Curvature effects on the bifunctional oxygen catalytic performance of single atom metal–N–C

Understanding the fundamental relationship between the structural information of electrocatalysts and their catalytic activities plays a key role in controlling many important electrochemical processes. Recently, single-atom catalysts (SACs) with the so-called MN₄ structure, consisting of a central transition metal quadruply bound to four pyridine nitrogen atoms all situated in an extended carbon-based matrix, have attracted intensive scientific attention owing to their exceptional catalytic performance. In this work, we perform the first-principles density functional theory (DFT) calculations to explore the curvature effects of the carbon matrix surfaces on the catalytic activities for two fundamental electrochemical processes, namely, the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Our DFT results suggest that the curved surface structure can weaken the interaction between the metal atom and the N-doped carbon matrix, modify the electronic structure of the metal atom, and thus increase the adsorption strength of the reaction intermediates, resulting in enhanced OER and ORR catalytic activities of MN₄ catalysts. More importantly, a prediction model is developed to evaluate the bifunctional catalytic activities of such catalysts based on their directly obtained parameters including the surface curvature of the catalysts, the number of d electrons of the metal element, and the electronegativity of the metal atom and its coordination atoms in MN₄ catalysts. This prediction model not only provides some candidates, for example, FeN₄, CoN₄ and OsN₄ for the ORR; CoN₄, NiN₄, RuN₄, RhN₄ and IrN₄ for the OER; and CoN₄, RuN₄, IrN₄ and OsN₄ for the bifunctional ORR and OER, but also reasonably links the structure of catalysts with their catalytic performance, providing new possibilities for the quick design of high-performance catalysts.