Improving the efficiency of Pt-based oxygen reduction reaction (ORR) catalysts while also reducing costs remains an important challenge in energy research. To this end, we synthesized highly stable and active carbon-supported Mo-doped PtCu (Mo-PtCu/C) nanoparticles (NPs) from readily available precursors in a facile one-pot reaction. Mo-PtCu/C displays two-to-fourfold-higher ORR half-cell kinetics than reference PtCu/C and Pt/C materials, a trend that was confirmed in proof-of-concept experiments by using a H2 /O2 microlaminar fuel cell. This Mo-induced activity increase mirrors observations for Mo-PtNi/C NPs and possibly suggests an emerging trend. Electrochemical-accelerated stability tests revealed that dealloying was greatly reduced in Mo-PtCu/C in contrast to the binary alloys PtCu/C and PtMo/C. Supporting DFT studies suggested that the exceptional stability of Mo-PtCu could be attributed to oxidative resistance of the Mo-doped atoms. Furthermore, our calculations revealed that oxygen could induce segregation of Mo to the catalytic surface, at which it effected beneficial changes to the surface oxygen adsorption energetics in the context of the Sabatier principle.
Keywords: alloys; density functional theory; doping; molybdenum; nanoparticles.
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