The Catalytic Reactivity of Alloys; Ethanol and Formic Acid Decomposition on Cu-Pd(110).
The Catalytic Reactivity of Alloys; Ethanol and Formic Acid Decomposition on Cu-Pd(110).
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DOI：
10.1021/acs.jpcc.2c04881
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发表时间：
2022-09-22
影响因子：
3.7
通讯作者：
Perkins, Neil
中科院分区：
文献类型：
--
作者：
Bowker, Michael;Holroyd, Richard;Perkins, Neil
考察了合金化的铜和钯对甲酸和乙醇的反应规律的影响。合金化对材料的电子结构有很大的影响，与单独的Pd相比，d带的能级降低并被填充。因此，预计反应性将受到合金化的强烈影响。甲酸的分解似乎就是这种情况，其程序升温脱附的分解温度因合金化而改变，并在各组分的温度之间(在350K，相比之下，Pd和Cu分别为250和470K)。然而，当选择不同的分子作为表面反应性的探针时，即乙醇，我们得出了非常不同的结论。这里可以看到该合金的两种元素的各自的反应模式，即铜上的脱氢(生成乙醛)和钯上的脱碳(生成甲烷和一氧化碳)。合金化对前一种途径的不稳定和后一种途径的稳定都有影响，但从这项工作中得出的主要结论是，决定反应活性的不是平均电子结构，而是表面组分的单个原子性质。只有单齿吸附才能真正探测到这一行为。
The effect of alloying Cu and Pd on the reactivity pattern for formic acid and for ethanol has been examined. The electronic structure of the material is strongly affected by the alloying, with the d-band lowered in energy and filled, compared with Pd alone. Hence the reactivity would be expected to be strongly affected by the alloying. This appears to be the case for formic acid decomposition, whose decomposition temperature in temperature-programmed desorption is shifted by alloying and is between the temperatures for the individual components (at 350 K, compared with 250 and 470 K for Pd and Cu, respectively). However, when a different molecule is chosen as the probe of surface reactivity, namely, ethanol, we come to a very different conclusion. Here the individual reactivity patterns for the two elemental components of the alloy are seen, namely, dehydrogenation on the Cu (to produce acetaldehyde) and decarbonylation on Pd (to methane and CO). There are effects of alloying on destabilizing the former pathway and stabilizing the latter, but the major conclusion from this work is that it is not average electronic structure that dictates reactivity but the individual atomic nature of the surface components. Only monodentate adsorbates truly probe this behavior.
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