Ionic Liquid-Modified Electrocatalysts: The Interaction of [C1C2Im][OTf] with Pt(1 1 1) and its Influence on Methanol Oxidation Studied by Electrochemical {IR} Spectroscopy

By Brummel, Olaf; Faisal, Firas; Bauer, Tanja; Pohako-Esko, Kaija; Wasserscheid, Peter; Libuda, J
Published in Electrochimica Acta NULL 2016

Abstract

Abstract Ionic liquids (ILs) have recently been proposed as modifying agents to tune the selectivity and the activity of electrocatalysts. In order to explore the origin of IL-induced effects on electrocatalytic reactions, we have investigated (i) the interaction of [C1C2Im][OTf]-water mixtures with Pt(1 1 1) single crystal electrodes and (ii) the influence of [C1C2Im][OTf] on methanol oxidation in acidic aqueous solution using cyclic voltammetry (CV) and electrochemical {IR} spectroscopy. We show that [C1C2Im][OTf] interacts strongly with the Pt(1 1 1) surface in the potential range from -0.2 VAg/AgCl to 0.65 VAg/AgCl, leading to partial blocking of the surface, partial suppression of hydrogen adsorption, and partial suppression of {OHads} formation. The interaction of the {IL} with Pt occurs in this potential range via specific adsorption of the [OTf]? anions which bind to Pt(1 1 1) via the SO3? group in a tilted adsorption geometry. The adsorption process is largely reversible as a function of the electrode potential, but shows a complex kinetics and becomes very slow at high {IL} coverage. Also, [C1C2Im][OTf] has a strong effect on the electro-oxidation of methanol in acidic solution. Adsorption of [OTf]? leads to partial blocking of the indirect oxidation pathway to CO. The onset potential for {CO} oxidation is found to be shifted to more positive values indicating hindered access of {H2O} to the electrode surface. {CO} and the [C1C2Im][OTf] form a mixed co-adsorption layer which is characterized by a strongly red-shifted {CO} stretching band. The effect is assigned to an IL-induced ligand effect in the mixed adsorbate layer and suggests that the direct modification of active centers by surface-bound {IL} species plays an important role in IL-modified electrocatalytic materials.

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