Nanoassemblies of colloidal gold nanoparticles by oxygen-induced inorganic ligand replacement

This article reports a novel method of the fabrication of floating ultrathin nanoporous films and superlattice-like bottom sediment flakes of colloidal gold nanoparticles (Au NPs) by the oxygen-induced ligand replacement of inorganic species. The two nanoassemblies were realized in a weighing bottle simply by aging the Au colloid, which was synthesized and stabilized using more divalent tin Sn(II) than required for the reduction of HAuCl(4). In situ Raman spectroscopy was employed to trace the assembly process, and we found that the protective Sn(II) species (mostly SnCl(3)(-)) of the gold colloid could be gradually replaced by Cl(-) ions in the solution, while the strongly chemically adsorbed Sn(II) species on the Au NPs was oxidized by O(2) from the air contact. The destabilized colloidal Au NPs by the ligand replacement of SnCl(3)(-) with Cl(-) first assembled into an ultrathin nanoporous film at the air-water interface and then sedimentated to the bottom. Superlattice-like sediment flakes of Au NPs can be obtained at lower temperature (approximately 5 degrees C). Particularly, this method does not involve any organic substances, providing clean ultrathin nanoporous films and superlattice-like flakes of Au NPs. The ultrathin nanoporous films and superlattice-like flakes of Au NPs can serve as SERS substrates with strong and long activity.