Design principle of carbon supported single atom catalyst – interplay between d-band periodicity and local hybridization

Carbon-based single atom catalyst has been widely investigated as a potential alternative for noble-metal-based catalysts for hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). Rationale design of such catalysts require not only physical intuitions but also practical descriptors that can be directly applied in experiments. In this work, we establish a practical theoretical framework based on a comprehensive dataset of single atom catalyst compromising 28 metals, 5 types of local environments and adsorption calculations for 4 adsorbates (e.g., H/O/OH/OOH). We disentangle the complex trend of H/OH adsorption as an interplay between d-band periodicity and local hybridization, allowing for the estimation of catalytic performance based solely on the number of valence electrons. By utilizing this dataset and theoretical framework, we have also identified several promising catalyst candidates and overlooked design strategies.