Abstract
We have proposed in 1992 that nanoparticles of layered compounds will be unstable against folding and close into fullerene-like structures and nanotubes (IF). Nanotubes and fullerene-like structures were prepared from numerous compounds with layered and recently also non-layered structure by various groups. Much progress has been achieved in the synthesis of inorganic nanotubes and fullerene-like nanoparticles of WS2 and MoS2 and many other metal dichalcogenides over the last few years. Substantial progress has been accomplished in the use of such nanoparticles for tribological applications and lately for impact resilient nanocomposites. These tests indicated that IF-MoS2 and IF-WS2 are heading for large scale applications in the automotive, machining, aerospace, electronics, defense, medical and numerous other kinds of industries. A few products based on these nanoparticles have been recently commercialized by “ApNano Materials, Inc”. Novel applications of inorganic nanotubes and fullerene-like nanoparticles in the fields of catalysis; microelectronics; Li rechargeable batteries; medical and opto-electronics will be discussed.
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H.W. Kroto, J.R. Heath, S.C. O’Brein, R.F. Curl, R.E. Smalley: C60: Buckminsterfullerene. Nature 318, 162 (1985).
S. Iijima: Helical microtubules of graphitic carbon. Nature 354, 56 (1991).
W. Krätschmer, L.D. Lamb, K. Fostiropoulos, D.R. Huffman: Solid C60—A new form of carbon. Nature 347, 354 (1990).
R. Tenne, L. Margulis, M. Genut, G. Hodes: Polyhedral and cylindrical structures of tungsten disulphide. Nature 360, 444 (1992).
R.R. Chianelli, E.B. Prestridge, T.A. Pecoraro, J.P. DeNeufville: Molybdenum disuflide in the poorly crystalline “Rag” structure. Science 203, 1105 (1979).
J.V. Sanders: Structure of catalytic particles. Ultramicroscopy 20, 33 (1986).
L. Margulis, G. Salitra, R. Tenne, M. Talianker: Nested fullerene-like structures. Nature 365, 113 (1993).
Y. Feldman, E. Wasserman, D.J. Srolovitz, R. Tenne: High rate, gas phase growth of MoS2 nested inorganic fullerenes and nanotubes. Science 267, 222 (1995).
Y. Rosenfeld Hacohen, E. Grunbaum, R. Tenne, J. Sloan, J.L. Hutchison: Cage structures and nanotubes of NiCl2. Nature 395, 336 (1998).
Y. Rosenfeld Hacohen, R. Popovitz-Biro, E. Grunbaum, Y. Prior, R. Tenne: Vapor-liquid-solid (VLS) growth of NiCl2 nanotubes via reactive gas laser ablation. Adv. Mater. 14, 1075 (2002).
A. Albu-Yaron, T. Arad, R. Popovitz-Biro, M. Bar-Sadan, Y. Prior, M. Jansen, R. Tenne: Closed-cage (fullerene-like) structures of Cs2O. Angew. Chem., Int. Ed. Engl. 44, 4169 (2005).
Y. Feldman, G.L. Frey, M. Homyonfer, V. Lyakhovitskaya, L. Margulis, H. Cohen, G. Hodes, J.L. Hutchison, R. Tenne: Bulk synthesis of inorganic fullerene-like MS2 (M = Mo, W) from the respective trioxides and the reaction mechanism. J. Am. Chem. Soc. 118, 5362 (1996).
J. Goldberger, R. He, Y. Zhang, S. Lee, H. Yan, H.J. Choi, P. Yang: Single-crystal gallium nitride nanotubes. Nature 422, 599 (2003).
L.W. Yin, Y. Bando, Y.C. Zhu, M.S. Li, C.C. Tang, D. Golberg: Single crytalline AlN nanotubes with carbon layer coating on the outer and inner surfaces via multiwall carbon nanotube-template-induced route. Adv. Mater. 17, 213 (2005).
L.W. Yin, Y. Bando, J.H. Zhan, M.S. Li, D. Golberg: Self-assembled highly faceted wurzite-type ZnS single-crystalline nanotubes with hexagonal cross-sections. Adv. Mater. 17, 1972 (2005).
