Distinction of Plasmonic Intrananoparticle and Internanoparticle Molecular Reaction Rates at the Three-Phase Contact Line of an Evaporating Sessile Droplet.

Molecular reactions on the surface of a plasmonic nanoparticle (intrananoparticle) and between nanoparticles (internanoparticle) may differ in kinetics, dynamics, and product selectivity. We report that the difficulty in distinguishing the kinetics in a dispersion medium could be overcome by probing the reactions at the three-phase contact line (TPCL) of an evaporating sessile droplet using surface-enhanced Raman spectroscopy (SERS). Thus, when an evaporating aqueous droplet on glass containing 4-aminothiophenol-stabilized Ag nanoparticles was monitored by SERS at the TPCL, dimerization into 4,4'-dimercaptoazobenzene followed two steps, each preceded by the loss of H-bonded water accordingly. On the basis of the results, we assigned the first step with a higher relative kinetic rate (∼3 times) to be an intrananoparticle reaction and the second one as an internanoparticle reaction. In D 2 O medium, the ratio of the rates was ∼1.8. The observed vibrational signatures of the losses of water molecules before reactions and product formations were accounted for by using density functional theoretical calculations.