Unravelling Distance-Dependent Inter-Site Interactions and Magnetic Transition Effects of Heteronuclear Single Atom Catalysts on Electrochemical Oxygen Reduction

Abstract: Inter-site interactions between single atom catalysts (SACs) in the high loading regime are critical to tuning the catalytic performance. However, the understanding on such interactions and their distance dependent effects remains elusive, especially for the heteronuclear SACs. In this study, we reveal the effects of the distance-dependent inter-site interaction on the catalytic performance of SACs. Using the density functional theory calculations, we systematically investigate the heteronuclear iron and cobalt single atoms co-supported on the nitrogen-doped graphene (FeN4-C and CoN4-C) for oxygen reduction reaction (ORR). We find that as the distance between Fe and Co SACs decreases, FeN4-C exhibits a reduced catalytic activity, which can be mitigated by the presence of an axial hydroxyl ligand, whereas the activity of CoN4-C shows a volcano-like evolution with the optimum reached at the intermediate distance. We further unravel that the transition towards the high-spin state upon adsorption of ORR intermediate adsorbates is responsible for the decreased activity of both FeN4-C and CoN4-C at short inter-site distance. Such high-spin state transition is also found to significantly shift the linear relation between hydroxyl (*OH) and hydroperoxyl (*OOH) adsorbates. These findings not only shed light on the SAC-specific effect of the distance-dependent inter-site interaction between heteronuclear SACs, but also pave a way towards shifting the long-standing linear relations observed in multiple-electron chemical reactions.