Simultaneous bulk and surface modifications of g-C3N4 via supercritical CO2-assisted post-treatment towards enhanced photocatalytic activity

Abstract

A high-temperature supercritical CO2 (ScCO2)-assisted post-treatment strategy is developed to simultaneously modify the bulk and surface structures of graphitic carbon nitride (g-C3N4) using ScCO2 as penetrant and a small amount of methanol/acetonitrile mixture as modifiers. Specifically, the product of modified g-C3N4 is obtained through the post-treatment of pristine g-C3N4 in a homogeneous ScCO2/methanol/acetonitrile system, continuously heating to reach a target temperature (330 °C, 15.2 MPa) without a residence time. With the assistance of ScCO2, organic molecules penetrate the interlayers of g-C3N4 and subsequently modify the in-plane structure of g-C3N4. Methanol induces the partial transformation of g-C3N4 into a carbon nitride with a poly(heptazine imide)-like structure and with abundant methyl and hydroxyl groups. Simultaneously, acetonitrile polymerizes into 2,4,6-trimethyl-1,3,5-triazine, which is then covalently grafted onto the surface of modified g-C3N4. Remarkably, the entire post-treatment process is completed within 5 min, achieving a final product yield of 92.3 %. The modified g-C3N4 photocatalyst achieves an H2-evolution rate of 2126.1 μmol·h−1·g−1 and a CO2-to-CO conversion rate of 874.1 µmol·h−1·g−1. This work provides a green, efficient, high-yield, and scalable strategy for preparing layered and porous non-metallic photocatalysts using supercritical fluids technology.