A. Rothschild, J. Sloan, R. Tenne: The growth of WS2 nanotubes phases. J. Am. Chem. Soc. 122, 5169 (2000).
Y.Q. Zhu, W.K. Hsu, N. Grobert, B.H. Chang, M. Terrones, H. Terrones, H.W. Kroto, D.R.M Walton: Production of WS2 nanotubes. Chem. Mater. 12, 1190 (2000).
W.K. Hsu, B.H. Chang, Y.Q. Zhu, W.Q. Han, H. Terrones, M. Terrones, N. Grobert, A.K. Cheetham, H.W. Kroto, D.R.M Walton: An alternative route to MoS2 nanotubes. J. Am. Chem. Soc. 122, 10155 (2000).
J. Cumings, A. Zettl: Mass-production of boron nitride double-wall nanotubes and nanococoons. Chem. Phys. Lett. 316, 211 (2000).
M.E. Spahr, P. Bitterli, R. Nesper, M. Müller, F. Krumeich, H.U. Nissen: Redox-active nanotubes of vanadium oxide. Angew. Chem., Int. Ed. Engl. 37, 1263 (1998).
G.H. Du, Q. Chen, R.C. Che, Z.Y. Yuan, L.M. Peng: Preparation and structure analysis of titanium oxide nanotubes. Appl. Phys. Lett. 79, 3702 (2001).
Y. Feldman, A. Zak, R. Popovitz-Biro, R. Tenne: New reactor for production of tungsten disulfide hollow onion-like (inorganic fullerene-like) nanoparticles. Solid State Sci. 2, 663 (2000).
A. Zak, Y. Feldman, V. Alperovich, R. Rosentsveig, R. Tenne: Growth mechanism of MoS2 fullerene-like nanoparticles by the gas phase synthesis. J. Am. Chem. Soc. 122, 11108 (2000).
L. Pauling: The structure of the chlorites. Proc. Natl. Acad. Sci. U.S.A. 16, 578 (1930).
N.N. Greenwood, A. Earnshaw: Chemistry of the Elements (Pergamon, Oxford, UK,1990).
P.W. Fowler, D.E. Manolopoulos: Ann. Atlas of Fullerenes (Oxford University Press, Cambridge, UK,1995).
M. Cote, M.L. Cohen, D.J. Chadi: Theoretical study of the structural and electronic properties of GaSe nanotubes. Phys. Rev. B 58, R4277 (1998).
G. Seifert, H. Terrones, M. Terrones, G. Jungnickel, T. Frauenheim: Structure and electronic properties of MoS2 nanotubes. Phys. Rev. Lett. 85, 146 (2000).
A.N. Enyashin, N.I. Medvedeva, Yu.E. Medvedeva, A.L. Ivanovskii: Electronic structure and magnetic states of crystalline and fullerene-like forms of nickel dichloride NiCl2. Phys. Solid State 47, 527 (2005).
M. Remskar, A. Mrzel, Z. Skraba, A. Jesih, M. Ceh, J. Demsar, P. Stadelmann, F. Levy, D. Mihailovic: Self-assembly of subnanometer-diameter single-wall MoS2 nanotubes. Science 292, 479 (2001).
P.A. Parilla, A.C. Dillon, K.M. Jones, G. Riker, D.L. Schulz, D.S. Ginley, M.J. Heben: The first inorganic fullerenes? Nature 397, 114 (1999).
P.A. Parilla, A.C. Dillon, B.A. Parkinson, K.M. Jones, J. Alleman, G. Riker, D.S. Ginley, M.J. Heben: Formation of nanooctahedra in molybdenum disulfide and molybdenum diselenide using pulsed laser vaporization. J. Phys. Chem. B 108, 6197 (2004).
M. Zhao, Y. Xia, F. Li, R.Q. Zhang, S.T. Lee: Strain energy and electronic structures of silicon carbide nanotubes: Density-functional calculations. Phys. Rev. B 71, 085312 (2005).
N.G. Chopra, A. Zettl: Measurement of the elastic modulus of a multi-wall boron nitride nanotube. Solid State Commun. 105, 297 (1998).
