From Triazines to Heptazines: Deciphering the Local Structure of Amorphous Nitrogen-Rich Carbon Nitride Materials

Nitrogen-rich carbon nitride (CN x , x >/= 1) network materials have been produced as disordered structures by a variety of precursor-based methods, many that involve solid-state thermolysis at or above 500 degrees C. One popular precursor building block is the triazine unit (C 3N 3), and most postulated amorphous CN x network structures are based on cross-linked triazine units. Since hydrogen is most often observed in the product, these materials are usually more appropriately described as CN x H y materials. Results from recent carbon nitride studies using larger conjugated heptazine (C 6N 7) precursors and from rigorous structural investigations of triazine to heptazine thermal conversion processes have prompted a reexamination of likely local structures present in amorphous carbon nitride networks formed by triazine thermolysis reactions. In the present study, the formation and local structure of a CN x H y material formed via the rapid and exothermic decomposition of a reactive triazine precursor, C 3N 3(NHCl) 3, was examined by byproduct gas mass spectrometry, NMR and IR spectroscopy, base hydrolysis, and crystallographic analysis. The combined results clearly indicate that the moderate-temperature ( approximately 400 degrees C) self-sustaining decomposition of trichloromelamine results in ring fragmentation and reorganization into a CN x H y product that contains predominantly larger heptazine-like structural building blocks. These results may have applicability to many other disordered carbon nitride materials that are formed via triazine thermolysis. It also provides clearer and more accurate structural guidance in the use of these carbon nitrides as photoactive materials or coordination supports for metal and nonmetal species.