Piperidine adsorption on two different silver electrodes: A combined surface enhanced Raman spectroscopy and density functional theory study

The surface enhanced Raman scattering (SERS) spectra of piperidine in silver colloid solution, on roughened silver electrode and on roughened silver electrode modified with silver nanoparticles were studied, and the high-quality SERS spectra of piperidine on roughened silver electrode modified with silver nanoparticles were obtained for the first time. Surface selection rules derived from the EM enhancement model were employed to deduce piperidine orientations on the different surfaces. On the basis of this, two models of piperidine adsorbed on the surface of the silver nanoparticles were built, and DFT-B3PW91/LanL2dz was applied to calculate the Raman frequencies. It proves that, at higher potential values, the piperidine is perpendicularly standing on the roughened silver electrode surface though its lone-electron pair, but in silver colloid solution and on the silver nanoparticles modified silver electrode the piperidine molecular lies flat on the silver surface. In the meantime, the potential dependent SERS of piperidine on the modified electrode were studied.