First, modified electrode surfaces were characterized using Scanning Electron Microscopy (SEM) imaging, Transmission Electron Microscopy (TEM) and Energy-Dispersive X-ray Spectroscopy (EDS)(Figure ). When AgNO3 alone was electrodeposited prior to the start of the reaction, the glassy carbon electrodes were coated with a gray film. The use of these modified electrodes yielded only 24% of product 39 between RAE 7 and vinyl iodide 5. SEM imaging showed that while large silver crystals formed (1-5 μm in diameter), there were very low levels of nanoparticulate silver on the electrode surface. However, addition of LiCl to this pre-reaction electrodeposition produced electrodes with improved reaction performance (41% NMR yield). SEM and TEM analyses of these electrode surfaces revealed the presence of nanoparticulate silver in sizes ranging 10-100 nm in diameter (See SI, Figures ). Controls verified the need for a halide source but, LiCl was not required in the coupling reactions since NiCl2 could serve as the halide donor in the preparative reactions. The reaction of AgNO3 and halides in solution will produce photosensitive silver halide salts that readily decompose. Electrodes modified using a AgNO3 and LiCl solution that had been allowed to stir for several minutes before electrolysis were evaluated in the coupling reaction. In such cases, only a 17% yield of 39 was obtained and very little nanoparticulate silver was observed in microscopic characterization (See SI, Figure ). Collectively, these results suggest that nanoparticulate silver electrodeposited before the crosscoupling reaction, is present and responsible, at least in part, for the improved performance.