Low‐Pt NiNC‐Supported PtNi Nanoalloy Oxygen Reduction Reaction Electrocatalysts—In Situ Tracking of the Atomic Alloying Process

We report and analyze a synthetic strategy toward low‐Pt platinum‐nickel (Pt‐Ni) alloy nanoparticle (NP) cathode catalysts for the catalytic electroreduction of molecular oxygen to water. The synthesis involves the pyrolysis and leaching of Ni‐organic polymers, subsequent Pt NP deposition, followed by thermal alloying, resulting in single Ni atom site (NiNC)‐supported PtNi alloy NPs at low Pt weight loadings of only 3–5 wt %. Despite low Pt weight loading, the catalysts exhibit more favorable Pt‐mass activities compared to conventional 20–30 wt % benchmark PtNi catalysts. Using in situ microscopic techniques, we track and unravel the key stages of the PtNi alloy formation process directly at the atomic scale. Surprisingly, we find that carbon‐encapsulated metallic Ni@C structures, rather than NiN( x ) sites, act as the Ni source during alloy formation. Our materials concepts offer a pathway to further decrease the overall Pt content in hydrogen fuel cell cathodes.