SCHEDULED MAINTENANCE
Effect of supporting electrolyte on the mediated reduction of [Fe(H2O)6]3+ by an osmium-containing poly(4-vinylpyridine) film
Abstract
The ability to control the mediation kinetics of [Fe(H2O)6]3+ reduction by [Os(bipy)2(PVP)10Cl]Cl films through electrode potential, film thickness and supporting electrolyte is demonstrated; bipy = 2,2′-bipyridyl, PVP = poly(4-vinylpyridine). In H2SO4, the mediated reduction is controlled by film thickness for surface coverages between 7 × 10–10 and 1 × 10–8 mol cm–2(Lk mechanism). For surface coverages > 10–7 mol cm–2 total catalysis is obtained where substrate diffusion in solution limits the reduction rate (LSk mechanism). In HClO4 the mediated reaction is of the surface type and occurs between [Fe(H2O)6]3+ still in solution and the film within a region of molecular dimensions (Sk″ mechanism). These observations are considered in relation to film structure and with regard to potential applications.
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