WO2008156320A1 - Magnetic nanocatalyst composition and method for the preparation thereof - Google Patents

Magnetic nanocatalyst composition and method for the preparation thereof Download PDF

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Publication number
WO2008156320A1
WO2008156320A1 PCT/KR2008/003485 KR2008003485W WO2008156320A1 WO 2008156320 A1 WO2008156320 A1 WO 2008156320A1 KR 2008003485 W KR2008003485 W KR 2008003485W WO 2008156320 A1 WO2008156320 A1 WO 2008156320A1
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magnetic
transition metal
nanoparticles
mixture
nanocatalyst
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PCT/KR2008/003485
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French (fr)
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Jaiwook Park
Min Serk Kwon
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Postech Academy-Industry Foundation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g

Definitions

  • the present invention relates to a magnetic nanocatalyst composition and a method for preparation thereof.
  • Nanocatalysts are widely used for various organic reactions due to their broad surface area and unique surface characteristics [Burda, C. et al., Chem. Rev. 2005, 105, 1025; Astruc, D. et al., Angew. Chem. Int. Ed. 2005, 44, 7852].
  • conventional nanocatalysts cannot be applied to a commercial process because their activity becomes low during reaction and it is hard to recover used catalysts from the reaction mixture.
  • most nanocatalysts are supported by a supporting material such as inorganic oxides, organic polymers, dendrimers, ionic liquids, etc. [Corma, A.
  • magnetic nanoparticles are known as that each of the particles forms a single magnetic domain, which produces unique magnetic characteristics different from that of a general bulk material comprising several magnetic domains. Due to this magnetic characteristic, there is a high possibility to use magnetic nanoparticles in various fields such as high-density magnetic storage devices, drug delivery vectors, sensors, etc.
  • Korean Patent Publication No. 2003-71233 discloses a recoverable organo-metallic catalyst which comprises organo-metallic complexes supported by magnetic nanoparticles.
  • a homogeneous catalyst can be used and the preparation is complicated since the organo-metallic complex should be separately prepared from a functional organic ligand before it is supported by magnetic nanoparticles.
  • a magnetic nanocatalyst composition which comprises a plurality of transition metal nanoparticles and a plurality of magnetic nanoparticles, wherein the transition metal nanoparticles and the magnetic nanoparticles are supported by a support material.
  • the transition metal nanoparticles have a particle size of from 1 nm to 100 nm in diameter and the magnetic nanoparticles have a particle size of from 1 nm to 500 nm in diameter.
  • the weight ratio between the transition metal nanoparticles and the magnetic nanoparticles is, preferably, in the range of from 1 : 0.1 to 1 : 100.
  • the transition metal may be selected from the group consisting of Pd, Pt, Ru 5 Os, Rh, Ir, Re, Mo, W, Cu, Ag, Au, Zn, In, Hf, Ta, Nb, V, and a mixture thereof.
  • the transition metal is Pd.
  • the magnetic nanoparticles can be one or more metal oxides whose metal is selected from the group consisting of Fe, Co, Ni, Mn, Pt, Cu, and Zn.
  • the metal is Fe.
  • the support material can be selected from the group consisting of silica, titania, alumina, zirconia, magnesia, and a mixture thereof.
  • a method for preparing a magnetic nanocatalyst composition comprising the steps of preparing a plurality of transition metal nanoparticles by heating a mixture of a transition metal complex, a precursor of a support material and, optionally, a metal chelate ligand; mixing the transition metal nanoparticles with a plurality of magnetic nanoparticles; and adding water to the resulting mixture to proceed with sol-gel reaction.
  • the metal chelate ligand can be selected from the group consisting of organic acid (C n COOH), organic amine (C n NH 2 ), alkane thiol (C n SH), phosphine (C n P), and a polymer (M n : 10,000 ⁇ n ⁇ 100,000), wherein C n is C 7 - C 30 hydrocarbon.
  • the precursor of the support material is selected from the group consisting of tetraalkylorthosilicate(Si(OR) 3 ), titanium tetraalkoxide (Ti(OR) 4 ), aluminum trialkoxide (Al(OR) 3 ), zirconium alkoxide (Zr(OR) 4 ), magnesium alkoxide
  • R is methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl or s-butyl.
  • the precursor of the support material and the metal chelate ligand are mixed with the transition metal complex in a mole ratios of from O to 1000 : 1 and from 0 to 1000 : 1, respectively, in the step of preparing a magnetic nanocatalyst composition.
  • the magnetic nanoparticles are preferably mixed with transition metal nanoparticles in a mole ratio of from 0.1 to 100 : 1, in the step of mixing the transition metal nanoparticles with a plurality of magnetic nanoparticles.
  • the magnetic nanoparticles are preferably mixed with the transition metal nanoparticle at a temperature in the range of from 20 ° C to 500 ° C .
