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Galvanic replacement dominates the structure of Pt decorated Cu@Pd nanoparticles. With proper Pt loading, it converts Cu@Pd-Pt from a surface disordered structure to multiple twin particles (MTPS) and gain the highest stability in the oxygen reduction reaction among the experimental samples.

A ternary metallic CuPdPt nanocatalyst (NC) is synthesized using a wet chemical reduction method, which is sequentially designed, in the presence of acid treated carbon nanotubes. This NC is a nanocrystal with a configuration of a Cu@Pd core and atomic Pt clusters (∼9 wt%) on the top (Cu@Pd/Pt). A residual current of 92.6%, 5.2 times higher than that of commercial Pt catalysts (at 0.85 V vs. RHE), is retained after 40 000 cycles of an accelerated degradation test (ADT). Atomic and electronic structure analyses show that such exclusive stability mainly results from electron localization at Pt clusters in heterogeneous interfaces of the Cu-Pd core. Most importantly, we develop a robust ternary NC, which shows outstanding MA, superior chemical durability, and ∼90 wt% lower Pt loading than commercial Pt NCs in the oxygen reduction reaction.

Hierarchical structures in shell with transition metal underneath is a promising design for high-performance and low-cost heterogeneous nanocatalysts (NCs). Such a design enables the optimum extent of synergetic effects in NC surface. It facilitates intermediate reaction steps and, therefore, boosts activity of NC in oxygen reduction reaction (ORR). In this study, carbon nanotube (CNT)-supported ternary metallic NC comprising Cu cluster -in-Pd cluster nanocrystal and surface decoration of atomic Pt clusters (14 wt %) is synthesized by using the wet chemical reduction method with sequence and reaction time controls. By annealing in H 2 environment (H 2 /N 2 = 9:1, 10 sccm) at 600 K for 2 h, specific activity of Cu@Pd/Pt is substantially improved by ∼2.0-fold as compared to that of the pristine sample and commercial Pt catalysts. By cross-referencing results of electron microscopic, X-ray spectroscopic, and electrochemical analyses, we demonstrated that reduction annealing turns ternary NC into complex of Cu 3 Pt alloy and Cu x Pd 1– x alloy. Such a transition preserves Pt and Pd in metallic phases, therefore improving the activity by ∼29% and the stability of NC in an accelerated degradation test (ADT) as compared to those of pristine Cu@Pd/Pt in 36 000 cycles at 0.85 V (vs RHE). This study presents robust H 2 annealing for structure stabilization of NC and systematic characterizations for rationalization of the corresponding mechanisms. These results provide promising scenarios for facilitation of heterogeneous NC in ORR applications.

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