Tuning the C/N Ratio of C‐Rich Graphitic Carbon Nitride (g‐C 3 N 4 ) Materials by the Melamine/Carboxylic Acid Adduct Route

C-rich graphitic carbonitride materials (CNx ) with a large range of compositions have been prepared thanks to the self-assembly, in different ratios, of melamine (M) and a panel of polycarboxylic acids (A) such as oxalic, tartaric and citric acid. The thermal conversion of the formed adducts (MAy ), led to CNx phases, with x ranging from 0.66 to 1.4 (x=1.33 for g-C3 N4 for comparison). The properties of these materials were examined by different techniques (XRD, Raman spectroscopy, TEM, TGA, XPS and DRIFT). It appears that the increase in the C content is associated with the disappearance of the long-range order of heptazine units and an increase in the sub-nanometer carbon-rich cluster size within the graphitic g-C3 N4 structure. This trend is followed by a significant increase in the interlayer spacing and a lower proportion of N=C-N bonds compared to C=C bonds. The thermal stability under an inert atmosphere of these phases and their UV-Visible absorbance properties were also investigated.