I. Kaplan-Ashir, S.R. Cohen, K. Gartsman, R. Rosentsveig, G. Seifert, R. Tenne: Mechanical behavior of WS2 nanotubes. J. Mater. Res. 19, 454 (2004).
I. Kaplan-Ashir, S.R. Cohen, K. Gartsman, V. Ivanovskaya, T. Heine, G. Seifert, I. Kanevsky, H.D. Wagner, R. Tenne: What makes the mechanical properties of (WS2) nanotubes distinguishable from those of classical macroscopic objects. Proc. Natl. Acad. Sci. U.S.A. 103, 523 (2006).
L. Rapoport, N. Fleischer, R. Tenne: Applications of WS2 (MoS2) inorganic nanotubes and fullerene-like nanoparticles for solid lubrication and for structural nanocomposites. J. Mater. Chem. 15, 1782 (2005).
C.M. Zelenski, P.K. Dorhout: Template synthesis of near-monodisperse microscale nanofibers and anotubules. J. Am. Chem. Soc. 120, 734 (1998).
M. Remskar, Z. Skraba, F. Cléton, R. Sanjinés, F. Lévy: MoS2 as microtubes. Appl. Phys. Lett. 69, 351 (1996).
M. Remskar, Z. Skraba, C. Ballif, R. Sanjinés, F. Lévy: Stabilization of the rhombohedral polytype in MoS2 and WS2 microtubes: TEM and AFM study. Surf. Sci. 435, 637 (1999).
H. Masuda, K. Fukuda: Ordered metal nanohole arrays made by a 2-step replication of honeycomb structures of anodic alumina. Science 268, 1466 (1995).
Y.D. Li, X.L. Li, R.R. He, J. Zhu, Z.X. Deng: Artificial lamellar mesostructures to WS2 nanotubes. J. Am. Chem. Soc. 124, 1411 (2002).
Y.Q. Zhu, W.K. Hsu, H. Terrones, N. Grobert, B.H. Chang, M. Terrones, B.Q. Wei, H.W. Kroto, D.R.M Walton, C.B. Boothroyd, I. Kinloch, G.Z. Chen, A.H. Windled, D.J. Frayd: Morphology, structure and growth of WS2 nanotubes. J. Mater. Chem. 10, 2570 (2000).
R. Rosentsveig, A. Margolin, Y. Feldman, R. Popovitz-Biro, R. Tenne: WS2 nanotube bundles and foils. Chem. Mater. 14, 471 (2002).
M.J. Yacaman, H. Lopez, P. Santiago, D.H. Galvan, I.L. Garzon, A. Reyes: Studies of MoS2 structures produced by electron irradiation. Appl. Phys. Lett. 69, 1065 (1996).
D. Vollath, D.V. Szabo: Nanoparticles from compounds with layered structures. Acta Mater. 48, 953 (2000).
C. Schuffenhauer, R. Popovitz-Biro, R. Tenne: Synthesis of NbS2 nanoparticles with (nested) fullerene-like structure (IF). J. Mater. Chem. 12, 1587 (2002).
J. Chen, S.L. Li, Z.L. Tao, F. Gao: Low-temperature synthesis of titanium disulfide nanotubes. Chem. Commun.980 (2003).
A. Margolin, R. Popovitz-Biro, A. Albu-Yaron, L. Rapoport, R. Tenne: Inorganic fullerene-like nanoparticles of TiS2. Chem. Phys. Lett. 411, 162 (2005).
M. Chhowalla, G.A.J Amaratunga: Thin films of fullerene-like MoS2 nanoparticles with ultra-low friction and wear. Nature 407, 164 (2000).
N. Sano, H. Wang, M. Chhowalla, I. Alexandrou, G.A.J Amaratunga, M. Naito, T. Kanki: Fabrication of inorganic molybdenum disulfide fullerenes by arc in water. Chem. Phys. Lett. 368, 331 (2003).
H.A. Therese, F. Rocker, A. Reiber, J. Li, M. Stepputat, G. Glasser, U. Kolb, W. Tremel: VS2 nanotubes containing organic-amine templates from the NT-VOx precursors and reversible copper intercalation in NT-VS2. Angew. Chem., Int. Ed. Engl. 44, 202 (2005).
