WO2003014011A1 - Solvothermal preparation of metal oxide nanoparticles - Google Patents

Solvothermal preparation of metal oxide nanoparticles Download PDF

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WO2003014011A1
WO2003014011A1 PCT/KR2002/001535 KR0201535W WO03014011A1 WO 2003014011 A1 WO2003014011 A1 WO 2003014011A1 KR 0201535 W KR0201535 W KR 0201535W WO 03014011 A1 WO03014011 A1 WO 03014011A1
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zno
ray diffraction
surface area
mvg
sem
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PCT/KR2002/001535
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French (fr)
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Yun Soo Kim
Chang Gyoun Kim
Ki Whan Sung
Jong Tae Lim
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Korea Research Institute Of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • C01F5/06—Magnesia by thermal decomposition of magnesium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Abstract

A nanoparticle of a metal oxide is prepared by pyrolyzing a compound of formula (I) in a solvent:RMOR' (I) wherein M is beryllium, zinc, magnesium or cadmium; and R and R' are independently a C1-5 alkyl group.

Description

Solvothermal Preparation of Metal Oxide Nanoparticles
Field of the Invention
The present invention relates to a solvothermal method for preparing a nano-sized metal oxide powder comprising pyrolyzing an organic compound of a divalent metal in a solvent.
Background of the Invention
A particulate material having a particle size in the range of several nm to 100 nm is referred to as a nano material which has a high surface area and physical properties quite different from the bulk material. Such nano-material can be used as a new photoelectronic material because of shift of its electron energy levels to shorter wavelengths. A nanoparticle has been conventionally prepared by flame pyrolysis, spray pyrolysis, sol-gel and inverse micelle micro- emulsion methods (see, e.g., G. Westin and M. Nygren, J. Mater. Sci. 27, 1617, 1992).
The flame pyrolysis method requires a special pyrolytic apparatus and a delicate process control to avoid the formation of hollow spherical particles. The sol-gel method requires the use of a high-pressure reactor in a super-critical dry process. The micelle emulsion method has an advantage in that the particle size is easily controlled, but has the problems of requiring a large quantity of a surfactant and difficulty in scaling up for large scale production.
The solvothermal pyrolysis method, on the other hand, involves pyrolysis of a suitable organometallic compound in a solvent, and therefore, it is easy to control the temperature, the particle size and the properties of the final product.
It is known that nanoparticles coagulate with each other to form large aggregates due to the reactive nature of the surface when the particles are formed (T. G. Dietz et al. J. Chem. Phys. 74, 6511, 1981). Accordingly, the solvothermal pyrolytic process has been conducted in the presence of a capping ligand to prevent the formation of particle aggregates. For example, Murray et al disclose a method using trioctylphosphine oxide (TOPO) as a capping ligand to produce CdSe nanoparticles (B. C. Murray et al. J. Am. Chem. Soc. 115, 8706, 1993). Further, it is reported that several nm particles of CdS or CdSe were prepared using TOPO as a capping ligand at a relatively low temperature (T. Trindade etal, Chem. Mater. 9, 523, 1997).
The present inventors have endeavored to develop a solvopyrolytic method for producing metal oxide nanoparticle at a relatively low temperature in the absence of added O2 by way of using a specific precursor.
Summary of the Invention
It is, therefore, an object of the present invention to provide a solvothermal method for preparing nanoparticles of a divalent metal oxide comprising pyrolyzing a divalent metal precursor having alkyl and alkoxy ligands at a relatively low temperature, with optional use of a capping ligand.
In accordance with one aspect of the present invention, there is provided a process for preparing a nanoparticle of metal oxide which comprises pyrolyzing a compound of formula (I) in a solvent:
RMOR' (I)
wherein M is beryllium, zinc, magnesium or cadmium; and R and R' are each independently a C1-5 alkyl group.
Detailed Description of the Invention
The present invention provides a method for preparing metal oxide nanoparticles by pyrolyzing an alkylmetal alkoxide of formula (I) in a solvent at a relatively low temperature.
