Add time:07/17/2019         Source:sciencedirect.com

The surface-enhanced resonance Raman scattering (SERS+RRS) spectra of meso-tetrakis(4-N-methylpyridyl)porphine (TMPyP) adsorbed at Ag electrode surfaces were measured at various electrode potentials. The potential dependence of the surface spectra were analysed by comparison with the ordinary resonance Raman spectra observed for TMPyP's (both in a diacid and free base forms) and reduction intermediates of TMPyP (i.e., a phlorin monocation, a neutral phlorin and a porphomethene). The SERS+RRS spectra of TMPyP in 1M HCl indicate that an adsorbate at 0V (vs.Ag/AgCl) exists as a neutral phlorin, and on scanning the electrode potential to −0.2 V, the phlorin is reduced to a porphomethene. On the other hand, the SERS+RRS spectra of TMPyP in an aqueous solution at pH 2.0 show that the adsorbate on the Ag electrode at 0V exists as TMPyP in a free base form, which is reduced to the neutral phlorin at −0.2 V. Thus, the electrochemical processes at the Ag electrode surface are quite different from the processes in aqueous media which have already been studied by using polarography and cyclic voltammetry. The difference clearly indicates that an adsorption effect on the Ag electrode plays an essential role in determining the reduction pathways.

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