P.M. Ajayan, O. Stephan, P. Redlich, C. Colliex: Carbon nanotubes as removable templates for metal oxide nanocomposites and nanostructures. Nature 375, 564 (1995).
P. Hoyer: Formation of a titanium dioxide nanotube array. Langmuir 12, 1411 (1996).
T. Kasuga, M. Hiramatsu, A. Hoson, T. Sekino, K. Niihara: Formation of titanium oxide nanotube. Langmuir 14, 3160 (1998).
A.R. Armstrong, J. Canales, P.G. Bruce: WO2Cl2 nanotubes and nanowires. Angew. Chem., Int. Ed. Engl. 43, 4899 (2004).
G.B. Saupe, C.C. Waraksa, H.N. Kim, Y.J. Han, D.M. Kaschak, D.M. Skinner, T.E. Mallouk: Nanoscale tubules formed by exfoliation of potassium hexaniobate. Chem. Mater. 12, 1556 (2000).
S.V. Krivovichev, V. Kahlenberg, R. Kaindl, E. Mersdorf, I.G. Tananaev, B.F. Myasoedov: Nanoscale tubules in uranyl selenates. Angew. Chem., Int. Ed. Engl. 44, 1134 (2005).
R. Popovitz-Biro, A. Twersky, Y. Rosenfeld Hacohen, R. Tenne: Nanoparticles of CdCl2 with closed cage structure. Isr. J. Chem. 41, 7 (2001).
L.Y. Yin, Y. Bando, D. Golberg, M.S. Li: Growth of single crystal InN nanotubes and nanowires by controlled-carbonitridation reaction route. Adv. Mater. 16, 1833 (2004).
J. Hu, Y. Bando, Z. Liu: Synthesis of gallium filled gallium oxide-zinc oxide composite coaxial nanotubes. Adv. Mater. 15, 1000 (2003).
M.R. Ghadiri, J.R. Granja, R.A. Milligan, D.E. McRee, N. Khazanovich: Self-assembling organic nanotubes based on a cyclic peptide architecture. Nature 366, 324 (1993).
M. Reches, E. Gazit: Casting metal nanowires within discrete self-assembled peptide nanotubes. Science 300, 625 (2003).
F. Jensen, H. Toftlund: Structure and stability of C24 and B12N12 isomers. Chem. Phys. Lett. 201, 89 (1993).
T. Oku, A. Nishiwaki, I. Narita, M. Gonda: Formation and structure of B24N24 clusters. Chem. Phys. Lett. 380, 620 (2003).
A. Rubio, J.L. Corkill, M.L. Cohen: Theory of graphitic boron nitride nanotubes. Phys. Rev. B 49, 5081 (1994).
G. Seifert, H. Terrones, M. Terrones, T. Frauenheim: Novel NbS2 metallic nanotubes. Solid State Commun. 115, 635 (2000).
I. Boustani, A. Quandt: Nanotubules of bare boron clusters: Ab initio and density functional study. Europhys. Lett. 39, 527 (1997).
G. Seifert, E. Hernandez: Theoretical prediction of phosphorus nanotubes. Chem. Phys. Lett. 318, 355 (2000).
M. Zhao, Y. Xia, D. Zhang, L. Mei: Stability and electronic structure of AlN nanotubes. Phys. Rev. B. 68, 235415 (2003).
S.M. Lee, Y.H. Lee, Y.G. Hwang, J. Elsner, D. Porezag, T. Frauenheim: Stability and electronic structure of GaN nanotubes from density-functional calculations. Phys. Rev. B 60, 7788 (1999).
A.N. Enyashin, Yu.N. Makurin, A.L. Ivanovskii: Electronic band structure of b-ZrNCl-based nanotubes. Chem. Phys. Lett. 387, 85 (2004).
A. Zak, Y. Feldman, H. Cohen, V. Lyakhovitskaya, G. Leitus, R. Popovitz-Biro, S. Reich, R. Tenne: Alkali metal intercalation of fullerene-like MS2 (M = W, Mo) nanoparticles and their properties in comparison with bulk (2H) material. J. Am. Chem. Soc. 124, 4747 (2002).
