Thermodynamically Stable Mesoporous C3N7 and C3N6 with Ordered Structure and Their Excellent Performance for Oxygen Reduction Reaction

Carbon nitrides with a high N/C atomic ratio (>2) are expected to offer superior basicity and unique electronic properties. However, the synthesis of these nanostructures is highly challenging since many parts of the C? N frameworks in the carbon nitride should be replaced with thermodynamically less stable N? N frameworks as the nitrogen content increases. Thermodynamically stable C₃N₇ and C₃N₆ with an ordered mesoporous structure are synthesized at 250 and 300 °C respectively via a pyrolysis process of 5‐amino‐1H‐tetrazole (5‐ATTZ). Polymerization of the precursor to the ordered mesoporous C₃N₇ and C₃N₆ is clearly proved by X‐ray and electron diffraction analyses. A combined analysis including diverse spectroscopy and FDMNES and density functional theory (DFT) calculations demonstrates that the N? N bonds are stabilized in the form of tetrazine and/or triazole moieties in the C₃N₇ and C₃N₆. The ordered mesoporous C₃N₇ represents the better oxygen reduction reaction (ORR) performances (onset potential: 0.81 V vs reversible hydrogen electrode (RHE), electron transfer number: 3.9 at 0.5 V vs RHE) than graphitic carbon nitride (g‐C₃N₄) and the ordered mesoporous C₃N₆. The study on the mechanism of ORR suggests that nitrogen atoms in the tetrazine moiety of the ordered mesoporous C₃N₇ act as active sites for its improved ORR activity.