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Shape-controlled synthesis of Pt-Ir nanocubes with preferential (100) orientation and their unusual enhanced electrocatalytic activities

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Abstract

Pt-Ir nanocubes with (100)-terminated facets were synthesized for the first time and their unusual high electrocatalytic activity for a model reaction (i.e., ammonia oxidation) was reported. The key parameters in controlling the shape of the Pt-Ir nanocubes were systematically investigated by transmission electron microscopy (TEM). The electrocatalytic activities of the prepared Pt-Ir and pure Pt nanoparticles (NPs) were characterized by cyclic voltammetry (CV). The results showed that the amount of W(CO)6 and the volume ratio of oleylamine and oleic acid play a significant role in the development of well-defined Pt-Ir nanocubes. The resultant Pt-Ir nanocubes exhibit (100) orientation, which has been confirmed by not only the structural characterization results from high-resolution TEM (HRTEM) and X-ray diffraction (XRD) but also hydrogen desorption profiles obtained from the CV measurements in H2SO4 solution. Lattice contraction of the Pt-Ir nanocubes were suggested by HRTEM and XRD measurements, and the electronic interactions between Pt and Ir in the Pt-Ir nanocubes were demonstrated by X-ray photoelectron spectroscopy. The Pt-Ir nanocubes show higher specific activity than pure Pt nanocubes and much higher specific activity than the polycrystalline Pt-Ir NPs. The much improved specific activity of the Pt-Ir nanocubes could be attributed to the reason that the introduction of Ir in the Pt-Ir nanocubes largely maintains the highly active Pt (100) sites and thus a positive synergistic effect through the addition of Ir to Pt could be achieved due to the possible bifunctional mechanism and the electronic effect.

摘要

同时控制纳米贵金属颗粒的形状(表面原子结构)和成分对进一步提升其性能具有重要意义. 针对铂铱合金纳米颗粒, 已有研究发现铱原子的引入会降低铂基合金纳米颗粒在一些体系中的催化活性. 本文首次制备了具有(100)择优晶面的铂铱立方体纳米颗粒, 并在一(100)敏感的模型反应(即氨的电催化氧化反应)中, 发现其特殊的高催化活性. 所制备的铂铱立方体纳米颗粒具有规则的(100)晶面特征, 并伴随有晶格收缩现象, 此外铂和铱存在电子交互作用. 铂铱立方体纳米颗粒的特定催化活性高于纯铂纳米颗粒, 并远高于普通多晶铂铱纳米颗粒. 该现象一方面可归因于具有高催化活性的铂(100)活性点, 另一方面可归因于铱和铂的协同效应. 以上研究结果表明, 在铂基合金纳米颗粒形状可控的前提下, 引入铱原子可进一步提升其催化活性, 这对于发展具有高催化活性的贵金属纳米颗粒具有一定的指导意义.

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Authors and Affiliations

  1. Tianjin Key Laboratory of Composite & Functional Materials, Department of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China

    Cheng Zhong, Yida Deng & Wenbin Hu

  2. State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China

    Jie Liu, Zhengyang Ni, Bin Chen & Wenbin Hu

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  1. Cheng Zhong
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  2. Jie Liu
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  3. Zhengyang Ni
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  4. Yida Deng
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  5. Bin Chen
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Correspondence to Wenbin Hu.

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Cheng Zhong became an associate professor at the State Key Laboratory of Metal Matrix Composites, Department of Materials Science & Engineering, Shanghai Jiao Tong University in 2012, and joined the Department of Materials Science & Engineering, Tianjin University in 2014. He graduated from Fudan University with a BSc in 2004 and a PhD in 2009. His recent research interests focus on developing micro/nanostructured materials for electrochemical and electrocatalysis applications.

Wenbin Hu is a professor at the Department of Materials Science & Engineering, Tianjin University. He graduated from Central-South University with a BSc in 1988. He received his MSc from Tianjin University in 1991, and PhD from Central-South University in 1994. His research interests focus on design, synthesis and characterization of advanced nanomaterials for energy storage and conversion applications.

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Zhong, C., Liu, J., Ni, Z. et al. Shape-controlled synthesis of Pt-Ir nanocubes with preferential (100) orientation and their unusual enhanced electrocatalytic activities. Sci. China Mater. 57, 13–25 (2014). https://doi.org/10.1007/s40843-014-0010-5

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