Process and apparatus for producing inorganic fullerene-like nanoparticles

• US 7,959,891 B2
• Filed: 01/04/2010
• Issued: 06/14/2011
• Est. Priority Date: 04/07/2005
• Status: Active Grant

• Current Assignee: A.Y.Y.T.-Technological Applications And Data Update, Ltd., Yeda Research and Development Co. Ltd. (Weizmann Institute of Science)
• Original Assignee: A.Y.Y.T.-Technological Applications And Data Update, Ltd., Yeda Research and Development Co. Ltd. (Weizmann Institute of Science)
• Inventors: Rapoport, Lev, Tenne, Reshef, Margolin, Alexander, Popovitz-Biro, Ronit
• Primary Examiner(s): Vanoy; Timothy C
• Application Number:
  US12/651,912
• Publication Number:
  US 20100172823A1
• Time in Patent Office: 526 Days
• Field of Search: 423/508, 423/509, 423/511, 423/561.1, 508/108, 508/110, 508/141, 508/165, 508/166, 508/167, 977/734, 977/773, 977/775, 977/810
• US Class Current: 423/508
• CPC Class Codes: B01J 19/0013 Controlling the temperature of the process
• CPC Class Codes: B01J 2219/182 horizontal
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 19/007 Tellurides or selenides of metals C01B19/002 takes precedence
• CPC Class Codes: C01G 1/12 Sulfides
• CPC Class Codes: C01G 23/007 Titanium sulfides C01G23/001 takes precedence
• CPC Class Codes: C01G 39/06 Sulfides
• CPC Class Codes: C01G 41/00 Compounds of tungsten
• CPC Class Codes: C01P 2004/34 hollow
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: Y10S 977/734 Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
• CPC Class Codes: Y10S 977/773 Nanoparticle, i.e. structure having three dimensions of 100 nm or less
• CPC Class Codes: Y10S 977/775 Nanosized powder or flake, e.g. nanosized catalyst
• CPC Class Codes: Y10S 977/81 Of specified metal or metal alloy composition

Abstract

The present invention provides a process for obtaining fullerene-like metal chalcogenide nanoparticles, comprising feeding a metal precursor selected from metal halide, metal carbonyl, organo-metallic compound and metal oxyhalide vapor into a reaction chamber towards a reaction zone to interact with a flow of at least one chalcogen material in gas phase, the temperature conditions in said reaction zone being such to enable the formation of the fullerene-like metal chalcogenide nanoparticles product. The present invention further provides novel IF metal chalcogenides nanoparticles with spherical shape and optionally having a very small or no hollow core exhibiting excellent tribological behaviour. The present invention further provides an apparatus for preparing various IF nanostructures.

Claims

1. A product comprising inorganic fullerene-like (IF) metal chalcogenide nanoparticles, the metal being selected from In, Ga, Sn and a transition metal, the transition metal being selected from Mo, W, V, Zr, Hf, Pt, Pd, Re, Nb, Ta, Ti, Cr and Ru, the nanoparticles comprising a plurality of molecular layers, a substantial portion of said nanoparticles having more than 40 molecular layers.

2. The product of claim 1, wherein the chalcogen is selected from S, Se or Te.

3. The product of claim 1, comprising the nanoparticles selected from TiS₂, TiSe₂, TiTe₂, WS₂, WSe₂, WTe₂, MoS₂, MoSe₂, MoTe₂, SnS₂, SnSe₂, SnTe₂, RuS₂, RuSe₂, RuTe₂, GaS, GaSe, GaTe, In₂S₃, In₂Se₃, In₂Te₃, InS, InSe, Hf₂S, HfS₂, ZrS₂, VS₂, ReS₂ and NbS₂.

4. The product of claim 1, being a nanocomposite comprising a mixture of the nanoparticles of at least two types selected from TiS₂, TiSe₂, TiTe₂, WS₂, WSe₂, WTe₂, MoS₂, MoSe₂, MoTe₂, SnS₂, SnSe₂, SnTe₂, RuS₂, RuSe₂, RuTe₂, GaS, GaSe, GaTe, In₂S₃, In₂Se₃, In₂Te₃, InS, InSe, Hf₂S, HfS₂, ZrS₂, VS₂, ReS₂ and NbS₂.

