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电化学(中英文) ›› 2012, Vol. 18 ›› Issue (2): 141-146.  doi: 10.61558/2993-074X.2895

• 化学电源近期研究专辑(武汉大学 杨汉西教授主编) • 上一篇    下一篇

电化学去合金化Pt(Pd)-Cu对氧的电催化还原活性的研究

杨瑞枝1,2,3*, Peter Strasser4, Michael Toney2,3   

  1. 1.苏州大学能源学院,江苏 苏州 215006; 2.斯坦福大学材料和能源科学研究所,美国 斯坦福 94025; 3.斯坦福国家同步辐射光源中心,美国 斯坦福 94025; 4.柏林科技大学化学化工学院,德国 柏林 10623
  • 收稿日期:2011-11-24 修回日期:2012-01-09 出版日期:2012-04-28 发布日期:2012-01-19
  • 通讯作者: 杨瑞枝 E-mail:yangrz@suda. edu. cn
  • 基金资助:

    苏州大学青年教师科学基金(No. SDY2011A04)和美国能源部基金(No. DE-AC02-76SF00515; No. LAB04-20)资助

Catalytic Activities of Electrochemically Dealloyed Pt(Pd)-Cu Catalysts for Oxygen Reduction Reaction

 YANG  Rui-Zhi1,2,3*, , Peter  Strasser4, Michael  Toney2,3   

  1. 1. School of Energy, Soochow University, Suzhou, 215006,China; 2. Stanford Institute for Materials and Energy Science, California 94025, USA; 3. Stanford Synchrotron Radiation Light Source, SLAC National Accelerator Laboratory, California 94025, USA; 4.Department of Chemistry, Chemical Engineering Division, Technical University Berlin, Berlin 10623, Germany
  • Received:2011-11-24 Revised:2012-01-09 Published:2012-04-28 Online:2012-01-19
  • Contact: YANG Rui-Zhi E-mail:yangrz@suda. edu. cn

摘要: 应用电化学去合金法制备了表面覆盖有Pt(Pd)原子层的Pt(Pd)-Cu合金催化剂,研究该催化剂在0.1 mol?L-1 HClO4酸性溶液中对氧气电化学还原的催化活性,并采用同步辐射反常X-射线衍射法(Anomalous X-ray Diffraction,AXRD)和表面X-射线散射法(Surface X-ray Scattering,SXS)从原子尺度研究了去合金化后催化剂的结构.分析对比纳米颗粒、薄膜和单晶3种不同形式的去合金化Pt-Cu的结构和催化活性以及Pt-Cu和Pd-Cu两种不同合金薄膜的结构和催化活性,结果表明表面应力是影响催化剂催化活性的关键因素,而应力大小则与去合金化后所形成的表面Pt(Pd)层的厚度相关;材料尺寸和组成元素等都影响表面Pt(Pd)层的厚度,提出可利用调控材料表面的应力来设计高催化活性的催化剂.

关键词: 氧气电化学还原反应, 电化学去合金, Pt(Pd)-Cu合金, 电催化剂

Abstract: The electrochemically dealloyed Pt(Pd)-Cu catalysts were prepared by electrochemical dealloying of Cu3Pt(Pd) and their catalytic activities toward oxygen reduction reaction (ORR) were studied in 0.1 mol?L-1 HClO4 . solutions. The structural features of the dealloyed Pt(Pd)-Cu were revealed by synchrotron-based anomalous X-ray diffraction (AXRD) and surface X-ray scattering (SXS) at an atomic scale. We established a relationship between the structure and the catalytic activity by comparing the ORR activity and the structure of dealloyed Cu3Pt nanoparticles with similarly dealloyed Cu3Pt thin films and Cu3Pt(111). The enhancement in the activity of the dealloyed Pt(Pd)-Cu is mainly attributed to the strain change in the Pt(Pd) overlayer formed on the surface after dealloying. The strain is related to the thickness of Pt(Pd) overlayer, which is affected by the size of the material and the diffusion coefficient of the constituent element. The catalytic activity for ORR can be tuned by the strain in the surface layer of a catalyst.

Key words: oxygen reduction reaction, electrochemical dealloying, Pt(Pd)-Cu alloy, electrocatalyst

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