Process and apparatus for producing inorganic fullerene-like nanoparticles

• US 7,641,886 B2
• Filed: 04/06/2006
• Issued: 01/05/2010
• 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:
  US11/911,095
• Publication Number:
  US 20080170984A1
• Time in Patent Office: 1,370 Days
• Field of Search: 422/110, 422/111, 422/129, 422/187, 422/198, 423/508, 423/509, 423/511, 423/561.1, 508/108, 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 (INi) selected from metal halide, metal carbonyl, organo-metallic compound and metal oxyhalide vapor into a reaction chamber (12) towards a reaction zone to interact with a flow of at least one chalcogen material (IN2) 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 and also exhibiting excellent tribological behavior. The present invention further provides an apparatus for preparing various IF nanostructures.

Claims

1. A process for producing inorganic fullerene-like (IF) metal chalcogenide nanoparticles, the process comprising:

(a) preparing a metal precursor vapor, selected from the group consisting of 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 in a direction opposite to that of the metal precursor vapor flow, and controlling temperature conditions in said reaction zone such as to enable the formation of inorganic fullerene-like (IF) metal chalcogenide nanoparticle product.

2. A process according to claim 1, further comprising:

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 chalcogenide 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.

3. The process according to claim 1, wherein said chalcogen material contains hydrogen.

4. The process according to claim 3, wherein said chalcogen material is selected from the group consisting of H₂S, H₂Se and H₂Te and mixtures thereof.

5. The process according to claim 1, wherein said metal is selected from the group consisting of In, Ga, Sn and a transition metal selected from the group consisting of Mo, W, V, Zr, Hf, Pt, Pd, Re, Nb, Ta, Ti, Cr and Ru.

6. The process according to claim 1, wherein said metal precursor is selected from the group consisting of 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, pPlatinum (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, and zirconium iodide.

7. The process according to claim 1, wherein said metal precursor is selected from the group consisting of 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.

8. The process according to claim 1, wherein said metal chalcogenide is selected from the group consisting of 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.

9. The process according to claim 1, comprising 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 degrees below the boiling point and up to the boiling point of said metal precursor.

10. The process according to claim 1, wherein the temperature within the reaction zone is in the range of 500 to 900°

C.

11. Fullerene-like (IF) metal chalcogenide nanoparticles obtainable by the process of claim 1.

12. TiS₂ nanoparticles obtainable by the process of claim 1.

15. Inorganic fullerene-like (IF) MoS₂ nanoparticles obtainable by the process of claim 1.

25. Inorganic fullerene-like (IF) WS₂ nanoparticles obtainable by the process of claim 1.

13. TiS₂ nanoparticles having fullerene-like structure and a diameter size of between 10-300 nm.

14. TiS₂ nanoparticles according to claim 13, comprising a hollow core of a diameter substantially not exceeding 5-10 nm and of about 50-120 molecular layers.

16. An apparatus for preparing IF nanostructures, the apparatus comprising:

a reaction chamber having a reaction zone, inlets for inputting reacting gases and defining a vertical path thereof towards the reaction zone, and an outlet;

a separate evaporation chamber for separately preparing a precursor vapor being one of the reacting gases to be input to the reaction chamber; and

a control unit configured and operable for controlling the precursor vapor flow from the evaporation chamber into and through the reaction chamber.

17. The apparatus of claim 16, wherein the reaction chamber is configured to be vertically oriented during the apparatus operation, said gas inlets being located at top and bottom sides of the chamber so as to direct the precursor vapor and the other reacting gas along vertical paths in opposite directions towards the reaction zone where the gases meet and react with each other.

18. The apparatus of claim 17, comprising an oven configured to enable installation of the reaction chamber therein, the oven being configured to define two temperature source regions in the reaction chamber.

19. The apparatus of claim 16, wherein the control unit comprises a valve arrangement associated with the evaporation chamber, said valve arrangement being configured to selectively provide a flow of a clean inert gas substantially free of the precursor vapor.

20. Inorganic fullerene-like (IF) metal chalcogenide nanoparticles having a plurality of molecular layers and characterized in that the number of said molecular layers exceeds 40.

21. IF metal nanoparticles according to claim 20, having no or a very small hollow core.

22. IF metal nanoparticles according to claim 20, comprising a hollow core of a diameter substantially not exceeding 5-10 nm and of about 50-120 molecular layers.

23. A product comprising a plurality of inorganic fullerene-like (IF) metal chalcogenide nanoparticles, a substantial portion of which having a number of molecular layers exceeding 40.

24. A product according to claim 23, wherein said substantial portion is at least 40% out of the total number of the IF nanoparticles.