  • Figs. IA to 1C transmission electron microscope(TEM) images of a palladium- iron oxide nanocatalyst of Example 1 ;
  • Fig. 2 magnetic properties of a palladium-iron oxide nanocatalyst of Example 1 by using Superconducting Quantum Interference Device (SQUID); and Figs. 3 A and 3B: photos showing hydrogenolysis of epichlorin using a palladium-iron oxide nanocatalyst of Example 2 and recovery of the nanocatalyst after the reaction.
  • SQUID Superconducting Quantum Interference Device
  • the magnetic nanocatalyst composition of the present invention comprises a plurality of transition metal nanoparticles and a plurality of magnetic nanoparticles, wherein the transition metal nanoparticles and the magnetic nanoparticles are supported by a support material.
  • the magnetic nanocatalyst composition of the present invention has a high activity and can be easily recovered from the reaction mixture by using a magnet due to its magnetic characteristic.
  • the inventive nanocatalyst composition can be used for various reactions, such as a ring opening reaction of epoxy compound, an oxidation reaction of alcohol, a hydrogenation reaction, a C-C coupling reaction, an alkylation reaction, etc.
  • the weight ratio between the transition metal nanoparticles and the magnetic nanoparticles is in the range of from 1 : 0.1 to 1 : 100, and the transition metal nanoparticles have a particle size of from 1 run to 100 nm in diameter and the magnetic nanoparticles have a particle size of from 1 nm to 500 nm in diameter.
  • the magnetic nanocatalyst composition of the present invention can be prepared by a method comprising the steps of: preparing a plurality of transition metal nanoparticles by heating a mixture of a transition metal complex, a precursor of a support material and, optionally, a metal chelate ligand; mixing the transition metal nanoparticles with a plurality of magnetic nanoparticles; and adding water to the resulting mixture to proceed with sol-gel reaction.
  • the transition metal is selected from the group consisting of Pd, Pt, Ru, Os, Rh, Ir, Re, Mo, W, Cu, Ag, Au, Zn, In, Hf 5 Ta, Nb, V, and a mixture thereof, preferably, Pd.
  • a formal anion such as hydride (H “ ), chloride (Cl “ ), cyanide (CN “ ), acetyl (CH 3 COO “ ), etc.
  • the metal chelate ligand is a compound which stabilizes the metal nanoparticles to have a uniform size.
  • the metal chelate ligand can be selected from the group consisting of organic acid (C n COOH), organic amine
  • the metal chelate ligand is oleic acid, oleyl amine, dodecane thiol, triphenyl phosphine, polyvinyl pyrrolidone, and a mixture thereof.
  • the magnetic nanocatalyst composition may comprise no metal chelate ligand.
  • the material chelate ligand can be mixed with the transition metal complex in a mole ratio of from 0 to 1000 : 1, preferably, 20 to 300 : 1.
  • hydrogen, metal hydride or alcohol preferably, ethanol, n-butanol, sec-butanol or z-butanol can be used as a reducing agent for reducing the transition metal complexes.
  • the precursor of the support material includes an alkoxide of metal oxide such as silica, titania, alumina, zirconia or magnesia, which is a conventional support material.
  • metal oxide such as silica, titania, alumina, zirconia or magnesia
  • the precursor of the support material can be mixed with the transition metal complex in a mole ratio of from 10 to 1000 : 1, preferably, 50 to 300 : 1.
  • the preparation of a plurality of transition metal nanoparticles is preferably carried out in a solvent that can dissolve the transition metal complex, such as tetrahydrofuran(THF), dichloromethane, chloroform, toluene, ethylacetate or a mixture thereof.
  • the reaction for preparing a plurality of transition metal nanoparticles is preferably carried out at a temperature in the range of from 20 °C to 500 ° C , particularly 20 0 C to 250 0 C .
  • the reaction is preferably conducted for about 5 minutes to 20 hours, depending on reaction temperature and mole ratios between reactants.
  • the resulting transition metal nanoparticles are mixed with a plurality of magnetic nanoparticles.
  • the magnetic nanoparticles used in the present invention can be prepared by a conventional method [Deng, H. et al., Angew. Chem. Int. Ed. 2005, 44, 2782].
  • the magnetic nanoparticles are preferably mixed with the transition metal nanoparticles in a mole ratio of from 0.1 to 100 : 1, particularly, 0.5 to 10 : 1.
  • the magnetic nanoparticles may be one or more metal oxides, which are Fe, Co, Ni, Mn, Pt, Cu, Zn, and a mixture thereof. Particularly, Fe is preferable.
  • the magnetic nanoparticles are dispersed in ethanol, acetone, tetrahydrofuran or ethylacetate, etc., and then, mixed with the transition metal nanoparticles to proceed with a reaction for about 5 minutes to 20 hours at a temperature in the range of 20 ° C to 500 ° C .
