Mechanism of Molecular Oxygen Reduction at the Cathode of a PEM Fuel Cell : Non-Electrochemical Reactions on Catalytic Pt Particles

Various catalytic reactions in proton exchange membrane (PEM) fuel cells are discussed, and the effects of different steps, parallel pathways, and side reactions are analyzed for the oxygen reduction reaction (ORR) mechanism. A suitable mechanism table is formulated for the prominent pathway of ORR. The kinetics of the proposed nonelectrochemical reactions on platinum surfaces are then studied using the B3LYP density functional theory (DFT) with the Wadt and Hay relativistic ECPs and basis sets augmented with a 4f function on Pt. The reactions considered are O2(ads) ↔ O(ads) + O(ads) (1), O2H(ads) ↔ O(ads) + OH(ads) (2), H2O(ads) ↔ H(ads) + OH(ads) (3), OH(ads) + OH(ads) ↔ O(ads) + H2O(ads) (4), and OH(ads) + O(ads) ↔ O(ads) + OH(ads) (5). Calibration calculations are carried out for reaction 1 on a single Pt atom using the CASSCF/MRCI method with a cc-pVDZ/relativistic ECP basis set for Pt and the aug-cc-pVDZ basis set for O. Comparison with B3LYP DFT calculations shows that the latter method overestimat...

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