5. The product of claim 1 comprising a lubricant comprising the nanoparticles selected from TiS₂, TiSe₂, TiTe₂, WS₂, WSe₂, WTe₂, MoS₂, MoSe₂, MoTe₂, SnS₂, SnSe₂, SnTe₂, RuS₂, RuSe₂, RuTe₂, GaS, GaSe, GaTe, In₂S₃, In₂Se₃, In₂Te₃, InS, InSe, Hf₂S, HfS₂, ZrS₂, VS₂, ReS₂ and NbS₂.

6. The product of claim 1, wherein the nanoparticles have a diameter of about 10-300 nm.

7. The product of claim 1, wherein said nanoparticles have no or a very small hollow core.

11. The product of claim 1, produced by the following process:

(a) preparing a metal precursor vapor, selected from metal halide vapor, metal carbonyl vapor, organo-metallic compound vapor and metal oxyhalide vapor, in a separate evaporation chamber;

(b) feeding the metal precursor vapor from said separate evaporation chamber into a reaction chamber to flow towards a reaction zone in said reaction chamber along a vertical path to interact with at least one chalcogen material in gas phase flowing towards said reaction zone in a vertical path, and controlling temperature conditions in said reaction zone such as to enable the formation of inorganic fullerene-like (IF) metal chalcogenide nanoparticle product.

12. The product of claim 11, wherein said chalcogen material is selected from H₂S, H₂Se and H₂Te and mixtures thereof.

13. The product of claim 11, wherein said process further comprises:

controllably varying the flow of said metal precursor vapor into said reaction chamber to control the amount, morphology and size of the so-produced inorganic fullerene-like (IF) metal calcogenide nanoparticles in solid form, the flow of the vapor of the metal precursor being controlled by at least one of the following;

(i) the rate of the flow of an inert gas driving said vapor into the reaction chamber;

(ii) the temperature used for heating the metal precursor to obtain a vapor of said metal precursor.

14. The product of claim 11, wherein said metal precursor is selected from the following compounds:

Chromium carbonyl, Chromium (III) iodide, Chromium (IV) chloride, Chromium (IV) fluoride, Chromium (V) fluoride, Chromium (VI) fluoride, Cromyl chloride, Trimethylgallium, Hafnium bromide, Hafnium chloride, Hafnium iodide, Trimethylindium, Molybdenum carbonyl, Molybdenum (V) chloride, Molybdenum (V) fluoride, Molybdenum (V) oxytrichloride, Molybdenum (VI) fluoride, Molybdenum (VI) oxytetrafluoride, Molybdenum (VI) oxytetrachloride, Molybdenum (VI) dioxydichloride, Niobium (IV) chloride, Niobium (IV) fluoride, Niobium (IV) iodide, Niobium (V) bromide, Niobium (V) chloride, Niobium (V) fluoride, Niobium (V) iodide, Niobium (V) oxybromide, Niobium (V) oxychloride, Niobium (V) dioxyfluoride, Palladium (II) bromide, Palladium (II) iodide, Platinum (II) bromide, Platinum (II) chloride, Platinum (II) iodide, Platinum (III) bromide, Platinum (III) chloride, Platinum (IV) bromide, Platinum (IV) chloride, Platinum (IV) fluoride, Platinum (IV) iodide, Platinum (VI) fluoride, Rhenium carbonyl, Rhenium (III) bromide, Rhenium (III) chloride, Rhenium (III) iodide, Rhenium (IV) chloride, Rhenium (IV) fluoride, Rhenium (V) bromide, Rhenium (V) chloride, Rhenium (V) fluoride, Rhenium (VI) chloride, Rhenium (VI) fluoride, Rhenium (VI) oxytetrachloride, Rhenium (VI) oxytetrafluoride, Rhenium (VII) fluoride, Rhenium (VII) trioxycloride, Rhenium (VII) trioxyfluoride, Rhenium (VII) dioxytrifluoride, Rhenium (VII) oxypentafluoride, Ruthenium dodecacarbonyl, Ruthenium (III) bromide, Ruthenium (III) chloride, Ruthenium (III) fluoride, Ruthenium (III) iodide, Ruthenium (IV) fluoride, Ruthenium (V) fluoride, Tantalum (V) bromide, Tantalum (V) chloride, Tantalum (V) fluoride, Tantalum (V) iodide, Titanium (III) bromide, Titanium (III) chloride, Titanium (IV) bromide, Titanium (IV) chloride, Titanium (IV) fluoride, Titanium (IV) iodide, Tungsten carbonyl, Tungsten (II) bromide, Tungsten (II) chloride, Tungsten (II) iodide, Tungsten (III) bromide, Tungsten (III) chloride, Tungsten (V) bromide, Tungsten (V) chloride, Tungsten (V) fluoride, Tungsten (V) oxytribromide, Tungsten (V) oxytrichloride, Tungsten (VI) bromide, Tungsten (VI) chloride, Tungsten (VI) dioxydibromide, Tungsten (VI) dioxydichloride, Tungsten (VI) dioxydiiodide, Tungsten (VI) fluoride, Tungsten (VI) oxytetrabromide, Tungsten (VI) oxytetrachloride, Tungsten (VI) oxytetrafluoride, Vanadium carbonyl, Vanadium (IV) chloride, Vanadium (IV) fluoride, Vanadium (V) fluoride, Vanadyl bromide, Vanadyl chloride, Vanadyl dibromide, Vanadyl dichloride, Vanadyl difluoride, Vanadyl tribromide, Vanadyl trichloride, Vanadyl trifluoride, Zirconium chloride, Zirconium fluoride, Zirconium iodide.