  • water is added to the resulting mixture in a mole ratio from 1 to 100 : 1, preferably, 2 to 100 : 1 to proceed with sol-gel reaction.
  • the sol-gel reaction is preferably carried out at a temperature in the range of from 20 "C to 500 ° C , particularly 20 ° C to 160 0 C .
  • the reaction is preferably conducted for about 10 minutes to 20 hours, depending on the reaction temperature and mole ratios between reactants.
  • the resulting product is filtered, washed with an appropriate solvent and dried to give the magnetic nanocatalyst composition of the present invention.
  • the solvent can be acetone, tetrahydrofuran, ethylacetate, diethylether, 1,4- dioxane, benzene, toluene, N,N-dimethylformamide, dimethylsulfoxide, methanol, ethanol, chloroform, etc. Acetone or ethylacetate is preferable.
  • the magnetic nanocatalyst composition of the present invention is in the form of solid powder which has a specific surface area of about 50 to 1000 super paramagnetic characteristics at room temperature and high activity in various organic reactions such as a ring opening reaction of epoxy compound, an oxidation reaction of alcohol, a hydrogenation reaction, a C-C coupling reaction, an alkylation reaction, etc.
  • the inventive magnetic nanocatalyst composition can be easily recovered from the reaction mixture by using a magnet.
  • the recovered nanocatalyst has substantionally the same activity even after several recycles.
  • Test 1 Measurement of physical characteristics of Pd-iron oxide nanocatalyst supported by aluminum hydroxide
  • Figs. IA to 1C are TEM images of palladium-iron oxide nanocatalyst supported by aluminum hydroxide obtained in Example 1.
  • Fig. IA shows iron oxide nanoparticles and palladium nanoparticles having a particle size of 100 run and 3 nm, respectively, supported by aluminum hydroxide.
  • Figs. IB and 1C are enlarged images of iron oxide nanoparticles and palladium nanoparticles, respectively.
  • the magnetic characteristic of the Pd-iron oxide nanocatalyst supported by aluminum hydroxide was measured by using SQUID.
  • the inventive Pd-iron nanocatalysts have super paramagnetic characteristics.
  • the activity of the nanocatalyst recovered from the reaction mixture by using an outside magnet was maintained even after 25 times recycle.
  • Example 1 108 mg (1.00 mmol) of benzylalcohol, 150 mg (1.2 mmol) of 2- phenylethylamine and 58 mg of the nanocatalyst (Pd: 2.0 mol%) of Example 1 were mixed and 5.0 ml of heptane was added thereto, then, the mixture was stirred for 20 hours at 90 ° C under an oxygen atmosphere (1 ami). After the reaction was completed, the nanocatalyst was separated by using an outside magnet.

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Abstract

A magnetic nanocatalyst composition comprising a plurality of transition metal nanoparticles and a plurality of magnetic nanoparticles, wherein the transition metal nanoparticles and the magnetic nanoparticles are supported by a support material has a high activity and can be easily recovered from a reaction mixture by using a magnet.

Description

MAGNETIC NANOCATALYST COMPOSITION AND METHOD FOR THE PREPARATION THEREOF
FIELD OF THE INVENTION
The present invention relates to a magnetic nanocatalyst composition and a method for preparation thereof.
BACKGROUND OF THE INVENTION
Nanocatalysts are widely used for various organic reactions due to their broad surface area and unique surface characteristics [Burda, C. et al., Chem. Rev. 2005, 105, 1025; Astruc, D. et al., Angew. Chem. Int. Ed. 2005, 44, 7852]. However, conventional nanocatalysts cannot be applied to a commercial process because their activity becomes low during reaction and it is hard to recover used catalysts from the reaction mixture. In order to solve these problems, most nanocatalysts are supported by a supporting material such as inorganic oxides, organic polymers, dendrimers, ionic liquids, etc. [Corma, A. et al., Science 2006, 313, 332; Oyamada, H. et al., Chem. Commun. 2006, 4297; Song, H. et al., J. Am. Chem. Soc. 2006, 128, 3027; Yamada, Y. M. A. et al., Org. Lett. 2006, 8, 1375; Wu, L. et al., Org. Lett. 2006, 8, 3605; and Wang, Y. et al., Chem. Commun. 2006, 2545]. However, these catalysts still have problems that their preparation processes are complicated and an additional filtration is required for recovering the catalysts.
Meanwhile, magnetic nanoparticles are known as that each of the particles forms a single magnetic domain, which produces unique magnetic characteristics different from that of a general bulk material comprising several magnetic domains. Due to this magnetic characteristic, there is a high possibility to use magnetic nanoparticles in various fields such as high-density magnetic storage devices, drug delivery vectors, sensors, etc.
