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The development of cathode oxygen reduction reaction (ORR) catalysts with high characteristics for practical, direct methanol fuel cells (DMFCs) has continuously increased the attention of researchers. In this work, interface-rich Au-doped PdBi (PdBiAu) branched one-dimensional (1D) alloyed nanochains assembled by sub-6.5 nm particles have been prepared, exhibiting an ORR mass activity (MA) of 6.40 A·mgPd−1 and long-term durability of 5,000 cycles in an alkaline medium. The MA of PdBiAu nanochains is 46 times and 80 times higher than that of commercial Pt/C (0.14 A·mgPt−1) and Pd/C (0.08 A·mgPd−1). The MA of binary PdBi nanochains also reaches 5.71 A·mgPd−1. Notably, the PdBiAu nanochains exhibit high in-situ carbon monoxide poisoning resistance and high methanol tolerance. In actual DMFC device tests, the PdBiAu nanochains enhance power density of 140.1 mW·cm−2 (in O2)/112.4 mW·cm−2 (in air) and durability compared with PdBi nanochains and Pt/C. The analysis of the structure–function relationship indicates that the enhanced performance of PdBiAu nanochains is attributed to integrated functions of surficial defect-rich 1D chain structure, improved charge transfer capability, downshift of the d-band center of Pd, as well as the synergistic effect derived from “Pd-Bi” and/or “Pd-Au” dual active sites.
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