Insights into the Proton Adsorption on Single-Atom Catalysts using a new Electrostatic Decomposition Model

Using the BAND and ADF modules in the AMS software suite, van Dam and Vermeeren (TheoCheM group, Vrije Universiteit Amsterdam) have uncovered how intrinsic properties of transition metal‑anchored, nitrogen‑doped graphene single‑atom catalysts govern their ability to adsorb substrates.

Single‑atom catalysts combine the advantages of homogeneous and heterogeneous catalysis, offering high activity, selectivity, and optimal metal usage. A key step for any reaction involving single-atom catalysts is how strongly a substrate binds to the single‑atom site. In their new J. Phys. Chem. C article, the authors study the adsorption of the most fundamental adsorbate, the proton, to understand the intrinsic adsorption properties of single-atom catalysts. Using (periodic) DFT calculations with BAND and ADF, the authors uncover that proton adsorption weakens from Ti‑ to Mn‑based single‑atom catalysts and then strengthens again from Mn to Co.

To explain this trend, they introduce a new extension of the energy decomposition analysis (EDA) that separates attractive and repulsive electrostatic contributions and distinguishes intrinsic effects stemming from the nature of the metal from geometric changes along the series of single-atom catalysts. This new theoretical model, combined with the identified bonding trends, delivers meaningful insights for the rational development of next-generation single‑atom catalysts.