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 successful 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.