Au-on-Ag nanostructure forin-situSERS monitoring of catalytic reactions

Dual-functionality Au-on-Ag nanostructures (AOA) were fabricated on a silicon substrate by first immobilizing citrate-reduced Ag nanoparticles (Ag NPs, ∼43 nm in diameter), followed by depositing ∼7 nm Au nanofilms (Au NFs) via thermal evaporation. Au NFs were introduced for their catalytic activity in concave-convex nano-configuration. Ag NPs underneath were used for their significant enhancement factor (EF) in surface-enhanced Raman scattering (SERS)-based measurements of analytes of interest. Rhodamine 6G (R6G) was utilized as the Raman-probe to evaluate the SERS sensitivity of AOA. The SERS EF of AOA is ∼37 times than that of Au NPs. Using reduction of 4-nitrothiophenol (4-NTP) by sodium borohydride (NaBH₄) as a model reaction, we demonstrated the robust catalytic activity of AOA as well as its capacity to continuously monitor via SERS the disappearance of reactant 4-NTP, emergence and disappearance of intermediate 4,4'-DMAB, and the appearance of product 4-ATP throughout the reduction process in real-time andin situ.