KR101621701B1 - Metal oxide nanoparticles and the prosess of manufacture - Google Patents
Metal oxide nanoparticles and the prosess of manufacture Download PDFInfo
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- KR101621701B1 KR101621701B1 KR1020140191894A KR20140191894A KR101621701B1 KR 101621701 B1 KR101621701 B1 KR 101621701B1 KR 1020140191894 A KR1020140191894 A KR 1020140191894A KR 20140191894 A KR20140191894 A KR 20140191894A KR 101621701 B1 KR101621701 B1 KR 101621701B1
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Abstract
The present invention relates to a process for producing a precursor containing oxygen by pyrolyzing a metal oxide or a metal carbonate represented by MO x (CO 2 ) y in an organic acid and an organic solvent; And a step of accumulating the precursor. The method is simple in production process, can uniformly control the shape of the metal oxide nanoparticles, and can be mass-produced.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to metal oxide nanoparticles and a method of manufacturing the same, and more particularly, to a method of manufacturing metal oxide nanoparticles by one-pot synthesis using a metal carbonate as a material.
Recently, interest in nanotechnology technology has been increasing in the medical, semiconductor, and general industries, and related researches are actively proceeding. Various kinds of metal oxide nanoparticles such as iron oxide and manganese oxide in medical image field, zinc oxide and cobalt oxide in electronic material field, and copper oxide and manganese oxide in catalyst field have been introduced as suitable materials for various fields. In order for these nanoparticles to have a realistic meaning as a material, it is necessary to make a manufacturing method that can control the uniform size and shape and can be mass-produced on an industrial scale.
Conventional manufacturing techniques can be roughly classified into a coprecipitation method of a metal salt in an aqueous solution phase and a pyrolysis of an organic metal complex compound on an organic solvent-a method of thermolysis of a solvent. However, in the coprecipitation method, it is not easy to control the shape and size of the particles because the surfactant does not act on the surface of the nanoparticles. In the case of the pyrolysis-solvent thermolysis method, an additional step of preparing the precursor organometallic complex is required The manufacturing cost is increased and mass production is not easy.
Other methods for producing nano-sized materials include pyrolysis pyrolysis, spray pyrolysis, and sol-gel method. Nanoparticles are formed due to the instability of nanoparticles when the nanoparticles are formed in the gas phase. So that it is not easy to control the size of the particles. In addition, pyrolysis pyrolysis requires a special pyrolysis unit and requires a high temperature thermal energy. Spray pyrolysis can be used to obtain spherical hollow particles having hollow hollows. . In addition, in the case of the sol-gel method, a high-pressure reactor and supercritical drying method must be used in order to obtain nanoparticles, which increases the process cost.
Accordingly, there is a demand for a new manufacturing technique capable of mass-producing metal oxide nanoparticles, simplifying the manufacturing steps, and controlling the shape of the nanoparticles.
The object of the present invention is to provide a production method capable of mass production and capable of producing metal oxide nanoparticles by a simple process.
The present invention relates to (1) a process for producing a precursor containing oxygen by pyrolyzing a metal oxide or a metal carbonate represented by the following formula (1) in an organic acid and an organic solvent; And (2) aggregating the precursor. The present invention also provides a method for producing metal oxide nanoparticles.
[Chemical Formula 1]
MO x (CO 2 ) y
In Formula 1,
M is a transition metal,
X is selected from 4/3, 3/2 and 1,
Y is 0 or 1.
According to an embodiment of the present invention, the transition metal is one or more selected from the group consisting of manganese (Mn), iron (Fe), and cobalt (Co)
When the transition metal is two or more,
The first transition metal is M ', the second transition metal is M'
Wherein M 'and M "are different from each other and are independently selected from manganese (Mn), iron (Fe) and cobalt (Co)
The metal oxide or metal carbonate may be selected from a compound represented by the following formula (2) or a mixture of the compounds represented by the following formulas (3) and (4).
