Preparation and voltammetric characterisation of bismuth-modified mesoporous platinum microelectrodes. Application to the electrooxidation of formic acid

In this paper mesoporous platinum microeletrodes (Pt-ME) modified with submonolayers of adsorbed bismuth (Bi-PtME) were prepared and characterised by cyclic voltammetry (CV). The mesoporous platinum films were electrodeposited from hexachloroplatinic acid dissolved in the aqueous domain of the lyotropic liquid crystalline phase of Brij 78^®, to form metal films with hexagonal arrays of nanometer-sized channels. Bismuth deposition was performed by different procedures involving either the spontaneous adsorption of bismuth onto the Pt surface from Bi³⁺ solutions, or by under potential deposition (UPD) of bismuth from Bi³⁺ solutions, by cycling the potential over an useful range, or applying a constant potential for a given time. The latter procedures provided high bismuth coverage (θ_Bi), whereas only small amounts of bismuth could be adsorbed from the simple immersion of the Pt-ME at open circuit. The coverage by irreversibly adsorbed bismuth was checked in a 0.5 M H₂SO₄ solution free of Bi³⁺ ions and exploiting the charge involved in the hydrogen adsorption/desorption, which decreased in proportion to the amount of platinum sites covered by bismuth. The ability of the prepared Bi-PtME towards the oxidation of formic acid was also investigated. It was found that Bi-PtME with θ_Bi = 0.6 provided stationary voltammograms characterised by a low hysteresis between the anodic and cathodic scans. The onset of the waves resulted shifted by about 150 mV towards less positive potentials with respect to that of the corresponding Pt-ME. At 0.1 M HCOOH current densities of about 70 mA cm⁻² were achieved. These results were discussed in terms of high tolerance towards the intermediate poisons of the Bi-PtME investigated here. Bi-PtME with much lower real surface area and bismuth coverage displayed both lower catalytic activity and tolerance to poisons.