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•Poisoning effect of benzene-containing hydrocarbon-based ionomers on Pt catalysts.•Two types of orientation-dependent adsorption of benzenesulfonic acid anion for Pt.•Changes in PZTC of Pt surface according to the sequence of electrolyte replacement.•Combination of various electrochemical analyses and XPS/TPD measurements.•Time-dependent anion adsorption affecting the long-term stability of fuel cell electrodes.
Membrane electrode assembly (MEA) is an essential component that mainly determines the performance of proton exchange membrane fuel cells (PEMFCs). In the electrodes of the MEA, ionomers are mixed with Pt-based nanoparticles to transfer protons to the Pt surface where electrochemical reactions take place. However, Pt catalysts suffer from the poisoning effect of ionomers with proton-conducting groups such as sulfonic acid (SA), resulting in performance deterioration. In particular, for emerging hydrocarbon-based ionomers, the benzene group, which is commonly used to improve their chemical structure, accelerates the poisoning effect. Herein, we experimentally simulate the adsorption of SA and benzenesulfonic acid (BSA) on Pt nanoparticles, revealing the orientation-dependent poisoning effect of BSA on the Pt surface.