Challenges and Opportunities in Engineering the Electronic Structure of Single-Atom Catalysts.

Controlling the electronic structure of transition-metal single-atom heterogeneous catalysts (SACs) is crucial to unlocking their full potential. The ability to do this with increasing precision offers a rational strategy to optimize processes associated with the adsorption and activation of reactive intermediates, charge transfer dynamics, and light absorption. While several methods have been proposed to alter the electronic characteristics of SACs, such as the oxidation state, band structure, orbital occupancy, and associated spin, the lack of a systematic approach to their application makes it difficult to control their effects. In this Perspective, we examine how the electronic configuration of SACs can be engineered for thermochemical, electrochemical, and photochemical applications, exploring the relationship with their activity, selectivity, and stability. We discuss synthetic and analytical challenges in controlling and discriminating the electronic structure of SACs and possible directions toward closing the gap between computational and experimental efforts. By bringing this topic to the center, we hope to stimulate research to understand, control, and exploit electronic effects in SACs and ultimately spur technological developments.