Structural investigation of graphitic carbon nitride via XRD and neutron diffraction

Graphitic carbon nitride (g-C₃N₄) has, since 2009, attracted great attention for its activity as a visible-light-active photocatalyst for hydrogen evolution. Since it was synthesized in 1834, g-C₃N₄ has been extensively studied both catalytically and structurally. Although its 2D structure seems to have been solved, its 3D crystal structure has not yet been confirmed. This study attempts to solve the 3D structure of graphitic carbon nitride by means of X-ray diffraction and of neutron scattering. Initially, various structural models are considered and their XRD patterns compared to the measured one. After selecting possible candidates as g-C₃N₄ structure, neutron scattering is employed to identify the best model that describes the 3D structure of graphitic carbon nitride. Parallel chains of tri-s-triazine units organized in layers with an A–B stacking motif are found to describe the structure of the synthesized graphitic carbon nitride well. A misalignment of the layers is favorable because of the decreased π–π repulsive interlayer interactions.