WO2004011700A1 - Methode de production de nanocristaux d'oxyde metallique recouverts de tensioactif, et produits obtenus par cette methode - Google Patents

Methode de production de nanocristaux d'oxyde metallique recouverts de tensioactif, et produits obtenus par cette methode Download PDF

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WO2004011700A1
WO2004011700A1 PCT/US2001/050394 US0150394W WO2004011700A1 WO 2004011700 A1 WO2004011700 A1 WO 2004011700A1 US 0150394 W US0150394 W US 0150394W WO 2004011700 A1 WO2004011700 A1 WO 2004011700A1
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group
surfactant
period
nanocrystals
reaction
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PCT/US2001/050394
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Paul A. Alivisatos
Joerg Rockenberger
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The Regents Of The University Of California
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Priority claimed from US09/702,219 external-priority patent/US6440213B1/en
Priority claimed from US09/721,126 external-priority patent/US6984369B1/en
Application filed by The Regents Of The University Of California filed Critical The Regents Of The University Of California
Priority to AU2001297624A priority Critical patent/AU2001297624A1/en
Publication of WO2004011700A1 publication Critical patent/WO2004011700A1/fr

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    • 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
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/605—Products containing multiple oriented crystallites, e.g. columnar crystallites
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • 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

Definitions

  • This invention relates to a process for making dispersable surfactant capped nanocrystals. More particularly, it relates to a process for making dispersable surfactant capped nanocrystals of metal oxides with non-hydroxylated particle surfaces using a non-hydrolylic single precursor approach, and to the nanocrystals made thereby. Still more particularly, it relates to a process for making dispersable surfactant capped nanocrystals of transition metal oxides.
  • coordinating surfactant means an organic molecule consisting of a polar headgroup and an apolar group providing stabilization against coagulation and precipitation of particles by binding to particle surfaces through the polar headgroup and allowing dispersion of particles in aliphatic, aromatic and halogenated hydrocarbons.
  • Figure 1 shows the result of the thermal analysis of iron, manganese and copper cupferronate in a TGA/DTA apparatus under N 2 -flow (left). To the right, the xrd patterns of the respective decomposition products are displayed.
  • Figure 2 and 3 present low-resolution TEM images as well as XRD patterns of ⁇ -Fe 2 O 3 ,
  • Figure 4 presents low-resolution TEM images as well as derived particle size
  • Figure 5 shows particle size distributions derived from low-resolution TEM imaging as a function of refluxing time after the precursor injection.
  • Figure 6 describes the increasing average particle size as the reaction precipitate is subsequently extracted with Toluene.
  • Figure 7 shows a low-resolution TEM image of a monolayer of individual ⁇ -Fe 2 O 3
  • top left High- resolution TEM image of one of the nanocrystals in this sample.
  • the indicated lattice plane distances correspond to the (113) and (201) lattice planes of tetragonal ⁇ -Fe 2 O 3 with ordered superlattice of the cation vacancies.
  • Top right FFT of the high-resolution TEM image looking down the [51-2] zone-axis.
  • Figure 8 and 9 present XRD patterns as well as FT-IR spectra of the iron, manganese and copper cupferronates, respectively.
  • the process comprises: (a) mixing a solution of a metal cupferron precursor complex of the formula M x Cup x , wherein M x is a metal ion in the oxidation state X selected from the group consisting of elements in Group 2, Group 3 - 12 of the 4 th period, Group 3 - 6 of the 5 th and 6 th period, Group 10 - 12 of the 5 th period, Group 12 of the 6 th period, and Group 13 th to 15 th , and the Lanthanide and Actinide series of the periodic table, and Cup is a N-substituted N-Nitroso hydroxylamine, with a coordinating surfactant , and (b) heating the mixture at a temperature and for a sufficient period of time to cause thermal decomposition of the M x Cup x precursor and formation of the desired nanocrystals.
  • M x is a metal ion in the oxidation state X selected from the group consisting of elements in Group 2, Group 3 - 12 of the
