CN1814549A - Method for preparing nano metal oxide - Google Patents
Method for preparing nano metal oxide Download PDFInfo
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- CN1814549A CN1814549A CN 200510006191 CN200510006191A CN1814549A CN 1814549 A CN1814549 A CN 1814549A CN 200510006191 CN200510006191 CN 200510006191 CN 200510006191 A CN200510006191 A CN 200510006191A CN 1814549 A CN1814549 A CN 1814549A
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Abstract
The invention relates to a nm metal oxide manufacture method. The metal consitituent taking reaction with amine through metal inorganic salt solution to gain deposition, adding one or more organic compounds in the depositing process and stabilizer, the product would be gained. The inorganic salt could be metal chloride, nitrate, sulfate, carboxylate and so on. It could used to make one oxide or mixture oxide of Ti, Zr, Hf, Fe, Co, Mn, Cr, V, Cu, Ni, Zn, Ce, Al, etc. The invention has the feature of the diameter of the metal oxide could be controlled, and high crystallinity.
Description
Technical field
The invention provides a kind of preparation method who is used for nano-metal-oxide, specifically, the aqueous solution of inorganic metal salt and organic amine reaction generate aqueous metal oxide, obtain metal oxide nanoparticles by calcining then.In the nano particle generative process, the organism of adding and the organic ammonium salt of generation stop nanoparticle growth and gathering as stablizer.The characteristics of the nano-oxide of this method preparation are: particle diameter distribution is narrow, characteristics such as degree of crystallinity height.
Background technology
Because nanoparticle has unique physics and chemical property, as magnetic property, photoelectric property, catalytic activity etc., so it has purposes widely.The synthesis of nano oxide process has non-hydrolytic sol gel method, metal alkoxide hydrolysis method, metal alkoxide thermal decomposition method, non-hydrated established law etc. at present.The raw material that these methods adopt is metal alkoxide mostly, and this is because metal alkoxide hydrolysis and polymeric speed are easy to control by the condition of conditioned reaction.Yet metal alkoxide is uncommon, costs an arm and a leg; And, store trouble to the water and air sensitivity.Consider the application prospect of nano-oxide, should adopt a kind of cheapness, precursor stable, safety is the feedstock production nano-oxide.From the abundant inorganic salt compound of originating, for example metal chloride, nitrate, vitriol, the application prospect of preparation nano-metal-oxide will be very wide.Yet the speed of these metal-salt hydrolysis is very fast, is difficult to control; The particle that generates is easy to assemble growth.Therefore, directly very difficult from inorganic salts compound nano-metal-oxide.Although adopting inorganic metal-salt is feedstock production metal nano oxide compound, and report has been arranged, the degree of crystallinity that the nano-metal-oxide that adopts these methods to prepare has is low, and the particle dia that has distributes wide, thereby has influence on its application.If, can be controlled at the gathering and the growth of nanoparticle in the preparation process, adopting inorganic salt so is that feedstock production metal nano oxide compound will become possibility.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of nano-metal-oxide.Present method has the nano-metal-oxide granular size can be controlled, and particle diameter distribution is narrow, characteristics such as degree of crystallinity height.
For achieving the above object, preparation method provided by the invention, earlier 0.01-1.0 is soluble in water in molar ratio with organic additive with the aqueous solution of inorganic metal salt, and 60-80 ℃ of reaction 10-20 minute down generates aqueous metal oxide and precipitates; Stir the precipitating action that adds stoichiometric organic amine and generation down again, ageing 5-10 hour, the gathering and the growth of nanoparticle in the control precipitation separated obtaining precipitating, 60-80 ℃ dry 24-48 hour; The dried 450-600 of being deposited in ℃ roasting 1-2 hour (or dried precipitation with ethanol extract the back after 80-100 ℃ of dry 1-2 hour again in 450-600 ℃ of roasting 1-2 hour), obtain metal oxide nanoparticles.