A compound of formula RMgOR' may be prepared by the method represented by Scheme 1, and a compound of formula RZnOR', by the method illustrated in Scheme 2.
Scheme 1
RMX + KOR' → RMOR' + KX
Scheme 2
R2M + HOR' → RMOR' + RH
wherein, X is Cl, Br or I.
A compound containing beryllium or cadmium may be similarly prepared by the method of Schemes I or II.
The method of the present invention can be performed without added 02 or air through pyrolyzing a compound of formula (I) in an organic solvent having a boiling point of 100 to 400 °C under an inert gas atmosphere. A solvent devoid of water and oxygen can be used and the solvent is preferably selected from dimethoxyethane, hexadecane, tetra(ethyleneglycol)dimethyl ether and dioctyl ether. The pyrolysis is preferably carried out at a temperature below 300 °C .
According to the present invention, the size of metal oxide nanoparticles resulting from the pyrolysis may be controlled by further incorporating in the solvent a capping ligand which adsorbs on, and pacifies, the surface of nanoparticles formed. The capping ligand is an organic compound containing an electron-donating functional group, and it is preferably 1,3-dimethyl- undecanomalonate, dioctylamine, tridodecylmethylamonium iodide, or a mixture thereof. The capping ligand is employed in an amount of 0.05 to 10 equivalents, preferably 0.5 to 5 equivalents, based on the amount of the alkylmetal alkoxide compound.
In case the particulate powder prepared by the pyrolysis of the present invention contains a small, minute amount of elemental metal besides metal oxide, it may be heat treated in an oxidizing atmosphere.
According to the present invention, metal oxide nanoparticles of a controlled size distribution can be prepared in a large scale and economic way.
The following Examples are intended only to further illustrate the present invention, and are not intended to limit the scope of the invention.
Example 1:
1.0 g of methylmagnesium tertiary butoxide and 0.016 g of dimethoxy ethane were added to 30 ml of hexadecane, stirred while slowly heating to 300 °C, and refluxed at 300 °C for 24 hours. The reaction mixture was filtered under an inert gas atmosphere, washed with hexane to remove residual hexadecane, and then dried at room temperature, to obtain 0.65 g of a brown powder which was verified as magnesium oxide nanoparticles having a surface area of 107.36 m7g by X-ray diffraction, SEM (Scanning Electron Microscopy) and BET (Brunauer/Emmett/Teller) methods.
X-ray diffraction: 2Θ = 42. 29°, MgO(200); 2Θ = 61. 41°, MgO(220); 2Θ = 78.59°, MgO(222)
SEM: Coagulated spherical particles with an average size of less than 10 nm.
Example 2 The procedure of Example 1 was repeated except for using 0.032 g of dimethoxyethane, to obtain a brown powder which was verified as magnesium oxide nanoparticles having a surface area of 235.93 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 42. 30°, MgO(200); 2Θ = 61. 32°, MgO(220); 2Θ = 77.37°, MgO(222)
SEM: Coagulated spherical particles with an average size of less than 10 nm.
Example 3
The procedure of Example 1 was repeated except for using 0.080 g of dimethoxyethane, to obtain a brown powder which was verified as magnesium oxide nanoparticles having a surface area of 243.78 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 42.52°, MgO(200); 2Θ = 61.48°, MgO(220); 2Θ = 77.59°, MgO(222)
SEM: Coagulated spherical particles with an average size less than 10 nm.
Example 4
The procedure of Example 1 was repeated except for using 0.80 g of dimethoxyethane, to obtain a brown powder which was verified as magnesium oxide nanoparticles having surface area of 230.18 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 41.92°, MgO(200); 2θ = 60.59°, MgO(220)
SEM: Coagulated spherical particles with an average size of less than 10 nm.
Example 5
The procedure of as Example 1 was repeated except that dimethoxyethane was not employed, to obtain a brown powder which was verified as magnesium oxide nanoparticles having surface area of 323.51 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 42.27°, MgO(200); 2Θ = 61.53°, MgO(220); 2Θ
= 77.52°, MgO(222)
SEM: Coagulated spherical particles with an average size of less than 10 nm.
