Shell-isolated nanoparticle-enhanced Raman spectroscopy of pyridine on smooth silver electrodes

The invention of shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) extends the study of Raman spectroscopy into surface electrochemistry on the SERS-inactive smooth electrodes. This work aims to investigate the electrochemical system perturbation brought about by spreading Au–core silica–shell nanoparticles (Au@SiO2 NPs) over the electrode surface for SHINERS. The differential capacitance measurements have shown SHINERS to cause the minimum of disturbance in the electrochemical system. The spectral features of SHINERS of pyridine adsorbed at smooth silver electrodes differs from that of SERS on the electrochemically roughened surface because pyridine interacts with silver much more strongly on the roughened electrode with many heterogeneous adsorption sites. Since most electrochemical data about surface adsorption are based on mechanically polished surface, the spectral information provided by the in situ SHINERS could be more reliable and better correlation.

► Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) was used.
► SHINERS has advantages over SERS to study adsorption on smooth electrodes.
► SHINERS has the mild perturbation to electrochemical interfaces.