15. The product of claim 11, wherein said metal precursor is selected from TiCl₄, WCl₆, WCl₅, WCl₄, WBr₅, WO₂Cl₂, WOCl₄, MoCl₅, Mo(CO)₅ and W(CO)₆, Ga(CH₃)₃, W(CH₂CH₃)₅ and In(CH₃)₃.

16. The product of claim 11, wherein said metal chalcogenide is selected from TiS₂, TiSe₂, TiTe₂, WS₂, WSe₂, WTe₂, MoS₂, MoSe₂, MoTe₂, SnS₂, SnSe₂, SnTe₂, RuS₂, RuSe₂, RuTe₂, GaS, GaSe, GaTe, In₂S₃, In₂Se₃, In₂Te₃, InS, InSe, Hf₂S, HfS₂, ZrS₂, VS₂, ReS₂ and NbS₂.

17. The product of claim 11, wherein said process comprises controlling the flow of the vapor of the metal precursor into said reaction chamber by controlling the temperature used for heating the metal precursor to be in the range of between 50 degree below the boiling point and up to the boiling point of said metal precursor.

18. The product of claim 11, wherein the temperature within the reaction zone is in the range of 500 to 900°

C.

19. The product of claim 1, wherein the nanoparticles have a hollow core of a diameter substantially not exceeding 5-10 nm.

8. A product comprising inorganic fullerene-like (IF) metal chalcogenide nanoparticles, the metal being selected from In, Ga, Sn and a transition metal, the transition metal being selected from Mo, W, V, Zr, Hf, Pt, Pd, Re, Nb, Ta, Ti, Cr and Ru, the nanoparticles comprising a plurality of molecular layers, an interlayer distance substantially not exceeding 1 nm.

9. The product of claim 8, being a nanocomposite comprising a mixture of the nanoparticles of at least two types selected from TiS₂, TiSe₂, TiTe₂, WS₂, WSe₂, WTe₂, MoS₂, MoSe₂, MoTe₂, SnS₂, SnSe₂, SnTe₂, RuS₂, RuSe₂, RuTe₂, GaS, GaSe, GaTe, In₂S₃, In₂Se₃, In₂Te₃, InS, InSe, Hf₂S, HfS₂, ZrS₂, VS₂, ReS₂ and NbS₂.

10. A lubricant comprising the inorganic fullerene-like (IF) metal chalcogenide nanoparticles, the metal being selected from In, Ga, Sn and a transition metal, the transition metal being selected from Mo, W, V, Zr, Hf, Pt, Pd, Re, Nb, Ta, Ti, Cr and Ru, the nanoparticles comprising a plurality of molecular layers, characterized by at least one of the following:

a substantial portion of said nanoparticles have more than 40 molecular layers; and

the nanoparticles have an interlayer distance substantially not exceeding 1 nm.