Hydrophobic Nanoreactor Soft‐Templating: A Supramolecular Approach to Yolk@Shell Materials

Abstract

Due to their unique morphology‐related properties, yolk@shell materials are promising materials for catalysis, drug delivery, energy conversion, and storage. Despite their proven potential, large‐scale applications are however limited due to demanding synthesis protocols. Overcoming these limitations, a simple soft‐templated approach for the one‐pot synthesis of yolk@shell nanocomposites and in particular of multicore metal nanoparticle@metal oxide nanostructures (MNP@MOx) is introduced. The approach here, as demonstrated for AuNP@ITOTR (ITOTR standing for tin‐rich ITO), relies on polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) inverse micelles as two compartment nanoreactor templates. While the hydrophilic P4VP core incorporates the hydrophilic metal precursor, the hydrophobic PS corona takes up the hydrophobic metal oxide precursor. As a result, interfacial reactions between the precursors can take place, leading to the formation of yolk@shell structures in solution. Once calcined these micelles yield AuNP@ITOTR nanostructures, composed of multiple 6 nm sized Au NPs strongly anchored onto the inner surface of porous 35 nm sized ITOTR hollow spheres. Although of multicore nature, only limited sintering of the metal nanoparticles is observed at high temperatures (700 °C). In addition, the as‐synthesized yolk@shell structures exhibit high and stable activity toward CO electrooxidation, thus demonstrating the applicability of our approach for the design of functional yolk@shell nanocatalysts.