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Oxygen Hydration Mechanism for the Oxygen Reduction Reaction at Pt and Pd Fuel Cell Catalysts
journal contributionposted on 2015-12-16, 18:38 authored by Yao Sha, Ted H. Yu, Boris V. Merinov, Pezhman Shirvanian, William A. Goddard
We report the reaction pathways and barriers for the oxygen reduction reaction (ORR) on platinum, both for gas phase and in solution, based on quantum mechanics calculations (PBE-DFT) on semi-infinite slabs. We find a new mechanism in solution: O2 → 2Oad (Eact = 0.00 eV), Oad + H2Oad → 2OHad (Eact = 0.50 eV), OHad + Had → H2Oad (Eact = 0.24 eV), in which OHad is formed by the hydration of surface Oad. For the gas phase (hydrophilic phase of Nafion), we find that the favored step for activation of the O2 is Had + O2ad → HOOad (Eact = 0.30 eV) → HOad + Oad (Eact = 0.12 eV) followed by Oad + H2Oad → 2OHad (Eact = 0.23 eV), OHad + Had → H2Oad (Eact = 0.14 eV). This suggests that to improve the efficiency of ORR catalysts, we should focus on decreasing the barrier for Oad hydration while providing hydrophobic conditions for the OH and H2O formation steps.