Effect of Se modification on RuSey/C electrocatalyst for oxygen reduction with phosphoric acid

Abstract

Carbon-supported Se-modified-Ru catalysts (RuSey/C) were synthesized, and their phosphate adsorption characteristics were evaluated using electrochemical techniques and in-situ X-ray absorption spectroscopy (XAS). When phosphoric acid was added, the ORR activity of unmodified Ru/C decreased by 26.8% because the active sites were blocked by electrochemical adsorption, as confirmed by CV. However, for RuSey/C, the ORR activity was enhanced with phosphoric acid (RuSe1.56/C: 63.8%), which indicates that the kinetics at each site increased to compensate for the site blocking effect. The XAS results demonstrated that, for RuSey/C, phosphoric acid molecules or phosphate anions primarily interacted with Se atoms, and the oxidation state of Ru atoms decreased. Therefore, it was concluded that the enhanced ORR kinetics originated from the decreased oxygen binding energy with larger electrostatic repulsion. (C) 2012 Elsevier B.V. All rights reserved.