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Layered transition metal dichalcogenides contain a number of crystal defects which significantly change their properties may be beneficial or detrimental for a specific application. We have prepared defect-rich multiwalled WS2 nanotubes by reductive sulfidization of W18O49 nanowires that were obtained solvothermally from tungsten chloride in different alcohols. The synthesis of the W18O49 nanowires was monitored and their morphological characteristics (e. g. length, rigidity and aspect ratio) are described in detail. The effect of morphology of the nanowires on the synthesis of WS2 nanotubes was investigated in order to obtain WS2 nanotubes that are highly solvent dispersible. Dispersions of the WS2 nanotubes in organic solvents were very stable for several days. The nanotubes could easily be functionalized with noble metals, metal oxides and Janus-type metal@metal oxide nanoparticles. The synthesis of nanowires and nanotubes and the immobilization of the nanoparticles is demonstrated by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) combined with energy dispersive X-ray spectroscopy (EDX), electron diffraction, X-ray diffraction (XRD) and Raman spectroscopy.

Closed WS2 nanoboxes were formed by topotactic sulfidization of a WO3/WO3 center dot 1/3H(2)O intergrowth precursor. Automated diffraction tomography was used to elucidate the growth mechanism of these unconventional hollow structures. By partial conversion and structural analysis of the products, each of them representing a snapshot of the reaction at a given point in time, the overall reaction can be broken down into a cascade of individual steps and each of them identified with a basic mechanism. During the initial step of sulfidization WO3 center dot 1/3H(2)O transforms into hexagonal WO3 whose surface allows for the epitaxial induction of WS2. The initially formed platelets of WS2 exhibit a preferred orientation with respect to the nanorod surface. In the final step individual layers of WS2 coalesce to form closed shells. In essence, a cascade of several topotactic reactions leads to epitactic induction and formation of closed rectangular hollow boxes made up from hexagonal layers.

Enlightened by the discovery of graphenes, a variety of inorganic analogues have been synthesized and characterized in recent years. Solvated Nb1-xWxS2 analogues of graphene-type sheets were prepared by lithiation and exfoliation of multistacked Nb1-xWxS2 coin roll nanowires (CRNWs), followed by in situ functionalization with gold nanoparticles to synthesize gold-loaded Nb1-xWxS2/Au nanocomposites. The Nb1-xWxS2 nanosheets and the corresponding Nb1-xWxS2/Au nanocomposites were characterized by high resolution electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and scanning force microscopy (AFM). The graphene-type sheets are stable in water and other solvents and can be functionalized similarly as chalcogen-terminated surfaces (e.g. with Au nanoparticles).

The MOCVD assisted formation of nested WS2 inorganic fullerenes (IF-WS2) was performed by enhancing surface diffusion with iodine, and fullerene growth was monitored by taking TEM snapshots of intermediate products. The internal structure of the core-shell nanoparticles was studied using scanning electron microscopy (SEM) after cross-cutting with a focused ion beam (FIB). Lamellar reaction intermediates were found occluded in the fullerene particles. In contrast to carbon fullerenes, layered metal chalcogenides prefer the formation of planar, plate-like structures where the dangling bonds at the edges are stabilized by excess S atoms. The effects of the reaction and annealing temperatures on the composition and morphology of the final product were investigated, and the strength of the WS2 shell was measured by intermittent contact-mode AFM. The encapsulated lamellar structures inside the hollow spheres may lead to enhanced tribological activities.

MoS2 nanotube bundles along with embedded nested fullerenes were formed in a gas phase reaction of molybdenum carbonyl and H2S gas with the assistance of I2. The amorphous Mo-S-I intermediates obtained through quenching a modified MOCVD reaction in a large temperature gradient were annealed at elevated temperature in an inert atmosphere. Under the influence of the iodine the amorphous precursor formed a surface film with an enhanced mobility of the molybdenum and sulfur components. Point defects within the MoS2 layers combined with the enhanced surface diffusion lead to a scrolling of the inherently instable MoS2 lamellae.