Electrochemical behaviour of ole®ns: oxidation at ruthenium±titanium dioxide and iridium±titanium dioxide coated electrodes

Abstract

The electrocatalytic behaviour of a series of ole®ns was studied on thermally prepared Ti/MO2 and Ti/M0:3Ti0:7O2 electrodes (M = Ru, Ir) in 1.0 M HClO4 in mixed solvent (AN/H2O, 40/60 v/v). The voltammetric investigation was limited to the potential region preceding the OER on these electrodes materials (E < 1:2 V vs SSCE). Aliphatic ole®ns (isophorone and cyclohexene) are inactive while the aromatic ole®ns show a single (safrole) or two (isosafrole) oxidation peaks. The overall catalytic activity of these electrode materials is about the same for both substrates. However, when morphological effects (differences in electrode surface area) are taken into account, normalizing the geometric current density (or faradaic charge) per surface site activity, a slightly better ef®ciency of the active surface sites is observed for Ru-based electrodes when compared to the equivalent Ir-based materials. Partial substitution of the noble metal catalysts by TiO2 results in a synergetic effect depressing the ef®ciency of the active surface sites of the TiO2-stabilized electrocatalysts. The decrease with potential cycling of the substrate oxidation current is attributed to dimeric/polymeric ®lm formation blocking the electrode surface. Re¯ectance and FTIR spectroscopy as well as ohmic resistance data support ®lm formation.