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Tuning the C/N Ratio of C-Rich Graphitic Carbon Nitride (g-C3N4) Materials by the Melamine/Carboxylic Acid Adduct Route
Authors:Arianit Gashi  Dr. Julien Parmentier  Dr. Philippe Fioux  Dr. Roman Marsalek
Affiliation:1. Department of Chemistry, University of Ostrava, 30. Dubna 22, Ostrava, 701 03 Czech Republic

Institut de Science des Matériaux de Mulhouse (IS2 M), Université de Strasbourg, Université de Haute-Alsace, 15 rue Jean Starcky, BP 2488, 68057 Mulhouse Cedex, France;2. Institut de Science des Matériaux de Mulhouse (IS2 M), Université de Strasbourg, Université de Haute-Alsace, 15 rue Jean Starcky, BP 2488, 68057 Mulhouse Cedex, France;3. Department of Chemistry, University of Ostrava, 30. Dubna 22, Ostrava, 701 03 Czech Republic

Abstract: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-C3N4 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-C3N4 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.
Keywords:adducts  carbonitrides  carbon-rich g-C3N4  doping  supramolecular chemistry
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