英国伦敦大学学院Rocreux, Romain团队报道了单原子合金催化剂上吸附物结合的十电子计数规则。相关研究成果于2024年1月23日发表于国际顶尖学术期刊《自然—化学》。

单原子合金最近已经作为高活性和选择性的合金催化剂出现。与纯金属不同，单原子合金跳出了近三十年前开发的用于预测催化性能的既定概念框架。尽管这为探索迄今为止无法实现的化学物质提供了机会，但这让研究人员没有一个简单的指南来设计能够催化靶向反应的单原子合金。

该文中，基于数千个密度泛函理论计算，研究人员揭示了吸附质与掺杂剂原子（通常是单原子合金表面的活性位点）结合的10电子计数规则。一种简单的分子轨道方法使这一规则和吸附质-掺杂剂相互作用的性质合理化。

此外，该直观模型可以加速单原子合金催化剂的合理设计。事实上，研究人员说明了电子计数规则提供的独特见解如何帮助确定，工业相关氢化反应中最有前途的掺杂剂，从而将潜在材料的数量减少一个数量级以上。

附：英文原文

Title: Ten-electron count rule for the binding of adsorbates on single-atom alloy catalysts

Author: Schumann, Julia, Stamatakis, Michail, Michaelides, Angelos, Rocreux, Romain

Issue&Volume: 2024-01-23

Abstract: Single-atom alloys have recently emerged as highly active and selective alloy catalysts. Unlike pure metals, single-atom alloys escape the well-established conceptual framework developed nearly three decades ago for predicting catalytic performance. Although this offers the opportunity to explore so far unattainable chemistries, this leaves us without a simple guide for the design of single-atom alloys able to catalyse targeted reactions. Here, based on thousands of density functional theory calculations, we reveal a 10-electron count rule for the binding of adsorbates on the dopant atoms, usually the active sites, of single-atom alloy surfaces. A simple molecular orbital approach rationalizes this rule and the nature of the adsorbate–dopant interaction. In addition, our intuitive model can accelerate the rational design of single-atom alloy catalysts. Indeed, we illustrate how the unique insights provided by the electron count rule help identify the most promising dopant for an industrially relevant hydrogenation reaction, thereby reducing the number of potential materials by more than one order of magnitude.

DOI: 10.1038/s41557-023-01424-6

Source: https://www.nature.com/articles/s41557-023-01424-6