Tip-enhanced Raman spectroscopy (TERS) takes advantage of the enhancement of the local electromagnetic field and of Raman scattering from surfaces to provide in situ chemical analysis at the nanoscale. Applications of the TERS technique in the ultrahigh vacuum and ambient conditions have clearly characterized the differences in the interactions between molecular adsorbates and specific binding sites on solid surfaces. Building on past developments, we have applied TERS to investigate the oxygen reduction reaction (ORR) catalyzed by iron (II) phthalocyanine (FePc) under electrochemical conditions (EC-TERS). Using EC-TERS, an iron-oxygen species was identified prior to the onset of ORR, and this species disappeared with increasing cathodic polarization. In addition, two configurations of FePc were observed on the Au(111) surface under applied potentials—FePc monomers in small well-ordered domains, and FePc molecules in aggregated clusters. Preliminary results suggest that the FePc monomers are more active towards ORR compared with the FePc aggregates.<br/>

Investigation of iron(II) phthalocyanine catalyzed oxygen reduction reaction using <i>operando</i> electrochemical tip-enhanced Raman spectroscopy

2019 Spring National Meeting

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Investigation of iron(II) phthalocyanine catalyzed oxygen reduction reaction using operando electrochemical tip-enhanced Raman spectroscopy