Modeling Single‐Atom Catalysis

Electronic structure calculations represent an essential complement of experiments to characterize single-atom catalysts (SACs), consisting of isolated metal atoms stabilized on a support, but also to predict new catalysts. However, simulating SACs with quantum chemistry approaches is not as simple as often assumed. In this work, the essential factors that characterize a reliable simulation of SACs activity are examined. The Perspective focuses on the importance of precise atomistic characterization of the active site, since even small changes in the metal atom's surroundings can result in large changes in reactivity. The dynamical behavior and stability of SACs under working conditions, as well as the importance of adopting appropriate methods to solve the Schrödinger equation for a quantitative evaluation of reaction energies are addressed. The Perspective also focuses on the relevance of the model adopted. For electrocatalysis this must include the effects of the solvent, the presence of electrolytes, the pH, and the external potential. Finally, it is discussed how the similarities between SACs and coordination compounds may result in reaction intermediates that usually are not observed on metal electrodes. When these aspects are not adequately considered, the predictive power of electronic structure calculations is quite limited.