The selective oxidation of propene to propene oxide (PO) is an industrially relevant and still challenging reaction that requires the design of highly specific catalysts able to improve simultaneously activity and selectivity. Metallic copper exhibits high selectivity toward propene epoxidation that drops when the catalyst surface is oxidized under reaction conditions. On the basis of previous work showing that small planar Cu₅ clusters are more resistant to oxidation than 3D ones, we have performed a detailed theoretical study of the mechanism of propene oxidation with molecular O₂ and atomic O adsorbed on both planar and 3D Cu₅ clusters. The desired pathways leading to PO as well as the undesired routes producing propanal, acetone, or allyl intermediates that finally evolve to acrolein or CO₂ have been considered, and the global analysis of all data indicates that planar Cu₅ clusters are promising candidates for the selective epoxidation of propene.

中文翻译：

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D ₅研究簇形态对Cu ₅催化丙烯环氧化的重要作用。

丙烯选择性氧化为环氧丙烷（PO）是一项与工业相关且仍具有挑战性的反应，需要设计能够同时提高活性和选择性的高特异性催化剂。金属铜对丙烯环氧化的选择性高，当催化剂表面在反应条件下被氧化时，铜的选择性降低。在先前的研究表明小的平面Cu ₅簇比3D簇更耐氧化的基础上，我们对分子O ₂和原子O吸附在平面和3D Cu ₅上的丙烯氧化机理进行了详细的理论研究。集群。已经考虑了导致PO的所需途径以及产生丙醛，丙酮或烯丙基中间体的不良途径，这些中间体最终演变为丙烯醛或CO ₂，并且对所有数据的整体分析表明，平面Cu ₅簇是有希望的候选化合物。丙烯的选择性环氧化。