UV–vis absorption and Raman spectroelectrochemistry have been used to study silver nanoparticle (AgNP) electrodeposition, allowing a better understanding about the metal nanoparticle (NP) formation process and its influence on the surface-enhanced Raman scattering (SERS) effect. These techniques have provided in situ information related to the synthesis of AgNPs by cyclic voltammetry. With a marker, such as cyanide anion (CN–), Raman spectroscopy has allowed us to study all changes that take place on a platinum electrode surface during the AgNP electrodeposition process. Raman spectra show different SERS behavior depending on the NPs generated. UV–vis absorption spectroelectrochemistry yields information on the changes in AgNP plasmon band during their electrodeposition while Raman signal is highly correlated with the kind of NPs generated. The methodology used in this work demonstrates that SERS effect depends strongly on nanoparticle size and shape