Also, there have been reported several processes for recovering magnetic nanoparticles from a reaction mixture by using a magnet without filtration by mixing the magnetic nanoparticles with a supporting material of homogeneous catalysts [Stevens, P. D. et al., Org. Lett. 2005, 7, 2085; Hu, A. et al., J. Am. Chem. Soc. 2005, 127, 12486] or inhomogeneous catalysts [Kim, J. et al., Angew. Chem. Int. Ed. 2006, 45, 4789; Yi, D. K. et al., Chem. Mater. 2006, 18, 2459]. However, these methods are unsuccessful due to low activity of catalyst, decomposition of catalyst, leaching of surface metal from the catalyst, complicated process for preparing the catalyst, etc. Moreover, Korean Patent Publication No. 2003-71233 discloses a recoverable organo-metallic catalyst which comprises organo-metallic complexes supported by magnetic nanoparticles. However, only a homogeneous catalyst can be used and the preparation is complicated since the organo-metallic complex should be separately prepared from a functional organic ligand before it is supported by magnetic nanoparticles.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a magnetic nanocatalyst composition which has a high activity, and can be easily recovered from the reaction mixture.
It is another object of the present invention to provide a method for the preparation of the magnetic nanocatalyst composition.
In accordance with one aspect of the present invention, there is provided a magnetic nanocatalyst composition which comprises a plurality of transition metal nanoparticles and a plurality of magnetic nanoparticles, wherein the transition metal nanoparticles and the magnetic nanoparticles are supported by a support material. Preferably, the transition metal nanoparticles have a particle size of from 1 nm to 100 nm in diameter and the magnetic nanoparticles have a particle size of from 1 nm to 500 nm in diameter.
Further, the weight ratio between the transition metal nanoparticles and the magnetic nanoparticles is, preferably, in the range of from 1 : 0.1 to 1 : 100.
In the present invention, the transition metal may be selected from the group consisting of Pd, Pt, Ru5 Os, Rh, Ir, Re, Mo, W, Cu, Ag, Au, Zn, In, Hf, Ta, Nb, V, and a mixture thereof. Preferably, the transition metal is Pd.
The magnetic nanoparticles can be one or more metal oxides whose metal is selected from the group consisting of Fe, Co, Ni, Mn, Pt, Cu, and Zn. Preferably, the metal is Fe.
Moreover, the support material can be selected from the group consisting of silica, titania, alumina, zirconia, magnesia, and a mixture thereof.
In accordance with another aspect of the present invention, there is provided a method for preparing a magnetic nanocatalyst composition, comprising the steps of preparing a plurality of transition metal nanoparticles by heating a mixture of a transition metal complex, a precursor of a support material and, optionally, a metal chelate ligand; mixing the transition metal nanoparticles with a plurality of magnetic nanoparticles; and adding water to the resulting mixture to proceed with sol-gel reaction.
In the method for preparing a magnetic nanocatalyst composition of the present invention, the transition metal complex can comprises a ligand selected from the group consisting of hydride (H"), chloride (Cl"), cyanide (CN"), acetyl (CH3COO"), triphenyl phosphine (P(C6H5)), dibenzylidene acetone (C6H5CH=CHCOCH=CHC6H5), carbonyl (CO), and dien (CH2CHCHCH2).
The metal chelate ligand can be selected from the group consisting of organic acid (CnCOOH), organic amine (CnNH2), alkane thiol (CnSH), phosphine (CnP), and a polymer (Mn: 10,000 < n < 100,000), wherein Cn is C7 - C30 hydrocarbon. Moreover, the precursor of the support material is selected from the group consisting of tetraalkylorthosilicate(Si(OR)3), titanium tetraalkoxide (Ti(OR)4), aluminum trialkoxide (Al(OR)3), zirconium alkoxide (Zr(OR)4), magnesium alkoxide
(Mg(OR)2) and a mixture thereof, wherein, R is methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl or s-butyl.
Preferably, the precursor of the support material and the metal chelate ligand are mixed with the transition metal complex in a mole ratios of from O to 1000 : 1 and from 0 to 1000 : 1, respectively, in the step of preparing a magnetic nanocatalyst composition. The magnetic nanoparticles are preferably mixed with transition metal nanoparticles in a mole ratio of from 0.1 to 100 : 1, in the step of mixing the transition metal nanoparticles with a plurality of magnetic nanoparticles.
Moreover, the magnetic nanoparticles are preferably mixed with the transition metal nanoparticle at a temperature in the range of from 20 °C to 500 °C .
