On the Sensitivity to Density-Functional Approximations for CO Binding Energies of Single-Atom Catalysts in...

Density functional theory (DFT) methods are the working horse in screening new catalytic materials. They are widely used to predict trends in binding energies, which are then used to compare the activity of different materials. The binding strength of CO is an important descriptor to the CO₂ reduction catalytic activity of the single transition metal atoms embedded on nitrogen-doped graphene (TM/NG). In this work, however, we show that CO binding strengths in different TM/NG has very different sensitivity to DFT methods. Specifically, Fe/NG CO binding energy changes dramatically with the percentage of exact exchange in the functional; Co/NG does less so, while Ni/NG nearly has no change. Such varying behaviors is a direct result of different local spin configurations, similar to the performance of DFT methods for metal porphyrin complexes. Therefore, caution should be exercised when using DFT binding energies for quantitative predictions in TM/NG single atom catalysis.