A. Johansson, G. Sambandamurthy, D. Shahar, N. Jacobson, R. Tenne: Nanowire acting as a superconducting quantum interference device. Phys. Rev. Lett. 95, 116805 (2005).
G.L. Frey, S. Elani, M. Homyonfer, Y. Feldman, R. Tenne: Optical absorption spectra of inorganic fullerene-like MS2 (M = Mo, W). Phys. Rev. B 57, 6666 (1998).
L. Scheffer, R. Rosentzveig, A. Margolin, R. Popovitz-Biro, G. Seifert, S.R. Cohen, R. Tenne: Scanning tunneling microscopy study of WS2 nanotubes. Phys. Chem. Chem. Phys. 4, 2095 (2002).
G.L. Frey, R. Tenne, M.J. Matthews, M.S. Dresselhaus, G. Dresselhaus: Raman and resonance Raman investigation of MoS2 nanoparticles. Phys. Rev. B 60, 2883 (1999) No.
P.M. Rafailov, C. Thomsen, K. Gartsman, I. Kaplan-Ashir, R. Tenne: The antenna effect in an individual WS2 nanotube. Phys. Rev. B 72, 205436 (2005).
E. Dobardziæ, B. Daki, M. Damnjanovic, I. Milosevic: Zero m phonons in MoS2 nanotubes. Phys. Rev. B 71, 121405 (2005).
L. Qian, Z.L. Dub, S.Y. Yang, Z.S. Jin: Raman study of titania nanotube by soft chemical process. J. Mol. Struct. 749, 103 (2005).
W. Chen, L. Mai, J. Peng, Q. Xu, Q. Zhu: Raman spectroscopic study of vanadium oxide nanotubes. J. Solid State Chem. 177, 377 (2004).
S.C. Hung, Y.K. Su, T.H. Fang, S.J. Chang, F.S. Juang, L.W. Ji, R.W. Chuang: Buckling instabilities in GaN nanotubes under uniaxial compression. Nanotechnology 16, 2203 (2005).
Y.Q. Zhu, T. Sekine, Y.H. Li, M.W. Fay, Y.M. Zhao, C.H. Patrick Poa, W.X. Wang, R. Martin, P.D. Brown, N. Fleischer, R. Tenne: Shock-absorbing and failure mechanism of WS2 and MoS2 nanoparticles with fullerene-like structure under shockwave pressures. J. Am. Chem. Soc. 127, 16263 (2005).
J. Chen, N. Kuriyama, H.T. Yuan, H.T. Takeshita, T. Sakai: Electrochemical hydrogen storage in MoS2 nanotubes. J. Am. Chem. Soc. 123, 11813 (2001).
J. Chen, S.L. Li, Z.L. Tao: Novel hydrogen storage properties of MoS2 nanotubes. J. Alloys Compd. 356–357, 413 (2003).
J. Chen, S.L. Li, Z.L. Tao, Y.T. Shen, C.X. Cui: Titanium disulfide nanotubes as hydrogen-storage materials. J. Am. Chem. Soc. 125, 5284 (2003).
R. Dominko, M. Gaberscek, D. Arcon, A. Mrzel, M. Remskar, D. Mihailovic, S. Pejovnik, J. Jamnik: Electrochemical preparation and characterization of Liz MoS2–x nanotubes. Electrochim. Acta 48, 3079 (2003).
M.E. Spahr, P. Stoschitzki-Bitterli, R. Nesper, O. Haas, P. Novak: Vanadium oxide nanotubes a new nanostructured redox-active material for the electrochemical insertion of lithium. J. Electrochem. Soc. 146, 2780 (1999).
S. Nordlinder, K. Edstrom, T. Gustafsson: The performance of vanadium oxide nanorolls as cathode material in a rechargeable lithium battery. Electrochem. Solid-State Lett. 4, A129 (2001).
A. Dobley, K. Ngala, T. Shoufeng, P.Y. Zavalij, M.S. Whittingham: Manganese vanadium oxide nanotubes: Synthesis, characterization, and electrochemistry. Chem. Mater. 13, 4382 (2001).
