Hybrid nanoscale inorganic cages

Cage structures exhibit inherent high symmetry and beauty, and both naturally occurring and synthetic molecular-scale cages have been discovered. Their characteristic high surface area and voids have led to their use as catalysts and catalyst supports, filtration media and gas storage materials(1,2). Nanometre-scale cage structures have also been synthesized, notably noble-metal cube-shaped cages prepared by galvanic displacement with promising applications in drug delivery and catalysis(3-6). Further functionality for nanostructures in general is provided by the concept of hybrid nanoparticles combining two disparate materials on the same system to achieve synergistic properties stemming from unusual material combinations(7-11). We report the integration of the two powerful concepts of cages and hybrid nanoparticles. A previously unknown edge growth mechanism has led to a new type of cage-structured hybrid metal-semiconductor nanoparticle; a ruthenium cage was grown selectively on the edges of a faceted copper(I) sulphide nanocrystal, contrary to the more commonly observed facet and island growth modes of other hybrids(7,12-15). The cage motif was extended by exploiting the open frame to achieve empty cages and cages containing other semiconductors. Such previously unknown nano-inorganic cage structures with variable cores and metal frames manifest new chemical, optical and electronic properties and demonstrate possibilities for uses in electrocatalysis.