The highly selective hydrogenation to remove olefins is a significant refining approach for the reformate. Herein, a library of transition metal for reformate hydrogenation is tested experimentally to validate the predictive level of catalytic activity from our theoretical framework, which combines ab initio calculations and microkinetic modeling, with consideration of surface H‐coverage effect on hydrogenation kinetics. The favorable H coverage of specific alloy surface under relevant hydrogenation condition, is found to be determined by its corresponding alloy composition. Besides, olefin hydrogenation rate is determined as a function of two descriptors, i.e. H coverage and binding energies of atomic hydrogen, paving the way to computationally screen on metal component in the periodic table. Evaluation of 172 bimetallic alloys based on the activity volcano map, as well as benzene hydrogenation rate, identifies prospective superior candidates and experimentally confirms that Zn3Ir1 outperforms pure Pd catalysts for the selective hydrogenation refining of reformate. The insights into H‐coverage‐related microkinetic modelling have enabled us to both theoretically understand experimental findings and identify novel catalysts, thus, bridging the gap between first‐principle simulations and industrial applications. This work provides useful guidance for experimental catalyst design, which can be easily extended to other hydrogenation reaction.

中文翻译：

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通过考虑氢覆盖的第一原理筛选发现 Pd 之外的用于重整油选择性加氢的合金催化剂

高选择性加氢去除烯烃是重整油的重要精炼方法。在此，对用于重整油加氢的过渡金属库进行了实验测试，以验证我们的理论框架的催化活性预测水平，该理论框架结合了从头计算和微动力学建模，并考虑了表面氢覆盖对加氢动力学的影响。研究发现，特定合金表面在相关氢化条件下的有利氢覆盖度是由其相应的合金成分决定的。此外，烯烃氢化率被确定为两个描述符的函数，即H覆盖率和原子氢的结合能，为计算筛选元素周期表中的金属成分铺平了道路。基于活性火山图和苯加氢速率对 172 双金属合金进行评估，确定了潜在的优质候选材料，并通过实验证实 Zn3Ir1 在重整油选择性加氢精炼方面优于纯 Pd 催化剂。对氢覆盖相关微动力学模型的深入了解使我们能够从理论上理解实验结果并识别新型催化剂，从而弥合第一原理模拟和工业应用之间的差距。这项工作为实验催化剂设计提供了有用的指导，可以很容易地扩展到其他加氢反应。