Example 6
1.5 g of methylzinc isopropoxide was dissolved in 10 ml of hexane, injected using a syringe into 30 ml of hexadecane refluxing at 300 °C in a refluxing apparatus, and refluxed for 30 minutes. The mixture was cooled, filtered under an inert gas atmosphere, washed with diethyl ether to remove residual hexadecane, and then dried at room temperature, to obtain 1.2 g of a white powder which was verified as ZnO nanoparticles having a surface area of 65.20 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 31.74°, ZnO(lOO); 2Θ = 36.21°, ZnO(lOl); 2Θ = 38.94°, ZnO(100); 2Θ = 43.17°, ZnO(lOl)
SEM: Coagulated spherical particles with an average size of 50-70 nm.
Example 7
1.5 g of methylzinc isopropoxide was dissolved in 30 ml of hexadecane and heated at 300 °C for 12 hours in a refluxing apparatus. The mixture was cooled, filtered under an inert gas atmosphere, washed with diethyl ether to remove residual hexadecane, and then dried at room temperature, to obtain 1.53 g of a gray powder which was verified as ZnO nanoparticles having a surface area of 127.16 mVg by X-ray diffraction, SEM and BET methods.
X-ray diff action: 2Θ = 31.50°, ZnO(100); 2Θ = 35.97°, ZnO(lOl); 2Θ = 38.75°, ZnO(100); 2θ = 42.96°, ZnO(lOl)
SEM: Coagulated spherical particles with an average size of 20-40 nm.
Example 8
The procedure of Example 7 was repeated except for heating the reaction mixture at 250 °C , to obtain a gray powder (1.25 g) which was verified as ZnO nanoparticles having a surface area of 16.35 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 31.71°, ZnO(100); 2Θ = 36.14°, ZnO(lOl); 2Θ = 38.93°, ZnO(lOO); 2Θ = 43.14°, ZnO(lOl)
SEM: Coagulated spherical particles with an average size of 40-60 nm.
Example 9
The procedure of Example 7 was repeated except for heating the reaction mixture at 200 °C, to obtained a white powder (1.12 g) which was verified as ZnO nanoparticles having a surface area of 93.37 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 31.73°, ZnO(100); 2θ = 36.09°, ZnO(lOl)
SEM: Coagulated spherical particles with an average size of 10-25 nm. Example 10
1.5 g of methylzinc isopropoxide dissolved in 20 ml of hexadecane was heated in a high pressure reactor at 200 °C for 10 hours. The mixture was cooled, filtered under an inert gas atmosphere, washed with diethyl ether to remove residual hexadecane, and then dried at room temperature, to obtain 1.25 g of a white powder which was verified as ZnO nanoparticles having a surface area of 97.83 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 31.68°, ZnO(lOO); 2Θ = 36.02°, ZnO(lOl); 2Θ = 43.10°, ZnO(lOl)
SEM: 40-60 nm coagulated aggregates of spherical particles with an average size less than 10 nm.
Example 11
The procedure of Example 10 was repeated except for heating at 150 °C , to obtained a white powder which was verified as ZnO nanoparticles having a surface area of 55.52 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 31.69°, ZnO(100); 2θ = 36.04°, ZnO(lOl)
SEM: Coagulated spherical particles with an average size of 30-50 nm.
Example 12
The procedure of Example 8 was repeated except for dissolving methylzinc isopropoxide in 30 ml of dioctyl ether, to obtain a gray powder (1.15 g) which was verified as ZnO nanoparticles having a surface area of 38.15 mVg by X-ray diffraction, SEM and BET methods. X-ray diffraction: 2Θ = 31.55°, ZnO(lOO); 2Θ = 36.00°, ZnO(lOl); 2Θ = 38.76°, ZnO(lOO); 2Θ = 42.98°, ZnO(lOl)
SEM: Coagulated spherical particles with an average size of 30-50 nm.
