Morphology Engineering in Multicomponent Hollow Metal Chalcogenide Nanoparticles

Hollow metal chalcogenide nanoparticles are widely applicable in environmental and energy-related processes. Herein, we synthesized such particles with large compositional and morphological diversity by combining scanning probe block copolymer lithography with a Kirkendall effect-based sulfidation process. We explored the influence of temperature-dependent diffusion kinetics, elemental composition and miscibility, and phase boundaries on the resulting particle morphologies. Specifically, CoNi alloys form single-shell sulfides for the synthetic conditions explored because Co and Ni exhibit similar diffusion rates, while CuNi alloys form sulfides with various types of morphologies (yolk-shell, double-shell, and single-shell) because Cu and Ni have different diffusion rates. In contrast, Co-Cu heterodimers form hollow heterostructured sulfides with varying void numbers and locations depending on synthesis temperature and phase boundary. At higher temperatures, the increased miscibility of CoS2 and CuS makes it energetically favorable for the heterostructure to adopt a single alloy shell morphology, which is rationalized using density functional theory-based calculations.