skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Graphitic carbon nitride C{sub 6}N{sub 9}H{sub 3}.HCl: Characterisation by UV and near-IR FT Raman spectroscopy

Abstract

The graphitic layered compound C{sub 6}N{sub 9}H{sub 3}.HCl was prepared by reaction between melamine and cyanuric chloride under high pressure-high temperature conditions in a piston cylinder apparatus and characterised using SEM, powder X-ray diffraction, UV Raman and near-IR Fourier transform Raman spectroscopy with near-IR excitation. Theoretical calculations using density functional methods permitted evaluation of the mode of attachment of H atoms to nitrogen sites in the structure and a better understanding of the X-ray diffraction pattern. Broadening in the UV and near-IR FT Raman spectra indicate possible disordering of the void sites within the graphitic layers or it could be due to electron-phonon coupling effects. - Graphical abstract: The graphitic layered compound C{sub 6}N{sub 9}H{sub 3}.HCl was prepared by reaction between melamine and cyanuric chloride under high pressure-high temperature conditions in a piston cylinder apparatus and characterised using SEM, powder X-ray diffraction, UV Raman and near-IR Fourier transform Raman spectroscopy using near-IR excitation. Theoretical calculations using density functional methods permitted evaluation of the mode of attachment of H atoms to nitrogen sites around the C{sub 12}N{sub 12} voids within the layered structure and also led to better understanding of the X-ray diffraction pattern. Sharp peaks in the UV Raman spectramore » are due to C{sub 3}N{sub 3} triazine ring units in the structure, that may be enhanced by resonance Raman effects. Broadening in the UV and near-IR FT Raman spectra indicate possible disordering within the graphitic layers or electron-phonon coupling effects.« less

Authors:
 [1];  [1];  [2];  [3];  [1];  [3];  [4]; ;  [1];  [1]
  1. Department of Chemistry and Materials Chemistry Centre, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)
  2. Universite Joseph Fourier, CNRS/INSU, Laboratoire de Planetologie de Grenoble UMR 5109, Batiment D de Physique, BP 53, 38041 Grenoble Cedex 9 (France)
  3. Laboratoire de Sciences de la Terre, Ecole Normale Superieure de Lyon, 46 allee d'Italie 69364 Lyon Cedex 7 (France)
  4. Centre de Recherche sur les Materiaux a Haute Temperature - CNRS F - 45071 Orleans Cedex 2 et Universite d'Orleans, F-45067 Orleans Cedex 2 (France)
Publication Date:
OSTI Identifier:
21372331
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 182; Journal Issue: 10; Other Information: DOI: 10.1016/j.jssc.2009.07.030; PII: S0022-4596(09)00336-3; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBON NITRIDES; DENSITY FUNCTIONAL METHOD; ELECTRON-PHONON COUPLING; GRAPHITE; HYDROCHLORIC ACID; INFRARED SPECTRA; MELAMINE; RAMAN SPECTRA; RAMAN SPECTROSCOPY; SCANNING ELECTRON MICROSCOPY; ULTRAVIOLET SPECTRA; VOIDS; X-RAY DIFFRACTION; AMINES; AZINES; CALCULATION METHODS; CARBON; CARBON COMPOUNDS; CHLORINE COMPOUNDS; COHERENT SCATTERING; COUPLING; DIFFRACTION; ELECTRON MICROSCOPY; ELEMENTS; HALOGEN COMPOUNDS; HETEROCYCLIC COMPOUNDS; HYDROGEN COMPOUNDS; INORGANIC ACIDS; INORGANIC COMPOUNDS; LASER SPECTROSCOPY; MICROSCOPY; MINERALS; NITRIDES; NITROGEN COMPOUNDS; NONMETALS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PNICTIDES; SCATTERING; SPECTRA; SPECTROSCOPY; TRIAZINES; VARIATIONAL METHODS

