Gas bubbling exfoliation strategy towards 3D g-C3N4 hierarchical architecture for superior photocatalytic H2 evolution

Abstract

Graphitic carbon nitride (g-C 3 N 4 ) shows a graphite-like layered structure, which provides a high theoretical value for solar-to-hydrogen evolution especially for a 2D nanostructure. However, conventional polycondensation induces a strong agglomeration and collapse of nanostructure, resulting in a relatively poor photocatalytic performance. To overcome this problem, we develop a gas bubbling exfoliation strategy with NH 4 Cl assistant to make ultrathin 2D g-C 3 N 4 nanosheets self-assembled into a 3D macroporous network on a large scale. The hierarchical structure significantly improves the specific surface area to 176.4 m 2 g −1 (11.6 times higher than the reference g-C 3 N 4 ), which allows a large water/g-C 3 N 4 interface for photocatalytic water reduction reaction. The ultrathin 2D g-C 3 N 4 nanosheets show a thickness of about 1.4 nm, which greatly suppress photoinduced carriers recombination and enhance charge transfer at the interface. Furthermore, the doping of N and Cl is achieved during synthesis. As a result, the resulting g-C 3 N 4 demonstrates a remarkable improvement in H 2 production of 12.89 mmol g -1 h −1 , which is 21 times higher than the g-C 3 N 4 obtained from the conventional condensation method. These explorations provide a facile guidance for the quasi 3D g-C 3 N 4 hierarchical architecture engineering even for various energy-related applications. • Ultrathin 2D g-C 3 N 4 nanosheets self-assembled into a 3D macroporous network. • Enhanced H 2 production of 12.89 mmol g -1 h −1 is achieved, which is 21 times higher. • The hierarchical structure improves the specific surface area to 176.4 m 2 g −1 . • The ultrathin 2D g-C 3 N 4 nanosheets show a thickness of about 1.4 nm.