Inorganic fullerene-like nanoparticles of TiS2

doi:10.1016/j.cplett.2005.05.094

Chemical Physics Letters

Volume 411, Issues 1–3, 5 August 2005, Pages 162-166

This paper is dedicated to the memory of a scholar and a teacher, Prof. Laurens Jansen (1923–2005) who was the director of the Advanced Studies Center in Battelle Institute, Geneva, during my post-doc years there

https://doi.org/10.1016/j.cplett.2005.05.094 Get rights and content

Abstract

Inorganic closed-cage nanoparticles of TiS₂ were synthesized using gas-phase synthesis. The reported nanoparticles are perfectly spherical with diameters centered between 60 and 80 nm, consisting from up to 80–100 concentric layers. The nucleation and growth mechanism was proposed for the formation of these nanoparticles. Tribological experiments emphasized the important role played by the spherical shape of the nanoparticles in providing rolling friction with a reduced friction coefficient and wear.

Introduction

The first closed-cage fullerene-like nanoparticles and nanotubes of WS₂ were obtained via sulfidization of thin films of the respective trioxides in 1992 [1], followed by MoS₂[2], [3] and the respective diselenides [4]. These structures received the generic name inorganic fullerene-like structures (IF), since the stimulus for their formation and their structure are similar to those of carbon fullerenes and nanotubes. More recently numerous other IF nanostructures have been synthesized using different methodologies. Thus elemental nanotubes, like Bi [5], [6] and Te [7]; transitional metal oxides, like V₂O₅[8], [9], H₂Ti₃O₇[10], Tl₂O [11]; halides (NiCl₂[12], CdI₂[13]), phosphates (Ti(HPO₄)₂ · H₂O [14]), chalcogenides (Bi₂S₃[15], Hf₂S [16], HfS₂ and ZrS₂[17], ReS₂[18], [19], NbS₂[20], TiS₂[21], [22], WS₂[23], MoS₂[24]) and other layered (2-D) structures (e.g., BN [25]) have been reported being synthesized as closed-cage nanostructures. The predecessor for such nanoparticles is a planar molecular sheet of a layered compound, which in the present case is a metal dichalcogenide. The shrinking size of the molecular sheet to the nano-regime leads to increasing rim/bulk atoms ratio making the planar nanosheet unstable and resulting in folding of the layers into seamless nanotubes and fullerene-like nanoparticles.

The elucidation of the conversion mechanism of trioxides of molybdenum and tungsten into MoS₂ and WS₂ closed-cage fullerene-like structures enabled both deeper understanding of the synthesis and the mass production of the material [26], [27], [28]. These nanoparticles were found to have a large number of potential applications particularly in the field of lubrication. The synthesis of both IF–WS₂ and IF–MoS₂ showed definitely that vertical reactors are preferable for the synthesis of the nanoparticles and IF in particular.

TiS₂ crystallizes in a layered (1T) structure, where the layers of titanium disulfide are stacked together via the relatively weak van-der-Waals forces. Each TiS₂ sheet consists of a layer of metal atoms, sandwiched between two chalcogen layers, with the metal atom bonded to six chalcogen atoms in an octahedral coordination [29]. The relationship between stoichiometry, structure and electrical conductivity of TiS₂ was investigated in the past [30].

The direct reaction between TiCl₄ and H₂S is commonly known synthetic route used for the production of pure titanium disulfide with a yield close to 90% [31] ${TiCl}_{4} + 2 H_{2} S \to {TiS}_{2} + 4 HCl$

In the present work, TiS₂ nanoparticles with nested fullerene-like structure, consisting of up to 100 concentric molecular layers and having quite a perfectly spherical shape, were obtained from the reaction of TiCl₄ and H₂S in a vertical reactor. The growth mechanism of these nanoparticles, which is radically different from the one proposed for fullerene-like WS₂ was partially elucidated. These nanoparticles are shown to provide excellent tribological behavior.

Section snippets

Experimental

A horizontal reactor initially used for this synthesis was later changed into a specially designed vertical set-up (Fig. 1a). The opposite flows of reacting gases (TiCl₄ and H₂S) come into contact within the reaction chamber of the hermitically closed quartz reactor at temperature, which varied from 650 to 800 °C. The nanoparticles, obtained in the reaction, move down to the filter, where the temperature is somewhat 50–80 °C lower, than in the reaction chamber. The TiCl₄ vapor is prepared by

Results and discussion

The use of the vertical reactor instead of the horizontal one resulted in a more perfect nanoparticles, smaller size distribution and higher yields. The resulting IF-TiS₂ nanoparticles were found to be more spherical, than those obtained with the horizontal reactor. The yield of the closed-cage nanostructures rose to about 80% (compared to 30% in the early experiments with the horizontal reactor). However, the higher yield of the IF nanoparticles could also be attributed to the lengthy

Acknowledgements

We are grateful to Dr. Yishai Feldman and Dr. Rita Rosentsveig for the fruitful discussions. We acknowledge the support of ‘NanoMaterials’ and the Israel science Foundation. R.T. is the director of the Helen and Martin Kimmel Center for Nanoscale Science.

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Inorganic fullerene-like nanoparticles of TiS2

Abstract

Introduction

Section snippets

Experimental

Results and discussion

Acknowledgements

Solid State Sci.

Mater. Res. Bull.

Adv. Phys.

Nature

Nature

Science

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Eur. J. Inorg. Chem.

Adv. Mater.

Nature

Angew. Chem., Intl. Ed.

Adv. Mater.

J. Am. Chem. Soc.

Nature

J. Mater. Chem.

J. Am. Chem. Soc.

Inorganic fullerene-like nanoparticles of TiS₂