Yolk-Shell Nanocomposites of a Gold Nanocore Encapsulated in an Electroactive Polyaniline Shell for Catalytic Aerobic Oxidation.

Abstract

Noble metal nanoparticles (NPs) have been widely applied in nanocatalysis owing to the benefits associated with their miniature size. However, improving their stability and reusability during catalytic applications still remains a great challenge. To this end, monodispersed gold@void@polyaniline yolk–shell nanocomposites (Au@void@PANI YSNs) were synthesized using bottom-up template-assisted methods. Au@SiO2 NPs, prepared from a modified sol–gel process, were used as templates for the thiol–ene click reaction with 4-vinylaniline (VAn) to immobilize the aniline moieties, which later performed as the initiation sites for the oxidative copolymerization of aniline from the outer surface of the Au@SiO2–VAn NPs with an electroactive PANI shell (Au@SiO2@PANI NPs). The silica layer sandwiched between the Au core and PANI shell was selectively removed by aqueous hydrofluoric acid to produce Au@void@PANI YSNs with a movable Au core. The electroactive PANI shell not only serves as a physical barrier that prevents the self-association of Au cores and provides a vacant cavity where chemical transformations take place on the Au cores in a controlled manner but also improves the activity and stability of Au cores due to the electrons delocalization and transfer from the Au d orbitals of the nanocores to the π-conjugated ligands of the PANI shell, as proved by the X-ray photoelectron spectroscopy results. The as-synthesized YSNs were found to perform as flexible and reusable heterogeneous catalysts with high catalytic efficiency for the aerobic oxidation of alcohol in aqueous solution. One may find the present study to be a general and effective way to fabricate monodispersed hollow nanomaterials in a controlled and green manner.