Yafeng Zhang, Hong Li, Fang Liu, Mengwei Li, Yong Zhang, Jinming Cai, Yangsheng Li, Fan Yang, Feng Yin, Junling Lu, Tao Zhang, Bing Yang
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引用次数: 0
摘要
稀合金在气体环境下的结构重组因其结构敏感性而对其催化性能产生了巨大影响,但其结构动力学及其内在机理仍然难以捉摸。在此,我们通过多维成像直接解析了 PdFe0.08 稀合金在 CO 或 O2 环境下的不同动态行为。气态 CO 与铁原子的较强结合刺激了铁从 PdFe0.08 中离析出来,导致铁岛的三维生长,而 O2 的离解吸附则导致离析的 FeO 作为封装覆盖层的二维逐层生长,并与下面的 Pd 表面紧密结合。这种不同的结构显著地调整了 CO 氧化的催化活性,在 CO 处理过的样品中显示出相当高的活性。我们的研究结果揭示了气体诱导的表面偏析中吸附金属与金属之间以及金属与金属之间相互作用的竞争机制,在合理设计具有动态调节结构和反应活性的稀合金时应高度重视这一点。
Revealing Dynamics and Competitive Mechanism of Gas-Induced Surface Segregation of PdFe0.08 Dilute Alloy by Multi-Dimensional Imaging.
The restructuring of dilute alloys under gas environments has shown a great impact on their catalytic performance due to intriguing structural sensitivity, but the structural dynamics and underlying mechanism remains elusive. Herein, we directly resolved the distinct dynamic behaviors of PdFe0.08 dilute alloys under CO or O2 environment by multidimensional imaging. The stronger binding of gaseous CO with Fe atoms stimulates Fe segregation out of the PdFe0.08, resulting in 3D growth of Fe islands, whereas the dissociative adsorption of O2 results in 2D layer-by-layer growth of segregated FeO as encapsulation overlayers that bind strongly with the Pd surface underneath. Such varied structures remarkably tune the catalytic activity for CO oxidation, showing a considerably high activity for a CO-treated sample. Our results reveal the competitive mechanism between adsorbate-metal and metal-metal interaction for gas-induced surface segregation, which should be highly considered for the rational design of dilute alloys with dynamically tuned structure and reactivity.
期刊介绍:
The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.