along with the furnace cooling
After deionized water and absolute ethyl alcohol cyclic washing, drying and grinding, it is exactly BaZrO to obtain white powder3Hollow structure nanometer
It is brilliant.
Embodiment 2
1) zirconium oxychloride 5mmol is dissolved in 10mL deionized waters, stirring and dissolving, concentration is added dropwise in resulting solution is
The ammonia spirit of 30% (mass percent), obtains the oxyhydroxide white precipitate of zirconium；
2) ethylenediamine 30mL is added in the oxyhydroxide white precipitate of zirconium, a certain amount of barium is separately added in stirring
Salt, keeps Ba:Zr mol ratios are 1:1, KOH concentration maintains 1M, after stirring certain hour, above-mentioned suspension is loaded and is reacted
Kettle；
3) closed reactor is put into into baking oven, after the solvent thermal reaction 24h at a temperature of 200 DEG C, after along with the furnace cooling
After deionized water and absolute ethyl alcohol cyclic washing, drying and grinding, it is exactly BaZrO to obtain white powder3Hollow structure nanometer
It is brilliant.
Embodiment 3
1) zirconium oxychloride 5mmol is dissolved in 10mL deionized waters, stirring and dissolving, appropriate concentration is added dropwise in resulting solution
For the ammonia spirit of 30% (mass percent), the oxyhydroxide white precipitate of zirconium is obtained；
2) ethylenediamine 30mL is added in the oxyhydroxide white precipitate of zirconium, a certain amount of barium is separately added in stirring
Salt, keeps Ba:Zr mol ratios are 1:1, KOH concentration maintains 3M, after stirring certain hour, above-mentioned suspension is loaded and is reacted
Kettle；
3) closed reactor is put into into baking oven, after the solvent thermal reaction 12h at a temperature of 200 DEG C, after along with the furnace cooling
After deionized water and absolute ethyl alcohol cyclic washing, drying and grinding, it is exactly BaZrO to obtain white powder3Hollow structure nanometer
It is brilliant.
Claims (10)
1. a kind of preparation method of barium zirconate hollow structure nanocrystalline material, it is characterised in that comprise the following steps：
1) it is zirconium oxychloride is soluble in water, it is well mixed, then ammoniacal liquor is added dropwise, obtain the oxyhydroxide white precipitate of zirconium；
2) ethylenediamine is added in the oxyhydroxide white precipitate of zirconium, barium salt is added in stirring, add KOH, the concentration dimension of KOH
Hold in 0.8mol/L～10mol/L, stir, obtain suspension, then suspension is loaded into reactor；
3) at a temperature of reactor being put into into 150 DEG C -220 DEG C after solvent thermal reaction 6h～36h, it is scrubbed afterwards, drying and grind
Afterwards, BaZrO is obtained3Hollow structure nanocrystalline material.
2. the preparation method of barium zirconate hollow structure nanocrystalline material according to claim 1, it is characterised in that step 1)
In, the amount of the material of described zirconium oxychloride is 2～8mol with the ratio of the volume of water：5～15L.
3. the preparation method of barium zirconate hollow structure nanocrystalline material according to claim 2, it is characterised in that step 1)
In, the amount of the material of described zirconium oxychloride is 4～6mol with the ratio of the volume of water：8～12L.
4. the preparation method of barium zirconate hollow structure nanocrystalline material according to claim 1, it is characterised in that step 1)
In, the mass percent of described ammoniacal liquor is 20%～40%.
5. the preparation method of barium zirconate hollow structure nanocrystalline material according to claim 1, it is characterised in that step 2)
In, described ethylenediamine and step 1) in the ratio of volume of water be 2～4:1.
6. the preparation method of barium zirconate hollow structure nanocrystalline material according to claim 1, it is characterised in that step 2)
In, barium and the mol ratio of zirconium in zirconium oxychloride are 0.95～1.2 in described barium salt：1.
7. the preparation method of barium zirconate hollow structure nanocrystalline material according to claim 1, it is characterised in that step 2)
In, the concentration of KOH maintains 0.8mol/L～4mol/L.
8. the preparation method of barium zirconate hollow structure nanocrystalline material according to claim 1, it is characterised in that step 3)
In, solvent thermal reaction 6h～24h at a temperature of reactor is put into into 180 DEG C -210 DEG C.
9. the preparation method of barium zirconate hollow structure nanocrystalline material according to claim 1, it is characterised in that step 3)
In, described washing is using water and ethanol cyclic washing.
10. the preparation method of barium zirconate hollow structure nanocrystalline material according to claim 1, it is characterised in that step
3) in, reactor is put in baking oven, solvent thermal reaction is carried out in the closed environment of reactor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592709A (en) * | 2018-12-26 | 2019-04-09 | 郑州振中电熔新材料有限公司 | A kind of preparation method of electric smelting barium zirconate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592709A (en) * | 2018-12-26 | 2019-04-09 | 郑州振中电熔新材料有限公司 | A kind of preparation method of electric smelting barium zirconate |
| CN109592709B (en) * | 2018-12-26 | 2021-05-25 | 郑州振中电熔新材料有限公司 | Preparation method of electric-melting barium zirconate |
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