Core–shell catalysts consisting of nanoporous cores for oxygen reduction reaction

Abstract

A comprehensive experimental study was conducted on the dealloying of PdNi₆ nanoparticles under various conditions. A two-stage dealloying protocol was developed to leach >95% of Ni while minimizing the dissolution of Pd. The final structure of the dealloyed particle was strongly dependent on the acid used and temperature. When H₂SO₄ and HNO₃ solutions were used in the first stage of dealloying, solid and porous particles were generated, respectively. The porous particles have a 3-fold higher electrochemical surface area per Pd mass than the solid ones. The dealloyed PdNi₆ nanoparticles were then used as a core material for the synthesis of core–shell catalysts. These catalysts were synthesized in gram-size batches and involved Pt displacement of an underpotentially deposited (UPD) Cu monolayer. The resulting materials were characterized by scanning transmission electron microscopy (STEM) and in situ X-ray diffraction (XRD). The oxygen reduction reaction (ORR) activity of the core–shell catalysts is 7-fold higher than the state-of-the-art Pt/C. The high activity was confirmed by a more than 40 mV improvement in fuel cell performance with a Pt loading of 0.1 mg cm⁻² by using the core–shell catalysts.