  • the process described below is focused primarily on the preparation of transition metal oxide nanocrystals, it is equally applicable to the formation of any metal oxide nanocrystal where the metal ( M x ) is a metal ion in the oxidation state X selected from the group consisting of elements in Group 2, Group 3 - 12 of the 4 th period, Group 3 - 6 of the 5 th and 6 th period, Group 10 - 12 of the 5 th period, Group 12 of the 6 th period, and Group 13 th to 15 th , and the Lanthanide and Actinide series of the periodic table.
  • the metal ( M x ) is a metal ion in the oxidation state X selected from the group consisting of elements in Group 2, Group 3 - 12 of the 4 th period, Group 3 - 6 of the 5 th and 6 th period, Group 10 - 12 of the 5 th period, Group 12 of the 6 th period, and Group 13 th to 15 th , and the Lanthanide and Actinide series of the
  • X will vary, depending on which metal is used in the formation of the precursor, and the oxidation state of the metal. In general, however, X will range from 1 to 4.
  • Metal Cupferron complexes M x Cup x (M: metal ion; Cup: N-nitroso N - phenylhydroxylamine, C6H5N(NO)O-), with the metal ion coordinated via the oxygen atoms of the Cup ligand in a bidentate manner, proved to be promising as molecular precursors.
  • Metal cupferronates are used in the precipitation or extraction of metal ions from aqueous solution, and are easily prepared for many metal elements (11).
  • injecting solutions of metal Cupferron complexes in octylamine into long-chain amines at 250-300 °C yields nanocrystals of iron oxide, manganese oxide,and copper oxide.
  • the preparation of the metal Cupferron precursor is based on the precipitation of metal ions from aqueous solution at a specific pH with Cupferron, the ammonium salt of N-nitroso N-phenylhydroxylamine (details of the synthesis and characterization of the metal cupferronates M Cup x (M: Fe, Cu, Mn) are provided infra).
  • Dried powders of metal cupferronates show sharp decomposition temperatures (see fig. 1, left) of 180 °C, 230 °C, and 205 °C for FeCup 3 , MnCup 2 , and CuCup 2 , respectively,
  • the reaction was stopped and the liquid was allowed to cool.
  • the flask contained nanocrystals of iron oxide, in both a dark-brown, clear liquid supernatant and a precipitate.
  • the latter results from the high concentration of nanocrystals and their limited solubility in trioctylamine at low temperature.
  • Adding 1-2 mL of organic solvents such as toluene, hexane, CHC1 3 , etc. to this precipitate yielded clear, deep-brown dispersions of iron oxide nanocrystals which were stable for weeks at room temperature.
  • Low-resolution TEM imaging revealed particles with an average size of 6.7 nm and a standard deviation of 1.4 nm.
  • the iron oxide nanocrystals could be reprecipitated as a brown powder.
  • Adding methanol to the supernatant of the reaction led to a brown precipitate of iron oxide nanocrystals, which could also be redispersed and reprecipitated by suitable solvents. For both fractions, dispersion and reprecipitation could be repeated several times.
  • the surfactant could be removed yielding typically about 50 - 60 mg of a brown insoluble powder after drying.
  • This powder still contained about 10 % of volatile compounds as indicated by thermal gravimetric analysis between 300 K and 1100 K in an O 2 atmosphere.
  • the overall yield of iron oxide is thereby estimated to 45 mg to 55 mg, which corresponds to about 50 % of the iron injected as cupferron complex.
  • Similar procedures were used in the synthesis of manganese oxide and copper oxide nanocrystals. In the case of manganese oxide, 4 ml of a 0.3 M solution of MnCup 2 in octylamine were injected into 7 g trioctylamine at 360 °C and refluxed for 10 min.
  • hexadecylamine was used as a surfactant to disperse the precipitated nanocrystalline copper oxide in organic solvents like toluene, hexane, CHC1 3 etc.
  • the reaction had to be stopped immediately after injection since the formation of metallic Cu instead of the copper oxide is favored at high temperatures under the strongly reducing conditions of the reaction.
  • 2 ml of a 0.3 M solution of CuCup 2 in octylamine were injected into 5.5 g hexadecylamine at 250 °C. The reaction was stopped by removing the heat as soon as the temperature reached again 230 °C.
  • the average particle size as determined from low-resolution TEM imaging is 6.9 ⁇ 2.5 nm (see fig. 2, right).
  • Powder XRD reveals the nanocrystalline nature of the described samples ( Figure 3).
  • the diffraction patterns were fitted with the program PowderCell (16) using structure
  • corresponding lattice planes are (113) and (201), respectively, and the FFT (top right) of the high-resolution image indicates that the particle was imaged along its [51-2] zone
