Misfit Layered Compounds: Insights into Chemical, Kinetic, and Thermodynamic Stability of Nanophases.

Abstract

ConspectusCompounds with layered structures (2D-materials), like transition metal-dichalcogenides (e.g., MoS₂), attracted a great deal of interest in the scientific community in recent years. This interest can be attributed to their unique lamellar structure, which induces large anisotropy in their physicochemical properties. Furthermore, owing to the weak van der Waals interaction between the layers, they can be cleaved along the a-b plane, which allows fabricating single layers with physical properties entirely different from the bulk material. Moreover, stacking layers of different 2D-materials on top of each other has led to a wealth of new observations, for instance, by twisting two layers with respect to each other and producing Moiré lattice. Another outstanding property of inorganic layer compounds is their tendency to form nanotubes, reported first (for WS₂) many years ago and subsequently from many other layered compounds.Among the 2D-materials, misfit layer compounds make a special class with an incommensurate and nonstoichiometric lattice made of an alternating layer with rocksalt structure, like LaS (O) and a layer with hexagonal structure, like TaS₂ (T). The lack of lattice commensuration between the two slabs leads to a built-in strain, which can be relaxed via bending. Consequently, nanotubes have been produced from numerous MLC compounds over the past decade and their structure was elucidated.Owing to their large surface area, nanostructures are generally metastable and tend to recrystallize into microscopic crystallites via different mechanisms, like Ostwald ripening, or chemically decompose and then recrystallize. The stability of nanostructures at elevated temperatures has been investigated quite scarcely so far. In this perspective, electron microscopy as well as synchrotron-based X-ray absorption and reflection techniques were used to elucidate the chemical selectivity and decomposition routes of rare-earth based MLC nanotubes prepared at elevated temperatures (800-1200 °C).As for the chemical selectivity, entropic effects are expected to dictate the random distribution of the chalcogen atoms on the anion sites of the MLC nanotubes at elevated temperatures. Nonetheless, the sulfur atoms were found to bind exclusively to the rare-earth atom (Ln = La, Sm) of the rocksalt slab and the selenium to the tantalum of the hexagonal TX₂ slab. This uncommon selectivity was not found in other kinds of nanotubes like WSe_2xS_2(1-x). In other series of experiments, the lack of utter symmetry in the multiwall nanotubes leads to exclusions of certain X-ray (0kl) reflections, which was used to distinguish them from the bulk crystallites. The transformation of Ln-based MLC nanotubes into microscopic flakes was followed as a function of the synthesis temperature (800-1200 °C) and the synthesis time (1-96 h). Furthermore, sequential high-temperature transformations of the (O-T) lattice into (O-T-T) and finally (O-T-T-T) phases via deintercalation of the LnS slab was observed. This autocatalytic process is reminiscent of the deintercalation of alkali atoms from different layered structure materials. Annealing at higher temperatures and for longer periods of time eventually leads to the decomposition of the ternary MLC into binary metal-sulfide phases, as well as partial oxidation of the product. This study sheds light on the complex mechanism of high-temperature chemical stability of the nanostructures.