Multiwall WS2 nanotubes have been synthesized from W18O49 nanowhiskers in substantial amounts for more than a decade. The established growth model is based on the "surface-inward" mechanism, whereby the high-temperature reaction with H2S starts on the nanowhisker surface, and the oxide-to-sulfide conversion progresses inward until hollow-core multiwall WS2 nanotubes are obtained. In the present work, an upgraded in situ SEM μReactor with H2 and H2S sources has been conceived to study the growth mechanism in detail. A hitherto undescribed growth mechanism, named "receding oxide core", which complements the "surface-inward" model, is observed and kinetically evaluated. Initially, the nanowhisker is passivated by several WS2 layers via the surface-inward reaction. At this point, the diffusion of H2S through the already existing outer layers becomes exceedingly sluggish, and the surface-inward reaction is slowed down appreciably. Subsequently, the tungsten suboxide core is anisotropically volatilized within the core close to its tips. The oxide vapors within the core lead to its partial out-diffusion, partially forming a cavity that expands with reaction time. Additionally, the oxide vapors react with the internalized H2S gas, forming fresh WS2 layers in the cavity of the nascent nanotube. The rate of the receding oxide core mode increases with temperatures above 900 °C. The growth of nanotubes in the atmospheric pressure flow reactor is carried out as well, showing that the proposed growth model (receding oxide core) is also relevant under regular reaction parameters. The current study comprehensively explains the WS2 nanotube growth mechanism, combining the known model with contemporary insight.

Central European Institute of Technology Brno University of Technology Purkyňova 123 61200 Brno Czech Republic

Chemistry and Physics of Materials University of Salzburg Jakob Haringer Strasse 2A 5020 Salzburg Austria

Department of Chemical Engineering Ariel University Ariel 4070814 Israel

Department of Molecular Chemistry and Materials Science Weizmann Institute of Science Rehovot 7610001 Israel

Faculty of Science Holon Institute of Technology Golomb Street 52 Holon 5810201 Israel

Institute of Physical Engineering Faculty of Mechanical Engineering Brno University of Technology Technická 2 616 69 Brno Czech Republic

Solid State and Structural Chemistry Unit Indian Institute of Science CV Raman Road Bangalore 560012 India

Thermo Fisher Scientific Vlastimila Pecha 12 62700 Brno Czech Republic

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