Effect of Chemical Charging/Discharging on Plasmonic Behavior of Silver Metal Nanoparticles Prepared using Citrate-Stabilized Cadmium Selenide Quantum Dots.

The thermodynamics and kinetics of the chemical and electrochemical charging of a catalyst surface are very important to understand its applicability as a catalyst material, particularly in redox catalysis. Through the present study, we hereby communicate the results obtained from our detailed investigations related to the effect of chemical charging on the plasmonic behavior of silver metal nanoparticles (Ag MNPs) as redox catalysts. Two different batches of Ag MNPs were prepared through thermally assisted chemical reduction of silver ions. The difference in these batches was the use or not of citrate-capped cadmium selenide quantum dots (Q-CdSe) for the reduction of solution-phase silver ions to their colloidal plasmonic phase. The charge on the surfaces of the Ag MNPs was varied by the chemical electron injection method by using BH ions from a NaBH solution. The processes of charging and discharging were monitored by using UV/Vis absorption spectroscopy. The impact of the concentration of the reductant on the charging and discharging processes was also investigated. The Ag MNPs were also tested for their voltammetric response, wherein it was observed that it was more difficult to oxidize the Ag MNPs prepared with Q-CdSe seeds than to oxidize Ag MNPs prepared without Q-CdSe particles. Our results demonstrate that Q-CdSe seeds not only enhance the redox catalytic activity of Ag MNPs but also provide stability towards polarization of their plasmonic behavior.