Citation Formats

McMillan, Paul F., E-mail: p.f.mcmillan@ucl.ac.u, Lees, Victoria, Quirico, Eric, Montagnac, Gilles, Sella, Andrea, Reynard, Bruno, Simon, Patrick, Bailey, Edward, Deifallah, Malek, and Cora, Furio, E-mail: uccacfu@ucl.ac.u. Graphitic carbon nitride C{sub 6}N{sub 9}H{sub 3}.HCl: Characterisation by UV and near-IR FT Raman spectroscopy. United States: N. p., 2009. Web. doi:10.1016/j.jssc.2009.07.030.
McMillan, Paul F., E-mail: p.f.mcmillan@ucl.ac.u, Lees, Victoria, Quirico, Eric, Montagnac, Gilles, Sella, Andrea, Reynard, Bruno, Simon, Patrick, Bailey, Edward, Deifallah, Malek, & Cora, Furio, E-mail: uccacfu@ucl.ac.u. Graphitic carbon nitride C{sub 6}N{sub 9}H{sub 3}.HCl: Characterisation by UV and near-IR FT Raman spectroscopy. United States. doi:10.1016/j.jssc.2009.07.030.
McMillan, Paul F., E-mail: p.f.mcmillan@ucl.ac.u, Lees, Victoria, Quirico, Eric, Montagnac, Gilles, Sella, Andrea, Reynard, Bruno, Simon, Patrick, Bailey, Edward, Deifallah, Malek, and Cora, Furio, E-mail: uccacfu@ucl.ac.u. 2009. "Graphitic carbon nitride C{sub 6}N{sub 9}H{sub 3}.HCl: Characterisation by UV and near-IR FT Raman spectroscopy". United States. doi:10.1016/j.jssc.2009.07.030.
@article{osti_21372331,
title = {Graphitic carbon nitride C{sub 6}N{sub 9}H{sub 3}.HCl: Characterisation by UV and near-IR FT Raman spectroscopy},
author = {McMillan, Paul F., E-mail: p.f.mcmillan@ucl.ac.u and Lees, Victoria and Quirico, Eric and Montagnac, Gilles and Sella, Andrea and Reynard, Bruno and Simon, Patrick and Bailey, Edward and Deifallah, Malek and Cora, Furio, E-mail: uccacfu@ucl.ac.u},
abstractNote = {The graphitic layered compound C{sub 6}N{sub 9}H{sub 3}.HCl was prepared by reaction between melamine and cyanuric chloride under high pressure-high temperature conditions in a piston cylinder apparatus and characterised using SEM, powder X-ray diffraction, UV Raman and near-IR Fourier transform Raman spectroscopy with near-IR excitation. Theoretical calculations using density functional methods permitted evaluation of the mode of attachment of H atoms to nitrogen sites in the structure and a better understanding of the X-ray diffraction pattern. Broadening in the UV and near-IR FT Raman spectra indicate possible disordering of the void sites within the graphitic layers or it could be due to electron-phonon coupling effects. - Graphical abstract: The graphitic layered compound C{sub 6}N{sub 9}H{sub 3}.HCl was prepared by reaction between melamine and cyanuric chloride under high pressure-high temperature conditions in a piston cylinder apparatus and characterised using SEM, powder X-ray diffraction, UV Raman and near-IR Fourier transform Raman spectroscopy using near-IR excitation. Theoretical calculations using density functional methods permitted evaluation of the mode of attachment of H atoms to nitrogen sites around the C{sub 12}N{sub 12} voids within the layered structure and also led to better understanding of the X-ray diffraction pattern. Sharp peaks in the UV Raman spectra are due to C{sub 3}N{sub 3} triazine ring units in the structure, that may be enhanced by resonance Raman effects. Broadening in the UV and near-IR FT Raman spectra indicate possible disordering within the graphitic layers or electron-phonon coupling effects.},
doi = {10.1016/j.jssc.2009.07.030},
journal = {Journal of Solid State Chemistry},
number = 10,
volume = 182,
place = {United States},
year = 2009,
month =
}
  • The atomic arrangement in sp{sup 2}-dominated carbon (C) and carbon nitride (CN{sub x}) thin films has been studied by Raman spectroscopy as a function of substrate temperature and, in the case of CN{sub x}, different N incorporation routes (growth methods). In this way, materials composing graphitelike, fullerenelike (FL), and paracyanogenlike structures have been compared. The results show that each type of arrangement results in a characteristic set of the Raman spectra parameters, which describe the degree of aromatic clustering, bond length, and angle distortion and order in sixfold structures. In the case of C films, the atomic structure evolves withmore » substrate temperature from a disordered network to nanocrystalline planar graphitic configurations, with a progressive promotion in size and ordering of sixfold ring clusters. Nitrogen incorporation favors the promotion of sixfold rings in highly disordered networks produced at low temperatures, but precludes the formation of extended graphiticlike clusters at elevated substrate temperatures (>700 K). In the latter case, N introduces a high degree of disorder in sixfold ring clusters and enhances the formation of a FL microstructure. The formation and growth of aromatic clusters are discussed in terms of substrate temperature, N incorporation, growth rate, film-forming sources, and concurrent bombardment by hyperthermal particles during growth.« less
  • No abstract prepared.
  • Cited by 115
  • Sulfonation of graphitic carbon nitride (g-CN) affords a polar and strongly acidic catalyst, Sg-CN, which displays unprecedented reactivity and selectivity in biodiesel synthesis and esterification reactions at room temperature.
  • A solvothermal method has been successfully applied to prepare crystalline carbon nitride from C{sub 3}N{sub 3}Cl{sub 3} and NaN{sub 3} in CCl{sub 4} at 180 deg. C without any catalyst. The final product was a reddish brown powder. X-ray diffraction pattern indicated that the prepared powder was well-crystallized graphitic carbon nitride. The atomic N/C ratio determined by combustion method was 1.63, indicating a high nitrogen concentration. XPS and FTIR studies showed that graphite-like sp{sup 2} bonded structure existed in the sample. Nanometer scale spherical particles and crinkly lamellas were found in the TEM morphologies.