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects and features of the present invention will become apparent from the following description of the invention, when taken in conjunction with the accompanying drawings, which respectively show:
Figs. IA to 1C: transmission electron microscope(TEM) images of a palladium- iron oxide nanocatalyst of Example 1 ;
Fig. 2: magnetic properties of a palladium-iron oxide nanocatalyst of Example 1 by using Superconducting Quantum Interference Device (SQUID); and Figs. 3 A and 3B: photos showing hydrogenolysis of epichlorin using a palladium-iron oxide nanocatalyst of Example 2 and recovery of the nanocatalyst after the reaction. DETAILED DESCRIPTION OF THE INVENTION
The magnetic nanocatalyst composition of the present invention comprises a plurality of transition metal nanoparticles and a plurality of magnetic nanoparticles, wherein the transition metal nanoparticles and the magnetic nanoparticles are supported by a support material. The magnetic nanocatalyst composition of the present invention has a high activity and can be easily recovered from the reaction mixture by using a magnet due to its magnetic characteristic. The inventive nanocatalyst composition can be used for various reactions, such as a ring opening reaction of epoxy compound, an oxidation reaction of alcohol, a hydrogenation reaction, a C-C coupling reaction, an alkylation reaction, etc.
In the magnetic nanocatalyst of the present invention, the weight ratio between the transition metal nanoparticles and the magnetic nanoparticles is in the range of from 1 : 0.1 to 1 : 100, and the transition metal nanoparticles have a particle size of from 1 run to 100 nm in diameter and the magnetic nanoparticles have a particle size of from 1 nm to 500 nm in diameter.
The magnetic nanocatalyst composition of the present invention can be prepared by a method comprising the steps of: preparing a plurality of transition metal nanoparticles by heating a mixture of a transition metal complex, a precursor of a support material and, optionally, a metal chelate ligand; mixing the transition metal nanoparticles with a plurality of magnetic nanoparticles; and adding water to the resulting mixture to proceed with sol-gel reaction.
The transition metal is selected from the group consisting of Pd, Pt, Ru, Os, Rh, Ir, Re, Mo, W, Cu, Ag, Au, Zn, In, Hf5 Ta, Nb, V, and a mixture thereof, preferably, Pd. A ligand for a complex formation can be a formal anion such as hydride (H"), chloride (Cl"), cyanide (CN"), acetyl (CH3COO"), etc., or can be a formal neutral such as triphenyl phosphine (P(C6H5)), dibenzylidene acetone (C6H5CH=CHCOCH-CH6H5), carbonyl (CO), dien (CH2CHCHCH2), etc.
Examples of the palladium complex include palladium(II) acetate (Pd(OAc)2), palladium(II)chloride (Pd(II)Cl2), palladium(II)nitrate (Pd(NOg)2), tetrakistriphenylphosphinpalladium(O) (Pd[P(C6H5)3]4), trisdibenzylideneacetonedipalladium(0)chloroform adduct((C6H5CH=CHCOCH=CHC6H5)3 Pd2CHCl3), or a mixture thereof, preferably, ρalladium(II)acetate (Pd(OAc)2).
In the present invention, the metal chelate ligand is a compound which stabilizes the metal nanoparticles to have a uniform size. The metal chelate ligand can be selected from the group consisting of organic acid (CnCOOH), organic amine
(CnNH2), alkane thiol (CnSH), phosphine(CnP), a polymer(Mn: 10,000<n≤l 00,000), etc., wherein Cn is C7 - C30 hydrocarbon. Preferably, the metal chelate ligand is oleic acid, oleyl amine, dodecane thiol, triphenyl phosphine, polyvinyl pyrrolidone, and a mixture thereof. Alternatively, the magnetic nanocatalyst composition may comprise no metal chelate ligand.
The material chelate ligand can be mixed with the transition metal complex in a mole ratio of from 0 to 1000 : 1, preferably, 20 to 300 : 1.
In the present invention, hydrogen, metal hydride or alcohol, preferably, ethanol, n-butanol, sec-butanol or z-butanol can be used as a reducing agent for reducing the transition metal complexes.
The precursor of the support material includes an alkoxide of metal oxide such as silica, titania, alumina, zirconia or magnesia, which is a conventional support material. Particularly, it is preferable to use tetraalkylorthosilicate(Si(OR)3), titanium tetraalkoxide (Ti(OR)4), aluminum trialkoxide (Al(OR)3), zirconium alkoxide (Zr(OR)4), magnesium alkoxide (Mg(OR)2) or a mixture thereof, wherein, R is C1-C4 alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or s-butyl.
The precursor of the support material can be mixed with the transition metal complex in a mole ratio of from 10 to 1000 : 1, preferably, 50 to 300 : 1. In the method of the present invention, the preparation of a plurality of transition metal nanoparticles is preferably carried out in a solvent that can dissolve the transition metal complex, such as tetrahydrofuran(THF), dichloromethane, chloroform, toluene, ethylacetate or a mixture thereof. In the present invention, the reaction for preparing a plurality of transition metal nanoparticles is preferably carried out at a temperature in the range of from 20 °C to 500 °C , particularly 200C to 2500C . The reaction is preferably conducted for about 5 minutes to 20 hours, depending on reaction temperature and mole ratios between reactants. Then, the resulting transition metal nanoparticles are mixed with a plurality of magnetic nanoparticles. The magnetic nanoparticles used in the present invention can be prepared by a conventional method [Deng, H. et al., Angew. Chem. Int. Ed. 2005, 44, 2782]. The magnetic nanoparticles are preferably mixed with the transition metal nanoparticles in a mole ratio of from 0.1 to 100 : 1, particularly, 0.5 to 10 : 1. In the present invention, the magnetic nanoparticles may be one or more metal oxides, which are Fe, Co, Ni, Mn, Pt, Cu, Zn, and a mixture thereof. Particularly, Fe is preferable.
