Accurate Control of All-Polymer Hollow Multishelled Spheres by One-Step Reaction–Diffusion

Hollow multishelled structures (HoMSs) enable material intriguing properties and diverse applications. However, constructing all-polymer HoMSs (p-HoMSs) remains a great challenge. Here, we first develop a one-step self-template strategy to synthesize p-HoMS spheres through controlled reaction–diffusion of a polyelectrolyte pair. Besides instant reaction, the high concentration and moderate molecular weight of one polyelectrolyte as the self-template are required to fulfill the key conditions (i.e., high cross-linking density and high diffusion difference of the two reactants) for the p-HoMS sphere fabrication. In consequence, scalable p-HoMSs are rationally designed with structural and composition control, including shell number, core size, and morphology. More importantly, this p-HoMS could facilely template the synthesis of hierarchical macroscopic HoMS metal oxide with a shell number up to 12. This self-template strategy provides a simple, general, controllable, and large-scale way for the fabrication of HoMS materials with various compositions, complex structures, and diverse functions, signifying for a new methodology in material science.