Molecular Origin of the Selectivity Differences between Palladium and Gold–Palladium in Benzyl Alcohol Oxidation: Different Oxygen Adsorption Properties
Molecular Origin of the Selectivity Differences between Palladium and Gold–Palladium in Benzyl Alcohol Oxidation: Different Oxygen Adsorption Properties
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DOI：
10.1002/cctc.201601295
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发表时间：
2017-01
期刊：
影响因子：
4.5
通讯作者：
A. Savara;C. E. Chan-Thaw;Jonathan E. Sutton;Di Wang;L. Prati;A. Villa
中科院分区：
文献类型：
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作者：
A. Savara;C. E. Chan-Thaw;Jonathan E. Sutton;Di Wang;L. Prati;A. Villa
苯甲醇在Pd/C上的氧化机理和微观动力学模型同样适用于苯甲醇在AuPd/C上的氧化。几乎所有的选择性差异可以解释为减少在AuPd上的氧吸附。在隔离氧吸附作为选择性差异的起源后，密度泛函理论被用来研究纯Pd表面、纯Au表面和合金化AuPd表面的氧吸附性质。计算结果表明，Au-Pd合金化降低了相对于纯Pd的氧吸附性能，这解释了选择性差异，与微观动力学模型一致。
The same mechanism and microkinetic model used for benzyl alcohol oxidation over Pd/C was shown to apply to benzyl alcohol oxidation over AuPd/C. Almost all of the selectivity differences could be explained by a decrease in oxygen adsorption on AuPd. After isolating oxygen adsorption as being the origin of the selectivity differences, density functional theory was used to investigate the oxygen adsorption properties of a pure Pd surface, a pure Au surface, and an alloyed AuPd surface. The calculations showed that Au–Pd alloying decreased the oxygen adsorption properties relative to pure Pd, which explained the selectivity differences, consistent with the microkinetic modeling.