Nanotubes from Lanthanide-Based Misfit-Layered Compounds: Understanding the Growth, Thermodynamic, and Kinetic Stability Limits

Chem Mater. 2024 Apr 30;36(9):4736-4749. doi: 10.1021/acs.chemmater.4c00481. eCollection 2024 May 14.

Abstract

Gaining insights into the kinetics and the thermodynamic limits of nanostructures in high-temperature reactions is crucial for controlling their unique morphology, phase, and structure. Nanotubes from lanthanide-based misfit-layered compounds (MLCs) have been known for more than a decade and were successfully produced mostly via a chemical vapor transport protocol. The MLC nanotubes show diverse structural arrangements and lattice disorders, which could have a salient impact on their properties. Though their structure and charge transfer properties are reasonably well understood, a lack of information on their thermodynamic and kinetic stability limits their scalable synthesis and their applicability in modern technologies. In this study, the growth, thermodynamic stability, and decomposition kinetics of lanthanide-based misfit nanotubes of two model compounds, i.e., (LaS)1.14TaS2 and (SmS)1.19TaS2 are elucidated in detail. The nanotubes were carefully analyzed via atomic resolution electron microscopy imaging and synchrotron-based X-ray and electron diffraction techniques, and the information on their morphology, phase, and structures was deduced. The key insights gained would help to establish the parameters to explore their physio-chemical properties further. Furthermore, this study sheds light on the complex issue of the high-temperature stability of nanotubes and nanostructures in general.