Three-Dimensional Hierarchical Seaweed-Derived Carbonaceous Network with Designed g-C3N4 Nanosheets: Preparation and Mechanism Insight for 4-Nitrophenol Photoreduction

The development of g-C₃N₄-based photocatalysts with abundant active sites is of great significance for photocatalytic reactions. Herein, a smart and robust strategy was presented to fabricate three-dimensional (3D) g-C₃N₄ nanosheet-coated alginate-based hierarchical porous carbon (g-C₃N₄@HPC), including coating melamine on calcium alginate (CA) hydrogel beads, freeze-drying hydrogel beads as well as pyrolysis at high temperatures. The resulting photocatalyst possessed a significantly high surface area and a large amount of interconnected macropores compared with porous carbon without the melamine coating. The unique structural features could effectively inhibit the curling and agglomeration of g-C₃N₄ nanosheets, provide abundant photocatalytic active sites, and promote mass diffusion. Therefore, the g-C₃N₄@HPC composite exhibited remarkable photocatalytic activity and outstanding stability toward the photoreduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH₄ under natural sunlight and simulated visible-light irradiation (λ > 420 nm) using a 300 W xenon lamp. Moreover, the mechanism toward the photocatalytic reaction was extensively studied by quenching experiments and electron spin resonance (ESR) experiments. The results showed that active hydrogen species were able to be achieved by following a dual-channel pathway in the NaBH₄ system, which included photocatalytic reduction of H⁺ ions and photocatalytic oxidation of BH₄^- ions. This work not only opens up a new way to design efficient photocatalysts for various reactions but also provides a reference for an in-depth study of the photoreduction mechanism.