  • CuCup 2 was prepared by adding dropwise 6 g ammonium cupferron dissolved in 200 ml H 2 O to a solution of 1.54 g CuCI 2 - 4H 2 0 in 1.4 1 H 2 O. The resulting blue-gray precipitate was filtered after 15 min and dissolved in pyridine yielding a deep green solution. The solution was concentrated in a rotavapor and filtered with a glass filter. To this solution a mixture of n-butanol and hexane was added until the solution was slightly turbid. After one day in a fridge at -20 °C the solution contained large deep-green crystals which were isolated from the supernatant by decanting and dried at 40 °C under vacuum.
  • the yield of the resulting blue-gray powder was typically 50 - 70 % with respect to copper.
  • the experimental powder x-ray diffraction pattern (see fig. 8, right) agrees very well with calculated patterns based on single crystal structure data.
  • the results of the elemental analysis (calc. values in brackets) are for CuCup 2 : 19 % (18.8 %) Cu, 43.1 % (42.7 %) C, 15.8 % (16.6 %) N, and 3.3 % (3.0 %) H.
  • Fig. 9 (right) shows the FT-IR spectrum of the complex which agrees well with literature results (15) and shows the Cu-O stretch vibration at 437 cm "1 .
  • trioctylamine was heated to 100 °C for 1 - 1.5 h and repeatedly evacuated to 20 mtorr and purged with Ar.
  • a solution of 0.3 M FeCup 3 in octylamine was treated the same way at 60 °C.
  • the reaction was initiated by the rapid injection of 4 ml of FeCup 3 stock solution into the trioctylamine at 300 °C under vigorous magnetic stirring and an Ar atmosphere.
  • a color change of the liquid from colorless to dark-brown and the evolution of gas indicated the decomposition of the metal cupferron complex.
  • the flask contained nanocrystals of iron oxide, both in a dark-brown, clear liquid supernatant and a precipitate.
  • the latter results from the high concentration of nanocrystals and their limited solubility in trioctylamine at low temperature.
  • Adding 1 - 2 ml of organic solvents like toluene, hexane, CHC1 3 , etc. to this precipitate yielded clear, deep-brown dispersions of iron oxide nanocrystals which were stable for weeks at room temperature.
  • Low-resolution TEM imaging revealed the presence of iron oxide nanocrystals with an average size of 6.7 ⁇ 1.4 nm (see fig. 2, left).
  • the reaction mixture was transferred into an excess of methanol (3 : 1) yielding a brown precipitate and a clear yellow-brown supernatant.
  • methanol 3 : 1
  • the precipitate can be dispersed in organic solvents like toluene, chloroform, hexane etc. Adding methanol to this dispersion yields again a brown precipitate. Redispersion and reprecipitation by suitable solvents could be repeated several times.
  • Example 8 Preparation of about 5 nm ⁇ -Fe?O? nanocrystals capped by hexadecylamine
  • the liquid reached a temperature of 280 °C and was refluxed at this temperature for another 48 min. After the heating was stopped, the reaction mixture was transferred at 100 °C into an excess of methanol (2:1). The resulting precipitate was isolated by centrifugation and could be redispersed in toluene, hexane, chloroform etc. By adding methanol to this dispersion, the nanocrystals could be reprecipitated. Redispersion and reprecipitation could be repeated several times.
  • trioctylamine was heated to 100 °C for 1 - 1.5 h and repeatedly evacuated to 20 mtorr and purged with Ar.
  • a solution of 0.3 M MnCup 2 in octylamine was treated the same way at 60 °C.
  • the reaction was initiated by the rapid injection of 4 ml of MnCup 2 stock solution into the trioctylamine at 360 °C under vigorous magnetic stirring and an Ar atmosphere.
  • a color change of the liquid from colorless to dark-brown and the evolution of gas indicated the decomposition of the metal cupferron complex.
  • the liquid was refluxed for 10 min. at 275 °C before heating was stopped.
  • the flask contained nanocrystals of manganese oxide, both in an orange-brown, clear liquid supernatant and a brown precipitate.
  • Adding 1 - 2 ml of organic solvents like toluene, hexane, CHC1 3 , etc. to this precipitate yielded clear, deep- brown dispersions of manganese oxide nanocrystals.
  • the manganese oxide nanocrystals could be reprecipitated as a brown powder.
  • methanol to the supernatant of the reaction lead to a brown precipitate, which could also be redispersed and reprecipitated by suitable solvents.
  • the liquid was transferred into an excess of methanol (3:1) yielding a brown precipitate which was isolated by centrifugation. This precipitate could be redispersed in organic solvents like toluene, hexane, chloroform and again reprecipitated by addition of methanol.
  • the average particle size and size-distribution as determined from low-resolution TEM imaging is 6.9 ⁇ 2.5 nm.
  • trioctylamine was heated to 100 °C for 1 - 1.5 h and repeatedly evacuated to 20 mtorr and purged with Ar.
  • a solution of 0.3 M CoCup 2 in octylamine was treated the same way at 60 °C. 4 ml of this solution were injected at 300 °C into the trioctylamine and refluxed for 20 min. at 230 °C.