Example 13
The procedure of Example 12 was repeated except for heating the reaction mixture at 200 °C , to obtain a white powder (1.0 g) which was verified as ZnO nanoparticles having a surface area of 21.42 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 31.59°, ZnO(lOO); 2Θ = 36.04°, ZnO(lOl)
SEM: 20-30 nm coagulated aggregates of spherical particles with an average size less than 10 nm.
Example 14
1.5 g of methylzinc isopropoxide dissolved in 30 ml of dioctyl ether was heated in a high pressure reactor at 200 °C for 10 hours. The mixture was cooled, filtered under an inert gas atmosphere, washed with diethyl ether to remove residual dioctyl ether, and then dried at room temperature to obtain 1.45 g of a white powder which was verified as ZnO nanoparticles having a surface area of 84.41 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 31.62°, ZnO(100); 2Θ = 36.02°, ZnO(lOl); : 2Θ = 38.74°, ZnO(100); 2θ = 42.97°, ZnO(lOl)
SEM: Coagulated spherical particles with an average size of 40-60 nm. Example 15
The procedure of Example 14 was repeated except for heating at 150 °C , to obtain a white powder (1.18 g) which was verified as ZnO nanoparticles having a surface area of 136.42 mVg by X-ray diffraction, SEM and BET methods.
X-ray diffraction: 2Θ = 31.70°, ZnO(100); 2Θ = 36.15°, ZnO(lOl)
SEM: 30-40 nm coagulated aggregates of spherical particles with an average size less than 10 nm.
Example 16
1.5 g of ethylzinc isopropoxide was dissolved in 10 ml of anhydrous tetrahydrofuran. 0.55 g (5 equivalents based on ethylzinc isopropoxide) of 1,3- dimethyl-2-undecanomalonate, a capping ligand, was dissolved in 20 ml of tetra(ethyleneglycol)dimethyl ether and heated to 200 °C. The tetrahydrofuran solution of ethylzinc isopropoxide was injected into the heated tetra(ethyleneglycol)dιmethyl ether solution using a syringe. The reaction mixture was kept at 150 °C for 10 hours and cooled (first precipitation). Then the mixture was centrifuged at 6000 rpm for 30 minutes to precipitate a light yellow powder, 0.2 g. 200 ml of tertiary distilled water was added to the supernatant solution to induce a second stage precipitation (second precipitation) and centrifuged at 6000 rpm for 30 minutes, to obtain 0.15 g of a light yellow powder. Each of two batches of powders was washed with diethyl ether, dried at room temperature, and verified to be ZnO nanoparticles by X-ray diffraction, TEM (Transmission Electron Microscopy) and BET methods. The presence of the capping ligand was confirmed by FT-IR.
X-ray diffraction and BET results:
1) The first precipitated powder showed wide and flat peaks at 2Θ
= 20-40° and 50-70° (surface area: 23.84 mVg). 2) The second precipitated powder showed characteristic peaks at
2Θ = 31.63°, ZnO(lOO); 2Θ = 36.14°, ZnO(lOl) (surface area: 39.44 mVg).
TEM (second precipitated powder): Coagulated spherical particles with an average size less than 10 nm.
FT-LR (second precipitated powder): C=0 characteristic peaks were shown at 1732 cm"1 and 1596 cm"1.
Example 17
The procedure of Example 16 was repeated except for dissolving 1,3- dimethyl-2-undecanomalonate in dioctyl ether, to obtain 0.12 g and 0.23 g of a white powder by the first and second precipitation, respectively, which were verified to be ZnO nanoparticles by X-ray diffraction, TEM and BET methods.
The presence of the capping ligand was confirmed by FT-IR.
X-ray diffraction and BET results: 1) The first precipitated powder showed wide and flat peaks at 2Θ = 20-
40° and 50-70° (surface area: 54.21 mVg). 2) The second precipitated powder showed characteristic peaks at 2Θ =
31.63°, ZnO(lOO); 2Θ = 35.01°, ZnO(lOl) (surface area: 7.36 mVg).
