Tunability of Interactions between the Core and Shell in Rattle-Type Particles Studied with Liquid-Cell Electron Microscopy

Abstract

Yolk-shell or rattle-type particles consist of a core particle that is free to move inside a thin shell. A stable core with a fully accessible surface is of interest in fields such as catalysis and sensing. However, the stability of a charged nanoparticle core within the cavity of a charged thin shell remains largely unexplored. Liquid-cell (scanning) transmission electron microscopy is an ideal technique to probe the core-shell interactions at nanometer spatial resolution. Here, we show by means of calculations and experiments that these interactions are highly tunable. We found that in dilute solutions adding a monovalent salt led to stronger confinement of the core to the middle of the geometry. In deionized water, the Debye length κ-1 becomes comparable to the shell radius Rshell, leading to a less steep electric potential gradient and a reduced core-shell interaction, which can be detrimental to the stability of nanorattles. For a salt concentration range of 0.5-250 mM, the repulsion was relatively long-ranged due to the concave geometry of the shell. At salt concentrations of 100 and 250 mM, the core was found to move almost exclusively near the shell wall, which can be due to hydrodynamics, a secondary minimum in the interaction potential, or a combination of both. The possibility of imaging nanoparticles inside shells at high spatial resolution with liquid-cell electron microscopy makes rattle particles a powerful experimental model system to learn about nanoparticle interactions. Additionally, our results highlight the possibilities for manipulating the interactions between core and shell that could be used in future applications.