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Comprehension of the impact of electrolyte nature and concentration on Pt degradation is essential for the improvement of durability of catalyst layers (CLs), which are the heart of polymer electrolyte membrane fuel cells (PEMFCs). Electrochemical and chemical dissolution of polycrystalline Pt in aqueous CF 3 SO 3 H, H 2 SO 4 , and HClO 4 solutions of different concentrations (c = 0.1 and 0.5 M) upon potential switching and holding in the 0.60−1.20 V versus RHE range is analyzed using inductively coupled plasma mass spectroscopy. This potential range mimics the conditions encountered in operating PEMFCs. Trifluoromethanesulfonic acid (CF 3 SO 3 H) is employed because it is the smallest fluorinated sulfonic acid and can serve as a model molecule. Degradation of Pt in H 2 SO 4 and HClO 4 solutions is examined for comparative analysis. The results reveal that the electrolyte concentration has a significant impact on Pt electrochemical and chemical dissolution. The amount of dissolved Pt in 0.1 M solutions of CF 3 SO 3 H, H 2 SO 4 , and HClO 4 is practically the same and lower than that in analogous 0.5 M solutions. However, the amount of dissolved Pt in 0.5 M H 2 SO 4 solution is greater than that in 0.5 M solutions of CF 3 SO 3 H or HClO 4 . The influence of anion nature and pH on Pt dissolution is examined in 0.1 and 0.5 M HClO 4 solutions without and with 1.0 × 10 −2 M H 2 SO 4 addition. The results show that under these conditions the anion nature has no or negligible impact on Pt dissolution, but pH significantly affects the process. An analysis of potential versus pH diagrams (Pourbaix diagrams) for acid solutions of different pH values suggests that Pt degradation (with the formation of Pt 2+ (aq) and Pt 4+ (aq)) might proceed through both electrochemical and chemical pathways.

The metal-binding affinity of the anionic poly-y-D-glutamyl capsule of Bacillus licheniformis was investigated by using Na+, Mg2+, Al3+, Ca2+, Cr3+, Mn2+, Fe3+, Ni2+, and Cu2+. Purified capsule was suspended in various concentrations of the chloride salts of the various metals, and after dialysis the bound metals were analyzed either by graphite furnace atomic absorption spectroscopy or by inductively coupled plasma-mass spectrometry. Exposure of purified capsule to excess concentrations of Na+ revealed it to contain 8.2 ,umol of anionic sites per mg on the basis of Na binding. This was confirmed by titration of the capsule with HCI and NaOH. Other metal ions were then added in ionic concentrations equivalent to 25, 50, 75, 100, 200, and 400% of the available anionic sites. The binding characteristics varied with the metal being investigated. Addition of Cu2+, Al3+, Cr3+, or Fe3+ induced flocculation. These metal ions showed the greatest affinity for B. licheniformis capsule in competitive-binding experiments. Flocculation was not seen with the addition of other metal ions. With the exception of Ni2+ and Fe3+ all capsule-metal-binding sites readily saturated. Ni2+ had low affinity for the polymer, and its binding was increased at high metal concentrations. Fe3+ binding resulted in the development of rust-colored ferrihydrite which itself could bind additional metal. Metal-binding characteristics of B. licheniformis capsule appear to be influenced by the chemical and physical properties of both the capsule and the metal ions.