Time Dependence and Signs of the Shift of the Surface Plasmon Resonance Frequency in Nanocages Elucidate the Nanocatalysis Mechanism in Hollow Nanoparticles

Surface plasmon resonance (SPR) wavelength of plasmonic nanopartides is sensitive to changes in the dielectric function of its exposed surface to the medium. Gold nanocages (AuNCs) have two surfaces (inner and outer) and thus two plasmon fields., When the dielectric of the medium changes around the outer surface only, the SPR shifts to different extent from that observed when the dielectric constant of the medium changes around both surfaces. This property of plasmonic AuNCs was used to elucidate the mechanism of the catalytic reduction of 4-nitro to 4-amino phenol, whether it is occurring within the cavity or on the exterior surface of the nanocages. For this purpose two types of nanocages were prepared, one with two plasmonic surfaces and the other with Au/Pt shell-shell nanocages, where only the external surface is plasmonic as gold is outside and Pt is inside. By following the time dependence of the plasmonic band shift resulting from the addition of the reactants and comparing the reaction kinetic parameters for two types of nanocages with those of the pure single metallic nanocages, it was concluded that the catalysis is taking place within the cavity in both types of hollow nanopartides.