Tetragonal Superlattice of Elongated Rhombic Dodecahedra for Sensitive SERS Determination of Pesticide Residues in Fruit

The self-assembly of plasmonic nanoparticles into highly ordered superlattices could pave the way toward novel nanomaterials for surface-enhanced Raman scattering (SERS). Here, we propose the formation of large-area superlattices of elongated rhombic dodecahedra in a vertical orientation via a controlled droplet evaporation process. Expectedly, the constant humidity of the experimental condition could control the evaporation speed of droplets and this procedure promotes the balance between driven depletion attraction and electrostatic repulsion in the system, leading to the generation of well-organized three-dimensional (3D) superlattices. The unique geometry of elongated rhombic dodecahedra could establish the tetragonal superlattices, which breaks the conventional hexagonal symmetry of gold nanorods. Specifically, the influence of the type and concentration of surfactants, the concentration of nanoparticles, and the amount of droplets on the preparation results were systematically investigated to find the optimal assembly parameters. Remarkably, such close-packed tetragonal arrays of vertically aligned elongated rhombic dodecahedra exhibit more excellent SERS performance compared with the traditional hexagonal superstructure of gold nanorods. Benefiting from the high sensitivity and reproducibility of elongated rhombic dodecahedron superlattices, their applications in the determination of pesticide residues in apple and grape peels were successfully demonstrated. As a result, this study may advance the production of innovative plasmonic nanomaterials for a broad range of fields.