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

Abstract

AbstractSingle-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.