These metal-salts can be metal chloride, nitrate, vitriol, carboxylate salt etc.
According to the present invention, can prepare the nano-oxide of elements such as Ti, Zr, Hf, Fe, Co, Mn, Cr, V, Cu, Ni, Zn, Ce, Al and the composite oxides nano particle of these elements.These elements in final product all the form with oxide compound exist.
According to the present invention, the organic additive that adds in the preparation process can be for organic acid, polyvalent alcohol, contain N compound or sulfocompound etc.
According to the present invention, the organic amine in the preparation process can an alkylamine, dialkylamine or trialkylamine.
Description of drawings
Fig. 1: (Fig. 1 a) and its particle size distribution (Fig. 1 b) for the transmission electron microscope photo of nano zirconium dioxide.
Fig. 2: the x-ray diffractogram of powder spectrum of nano zirconium dioxide.
Fig. 3: Co
3O
4Transmission electron microscope photo (Fig. 3 a) and its x-ray diffractogram of powder spectrum (Fig. 3 b).
Fig. 4: the transmission electron microscope photo of manganese oxide.
Fig. 5: the transmission electron microscope photo of zinc oxide.
Fig. 6: ZrO
2-NiO (Fig. 6 a), ZrO
2-Co
3O
4(Fig. 6 b) and ZrO
2-Co
3O
4The transmission electron microscope photo of-NiO (Fig. 6 c).
Fig. 7: the transmission electron microscope photo of regulating the add-on rear oxidation zirconium of stablizer.
Fig. 8: adopting polyoxyethylene glycol is the zirconic transmission electron microscope photo of stablizer preparation.
Fig. 9: adopting di-n-propylamine is the transmission electron microscope photo of the cobalt oxide of precipitation agent preparation.
Figure 10: diameter is the transmission electron microscope photo of 30 nanometer cobalt oxides.
Figure 11: zirconium oxychloride is that (Figure 11 a) and its particle size distribution (Figure 11 b) for the transmission electron microscope photo of the nano zirconium dioxide of raw material.
Embodiment
Below by example in detail the present invention is described in detail:
Embodiment one: adopting zirconium nitrate is feedstock production nanometer ZrO
2
Get 162.5mmol zirconium nitrate and 32.4mmol cetyl trimethylammonium bromide and be dissolved in the 730mL water, then in the water-bath that is placed into 80 degree.After 20 minutes, under intense stirring condition, add the 650mmol triethylamine fast in above-mentioned solution, then, ageing 8 hours.Precipitation obtains by centrifugation, under the 80 degree conditions dry 48 hours then.After dried sample is used the extraction using alcohol organism, dry 2 hours of 100 degree.At last, in flowing air, 500 degree calcinings 2 hours obtain the zirconium dioxide that mean diameter is 13 nanometers.Its transmission electron microscope photo and particle size distribution are seen Fig. 1 a and Fig. 1 b; By x-ray diffractogram of powder spectrum (Fig. 2) as can be known its crystalline phase be mainly the monocline crystalline phase, contain a spot of cubic crystalline phase simultaneously.
Embodiment two: nano Co
3O
4Preparation
Get 124.5mmol Co (NO
3)
26H
2O and 25mmol cetyl trimethylammonium bromide are dissolved in the 750mL water, then in the water-bath that is placed into 80 degree.After 20 minutes, under intense stirring condition, add the 249mmol triethylamine fast in above-mentioned solution, then, ageing 8 hours.Precipitation obtains by centrifugation, under the 80 degree conditions dry 48 hours then.After dried sample is used the extraction using alcohol organism, dry 2 hours of 120 degree.At last, in flowing air, 300 degree calcinings 2 hours obtain the Co that nanometer diameter is 50 nanometers
3O
4Its transmission electron microscope photo and x-ray diffractogram of powder spectrum are seen Fig. 3.
Embodiment three: the preparation of nano manganese oxide.