(2)
(M'M ") O x (CO 2 ) y
(3)
M'O x (CO 2 ) y
[Chemical Formula 4]
M "O x (CO 2 ) y
According to an embodiment of the present invention, the step (1) may be carried out at 250 to 350 ° C for 20 to 120 minutes under a stream of oxygen: argon = 0: 1 to 1: 1 by volume.
According to an embodiment of the present invention, the organic amine may be added after the decomposition and the reaction may be further performed for 30 to 180 minutes.
The organic acid may have a carboxylic acid moiety that is selected from unsaturated fatty acids of C 16 or C 18 -30 -30 saturated fatty acids of, specifically, stearic acid, palmitic acid, oleic acid, El fluoride acid, foil sensan, linoleic acid, arachidonic Acid, erucic acid, and behenic acid.
The organic amine may be one or more selected from oleamine, octadecylamine and trioctylamine.
According to one embodiment of the present invention, the size of the nanoparticles can be controlled according to the mixing ratio of the organic amine.
According to one embodiment of the present invention, the organic solvent may be at least one selected from neutral saturated or unsaturated hydrocarbons having a boiling point of 250 to 350 ° C or higher, and specific examples thereof include benzyl ether, octadecane, octadecene, Decene, icosene, icosan, and squalene.
According to an embodiment of the present invention, the content of the organic acid to the metal oxide or the metal carbonate may be 2 to 10 equivalents, and the content of the organic amine to the metal oxide or the metal carbonate may be 2 to 10 equivalents.
The method of producing metal oxide nanoparticles according to the present invention can uniformly control the morphology of metal oxide nanoparticles, simplify the manufacturing process, and can increase the production scale, thereby reducing the manufacturing cost of the metal oxide nanoparticles .
1 is a diagram schematically illustrating a synthesis method according to the present invention.
2 is an electron microscope image of manganese (II) oxide nanoparticles according to an embodiment of the present invention.
3 is an electron microscope image of iron oxide (II, III) nanoparticles according to an embodiment of the present invention.
4 is an electron microscope image of manganese ferrite (II, III) nanoparticles according to an embodiment of the present invention.
5 is an image of a natural metal oxide or metal carbonate.
FIG. 6A is a graph showing the superficial magnetic magnetic capability of iron oxide nanoparticles prepared according to an embodiment of the present invention, and FIG. 6B is a graph showing the effect of the iron oxide nanoparticles according to the present invention on the NIH3T6.7 tumor micro- It is an image that evaluates the imaging ability.
Hereinafter, the present invention will be described in more detail.
The present invention relates to a process for producing an MO-type precursor by thermal decomposition of a metal oxide or metal carbonate, which can be obtained in a natural state, such as a metal carbonate or a metal oxide, in an organic solvent. The obtained precursor is integrated to form a metal oxide nanoparticle In a large amount.
The metal oxide nanoparticles according to the present invention can be obtained by (1) pyrolyzing a metal oxide or metal carbonate represented by the following formula (1) in an organic acid and an organic solvent to prepare a precursor containing oxygen; And (2) aggregating the precursor.
[Chemical Formula 1]
MO x (CO 2 ) y
In Formula 1,
M is a transition metal,
X is selected from 4/3, 3/2 and 1,
Y is 0 or 1.
In the above formula (1), X is 4/3 means M 3 O 4 (CO 2 ) y , and X is 3/2 means M 2 O 3 (CO 2 ) y .
According to the present invention, the oxygen-containing precursor may preferably be MO.
According to the present invention, the transition metal may be one or more selected from the group consisting of manganese (Mn), iron (Fe), and cobalt (Co)
Specifically, when the transition metal is two or more,
The first transition metal is M ', the second transition metal is M'
M 'and M "are different from each other and may be independently selected from among Mn, Fe, and Co.
The metal oxide or metal carbonate may be selected from a compound represented by the following formula (2) or a mixture of the compounds represented by the following formulas (3) and (4).