Preferably, the magnetic nanoparticles are dispersed in ethanol, acetone, tetrahydrofuran or ethylacetate, etc., and then, mixed with the transition metal nanoparticles to proceed with a reaction for about 5 minutes to 20 hours at a temperature in the range of 20 °C to 500 °C .
Then, water is added to the resulting mixture in a mole ratio from 1 to 100 : 1, preferably, 2 to 100 : 1 to proceed with sol-gel reaction. The sol-gel reaction is preferably carried out at a temperature in the range of from 20 "C to 500 °C , particularly 20 °C to 1600C . The reaction is preferably conducted for about 10 minutes to 20 hours, depending on the reaction temperature and mole ratios between reactants.
The resulting product is filtered, washed with an appropriate solvent and dried to give the magnetic nanocatalyst composition of the present invention. The solvent can be acetone, tetrahydrofuran, ethylacetate, diethylether, 1,4- dioxane, benzene, toluene, N,N-dimethylformamide, dimethylsulfoxide, methanol, ethanol, chloroform, etc. Acetone or ethylacetate is preferable.
The magnetic nanocatalyst composition of the present invention is in the form of solid powder which has a specific surface area of about 50 to 1000
Figure imgf000010_0001
super paramagnetic characteristics at room temperature and high activity in various organic reactions such as a ring opening reaction of epoxy compound, an oxidation reaction of alcohol, a hydrogenation reaction, a C-C coupling reaction, an alkylation reaction, etc.
The inventive magnetic nanocatalyst composition can be easily recovered from the reaction mixture by using a magnet. The recovered nanocatalyst has substantionally the same activity even after several recycles.
The following examples are intended to illustrate the present invention, however these examples are not to be construed to limit the scope of the invention.
EXAMPLES
Preparation of catalyst
Example 1: Preparation of Pd-iron oxide nanocatalyst supported by aluminum hydroxide
1-1. Preparation of iron oxide nanopaticles
540 mg (2.00 mmol) of FeCl6-OH2O and 16.0 g of ethylene glycol were added to a 100 ml vessel equipped with a cooler and stirred for 10 minutes at room temperature. Then, 1.60 g of sodium acetate and 400 mg of polyethylene glycol
(Mn=400) were added to the vessel and the reaction mixture heated for 6 hours at
200 "C . The resulting mixture was cooled and centrifuged to obtain a solid residue. The solid residue was washed 3 times with 10 ml of ethanol and dried by evaporating the solvent to obtain 182 mg of iron oxide nanoparticles having an average particle size of 100 run. The specific procedure for preparation of the iron oxide nanoparticles was taken from the published article [Deng, H. et al., Angew. Chem. Int. Ed. 2005, 44, 2782].
1-2. Preparation of Pd-iron oxide nanoparticles supported by sodium aluminum
115 mg (0.512 mmol) of Palladium (II) acetate and 1.00 niL of tetrahydrofuran were added to a 50 mL vessel and stirred for 10 minutes at room temperature. Then, 4.00 g (16.2 mmol) of aluminum tri-sec-butoxide and 1.00 mL of 2-butanol were added to the mixture and the resulting mixture heated for 20 minutes at 50 °C . 100 mg of the iron oxide nanoparticles obtained in item 1.1 above were dispersed into 2.00 mL of ethanol. The dispersion was added to the mixture slowly and stirred for 10 minutes at the same temperature. Then, 3.00 mL of water was added to the reaction mixture and the mixture was heated for 30 minutes at the same temperature. After the reaction was completed, the reaction mixture was cooled, the solvent was removed therefrom and the resulting residue was washed 3 times with 10 mL of acetone. The resuling solid residue was dried for 5 hours at 1200C to obtain 1.37 g of Pd-iron oxide nanocatalyst supported by aluminum hydroxide (Pd: 3.66%, iron: 2.74%, specific surface area: 579 m2g"!)
Test 1: Measurement of physical characteristics of Pd-iron oxide nanocatalyst supported by aluminum hydroxide
Figs. IA to 1C are TEM images of palladium-iron oxide nanocatalyst supported by aluminum hydroxide obtained in Example 1. Fig. IA shows iron oxide nanoparticles and palladium nanoparticles having a particle size of 100 run and 3 nm, respectively, supported by aluminum hydroxide. Figs. IB and 1C are enlarged images of iron oxide nanoparticles and palladium nanoparticles, respectively. The magnetic characteristic of the Pd-iron oxide nanocatalyst supported by aluminum hydroxide was measured by using SQUID. As can be seen from Fig. 2, the inventive Pd-iron nanocatalysts have super paramagnetic characteristics.
