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Oxygen reduction on nanocrystalline ruthenia - local structure effects

机译:氧化氧化铝钌 - 局部结构效应的氧气还原

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摘要

Nanocrystalline ruthenium dioxide and doped ruthenia of the composition Ru1-xMxO2 (M = Co, Ni, Zn) with 0 <= x <= 0.2 were prepared by the spray-freezing freeze-drying technique. The oxygen reduction activity and selectivity of the prepared materials were evaluated in alkaline media using the RRDE methodology. All ruthenium based oxides show a strong preference for a 2-electron oxygen reduction pathway at low overpotentials. The catalysts' selectivity shifts towards the 4-electron reduction pathway at high overpotentials (i.e. at potentials below 0.4 V vs. RHE). This trend is particularly noticeable on non-doped and Zn-doped catalysts; the materials containing Ni and Co produce a significant fraction of hydrogen peroxide even at high overpotentials. The suppression of the 4-electron reduction pathway on Ni and Co-doped catalysts can be accounted for by the presence of the Ni and Co cations in the cus binding sites as shown by the DFT-based analyses on non-doped and doped catalysts.
机译:通过喷雾冷冻冷冻干燥技术制备组合物Ru1-XMXO2(M = CO,Ni,Zn)的组合物Ru1-XMXO2(M = CO,Ni,Zn)的纳米晶钌和掺杂的钌。 使用RRDE方法在碱性培养基中评估制备的材料的氧还原活性和选择性。 所有钌的氧化物在低过电位下表现出为2氧化氧还原途径的强烈偏好。 催化剂的选择性在高过电位下朝向4-电子还原途径(即,在0.4V与RHE以下的电位下)。 在非掺杂和Zn掺杂的催化剂上尤其明显这种趋势; 含有Ni和Co的材料即使在高过电位上也产生显着的过氧化氢。 通过CUS结合位点中的Ni和Co阳离子的存在,可以考虑Ni和共掺杂催化剂上的4-电子还原途径的抑制,如非掺杂和掺杂催化剂上的DFT基础分析所示。

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  • 来源
    《RSC Advances》 |2015年第2期|共9页
  • 作者单位

    Acad Sci Czech Republic J Heyrovsky Inst Phys Chem Dept Electrocatalysis CR-18223 Prague Czech Republic;

    Northeastern Univ Dept Chem &

    Chem Biol Boston MA 02115 USA;

    Acad Sci Czech Republic J Heyrovsky Inst Phys Chem Dept Electrocatalysis CR-18223 Prague Czech Republic;

    Acad Sci Czech Republic J Heyrovsky Inst Phys Chem Dept Electrocatalysis CR-18223 Prague Czech Republic;

    Tech Univ Denmark Dept Phys Ctr Atom Scale Mat Design DK-2800 Lyngby Denmark;

    Tech Univ Denmark Dept Phys Ctr Atom Scale Mat Design DK-2800 Lyngby Denmark;

    Acad Sci Czech Republic J Heyrovsky Inst Phys Chem Dept Electrocatalysis CR-18223 Prague Czech Republic;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;
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