(2)
(M'M ") O x (CO 2 ) y
(3)
M'O x (CO 2 ) y
[Chemical Formula 4]
M "O x (CO 2 ) y
If the transition metal is one selected from the group consisting of manganese (Mn), iron (Fe), and cobalt (Co), the metal oxide or metal carbonate may be selected from among the compounds represented by the above Chemical Formula 3 or Chemical Formula 4 .
According to the invention, the organic acid is a C 16 -30 and the can have a carboxylic acid moiety that is selected from a saturated fatty acid or unsaturated fatty acids of C 18 -30, may be a compound not less than a boiling point of 300 ℃, specifically, the organic acid is stearic acid , Palmitic acid, oleic acid, elaidic acid, benzoic acid, linoleic acid, arachidonic acid, erucic acid, and behenic acid.
The step (1) may be carried out at 250 to 350 ° C for 20 to 120 minutes under a stream of oxygen: argon = 0: 1 to 1: 1 by volume,
If the reaction temperature is lower than the above range, the metal oxide or the metal carbonate is hardly pyrolyzed, and it is difficult for the MO-type precursor to be produced.
The content of the organic acid relative to the metal oxide or the metal carbonate may be 2 to 10 equivalents, preferably 3 to 6 equivalents. If the content of the organic acid is less than the above range, the metal oxide or the metal carbonate is difficult to dissociate sufficiently The non-pyrolyzed metal oxide or metal carbonate may remain, and if it exceeds the above range, the byproducts of the reaction increase, which is not preferable.
According to the present invention, the organic solvent may be one or more selected from neutral saturated or unsaturated hydrocarbons having a boiling point of 250 to 350 ° C or higher. Specific examples thereof include benzyl ether, octadecene, octadecene, nonadecene, , Icosaic acid and squalene.
Next, the step (1) may further include adding organic amine after pyrolysis and allowing the reaction to proceed for 30 to 180 minutes, and the reaction may be carried out at 250 to 350 ° C.
The organic amine may be added so that the size of the nanoparticles can be uniformly grown. The organic amine may be a compound having a boiling point of 300 ° C or higher and a proton acceptor, and may be selected from oleamine, octadecylamine and trioctylamine Or more.
Particularly, the size of the metal oxide nanoparticles prepared by mixing two or more of the above organic amines can be controlled. For example, when trioctylamine is used alone as an organic amine, metal oxide nanoparticles having a particle size of 5 to 50 can be prepared. When oleamine is used as the organic amine, metal having a particle size of 50 to 300 nm Oxide nanoparticles can be produced. Accordingly, the metal oxide nanoparticles having various sizes ranging from 5 to 300 nm in particle size and controlled in particle size can be prepared by setting the composition ratio to be 2 or more including the above-mentioned organic amines.
According to the present invention, the content of the organic amine to the metal oxide or metal carbonate may be 2 to 10 equivalents, preferably 3 to 6 equivalents. If the content of the organic amine is less than the above range, it is difficult to improve the size of the metal oxide nanoparticles. If the content exceeds the above range, reaction byproducts increase and metal oxide nanoparticles having uneven sizes may be produced.
The metal oxide nanoparticles produced by the method of the present invention may have a particle size of 5 to 300 nm.
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent to those skilled in the art, however, that these examples are provided to further illustrate the present invention, and the scope of the present invention is not limited thereto.
Example
Example 1. Preparation of manganese (II) oxide nanoparticles
Example 1.1.
30 mmol of mildew-ground manganese (MnO, Mn 3 O 4 , MnO (CO 2 ) or a mixture thereof), 4 equivalents of oleic acid and 6 equivalents of 1-octadecene were added to the reaction vessel. An oxygen / argon mixed gas (mixing ratio 0: 1 vol.%) Was supplied to the reaction vessel at a flow rate of 50 cc / min and reacted at 320 DEG C for 60 minutes. After confirming that the reaction solution became transparent, 4 equivalents of trioctylamine was added and reacted for 1 hour to synthesize bright blue-green manganese (II) oxide nanoparticles.