TEM (second precipitated powder): Coagulated spherical particles with an average size less than 10 nm.
FT-IR (second precipitated powder): C=0 characteristic peaks were shown at 1732 cm"1 and 1596 cm"1.
Example 18
1.5 g of ethylzinc isopropoxide was dissolved in 20 ml of tetra(ethyleneglycol)dimethyl ether. 0.55 g (5 equivalents based on ethylzinc isopropoxide) of l,3-dimethyl-2-undecanomalonate, a capping ligand, was dissolved in 5 ml of tetra(ethyleneglycol)dimethyl ether. 20 ml of tetra(ethyleneglycol)dimethyl ether was heated to 200 °C in a refluxing apparatus. The tetra(ethyleneglycol)dimethyl ether solution of ethylzinc isopropoxide was injected into the heated tetra(ethyleneglycol)dimethyl ether using a syringe, and the tetra(ethyleneglycol)dimethyl ether solution of 1,3- dimethyl-2-undecanomalate was also injected 5 minutes later. The reaction mixture was kept at 150 °C for 10 hours and cooled. Then, the mixture was centrifuged at 6000 rpm for 30 minutes to precipitate a white powder, 2.75 g. The obtained powder was washed with diethyl ether, dried at room temperature, and verified to be ZnO nanoparticles by X-ray diffraction, TEM and BET methods. The presence of the capping ligand was confirmed by FT-IR.
X-ray diffraction and BET result: The precipitated powder showed wide and flat peaks at 2Θ = 20-40° and 50-70° (surface area: 52.13 mVg).
TEM: Spherical particles with an average size less than 10 nm.
FT-IR: A wide C=0 characteristic peak was shown at 1591 cm"1.
Example 19
1.5 g of ethylzinc isopropoxide was dissolved in 20 ml of tetra(ethyleneglycol)dimethyl ether. 0.55 g (5 equivalents based on ethylzinc isopropoxide) of l,3-dimethyl-2-undecanomalate, a capping ligand, was dissolved in 5 ml of tetra(ethyleneglycol)dimethyl ether. 20 ml of tetra(ethyleneglycol)dimethyl ether was heated to 200 °C in a refluxing apparatus. The tetra(ethyleneglycol)dimethyl ether solution of ethylzinc isopropoxide was injected into the heated tetra(ethyleneglycol)dimethyl ether using a syringe, and the tetra(ethyleneglycol)dimethyl ether solution of 1,3- dimethyl-2-undecanomalate was also injected 5 minutes later. The reaction mixture was kept at 150 °C for 40 minutes and cooled (first precipitation). Then the mixture was centrifuged at 6000 m for 30 minutes to precipitate a light yellow powder, 0.15 g. 200 ml of ethanol was added to supernatant solution to induce a second stage precipitation (second precipitation) and centrifuged at 6000 •φm for 30 minutes, to obtain 1.05 g of a light yellow powder. Each of the two batches of powders was washed with diethyl ether, dried at room temperature, and verified to be ZnO nanoparticles by X-ray diffraction, TEM and BET methods. The presence of the capping ligand was confirmed by FT-IR.
X-ray diffraction and BET results: 1) The first precipitated powder showed characteristic peaks at 2Θ =
31.58°, ZnO(100); 2Θ = 35.91°, ZnO(lOl) (surface area: 18.38 mVg). 2) The second precipitated powder showed wide and flat peaks at 2Θ = 20-40° and 50-70° (surface area: 18.12 mVg).
TEM (second precipitated powder): Coagulated spherical particles with an average size less than 10 nm.
FT-IR (second precipitated powder): C=O characteristic peaks were shown at 1732 cm"1 and 1596 cm"1.
Example 20
The procedure of Example 19 was repeated except that the first precipitation was performed for 4 hours, to obtain 0.3 g and 1.52 g of light yellow powders at the first and second precipitation steps, respectively, which were verified as to be ZnO nanoparticles by X-ray diffraction, TEM and BET methods.
