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ACS Nano. 2015 Mar 24;9(3):2635-47. doi: 10.1021/nn506387w. Epub 2015 Feb 16.

Atomic layer-by-layer deposition of platinum on palladium octahedra for enhanced catalysts toward the oxygen reduction reaction.

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†School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United States.
‡The Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, Atlanta, Georgia 30332, United States.
§Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.
∥Department of Materials Science and Engineering, University of Texas at Dallas, Richardson, Texas 75080, United States.


We systematically evaluated two different approaches to the syntheses of Pd@PtnL (n = 2-5) core-shell octahedra. We initially prepared the core-shell octahedra using a polyol-based route by titrating a Pt(IV) precursor into the growth solution containing Pd octahedral seeds at 200 °C through the use of a syringe pump. The number of Pt atomic layers could be precisely controlled from two to five by increasing the volume of the precursor solution while fixing the amount of seeds. We then demonstrated the synthesis of Pd@PtnL octahedra using a water-based route at 95 °C through the one-shot injection of a Pt(II) precursor. Due to the large difference in reaction temperature, the Pd@PtnL octahedra obtained via the water-based route showed sharper corners than their counterparts obtained through the polyol-based route. When compared to a commercial Pt/C catalyst based upon 3.2 nm Pt particles, the Pd@PtnL octahedra prepared using both methods showed similar remarkable enhancement in terms of activity (both specific and mass) and durability toward the oxygen reduction reaction. Calculations based upon periodic, self-consistent density functional theory suggested that the enhancement in specific activity for the Pd@PtnL octahedra could be attributed to the destabilization of OH on their PtnL*/Pd(111) surface relative to the {111} and {100} facets exposed on the surface of Pt/C. The destabilization of OH facilitates its hydrogenation, which was found to be the rate-limiting step of the oxygen reduction reaction on all these surfaces.


core−shell nanocrystals; density functional theory; octahedra; oxygen reduction reaction; platinum-based electrocatalysts


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