Example 1.2.
Manganese (II) oxide nanoparticles were prepared in the same manner as in Example 1.1 except that 4 equivalents of oleamine was added instead of 4 equivalents of trioctylamine to synthesize manganese (II) oxide nanoparticles.
Example 1.3.
Manganese (II) oxide nanoparticles were synthesized in the same manner as in Example 1.1 except that 2 equivalents of oleamine and 2 equivalents of trioctylamine were added in place of 4 equivalents of trioctylamine to synthesize manganese (II) oxide nanoparticles .
2 is an electron microscope image of the manganese oxide nanoparticles prepared according to Example 1.1, and the right image of FIG. 2 is an electron micrograph of the manganese oxide nanoparticles prepared according to Example 1.3. It can be seen that the size of the manganese oxide nanoparticles was regulated according to the contents of oleamine and trioctylamine.
Example 2: Preparation of iron oxide nanoparticles
Example 2.1
30 mmol of ground flour (Fe 2 O 3 , Fe 3 O 4 , FeO (CO 2 ) or a mixture thereof), 4 equivalents of oleic acid and 6 equivalents of 1-octadecene were added to a fine powder. An oxygen / argon mixed gas (mixing ratio 2: 8% by volume) was supplied to the reaction vessel at a flow rate of 50 cc / min and reacted at 320 ° C for 60 minutes. After confirming that the reaction solution became transparent, 4 equivalents of trioctylamine was added and reacted for 1 hour to synthesize black iron oxide (II, III) nanoparticles.
Example 2.2
Iron oxide (II, III) nanoparticles were synthesized in the same manner as in Example 2.1 except that 4 equivalents of oleamine was added instead of 4 equivalents of oleamine.
Example 2.3.
(II, III) nanoparticles were synthesized in the same manner as in Example 2.1 except that 2 equivalents of oleamine and 2 equivalents of trioctiamine were added in place of 4 equivalents of trioctylamine to prepare iron oxide (II, III) nanoparticles Were synthesized.
The left image of FIG. 3 is an electron microscope image of the iron oxide nanoparticles prepared according to Example 1.1, and the right image of FIG. 3b is an electron scanning microscope image of the iron oxide nanoparticles prepared according to Example 1.3. It can be seen that the sizes of the iron oxide nanoparticles were controlled and grown according to the contents of oleamine and trioctylamine.
Example 3. Preparation of manganese ferrite (II, III) nanoparticles
Iron salt, ground to a fine powder (Fe 2 O 3, Fe 3 O 4, FeO (CO 2) or mixtures thereof), 20 mmol, manganese (MnO, Mn 3 O 4, MnO (CO 2) or a mixture thereof). 10 mmol, 8 equivalents of oleic acid and 2 equivalents of 1-octadecene were placed in a reaction vessel. An oxygen / argon mixed gas (mixing ratio 0: 1 vol.%) Was supplied to the reaction vessel at a flow rate of 50 cc / min and reacted at 320 DEG C for 60 minutes. After confirming that the reaction solution became transparent, 4 equivalents of trioctylamine was added and reacted for 2 hours to synthesize black manganese ferrite (II, III) nanoparticles.
4 is an electron microscope image of the manganese ferrite nanoparticles prepared according to Example 3. FIG.
Test Example 1. Evaluation of superparamagnetic magnetic capability of iron oxide nanoparticles
A sample of the iron oxide nanoparticles obtained in Example 2.1 was subjected to a hysteresis in a range of ± 2 tesla using a sample vibrating sample magnetometer. Iron samples were quantitatively analyzed by inductively coupled plasma atomic emission spectroscopy (ICP-AES).
Test Example 2. NIH3T6.7 Tumor Evaluate MRI T2-contrast ability in small animal models
The aqueous iron oxide nanoparticles obtained in Example 2.1 were stabilized by using a surfactant polymer and then injected into a mouse model of fibroblast (NIH3T6.7 cell) to obtain MRI images of tumor tissues.
