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. Thermodynamically stable C3N7 and C3N6 are discovered for the first time via stabilization of NN bonds in tetrazine and/or triazole moieties through a low‐temperature pyrolysis process of 5‐amino‐1H‐tetrazole. Triazole‐based mesoporous C3N7 exhibits better oxygen reduction reaction activity than s‐heptazine‐based carbon nitrides due to its inordinate core structure.