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.