Claims (11)
(2) aggregating the precursor; and (2)
[Chemical Formula 1]
MO x (CO 2 ) y
In Formula 1,
M is a transition metal,
X is selected from 4/3, 3/2 and 1,
Y is 0 or 1.
Wherein the step (1) is carried out at 250 to 350 ° C for 20 to 120 minutes under a stream of oxygen: argon = 0: 1 to 1: 1 by volume.
Further comprising the step of adding an organic amine after the thermal decomposition and allowing the reaction to proceed for 30 to 180 minutes.
Wherein the organic acid is selected from C 16 -30 saturated fatty acids or C 18 -30 unsaturated fatty acids and has a carboxylic acid residue.
Wherein the organic acid is at least one selected from stearic acid, palmitic acid, oleic acid, elaidic acid, benzoic acid, linoleic acid, arachidonic acid, erucic acid and behenic acid .
Wherein the organic amine is one or more selected from oleamine, octadecylamine and trioctylamine.
Wherein the size of the nanoparticles is controlled according to the mixing ratio of the organic amine.
Wherein the organic solvent is at least one selected from benzyl ether, octadecane, octadecene, nonadecene, icosen, icosen, and squalene.
Wherein the content of the organic acid with respect to the metal oxide or the metal carbonate is 2 to 10 equivalents.
Wherein the content of the organic amine to the metal oxide or the metal carbonate is 2 to 10 equivalents.
The transition metal is one or more selected from the group consisting of manganese (Mn), iron (Fe) and cobalt (Co)
When the transition metal is two or more,
The first transition metal is M ', the second transition metal is M'
Wherein M 'and M "are different from each other and are independently selected from manganese (Mn), iron (Fe) and cobalt (Co)
Wherein the metal oxide or metal carbonate is selected from the group consisting of a compound represented by the following Chemical Formula 2 or a mixture of compounds represented by the following Chemical Formulas 3 and 4:
(2)
(M'M ") O x (CO 2 ) y
(3)
M'O x (CO 2 ) y
[Chemical Formula 4]
M "O x (CO 2 ) y
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| KR101902532B1 (en) * | 2016-09-28 | 2018-09-28 | 재단법인 전남생물산업진흥원 | Apparatus for Mass Production of Metal Oxide Nanoparticles |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100604975B1 (en) | 2004-11-10 | 2006-07-28 | 학교법인연세대학교 | Preparation Method of Magnetic and Metal Oxide Nanoparticles |
| US20070140951A1 (en) | 2003-12-11 | 2007-06-21 | The Trustees Of Columbia University In The City Of New York | Nano-sized particles, processes of making, compositions and uses thereof |
| KR101345097B1 (en) | 2010-08-11 | 2013-12-26 | 고려대학교 산학협력단 | Novel manganese oxide nanopaticle and contrast agent comprising the same |
| KR101446840B1 (en) | 2012-11-06 | 2014-10-08 | 한국생산기술연구원 | Manufacturing method for iron powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070140951A1 (en) | 2003-12-11 | 2007-06-21 | The Trustees Of Columbia University In The City Of New York | Nano-sized particles, processes of making, compositions and uses thereof |
| KR100604975B1 (en) | 2004-11-10 | 2006-07-28 | 학교법인연세대학교 | Preparation Method of Magnetic and Metal Oxide Nanoparticles |
| KR101345097B1 (en) | 2010-08-11 | 2013-12-26 | 고려대학교 산학협력단 | Novel manganese oxide nanopaticle and contrast agent comprising the same |
| KR101446840B1 (en) | 2012-11-06 | 2014-10-08 | 한국생산기술연구원 | Manufacturing method for iron powder |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101902532B1 (en) * | 2016-09-28 | 2018-09-28 | 재단법인 전남생물산업진흥원 | Apparatus for Mass Production of Metal Oxide Nanoparticles |
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