通过计算深入了解 Rh(111) 和 Ru(0001) 上 γ-戊内酯加氢脱氧的选择性

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science Pub Date : 2024-10-16 DOI:10.1016/j.susc.2024.122624

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引用次数: 0

摘要

我们结合密度泛函理论和微动力学，探讨了在 Ru 和 Rh 催化剂上观察到的对烷烃、酮类和醇类加氢脱氧产物的选择性差异。我们以 γ-戊内酯为模型化合物，研究了反应机理，以确定决定选择性的物种。我们还探讨了共吸附水分子以及较高吸附剂表面覆盖率对反应壁垒和能量的影响。计算结果表明，所需的烷烃产物在 Ru 上是由酮中间体形成的，而在 Rh 上则是通过酮和醇形成的，不过在 Rh 上对烷烃的选择性要比在 Ru 上低得多。

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Computational insight into the selectivity of γ-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001)

The observed difference in the selectivity towards alkane, ketone, and alcohol hydrodeoxygenation products over Ru and Rh catalysts is explored using a combination of density functional theory and microkinetics. Using

γ

-valerolactone as a model compound, we investigate the reaction mechanism in order to identify selectivity determining species. The effect of the coadsorbed water molecule as well as the higher adsorbate surface coverage on reaction barriers and energies is explored as well. The performed calculations suggest that the desired alkane product is formed from a ketone intermediate on Ru, and through both ketone and alcohol on Rh, although the selectivity towards alkane on Rh is much lower than on Ru.

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来源期刊

Surface Science 化学-物理：凝聚态物理

CiteScore

3.30

自引率

5.30%

发文量

137

审稿时长

25 days

期刊介绍： Surface Science is devoted to elucidating the fundamental aspects of chemistry and physics occurring at a wide range of surfaces and interfaces and to disseminating this knowledge fast. The journal welcomes a broad spectrum of topics, including but not limited to: • model systems (e.g. in Ultra High Vacuum) under well-controlled reactive conditions • nanoscale science and engineering, including manipulation of matter at the atomic/molecular scale and assembly phenomena • reactivity of surfaces as related to various applied areas including heterogeneous catalysis, chemistry at electrified interfaces, and semiconductors functionalization • phenomena at interfaces relevant to energy storage and conversion, and fuels production and utilization • surface reactivity for environmental protection and pollution remediation • interactions at surfaces of soft matter, including polymers and biomaterials. Both experimental and theoretical work, including modeling, is within the scope of the journal. Work published in Surface Science reaches a wide readership, from chemistry and physics to biology and materials science and engineering, providing an excellent forum for cross-fertilization of ideas and broad dissemination of scientific discoveries.