Structural Investigation of Graphitic Carbon Nitride via XRD and Neutron Diffraction

TLDR

Graphitic carbon nitride has been studied for over a century, yet its three‑dimensional crystal structure remains unconfirmed despite a known two‑dimensional arrangement. The study aims to determine the 3D structure of g‑C₃N₄ using X‑ray diffraction and neutron scattering. Researchers evaluated multiple structural models by comparing calculated XRD patterns to experimental data, then employed neutron scattering to select the model that best fits the 3D structure. The resulting structure consists of parallel tri‑s‑triazine chains stacked in an A–B motif, with layer misalignment reducing π–π repulsion.

Abstract

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.