Self-assembly of hard anions around cationic gold nanorods: potential structures for SERS

The placement of polyoxometalates next to the surface of noble metallic nanoparticles has been found to enhance the surface-enhanced Raman scattering (SERS) effect. The enhancement is believed to stem from either charge (electrostatic attraction) or chemical effects. Anisotropic gold nanorods are recognized as useful nanostructures for SERS, mainly due to the high electric field enhancement at their ends. The presented work examines the use of a polyoxometalate encapsulated gold nanorod for SERS, to assess whether the two enhancement pathways would be synergetic. For this, a gold nanorod-polyoxometalate composite was synthesized by coating cetyltrimethylammonium bromide-stabilized gold nanorods with a silicotungstic Keggin anion through electrostatic attraction. The structure was characterized, confirming that the nanorods have been fully encapsulated by the polyoxometalate. The SERS performance of the composite was assessed in solution using crystal violet as a SERS indicator, finding an analytical enhancement factor of 1.8 × 10⁴ in colloidal solution. The enhancement mechanism was examined first by comparison to gold nanorods stabilized by a cetyltriethylammonium bromide bilayer, cationic thiol bound polyoxometalate, and polyelectrolyte coating. Next, composites made using polyoxometalates of different atomic composition and charge were examined. It was concluded that the polyoxometalate charge had a noticeable effect on the enhancement while the atomic composition did not. Furthermore, high enhancement is observed mainly in cases where the nanorod monolayer allows the sequestration of the dye molecule into the nanoparticle's ligand layer. The proposed mechanism therefore involves the negative charge of the polyoxometalate attracting the positively charged dye, and facilitating the sequestration of the dye within the ligand bilayer, closer to the nanorod's surface.