Structure-tunable supraparticle assemblies of hollow cupric oxide sheathed with nanographenes

Self-assembled supraparticles (SPs), a secondary structure of clustered nanoparticles, have attracted considerable interest owing to their highly tunable structure, composition, and morphology from their primary nanoparticle constituents. In this study, hierarchically assembled hollow Cu₂O SPs were prepared using a cationic polyelectrolyte poly(diallyl dimethylammonium chloride) (PDDA) during the formation of Cu₂O nanoparticles. The concentration-dependent structural transformation of PDDA from linear chains to assembled droplets plays a crucial role in forming a hollow colloidal template, affording the self-assembly of Cu₂O nanoparticles as a secondary surfactant. The use of the positively charged PDDA also affords negatively charged nanoscale graphene oxide (NGO), an electrical and mechanical supporter to uniformly coat the surface of the hollow Cu₂O SPs. Subsequent thermal treatment to enhance the electrical conductivity of NGO within the NGO/Cu₂O SPs allows for the concomitant phase transformation of Cu₂O to CuO, affording reduced NGO/CuO (RNGO/CuO) SPs. The uniquely structured hollow RNGO/CuO SPs achieve improved electrochemical properties by providing enhanced electrical conductivity and electroactive surface area.