Inorganic Nanomaterials from Nanotubes to Fullerene-Like Nanoparticles

Following the striking discovery of carbon fullerenes and carbon nanotubes, it was realized by the author and his teammates in 1992 that such nanostructures are not unique to carbon. In fact, hollow closed structures are common to probably most if not all inorganic compounds with layered structures, like WS₂, MoSe₂, BN, NiCl₂, Cs₂O and many others. These highly anisotropic compounds suffer from inherent instability when prepared in nano-sizes and close on themselves to form hollow closed structures in the form of inorganic fullerene-like (IF) nanoparticles or nanotubules (INT).

The book takes the reader from the discovery stage, where some fundamental ideas in this field were developed, through the systematic effort to synthesize IF and INT in larger amounts and elucidate their structure. In a few cases, like BN nanotubes and WS₂ IF nanoparticles, new strategies permitted synthesis of macroscopic amounts and subsequently systematic study of their properties, offering thereby numerous applications. The reader is taken through this never-ending evolutionary process with a few recent examples demonstrated. The field stands in the crossroads between solid state inorganic chemistry, nanotechnology, materials chemistry and nanomechanical engineering.

• Discovery Stage: Preamble to the Discovery Phase in the Early Years:
  • Polyhedral and Cylindrical Structures of Tungsten Disulphide (R Tenne, L Margulis, M Genut, and G Hodes)
  • Nested Fullerene-Like Structures (L Margulis, G Salitra, R Tenne, and M Talianker)
  • Nested Polyhedra of MX₂ (M=W,Mo;X=S,Se) Probed by High-Resolution Electron Microscopy and Scanning Tunneling Microscopy (M Hershfinkel, L A Gheber, V Volterra, J L Hutchison, L Margulis, and R Tenne)
  • High-Rate, Gas-Phase Growth of MoS₂ Nested Inorganic Fullerenes and Nanotubes (Y Feldman, E Wasserman, D J Srolovitz, and R Tenne)
  • Morphology of Nested Fullerenes (D J Srolovitz, S A Safran, M Homyonfer, and R Tenne)
  • Doped and Heteroatom-Containing Fullerene-Like Structures and Nanotubes (R Tenne)
  • TEM Study of Chirality in MoS₂ Nanotubes (L Margulis, P Dluzewski, Y Feldman, and R Tenne)
  • Intercalation of Inorganic Fullerene-Like Structures Yields Photosensitive Films and New Tips for Scanning Probe Microscopy (M Homyonfer, B Alperson, Yu Rosenberg, L Sapir, S R Cohen, G Hodes, and R Tenne)
  • Cage Structures and Nanotubes of NiCl₂ (Y Rosenfeld Hacohen, E Grunbaum, R Tenne, J Sloan, and J L Hutchison)
• Synthesis: Preamble to the Synthesis:
  • Bulk Synthesis of Inorganic Fullerene-Like MS₂ (M=Mo,W) from the Respective Trioxides and the Reaction Mechanism (Y Feldman, G L Frey, M Homyonfer, V Lyakhovitskaya, L Margulis, H Cohen, G Hodes, J L Hutchison, and R Tenne)
  • Kinetics of Nested Inorganic Fullerene-Like Nanoparticle Formation (Y Feldman, V Lyakhovitskaya, and R Tenne)
  • Growth Mechanism of MoS₂ Fullerene-Like Nanoparticles by Gas Phase Synthesis (A Zak, Y Feldman, V Alperovich, R Rosentsveig, and R Tenne)
  • Growth of WS₂ Nanotubes Phases (A Rothschild, J Sloan, and R Tenne)
  • New Reactor for Production of Tungsten Disulfide Hollow Onion-Like (Inorganic Fullerene-Like) Nanoparticles (Y Feldman, A Zak, R Popovitz-Biro, and R Tenne)
  • Stability of Metal Chalcogenide Nanotubes (G Seifert, T Köhler, and R Tenne)
  • Synthesis of NbS₂ Nanoparticles with (Nested) Fullerene-Like Structure (IF) (C Schuffenhauer, R Popovitz-Biro, and R Tenne)
  • Synthesis of SnS₂/SnS Fullerene-Like Nanoparticles: A Superlattice with Polyhedral Shape (S Y Hong, R Popovitz-Biro, Y Prior, and R Tenne)
  • Preparation and Structural Characterization of Stable Cs₂O Closed-Cage Structures (A Albu-Yaron, T Arad, R Popovitz-Biro, M Bar-Sadan, Y Prior, M Jansen, and R Tenne)
  • Synthesis of Fullerene-Like MoS₂ Nanoparticles and Their Tribological Behavior (R Rosentsveig, A Margolin, A Gorodnev, R Popovitz-Biro, Y Feldman, L Rapoport, Y Novema, G R Samorodnitzky-Naveh, and R Tenne)
  • Insight into the Growth Mechanism of WS₂ Nanotubes in the Scaled-Up Fluidized Bed-Reactor (A Zak, L Sallacan-Ecker, A Margolin, M Genut, and R Tenne)
