Gradient-Concentration Design of Stable Core-Shell Nanostructure for Acidic Oxygen Reduction Electrocatalysis.

Manipulating the surface structure of electrocatalysts at the atomic level is of primary importance to simultaneously achieve the activity and stability dual-criteria in oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, a durable acidic ORR electrocatalyst with the "defective-armored" structure of Pt shell and Pt-Ni core nanoparticle decorated on graphene (Pt-Ni@PtD /G) using a facile and controllable galvanic replacement reaction to generate gradient distribution of Pt-Ni composition from surface to interior, followed by a partial dealloying approach, leaching the minor nickel atoms on the surface to generate defective Pt skeleton shell, is reported. The Pt-Ni@PtD /G catalyst shows impressive performance for ORR in acidic (0.1 m HClO4 ) electrolyte, with a high mass activity of threefold higher than that of Pt/C catalyst owing to the tuned electronic structure of locally concave Pt surface sites through synergetic contributions of Pt-Ni core and defective Pt shell. More importantly, the electrochemically active surface areas still retain 96% after 20 000 potential cycles, attributing to the Pt atomic shell acting as the protective "armor" to prevent interior Ni atoms from further dissolution during the long-term operation.