General Pyrolysis for High-Loading Transition Metal Single Atoms on 2D-Nitro-Oxygeneous Carbon as Efficient ORR Electrocatalysts.

Single-atom catalysts (SACs) possess the potential to involve the merits of both homogeneous and heterogeneous catalysts altogether and thus have gained considerable attention. However, the large-scale synthesis of SACs with rich isolate-metal sites by simple and low-cost strategies has remained challenging. In this work, we report a facile one-step pyrolysis that automatically produces SACs with high metal loading (5.2-15.9 wt %) supported on two-dimensional nitro-oxygenated carbon (M-2D-NOC) without using any solvents and sacrificial templates. The method is also generic to various transition metals and can be scaled up to several grams based on the capacity of the containers and furnaces. The high density of active sites with N/O coordination geometry endows them with impressive catalytic activities and stability, as demonstrated in the oxygen reduction reaction (ORR). For example, Fe-2D-NOC exhibits an onset potential of 0.985 V vs RHE, a half-wave potential of 0.826 V, and a Tafel slope of -40.860 mV/dec. Combining the theoretical and experimental studies, the high ORR activity could be attributed its unique FeO-NO structure, which facilitates effective charge transfer between the surface and the intermediates along the reaction, and uniform dispersion of this active site on thin 2D nanocarbon supports that maximize the exposure to the reactants.