The presence of the capping ligand was confirmed by FT-IR.
X-ray diffraction and BET results:
1) The first precipitated powder showed characteristic peaks at 2Θ = 31.58°, ZnO(100); 2Θ = 35.91°, ZnO(lOl), which are overall wide and low (surface area: 12.34 mVg). 2) The second precipitated powder showed wide and flat peaks at 2Θ = 20-40° and 50-70° (surface area: 51.46 mVg).
TEM (second precipitated powder): Coagulated spherical particles with an average size less than 10 nm.
FT-IR (second precipitated powder): C=O characteristic peaks were shown at 1732 cm"1 and 1600 cm"1.
Example 21
1.5 g of ethylzinc isopropoxide was dissolved in 20 ml of hexadecane.
11.98 g of dioctylamine (5 equivalents based on ethylzinc isopropoxide), which is employed for both as a capping ligand and a solvent, was heated to 200 °C in a refluxing apparatus. The hexadecane solution of ethylzinc isopropoxide was injected into the heated dioctylamine using a syringe. The reaction mixture was kept at 150 °C for 4 hours and cooled (first precipitation). Then, the mixture was centrifuged at 6000 φm for 30 minutes to precipitate a white powder, 0.15 g.
200 ml of ethanol was added to the supernatant solution to induce a second stage of precipitation (second precipitation) and centrifuged at 6000 φm for 30 minutes to obtain 1.44 g of a white powder. Each of the two batches was washed with diethyl ether, dried at room temperature, and verified to be ZnO nanoparticles by
X-ray diffraction, TEM and BET methods. The presence of the capping ligand was confirmed by FT-IR.
X-ray diffraction and BET results:
1) The first precipitated powder showed characteristic peaks at 2Θ = 31.81°, ZnO(100); 2Θ = 35.43°, ZnO(lOl), which were overall wide and flat (surface area: 43.37 mVg). 2) The second precipitated powder showed wide and flat peaks at 2Θ =
20-40° and 50-70° (surface area: 40.67 mVg).
TEM (second precipitated powder): Coagulated spherical particles with an average size less than 10 nm.
FT-LR (second precipitated powder): Characteristic peaks of carbon chain were shown at 2956 cm"1 and 1465 cm"1.
Example 22
The procedure of Example 21 was repeated except for heating dioctylamine to 250 °C and performing the first precipitation at 200 °C, to obtain 0.14 g and 0.5 g of white powders at the first and second precipitation steps, respectively, which were verified to be ZnO nanoparticles by X-ray diffraction, TEM and BET methods. The presence of the capping ligand was confirmed by FT-IR.
X-ray diffraction and BET results:
1) The first precipitated powder showed characteristic peaks at 2Θ = 31.62°, ZnO(lOO); 2Θ = 36.153°, ZnO(lOl); 2Θ = 43.10°, ZnO(lOl) which were overall wide. The peak of ZnO(lOl) was overlapped within a wide peak, (surface area: 85.56 mVg) 2) The second precipitated powder showed ZnO characteristic peaks at
2Θ = 31-36° which are widely overlapped each other (surface area: 41.68 mVg).
TEM (second precipitated powder): Coagulated spherical particles with an average size less than 10 nm.
FT-LR (second precipitated powder): Characteristic peaks of carbon chain were shown at 2956 cm"1 and 1465 cm"1.
Example 23
The procedure of Example 22 was repeated except that the first precipitation was performed at 150 °C , to obtain 0.16 g and 0.64 g of white powders at the first and second precipitation steps, respectively, which were verified as ZnO nanoparticles by X-ray diffraction, TEM and BET methods. The presence of the capping ligand was confirmed by FT-IR.
X-ray diffraction and BET result:
1) The first precipitated powder showed characteristic peaks at 2Θ = 31.59°, ZnO(lOO); 2Θ = 36.14°, ZnO(lOl) (surface area: 69.26 mVg).
2) The second precipitated powder showed ZnO characteristic peaks at 2Θ = 31-36° which were widely overlapped each other (surface area:
79.06 mVg).