Various reactions using Pd-iron oxide nanocatalyst supported by aluminun hydroxide
Example 2
OH
Ck catal yst (2mol %) ,H2 (1 a1:m) ,RT Y
Cl A- ,Cl
92 mg (1.0 mmol) of epichlorohydrin and 58 mg of the nanocatalyst (Pd: 2.0 mol%) of Example 1 were mixed and 2.0 niL of ethylacetate was added thereto.
Then, the mixture was stirred for 4 hours at room temperature under a hydrogen atmosphere (1 atm) as shown in Fig. 3 A. After the reaction was completed, the nanocatalyst was separated by using an outside magnet as shown in Fig. 3B. The solvent was removed from the resulting solution, and the resulting residue was purified by using a silica gel column (eluent: hexane/ethylacetate = 10/1) to obtain 94 mg of 1- chloro-2-ρropanol (yield: >99%).
The activity of the nanocatalyst recovered from the reaction mixture by using an outside magnet was maintained even after 25 times recycle.
Examples 3 to 13
A hydrogenolysis reaction was proceeded with various epoxy compounds as described in Table 1 under the same condition as Example 2, and the results are shown in Table 1. [Table 1]
Example Reactant Product Hours(h) Yield(%)
Figure imgf000013_0001
PH
10 OH 5,0 >99
Figure imgf000013_0002
Example 14
Ph
Figure imgf000013_0003
180 mg (1.00 mmol) of trans-stilbene and 58 mg of the Pd-iron oxide nanocatalyst (Pd: 2.0 mol%) of Example 1 were mixed and 2.0 mL of ethylacetate was added thereto, then, the mixture was stirred for 1 hour at room temperature under a hydrogen atmosphere (1 atm). After the reaction was completed, the nanocatalyst was separated by using an outside magnet. The solvent was removed from the resulting solution, and the resulting residue was purified by using a silica gel column (eluent: hexane/ethylacetate = 10/1) to obtain 182 mg of 1,2-diphenylethane (yield: 100%)
Example 15
catal yst (5mo l %) ,H2 (1 atm) ,RT
Figure imgf000014_0001
Figure imgf000014_0002
120 mg (1.00 mmol) of acetophenone and 145 mg of the nanocatalyst (Pd: 5.0 mol%) of Example 1 were mixed and 2.0 ml of ethylacetate was added thereto, then, the mixture was stirred for 10 hours at room temperature under a hydrogen atmosphere (1 atm). After the reaction was completed, the nanocatalyst was separated by using an outside magnet. The solvent was removed from the resulting solution, and the resulting residue was purified by using a silica gel column (eluent: hexane/ethylacetate = 10/1) to obtain 114 mg of phenylethylacohol (yield: 93 %).
Example 16
catal yst(5mol%) ,02 (1atm) ,RT
Figure imgf000014_0004
122 mg (1.00 mmol) of phenylethylalcohol and 145 mg of the nanocatalyst (Pd:
5.0 mol%) of Example 1 were mixed and 2.0 ml of toluene was added thereto, then, the mixture was stirred for 12 hours at room temperature under an oxygen atmosphere (1 arm). After the reaction was completed, the nanocatalyst was separated by using an outside magnet. The solvent was removed from the resulting solution, and the resulting residue was purified by using a silica gel column (eluent: hexane/ethylacetate = 10/1) to obtain 120 mg of acetophenone (yield: >99 %).
Example 17
Ph^OH + NHa^^™ Ph^N^^™
108 mg (1.00 mmol) of benzylalcohol, 150 mg (1.2 mmol) of 2- phenylethylamine and 58 mg of the nanocatalyst (Pd: 2.0 mol%) of Example 1 were mixed and 5.0 ml of heptane was added thereto, then, the mixture was stirred for 20 hours at 90 °C under an oxygen atmosphere (1 ami). After the reaction was completed, the nanocatalyst was separated by using an outside magnet. The solvent was removed from the resulting solution, and the resulting residue was purified by using a silica gel column (eluent: hexane/ethylacetate = 10/1) to obtain 188 mg of N- benzylidene-2-phenethylamine (yield: 90 %).
Example 18
9 ^. catalyst (2 mol%), Ar 9
Jl + HCT Ph Jl ^s.
