A versatile synthesis route for metal@SiO2 core–shell nanoparticles using 11-mercaptoundecanoic acid as primer

Abstract

Applying the Stober method to directly coat noble metal nanoparticles (NPs) such as gold (Au) and silver (Ag) NPs with silica shells presents challenges, since the noble metal NPs are not stable in alcoholic solution and have low chemical affinity for silica. This paper describes a method which uses 11-mercaptoundecanoic acid (MUA) as a linker molecule between the silica shell and the noble metal NPs. MUA binds strongly to the surface of the NPs via a metal–S bond by replacing the standard capping agents on the surface of the NPs. Upon MUA stabilization, the NPs can be transferred into alcohol solution and show chemical affinity for silica. The MUA-modified NPs can be directly coated with thickness controlled, smooth and homogeneous silica shells via the standard Stober method by varying the amount of tetraethoxysilane (TEOS). Compared with methods reported in the literature for the coating of such particles, this method can not only be used to successfully coat citrated-stabilized Au or Ag NPs, but can also be extended to encapsulate oleylamine (OA)-stabilized Au NPs and cetyltrimethylammonium bromide (CTAB)-stabilized Au nanorods (NRs) by using MUA to displace the original ligand on the surface of the NPs. Additionally, the obtained metal@SiO2 core–shell NPs have been successfully applied as plasmonic nanoantennas for fluorescence enhancement in metal@SiO2@fluorophore NPs.