The employing manganous nitrate is a raw material, and the mol ratio of raw material and preparation process and embodiment one are identical.Obtain the manganese oxide that mean diameter is 40 nanometers.Its transmission electron microscope photo is seen Fig. 4.
Embodiment four: the preparation of nano zine oxide.
The employing zinc nitrate is a raw material, and the mol ratio of raw material and preparation process and embodiment one are identical.Obtain the zinc oxide that mean diameter is 30 nanometers.Its transmission electron microscope photo is seen Fig. 5.
Embodiment five: the preparation of nano composite oxide
By nanometer ZrO
2-NiO, ZrO
2-Co
3O
4And ZrO
2-Co
3O
4The preparation of three kinds of composite oxides of-NiO specifies the preparation of nano composite oxide.
The cetyl trimethylammonium bromide of 112mmol zirconium nitrate and requirement (mol ratio of cetyl trimethylammonium bromide and metal is 0.2) and other metal nitrates are (at ZrO
2-Co
3O
4Middle Co/Zr mol ratio is 0.286; At ZrO
2Among-the NiO, the Ni/Zr mol ratio is 0.143; At ZrO
2-Co
3O
4Co/Ni and (Co+Ni) among-the NiO/Zr is respectively 2 and 0.429) be dissolved in the 500ml water.The amount of triethylamine is calculated by the reaction of nitrate and alkali.Preparation process and embodiment one are identical.The nanometer ZrO that obtains
2-NiO, ZrO
2-Co
3O
4And ZrO
2-Co
3O
4The average particle diameter of-NiO is respectively: 10,15,15 nanometers.Their transmission electron microscope photo is seen Fig. 6 a, Fig. 6 b, Fig. 6 c.
Embodiment six: the influence that adds the amount of stablizer
With the zirconium nitrate be feedstock production nanometer ZrO
2Process in, the mol ratio that changes cetyl trimethylammonium bromide and zirconium is 0.8, other preparation process is identical with embodiment one with proportioning raw materials.Having obtained mean diameter is the particle of 10 nanometers.Their transmission electron microscope photo is seen Fig. 7.
Embodiment seven: the influence of different types of stablizer
With the zirconium nitrate be feedstock production nanometer ZrO
2Process in, add polyoxyethylene glycol (molecular-weight average 5000) and replace cetyl trimethylammonium bromide as additive, other preparation process is identical with embodiment one with proportioning raw materials.Having obtained mean diameter is the particle of 8 nanometers.Its transmission electron microscope photo is seen Fig. 8.
Embodiment eight: the influence of different types of organic amine
Below with in nano Co
3O
4Preparation process in, adopt di-n-propyl amine to replace triethylamine as precipitation agent, the influence of different organic amines to nanoparticle is described.Other preparation process is identical with embodiment two with proportioning raw materials.Having obtained mean diameter is the particle of 50 nanometers.Its transmission electron microscope photo is seen Fig. 9.
Embodiment nine: the control of diameter of nano particles
By regulating the size control that realizes nanoparticle in the concentration of raw material, below with nano Co
3O
4Preparation illustrate.
Get 12.5mmol Xiao Suangu and 2.5mmol cetyl trimethylammonium bromide and be dissolved in the 750mL water, cobalt is identical with embodiment two with other preparation process with the mol ratio of triethylamine.Obtain the Co of 30 nanometers
3O
4Their transmission electron microscope photo is seen Figure 10.
Embodiment ten: the feedstock production nano-oxide particles that adopts other
ZrO
2Adopting zirconium oxychloride is feedstock production nanometer ZrO
2Method.Except the mol ratio of zirconium and triethylamine becomes 0.5, other step is identical with preparation method among the embodiment one.In obtaining on average still is the ZrO of 13 nanometers
2Its transmission electron microscope photo and particle size distribution are seen Figure 11 a and Figure 11 b.
