Surface spectators and their role in relationships between activity and selectivity of the oxygen reduction reaction in acid environments

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Abstract

Abstract We use the rotating ring disk (RRDE) method to study activity-selectivity relationships for the oxygen reduction reaction (ORR) on Pt(111) modified by various surface coverages of adsorbed CN<inf>ad</inf> (Θ<inf>CNad</inf>). The results demonstrate that small variations in Θ<inf>CNad</inf> have dramatic effect on the ORR activity and peroxide production, resulting in "volcano-like" dependence with an optimal surface coverage of Θ<inf>CNad</inf> = 0.3 ML. These relationships can be simply explained by balancing electronic and ensemble effects of co-adsorbed CN<inf>ad</inf> and adsorbed spectator species from the supporting electrolytes, without the need for intermediate adsorption energy arguments. Although this study has focused on the Pt(111)-CN<inf>ad</inf>/H<inf>2</inf>SO<inf>4</inf> interface, the results and insight gained here are invaluable for controlling another dimension in the properties of electrochemical interfaces.

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Ciapina, E. G., Lopes, P. P., Subbaraman, R., Ticianelli, E. A., Stamenkovic, V., Strmcnik, D., & Markovic, N. M. (2015). Surface spectators and their role in relationships between activity and selectivity of the oxygen reduction reaction in acid environments. Electrochemistry Communications, 60, 30–33. https://doi.org/10.1016/j.elecom.2015.07.020

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