PrT ^- Rr ^^ Ph 120 mg (1.00 mmol) of acetophenone, 130 mg (1.2 mmol) of benzylalcohol and
58 mg of the nanocatalyst (Pd: 2.0 mol%) of Example 1 were mixed and 636 mg of potassium phosphate and 5.0 niL of toluene were added thereto, then, the mixture was stirred for 5 hours at 110°C under an argon atmosphere. After the reaction was completed, the nanocatalyst was separated by using an outside magnet. The solvent was removed from the resulting solution, and the resulting residue was purified by using a silica gel column (eluent: hexane/ethylacetate = 10/1) to obtain 197 mg of 1,3- dipheylpropane-1-on (yield: 94 %).
Example 19
Figure imgf000016_0001
154 mg (1.00 mmol) of 2-iutrobenzylalcohol and 58 mg of nanocatalyst (Pd:
2.0 mol%) of Example 1 were mixed and 5.00 mL of toluene was added thereto, then, the mixture was stirred for 4 hours at room temperature under a hydrogen atmosphere (1 arm). 144 mg (1.20 mmol) of acetophenone and 636 mg of potassium phosphate were added thereto, then, the mixture was stirred for 10 hours at 110°C under an argon atmosphere. After the reaction was completed, the nanocatalyst was separated by using an outside magnet. The solvent was removed from the resulting solution, and the resulting residue was purified by using a silica gel column (eluent: hexane/ethylacetate = 10/1) to obtain 176 mg of 2-phenylquinoline (yield: 86 %).

Claims

WHAT IS CLAIMED IS:
1. A magnetic nanocatalyst composition comprising a plurality of transition metal nanoparticles and a plurality of magnetic nanoparticles, wherein the transition metal nanoparticles and the magnetic nanoparticles are supported by a support material.
2. The magnetic nanocatalyst composition of claim 1, wherein the transition metal nanoparticles have a particle size of from 1 run to 100 nm in diameter and the magnetic nanoparticles have a particle size of from 1 nm to 500 nm in diameter.
3. The magnetic nanocatalyst composition of claim 1 , wherein the weight ratio between the transition metal nanoparticles and the magnetic nanoparticles is in the range of from 1 : 0.1 to 1 : 100.
4. The magnetic nanocatalyst composition of claim 1, wherein the transition metal is selected from the group consisting of Pd, Pt, Ru, Os, Rh, Ir, Re, Mo, W, Cu, Ag, Au, Zn, In, Hf, Ta, Nb, V, and a mixture thereof.
5. The magnetic nanocatalyst composition of claim 4, wherein the transition metal is Pd.
6. The magnetic nanocatalyst composition of claim 1, wherein the magnetic nanoparticles are one or more metal oxides whose metal is selected from the group consisting of Fe, Co, Ni, Mn, Pt, Cu, and Zn.
7. The magnetic nanocatalyst composition of claim 6, the metal is Fe.
8. The magnetic nanocatalyst composition of claim 1, the support material is selected from the group consisting of silica, titania, alumina, zirconia, magnesia, and a mixture thereof.
9. A method for preparing a magnetic nanocatalyst composition, comprising the steps of:
(a) preparing a plurality of transition metal nanoparticles by heating a mixture of a transition metal complex, a precursor of a support material and, optionally, a metal chelate ligand;
(b) mixing the transition metal nanoparticles with a plurality of magnetic nanoparticles; and
(c) adding water to the resulting mixture to proceed with sol-gel reaction.
10. The method of claim 9, wherein the transition metal complex comprises a ligand selected from the group consisting of hydride (H"), chloride (Cl"), cyanide (CN"), acetyl (CH3COO"), triphenyl phosphine (P(C6H5)), dibenzylidene acetone (C6H5CH=CHCOCH=CHC6H5), carbonyl (CO), and dien (CH2CHCHCH2).
11. The method of claim 9, wherein the metal chelate ligand is selected from the group consisting of organic acid (CnCOOH), organic amine (CnNH2), alkane thiol (CnSH), phosphine (CnP), and polymer (Mn: 10,000<n<l 00,000), wherein Cn is C7 - C3Q hydrocarbon.
12. The method of claim 9, wherein the precursor of the support material is selected from the group consisting of tetraalkylorthosilicate(Si(OR)4), titanium tetraalkoxide (Ti(OR)4), aluminum trialkoxide (Al(OR)3), zirconium alkoxide (Zr(OR)4), magnesium alkoxide (Mg(OR)2) and a mixture thereof, wherein, R is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or s-butyl.
13. The method of claim 9, wherein the precursor of the support material is mixed with the transition metal complex in step (a) in a mole ratio of from 10 to 1000 : 1.
14. The method of claim 9, wherein the metal chelate ligand is mixed with the transition metal complex in step (a) in a mole ratio of from 0 to 1000 : 1.
15. The method of claim 9, wherein the magnetic nanoparticles are mixed with the transition metal nanoparticles in step (b) in a mole ratio of from 0.1 to 100 : 1.
16. The method of claim 9, wherein the magnetic nanoparticles are mixed with the transition metal nanoparticles at a temperature in the range of from 20 °C to 500 °C .
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