Claims (4)
1. the preparation method of a nano-metal-oxide, its key step is:
A) 0.01-1.0 is soluble in water in molar ratio for organic additive and inorganic metal salt, and 60-80 ℃ was reacted 10-20 minute down;
B) stir and to add stoichiometric organic amine down, ageing 5-10 hour, separate obtaining precipitation, 60-80 ℃ dry 24-48 hour;
C) dried being deposited in 450-600 ℃ of roasting 1-2 hour;
Described organic additive is polyvalent alcohol, carboxylic acid, nitrogenous compound or sulfocompound;
Described organic amine is an alkylamine, dialkylamine or trialkylamine.
2. in accordance with the method for claim 1, it is characterized in that inorganic metal salt is: metal chloride, nitrate, vitriol or carboxylate salt.
3. in accordance with the method for claim 1, it is characterized in that nano-metal-oxide is the oxide compound of a kind of element among Ti, Zr, Hf, Fe, Co, Mn, Cr, V, Cu, Ni, Zn, Ce, the Al or the mixed oxide of several elements.
4. in accordance with the method for claim 1, it is characterized in that the dried precipitation of step b is extracted with ethanol, the 80-100 ℃ of roasting of carrying out step c after dry 1-2 hour again.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274771B (en) * | 2007-03-30 | 2010-09-29 | 清华大学 | Preparation for metallic oxide nanocrystal |
| CN101723434B (en) * | 2008-10-22 | 2012-02-22 | 国家纳米科学中心 | Ternary oxide nano material, ternary oxide nano structure and preparation method thereof |
| CN102407127A (en) * | 2011-11-23 | 2012-04-11 | 中国科学院生态环境研究中心 | Cobalt cerium composite metal oxide, its preparation method and its application |
| WO2015149494A1 (en) * | 2014-04-01 | 2015-10-08 | 中国科学院生态环境研究中心 | Preparation method and use of ce-ti-al ternary compound micro-/nano-metal oxide |
| CN108940308A (en) * | 2018-07-18 | 2018-12-07 | 福州大学 | A kind of preparation of platinum cobalt composition metal photo-thermal catalyst and its application in methane carbon dioxide reformation |
| CN110743527A (en) * | 2019-11-08 | 2020-02-04 | 南京工业大学 | Preparation method of mesoporous ozone catalyst |
-
2005
- 2005-01-31 CN CN 200510006191 patent/CN1814549A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274771B (en) * | 2007-03-30 | 2010-09-29 | 清华大学 | Preparation for metallic oxide nanocrystal |
| CN101723434B (en) * | 2008-10-22 | 2012-02-22 | 国家纳米科学中心 | Ternary oxide nano material, ternary oxide nano structure and preparation method thereof |
| CN102407127A (en) * | 2011-11-23 | 2012-04-11 | 中国科学院生态环境研究中心 | Cobalt cerium composite metal oxide, its preparation method and its application |
| CN102407127B (en) * | 2011-11-23 | 2014-05-07 | 中国科学院生态环境研究中心 | Cobalt cerium composite metal oxide, its preparation method and its application |
| WO2015149494A1 (en) * | 2014-04-01 | 2015-10-08 | 中国科学院生态环境研究中心 | Preparation method and use of ce-ti-al ternary compound micro-/nano-metal oxide |
| CN108940308A (en) * | 2018-07-18 | 2018-12-07 | 福州大学 | A kind of preparation of platinum cobalt composition metal photo-thermal catalyst and its application in methane carbon dioxide reformation |
| CN108940308B (en) * | 2018-07-18 | 2021-06-01 | 福州大学 | Preparation of platinum-cobalt composite metal photo-thermal catalyst and application of platinum-cobalt composite metal photo-thermal catalyst in methane carbon dioxide reforming |
| CN110743527A (en) * | 2019-11-08 | 2020-02-04 | 南京工业大学 | Preparation method of mesoporous ozone catalyst |
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Open date: 20060809 |