  • Core–Shell PbI₂@WS₂ Inorganic Nanotubes from Capillary Wetting (R Kreizman, S-Y Hong, J Sloan, R Popovitz-Biro, A Albu-Yaron, G Tobias, B Ballesteros, B G Davis, M L H Green, and R Tenne)
  • Synthesis of Copious Amounts of SnS₂ and SnS₂/SnS Nanotubes with Ordered Superstructures (G Radovsky, R Popovitz-Biro, M Staiger, K Gartsman, C Thomsen, T Lorenz, G Seifert, and R Tenne)
  • Controlled Doping of MS₂ (M=W,Mo) Nanotubes and Fullerene-Like Nanoparticles (L Yadgarov, R Rosentsveig, G Leitus, A Albu-Yaron, A Moshkovich, V Perfilyev, R Vasic, A I Frenkel, A Enyashin, G Seifert, L Rapoport, and R Tenne)
  • New High-Temperature Pb-Catalyzed Synthesis of Inorganic Nanotubes (O Brontbein, D G Stroppa, R Popovitz-Biro, A Albu-Yaron, M Levy, D Feuerman, L Houben, R Tenne, and J M Gordon)
• Characterization: Preamble to the Characterization:
  • Optical-Absorption Spectra of Inorganic Fullerenelike MS₂ (M=Mo,W) (G L Frey, S Elani, M Homyonfer, Y Feldman, and R Tenne)
  • Scanning Tunneling Microscope Induced Crystallization of Fullerene-Like MoS₂ (M Homyonfer, Y Mastai, M Hershfinkel, V Volterra, J L Hutchison, and R Tenne)
  • Raman and Resonance Raman Investigation of MoS₂ Nanoparticles (G L Frey, R Tenne, M J Matthews, M S Dresselhaus, and G Dresselhaus)
  • Alkali Metal Intercalated Fullerene-Like MS₂ (M=W,Mo) Nanoparticles and Their Properties (A Zak, Y Feldman, V Lyakhovitskaya, G Leitus, R Popovitz-Biro, E Wachtel, H Cohen, S Reich, and R Tenne)
  • On the Mechanical Behavior of WS₂ Nanotubes Under Axial Tension and Compression (I Kaplan-Ashiri, S R Cohen, K Gartsman, V Ivanovskaya, T Heine, G Seifert, I Wiesel, H D Wagner, and R Tenne)
  • Structure and Stability of Molybdenum Sulfide Fullerenes (A N Enyashin, S Gemming, M Bar-Sadan, R Popovitz-Biro, S Y Hong, Y Prior, R Tenne, and G Seifert)
  • Toward Atomic-Scale Bright-Field Electron Tomography for the Study of Fullerene-Like Nanostructures (M Bar-Sadan, L Houben, S G Wolf, A Enyashin, G Seifert, R Tenne, and K Urban)
  • Intercalation of Alkali Metal in WS₂ Nanoparticles, Revisited (F Kopnov, Y Feldman, R Popovitz-Biro, A Vilan, H Cohen, A Zak, and R Tenne)
  • Atom by Atom: HRTEM Insights into Inorganic Nanotubes and Fullerene-Like Structures (M Bar-Sadan, L Houben, A Enyashin, G Seifert, and R Tenne)
  • Torsional Stick-Slip Behavior in WS₂ Nanotubes (K S Nagapriya, O Goldbart, I Kaplan-Ashiri, G Seifert, R Tenne, and E Joselevich)
  • MoS₂ Hybrid Nanostructures: From Octahedral to Quasi-Spherical Shells within Individual Nanoparticles (A Albu-Yaron, M Levy, R Tenne, R Popovitz-Biro, M Weidenbach, M Bar-Sadan, L Houben, A N Enyashin, G Seifert, D Feuermann, E A Katz, and J M Gordon)
  • Friction Mechanism of Individual Multilayered Nanoparticles (O Tevet, P Von-Huth, R Popovitz-Biro, R Rosentsveig, H D Wagner, and R Tenne)
• Application: Preamble for the Applications:
  • Hollow Nanoparticles of WS₂ as Potential Solid-State Lubricants (L Rapoport, Yu Bilik, Y Feldman, M Homyonfer, S R Cohen, and R Tenne)
  • Inorganic Fullerene-Like Material as Additives to Lubricants: Structure-Function Relationship (L Rapoport, Y Feldman, M Homyonfer, H Cohen, J Sloan, J L Hutchison, and R Tenne)
  • WS₂ Nanotubes as Tips in Scanning Probe Microscopy (A Rothschild, S R Cohen, and R Tenne)
  • Slow Release of Fullerene-Like WS₂ Nanoparticles from Fe–Ni Graphite Matrix: A Self-Lubricating Nanocomposite (L Rapoport, M Lvovsky, I Lapsker, V Leshchinsky, Yu Volovik, Y Feldman, A Margolin, R Rosentsveig, and R Tenne)
  • Wear and Friction of Ni-P Electroless Composite Coating Including Inorganic Fullerene-Like WS₂ Nanoparticles (W X Chen, J P Tu, Z D Xu, R Tenne, R Rosenstveig, W L Chen, and H Y Gan)
  • Shock-Wave Resistance of WS₂ Nanotubes (Y Q Zhu, T Sekine, K S Brigatti, S Firth, R Tenne, R Rosentsveig, H W Kroto, and D R M Walton)
  • Self-Lubricating Coatings Containing Fullerene-Like WS₂ Nanoparticles for Orthodontic Wires and Other Possible Medical Applications (A Katz, M Redlich, L Rapoport, H D Wagner, and R Tenne)
  • The Effect of Tungsten Sulfide Fullerene-Like Nanoparticles on the Toughness of Epoxy Adhesives (M Shneider, H Dodiuk, S Kenig, and R Tenne)
  • High Lubricity of Re-Doped Fullerene-Like MoS₂ Nanoparticles (L Rapoport, A Moshkovich, V Perfilyev, A Laikhtman, I Lapsker, L Yadgarov, R Rosentsveig, and R Tenne)