Exploring the Role of Miniemulsion Nanodroplet Confinement on the Crystallization of MoO₃: Morphology Control and Insight on Crystal Formation by In Situ Time-Resolved SAXS/WAXS

Enclosed nanoscale volumes, i.e., confined spaces, represent a fascinating playground for the controlled synthesis of inorganic materials, albeit their role in determining the synthetic outcome is currently not fully understood. Herein, we address the synthesis of MoO₃ nano- and microrods with hexagonal section in inverse miniemulsion droplets and batch conditions, evaluating the effects of spatial confinement offered by miniemulsion droplets on their crystallization. Several synthetic parameters were systematically screened and their effect on the crystal structure of h-MoO₃, as well as on its size, size distribution and morphology, were investigated. Moreover, a direct insight on the crystallization pathway of MoO₃ in both synthetic conditions and as a function of synthetic parameters was provided by an in situ time-resolved SAXS/WAXS study, that confirmed the role of miniemulsion confined space in altering the stepwise process of the formation of h-MoO₃.