The phase diagram and hardness of carbon nitrides

Dong, Huafeng; Oganov, Artem R.; Zhu, Qiang; Qian, Guang-Rui

doi:10.1038/srep09870

The phase diagram and hardness of carbon nitrides

Journal Article · Wed May 06 00:00:00 EDT 2015 · Scientific Reports

DOI:https://doi.org/10.1038/srep09870· OSTI ID:1184778

Dong, Huafeng ^[1]; Oganov, Artem R. ^[2]; Zhu, Qiang ^[3]; Qian, Guang-Rui ^[3]

Stony Brook Univ., NY (United States). Dept. of Geosciences and Center for Materials by Design, Inst. for Advanced Computational Science; BROOKHAVEN SCIENCE ASSOCIATES, LLC
Stony Brook Univ., NY (United States). Dept. of Geosciences and Center for Materials by Design, Inst. for Advanced Computational Science; Moscow Inst. of Physics and Technology (Russian Federation); Northwestern Polytechnical Univ., Xi'an (China). School of Materials Science]; Zhu, Qiang [Stony Brook Univ., NY (United States). Dept. of Geosciences and Center for Materials by Design, Inst. for Advanced Computational Science
Stony Brook Univ., NY (United States). Dept. of Geosciences and Center for Materials by Design, Inst. for Advanced Computational Science

Novel superhard materials, especially those with superior thermal and chemical stability, are needed to replace diamond. Carbon nitrides (C-N), which are likely to possess these characteristics and have even been expected to be harder than diamond, are excellent candidates. Here we report three new superhard and thermodynamically stable carbon nitride phases. Based on a systematic evolutionary structure searches, we report a complete phase diagram of the C-N system at 0–300 GPa and analyze the hardest metastable structures. Surprisingly, we find that at zero pressure, the earlier proposed graphitic-C₃N₄ structure (P6-bar m2) is dynamically unstable, and we find the lowest-energy structure based on s-triazine unit and s-heptazine unit.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: Government of the Russian Federation; National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1184778

Journal Information:: Scientific Reports, Journal Name: Scientific Reports Vol. 5; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Ionothermal Synthesis of Crystalline, Condensed, Graphitic Carbon Nitride Bojdys, Michael J.; Müller, Jens-Oliver; Antonietti, Markus Chemistry - A European Journal, Vol. 14, Issue 27 https://doi.org/10.1002/chem.200800190	journal	September 2008
Semiempirical GGA-type density functional constructed with a long-range dispersion correction Grimme, Stefan Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799 https://doi.org/10.1002/jcc.20495	journal	January 2006
Structure and stability of carbon nitride under high pressure and high temperature up to 125GPa and 3000K Kojima, Yohei; Ohfuji, Hiroaki Diamond and Related Materials, Vol. 39 https://doi.org/10.1016/j.diamond.2013.07.006	journal	October 2013
How Evolutionary Crystal Structure Prediction Works—and Why Oganov, Artem R.; Lyakhov, