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One-Pot Synthesis of Pd@Pt                         nL                          Core-Shell Icosahedral Nanocrystals in High Throughput through a Quantitative Analysis of the Reduction Kinetics
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One-Pot Synthesis of Pd@Pt nL Core-Shell Icosahedral Nanocrystals in High Throughput through a Quantitative Analysis of the Reduction Kinetics

Chi-Ta Lee, Helan Wang, Ming Zhao, Tung-Han Yang, Madeline VaraYounan Xia
Chemistry - A European Journal, 卷.25(20), 頁碼.5322-5329
04/2019
PMID: 30768814

摘要

core–shell kinetic study one-pot oxygen reduction reaction platinum Catalysis Organic Chemistry
The rational design and implementation of a one-pot method is reported for the facile synthesis of Pd@Pt nL (nL denotes the number of Pt atomic layers) core-shell icosahedral nanocrystals in a single step. The success of this method relies on the use of Na 2 PdCl 4 and Pt(acac) 2 as the precursors to Pd and Pt atoms, respectively. Our quantitative analysis of the reduction kinetics indicates that the Pd II and Pt II precursors are sequentially reduced with a major gap between the two events. Specifically, the Pd II precursor is reduced first, leading to the formation of Pd-based icosahedral seeds with a multiply-twinned structure. In contrast, the Pt II precursor prefers to take a surface reduction pathway on the just-formed icosahedral seeds. As such, the otherwise extremely slow reduction of the Pt II precursor can be dramatically accelerated through an autocatalytic process for the deposition of Pt atoms as a conformal shell on each Pd icosahedral core. Compared to the conventional approach of seed-mediated growth, the throughput for the one-pot synthesis of Pd@Pt nL core-shell nanocrystals can be increased by more than 30-fold. When used as catalysts, the Pd@Pt 4.5L core-shell icosahedral nanocrystals show specific and mass activities of 0.83 mA cm −2 and 0.39 A mg Pt −1 , respectively, at 0.9 V toward oxygen reduction. The Pt-based nanocages derived from the core-shell nanocrystals also show enhanced specific (1.45 mA cm −2 ) and mass activities (0.75 A mg Pt −1 ) at 0.9 V, which are 3.8 and 3.3 times greater than those of the commercial Pt/C, respectively.

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