Isotype heterojunction: tuning the heptazine/triazine phase of crystalline nitrogen-rich C3N5 towards multifunctional photocatalytic applications

Abstract

Photocatalytic technology has been well studied as a means to achieve sustainable energy generation through water splitting or chemical synthesis. Recently, a low C/N atomic ratio carbon nitride allotrope, C₃N₅, has been found to be highly prospective due to its excellent electronic properties and ample N-active sites compared to g-C₃N₄. Tangentially, crystalline g-C₃N₄ has also been a prospective candidate due to its improved electron transport and extended π-conjugated system. For the first time, our group successfully employed a one-step molten salt calcination method to prepare novel N-rich crystalline C₃N₅ and elucidate the effect of calcination temperature on the heptazine/triazine phase. Calcination temperatures of 500 °C (CC3N5-500) and 550 °C (CC3N5-550) lead to crystalline carbon nitride with both heptazine and triazine phases, forming an intimate isotype heterojunction for robust interfacial charge separation. An excellent photocatalytic hydrogen evolution rate (359.97 μmol h⁻¹; apparent quantum efficiency (AQE): 12.86% at 420 nm) was achieved using CC3N5-500, which was 15-fold higher than that of pristine C₃N₅. Furthermore, CC3N5-500 exhibited improved activity for simultaneous benzyl alcohol oxidation and hydrogen production, as well as H₂O₂ production (AQE: 9.49% at 420 nm), signifying its multitudinous photoredox capabilities. Moreover, the recyclability tests of the optimal CC3N5-500 on a 3D-printed substrate also showed a 92% performance retention after 4 cycles (16 h). This highlights that crystalline C₃N₅ significantly augmented the reaction performance for diverse multifunctional solar-driven applications. As such, these results serve as a guide toward the structural tuning of 2D metal-free carbon nanomaterials with tunable crystallinity toward achieving boosted photocatalysis.