Benzene Adsorption: A Significant Inhibitor for the Hydrogen Oxidation Reaction in Alkaline Conditions

Slow hydrogen oxidation reaction (HOR) kinetics on Pt under alkaline conditions is a significant technical barrier for the development of high-performance hydroxide exchange membrane fuel cells. Here we report that benzene adsorption on Pt is a major factor responsible for the sluggish HOR. Furthermore, we demonstrate that bimetallic catalysts, such as PtMo/C, PtNi/C, and PtRu/C, can reduce the adsorption of benzene and thereby improve HOR activity. In particular, the HOR voltammogram of PtRu/C in 0.1 M benzyl ammonium showed minimal benzene adsorption. Density functional theory calculations indicate that the adsorption of benzyl ammonium on the bimetallic PtRu is endergonic for all four possible orientations of the cation, which explains the significantly better HOR activity observed for the bimetallic catalysts. The new HOR inhibition mechanism described here provides insights for the design of future polymer electrolytes and electrocatalysts for better-performing polymer membrane-based fuel cells.