Moderation of Oxidative Damage on Aromatic Hydrocarbon-Based Polymers

Abstract

During the operation of aromatic hydrocarbon-based proton exchange membrane fuel cells, formed radical species attack the membrane. The most deleterious radical formed is HO·, both strongly electrophilic and oxidising. Oligomers of α-methylstyrene sulfonates (PAMSS) were used as model compounds. We report on the complex reaction cascade following the oxidative attack on aromatic cores bearing proton conductive sulfonate groups. UV-absorption bands of initial oxidation products indicate the formation of radical adducts and aromatic cation radicals. Subsequently, a transformation associated with an absorbance build-up at 580 nm is observed, presumably also related to aromatic cation radicals. Build-up and decay are significantly accelerated at high ionic strength levels that are also typical in fuel cells. Increased ionic strength causes phase separation: dynamic light scattering experiments indicate particle formation that is dependent both on chain length and on ionic strength. Aromatic cation radicals are known strong oxidants. With a presumed redox potential of E°((PAMSS-580 nm)·+/PAMSS) ∼ 2 V this oxidizing species should react also with mediocre reductants. Here, Mn(II) was oxidised to Mn(III) with rate constants of (5–10) × 106 M−1s−1. Implications for experimental design of kinetics experiments and understanding chemical mechanisms are discussed.