Adjustable n→π* electronic transition by sulfonated benzene functionalized g-C3N4 for enhanced photocatalytic H2 generation

Abstract

The photocatalytic efficiency of graphitic carbon nitride (g-C3N4) in hydrogen production is primarily hindered by its poor absorption of visible light, rapid recombination of electron-hole pairs, and the absence of hydroxyl radical formation. Herein, a novel g-C3N4 nanosheets functionalized with sulfonic acid groups were effectively produced through thermal polymerization of melamine and 2, 4-diamino-6-phenyl-1, 3, 5-triazine (DPT), followed by sulfonation treatment. The introduction of the phenyl group brings about alterations to the initial symmetrical arrangement of g-C3N4, leading to the disruption of certain hydrogen bonds. This, in turn, facilitates the movement of electrons from the n to π* orbitals, resulting in enhanced light absorption and improved efficiency in charge separation. Moreover, it induces modifications to the band structure and amplifies the production of hydroxyl radicals. Additionally, the introduction of sulfonic acid enhances the water affinity and the ability of dispersing graphitic carbon nitride in water. The optimized sulfonated benzene-substituted g-C3N4 (1000-BCN-SO3H) with a melamine to DPT ratio of 4:1 exhibits a maximum hydrogen production rate of 6.52 mmol·h−1·g−1 under simulated sunlight irradiation with good cycling stability, which is 3.93 times higher than that of g-C3N4 nanosheets. This research offers a promising opportunity for a novel approach in advancing carbon nitride materials for effective photocatalytic processes.