  • the liquid was allowed to cool to 100 °C and transferred into an excess of methanol (3:1).
  • the resulting grey precipitate could be redispersed in toluene, chloroform or hexane.
  • the nanocrystals could be recovered as a powder.
  • the preferred metals for use in preparing the M x Cup ⁇ precursor for use in the process of this invention are transition metals, more preferably either Fe, Mn, or Cu.
  • Cup compound most commonly used in the formation of the precursor is N-nitroso-N-phenyl-hydroxylamine
  • any N-substituted N-nitroso-hydroxylamine of the formula RN2O2 where R is a phenyl, benzyl, naphtyl, biphenyl, methyl, propyl, etc. would be suitable for use.
  • Specific compounds include, for example, N-nitroso-N- phenyl-hydroxylamine, N-nitroso-N[l]-naphthyl-hydroxylamine, N-nitroso-N-biphenyl- 4-yl-hydroxylamine, N-nitroso-N[2]-fluorenyl-hydroxylamine, N-nitroso-N-benzyl- hydroxylamine, N-nitroso-N-(4-nitrophenyl)-hydroxylamine, N-nitroso-N-trityl- hydroxylamine, and N-nitroso-N-isopropyl-hydroxylamine, their salts, such as ammonium salts, and the like.
  • the coordinating surfactant is preferably arnine based, and most preferably is trioctylamine, or hexadecylamine.
  • Other suitable amines include dioctylamine,and dibenzylamine.
  • Still other suitable surfactants include primary, secondary or tertiary alkyl-or aryl-amines; primary, secondary or tertiary alkyl-or aryl-phosphines, such as tributylphosphine, triphenylphosphine; primary, secondary or tertiary alkyl- or aryl- phosphine oxides such as octylphosphine oxide, and dihexylphosphine oxide and trioctylphosphine oxide; dialkyl-, diaryl- or aryl-alkyl-ethers such as dioctylether, and dibenzylether; carboxylic acids such as oleic acid, and lauric acid; and
  • the process is carried out in an inert atmosphere in the absence of water, air , or oxygen.
  • the preferred inert atmosphere is argon gas, but nitrogen or any other inert gas can be used.
  • the mixture of metal cupferron complex and coordinating surfactant is heated to a temperature sufficient to cause the thermal decomposition of the precursor and formation of the nanocrystals.
  • the temperature to which the mixture is heated can range from 150 to 400 degrees C, preferably from 220 to 350 degrees C, and most preferably from 250 to 300 degrees C. The exact temperature to which the mixture is heated will depend on the reactants and the duration that heat is applied.
  • the nanocrystals produced by the process of this invention range from about 2 to about 20 nm in diameter. Crystals of varying sizes within this range can be achieved by varying the reaction conditions, such as time, temperature, choice of surfactant and precursor to surfactant ratio, as will be apparent to those skilled in the art.
  • the nanocrystals produced by the method of the invention are dispersable in organic solvents such as toluene, chloroform, and hexane and other aromatic, halogenated or aliphatic hydrocarbons.
  • the process of the invention comprising mixing the metal cupferron precursor with the coordinating surfactant, and heating the mixture until decomposition of the precursor occurs, and formation of the desired nanocrystals is achieved.
  • the preferred mode by which this is accomplished is to inject the precursor into a hot liquid surfactant and maintain it at the desired temperature and for a sufficient period of time for the reaction to occur.
  • mixing also includes injection of the precursor into a hot liquid surfactant. Any other means of mixing the two can be used, however.

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Abstract

L'invention concerne une méthode de production de nanocristaux d'oxyde métallique recouverts de tensioactif, qui peuvent être dispersés dans des solvants organiques. La méthode consiste à décomposer un complexe de cupferron métallique représenté par la formule MxCupx, dans laquelle M est métal, et Cup est N-nitrosohydroxylamine N-substitué, en présence d'un tensioactif de coordination. La réaction est conduite à une température comprise entre environ 150 et 400° C, pendant une durée suffisante pour terminer la réaction. L'invention concerne en outre des composés obtenus par cette méthode.
PCT/US2001/050394 2000-10-30 2001-10-25 Methode de production de nanocristaux d'oxyde metallique recouverts de tensioactif, et produits obtenus par cette methode WO2004011700A1 (fr)

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US09/702/219 2000-10-30
US09/702,219 US6440213B1 (en) 1999-10-28 2000-10-30 Process for making surfactant capped nanocrystals
US09/721,126 2000-11-22
US09/721,126 US6984369B1 (en) 1999-10-28 2000-11-22 Process for making surfactant capped metal oxide nanocrystals, and products produced by the process

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