J. Li, Z. Tang, Z. Zhang: H-titanate nanotube: A novel lithium intercalation host with large capacity and high rate capability. Electrochem. Comm. 7, 62 (2005).
L. Rapoport, Yu. Bilik, Y. Feldman, M. Homyonfer, S.R. Cohen, R. Tenne: Hollow nanoparticles of WS2 as potential solid-state lubricants. Nature 387, 791 (1997).
L. Joly-Pottuz, F. Dassenoy, M. Belin, B. Vacher, J.M. Martin, N. Fleischer: Ultralow-friction and wear properties of IF-WS2 under boundary lubrication. Tribol. Lett. 18, 477 (2005).
J.J. Hu, J.S. Zabinski: Nanotribology and lubrication mechanisms of inorganic fullerene-like MoS2 nanoparticles investigated using lateral force microscopy (LFM). Tribol. Lett. 18, 173 (2005).
R. Greenberg, G. Halperin, I. Etsion, R. Tenne: The effect of WS2 nanoparticles on friction reduction in various lubrication regimes. Tribol. Lett. 17, 179 (2004).
W.X. Chen, Z.D. Xu, R. Tenne, R. Rosenstveig, W.L. Chen, H.Y. Gan, J.P. Tu: Wear and friction of Ni–P electroless composite coating including inorganic fullerene-like WS2 nanoparticles. Adv. Eng. Mater. 4, 686 (2002).
Y. Golan, C. Drummond, J. Israelachvili, R. Tenne: In situ imaging of shearing contacts in the surface forces apparatus. Wear 245, 190 (2000).
A. Rothschild, S.R. Cohen, R. Tenne: WS2 nanotubes as tips in scanning-probe microscopy. Appl. Phys. Lett. 75, 4025 (1999).
J.F. Xu, R. Czerw, S. Webster, D.L. Carroll, J. Ballato, R. Nesper: Nonlinear optical transmission in VOx nanotubes and VOx nanotube composites. Appl. Phys. Lett. 81, 1711 (2002).
L. Krusin-Elbaum, D.M. Newns, H. Zeng, V. Derycke, J.Z. Sun, R. Sandstrom: Room-temperature ferromagnetic nanotubes controlled by electron or hole doping. Nature 431, 672 (2004).
L. Qian, F. Teng, Z.S. Jin, Z.J. Zhang, T. Zhang, Y.B. Hou, S.Y. Yang, X.R. Xu: Improved optoelectronic characteristics of light-emitting diodes by using a dehydrated nanotube titanic acid (DNTA)-polymer nanocomposites. J. Phys. Chem. B 108, 13928 (2004).
H. Tokudome, M. Miyauchi: Electrochromism of titanate-based nanotubes. Angew. Chem., Int. Ed. Engl. 44, 1974 (2005).
M. Adachi, Y. Murata, I. Okada, S. Yoshikawa: Formation of titania nanotubes and applications for dye-sensitized solar cells. J. Electrochem. Soc. 150, G488 (2003).
G.K. Mor, K. Shankar, M. Paulose, O.K. Varghese, C.A. Grimes: Use of highly-ordered TiO2 nanotube arrays in dye-sensitized solar cells. Nano. Lett. 6, 215 (2006).
G.K. Mor, M.A. Carvalho, O.K. Varghese, M.V. Pishko, C.A. Grimes: A room-temperature TiO2-nanotube hydrogen sensor able to self-clean photoactively from environmental contamination. J. Mater. Res. 19, 628 (2004).
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This author was an editor of this focus issue during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http://www.mrs.org/jmr_policy
This review article is based on the author’s 2005 MRS Medal talk titled “Inorganic Nanotubes and Inorganic Fullerene-Like Materials: From Concept to Applications,” presented at the 2005 MRS Fall Meeting on November 30, 2005.
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Tenne, R. Inorganic nanotubes and fullerene-like nanoparticles. Journal of Materials Research 21, 2726–2743 (2006). https://doi.org/10.1557/jmr.2006.0354
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DOI: https://doi.org/10.1557/jmr.2006.0354