Breaking Down SERS Detection Limit: Engineering of a Nanoporous Platform for High Sensing and Technology

In this study, nanoporous gold (NPG) was synthesized by free corrosion dealloying of an amorphous precursor, Au₂₀Cu₄₈Ag₇Pd₅Si₂₀ (at. %), in a mixture of nitric and hydrofluoric acid, starting from amorphous melt-spun ribbons. NPG revealed a 3D nanoporous structure composed of pores and multigrain ligaments of an average size of 60 nm. NPG was further anodized in oxalic acid at 8 V vs. Ag/AgCl reference electrode to obtain a bimodal morphology composed of ligaments disrupted in finer features. Both NPG and anodized samples (A-NPG) were found to be mechanically stable to bending and active for surface-enhanced Raman scattering (SERS). SERS activity of samples was investigated using 4,4'-bipyridine as a probe molecule. A detection limit of 10^-16 M was found for both samples, but in A-NPG, the signal was strongly enhanced. The extremely high enhancement obtained for A-NPG is attributed both to the small size of ligaments and crystals of which they are made, as well as to the nanometric features resulting from anodization treatment. Such a microstructure showed homogenous SERS response in terms of average enhancement all across the surface, as demonstrated by mapping measurements. Furthermore, NPG and A-NPG were tested as electrodes for electrocatalytic applications, showing good properties. The engineering steps from the amorphous precursor to A-NPG led us to obtain a high-sensing platform, with extremely low detection limit and intrinsic properties, that might significantly contribute to the cutting-edge technology of the future.