Observing the Overgrowth of a Second Metal on Silver Cubic Seeds in Solution by Surface-Enhanced Raman Scattering

We report the development of an isocyanide-based molecular probe for in situ characterizing the overgrowth of a second metal on silver nanocrystal seeds in solution by surface-enhanced Raman scattering (SERS). As the first demonstration, we elucidate that the vibrational frequency of 2,6-dimethylphenyl isocyanide (2,6-DMPI) can serve as a distinctive reporter for capturing the nucleation of Pt on the edges of Ag nanocubes in the aqueous solution containing a Pt precursor, ascorbic acid, and poly(vinylpyrrolidone) under ambient conditions. Our success relies on the difference in stretching frequency for the NC bond when the isocyanide group binds to the Ag and Pt atoms. Specifically, sigma donation from the antibonding sigma* orbital of the -NC group to the d-band of Ag would strengthen the NC bond, blue shifting the stretching frequency. In contrast, pi-back-donation from the d-band of Pt to the pi* antibonding orbital of the -NC group would weaken the NC bond, leading to a red shift of stretching frequency. Therefore, it is feasible to in situ characterize the outermost surface that consists of both newly deposited Pt atoms and remaining Ag atoms by following the stretching frequencies and intensities of 2,6-DMPI in real time. Because the SERS hot spots on the edges of Ag nanocubes coincide with the {110} facets preferred for the nucleation of Pt atoms, this technique is capable of resolving 27 Pt atoms being deposited on each edge of a 39 mn Ag nanocube in the original growth solution. Collectively, in situ SERS, with its consummate sensitivity to molecular structure and bonding of isocyanide-based molecular probe, could elucidate the mechanistic details involved in the seeded overgrowth of a catalytically significant metal, such as Pt, Pd, Ir, Rh, and Ru, on the surface of a Ag or Au nanocrystal seed.