TEM (second precipitated powder): Coagulated spherical particles with an average size less than 10 nm.
FT-IR (second precipitated powder): Characteristic peaks of carbon chain were shown at 2956 cm"1 and 1465 cm"1.
Example 24
1.5 g of ethylzinc isopropoxide was dissolved in 20 ml of tetra(ethyleneglycol)dimethyl ether. 0.5 g of tridodecylmethylammonium iodide (0.07 equivalents based on ethylzinc isopropoxide), a capping ligand, was heated to 250 °C in a refluxing apparatus. The tetra(ethyleneglycol)dimethyl ether solution of ethylzinc isopropoxide was injected into the heated tridodecylmethylammonium iodide using a syringe. The reaction mixture was kept at 150 °C for 4 hours. Then, the mixture was cooled to 100 °C and the precipitate was separated from the solution using a filtering rod. The precipitate thus obtained was dissolved in ethanol and 200 ml of tertiary distilled water was added thereto to precipitate a light yellow powder (first precipitation). The mixture was centrifuged at 6000 φm for 30 minutes to obtain a light yellow powder, 0.14 g. 200 ml of tertiary distilled water was added to the supernatant solution to induce a second stage precipitation (second precipitation) and centrifuged at 6000 φm for 30 minutes, to obtain 0.34 g of a light yellow powder. Each of the two batches of powders was washed with diethyl ether and ethanol, dried at room temperature, and verified to be ZnO nanoparticles by X-ray diffraction, TEM and BET method. The presence of the capping ligand was confirmed by FT-IR.
X-ray diffraction and BET results:
1) The first precipitated powder showed characteristic peaks at 2Θ =
1.72°, ZnO(lOO); 2Θ = 36.64°, ZnO(lOl) (surface area: 50.53 mVg). 2) The second precipitated powder showed characteristic peaks at 2Θ =
31.53°, ZnO(lOO); 2Θ = 36.04°, ZnO(lOl) (surface area: 65.01 m'/g).
TEM (second precipitated powder): Coagulated spherical particles with an average size less than 10 nm.
FT-IR (second precipitated powder): Characteristic peaks of carbon chain at 2956 cm"1 and 1465 cm"1 , and characteristic peak of C-N at 1030 cm"1 were shown.
While the invention has been described with respect to the above specific embodiments, it should be recognized that various modifications and changes may be made to the invention by those skilled in the art which also fall within the scope of the invention as defined by the appended claims.

Claims

What is claimed is:
1. A process for preparing a nanoparticle of a metal oxide which comprises pyrolyzing a compound of formula (I) in a solvent:
RMOR' (I)
wherein M is beryllium, zinc, magnesium or cadmium; and R and R' are each independently a C1-5 alkyl group.
2. The process of claim 1, wherein said M is zinc or magnesium.
3. The process of claim 1, which is conducted in the absence of 02.
4. The process of claim 1, wherein the solvent is an organic solvent having a boiling point in the range of 100 to 400 °C .
5. The process of claim 4, wherein the organic solvent is hexadecane, tetra(ethyleneglycol)dimethyl ether, dimethoxyethane, dioctyl ether or a mixture thereof.
6. The process of claim 1, wherein the pyrolysis is carried out at a temperature below 300 °C.
7. The process of claim 1, wherein the pyrolysis is carried out in the presence of an organic compound selected from the group consisting of 1,3- dimethyl-2-undecanomalonate, dioctylamine, tridodecylmethylammonium iodide and a mixture thereof.
8. The process of claim 7, wherein the organic compound is employed in an amount ranging from 0.05 to 10 equivalents based on the amount of the compound of formula (I).
9. The process of claim 8, wherein the organic compound is employed in an amount ranging from 0.5 to 5 equivalents based on the amount of the compound of formula (I).
PCT/KR2002/001535 2001-08-10 2002-08-10 Solvothermal preparation of metal oxide nanoparticles WO2003014011A1 (en)

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