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The integration of voltammetry, surface-enhanced Raman spectroscopy (SERS) and density functional theory (DFT) has helped in disclosing the mechanistic origin of the electrocatalytic properties of silver cathodes during the reduction of benzyl chloride. The mechanism has bridged classical electroreduction mechanisms and oxidative additions similar to those occurring during organometallic homogeneous activation of organic halides by low-valent transition-metal complexes.

An in situ electrochemical surface-enhanced Raman spectroscopic study was carried out to characterize various surface species in different electrode potential regions and gain better insight into the electrocatalytic mechanism of silver on reduction of benzyl chloride. The benzyl radical and its anionic derivate as the key intermediates bonded on a silver electrode implied that the pathway could drastically differ from the outer sphere concerted electron reduction at inert electrodes.

A laser with low power signal was used to perform surface-enhanced Raman spectroscopy (SERS) to chemically transform para-aminothiophenol to 4,4'-dimercaptoazobenzene (DMAB) on a roughened silver surface. The erroneous interpretation of the distorted experimental result for laser induced surface reaction could be effectively avoided by using defocusing method to perform reliable SERS characterization and identification.