Single-atom electrocatalysis from first principles: Current status and open challenges

Single-atom catalysts (SACs) are heterogenous catalysts with elements in common with coordination compounds. We discuss some fundamental elements required for the suc-cessful computational modeling of SACs for electrocatalytic applications. The first two aspects are the role played by the exchange-correlation functional adopted within a given DFT approach and the role of the local coordination of the active transition metal atom. Next, we discuss new intermediates that can form on SACs and that are not present on extended metal electrodes and how to model solvation, with particular emphasis on the fact that on SACs water can not only act as a solvent but also as a ligand. Finally, we discuss challenges related to the inclusion of pH and voltage in the models and some open issue concerning the rational design of new SACs.

Automated summary

This article discusses several fundamental elements required for successful computational modeling of single-atom catalysts (SACs) for electrocatalytic applications, including the role of the adopted exchange-correlation functional within a given DFT approach and the role of the local coordination of the active transition metal atom. Next, it explores new intermediates that can form on SACs, which are not present on extended metal electrodes, and how to model solvation, with a focus on the dual role of water as both a solvent and a ligand on SACs. Finally, challenges related to the inclusion of pH and voltage in models and some open issues concerning the rational design of new SACs are discussed.