Triazoles: A New Class of Precursors for the Synthesis of Negatively Charged Carbon Nitride Derivatives

Abstract

Carbon nitride polymers were prepared for the first time by the pyrolysis of 3,5-disubstituted-1,2,4-triazole derivatives, namely, 3,5-diamino-1,2,4-triazole [<b>1</b>] and 3-amino-1,2,4-triazole-5-thiol [<b>2</b>], in bulk as well as in LiCl/KCl salt melts. The reaction of [<b>1</b>] and [<b>2</b>] in bulk yields condensed heptazine-based polymers, while in LiCl/KCl eutectics it leads to the formation of well-defined potassium poly­(heptazine imides), according to the results of ¹³C NMR and XPS investigations, whose formation resembles that of emeraldine salts of polyaniline. The density functional calculations supported the structural model suggested for potassium poly­(heptazine imide) polymer. Owing to the specific reaction path, the products obtained from triazoles therefore show electronic properties rather different to known carbon nitrides, such as band gap and conduction and valence bands positions. With the degree of crystallinity of the reference materials, triazole-derived carbon nitrides are characterized by almost complete absence of steady photoluminescence, since charge separation and delocalization upon excitation seem to be improved. As a consequence, photocatalysts prepared from [<b>2</b>] outperform classical carbon nitrides in a model dye degradation reaction and mesoporous graphitic carbon nitride in hydrogen evolution reaction under visible light irradiation. On its turn, [<b>1</b>] can be conveniently used as a comonomer in order to prepare carbon nitrides with improved visible light absorption