Atomistic Explanation of the Dramatically Improved Oxygen Reduction Reaction of Jagged Platinum Nanowires, 50 Times Better than Pt.

Pt is the best catalyst for the oxygen reduction reactions (ORRs), but it is far too slow. Huang and co-workers showed that dealloying 5 nm Ni7Pt3 nanowires (NW) led to 2 nm pure Pt jagged NW (J-PtNW) with ORRs 50 times faster than Pt/C. They suggested that the undercoordinated surface Pt atoms, mechanical strain, and high electrochemically active surface area (ECSA) are the main contributors. We report here multiscale atomic simulations that further explain this remarkably accelerated ORR activity from an atomistic perspective. We used the ReaxFF reactive force field to convert the 5 nm Ni7Pt3 NW to the jagged 2 nm NW. We applied quantum mechanics to find that 14.4% of the surface sites are barrierless for Oads + H2Oads → 2OHads, the rate-determining step (RDS). The reason is that the concave nature of many surface sites pushes the OH bond of the H2Oads close to the Oads, leading to a dramatically reduced barrier. We used this observation to predict the performance improvement of the J-PtNW relative to Pt (111). Assuming every surface site reacts independently with this predicted rate leads to a 212-fold enhancement at 298.15 K, compared to 50 times experimentally. The atomic structures of the active sites provide insights for designing high-performance electrocatalysts for ORR.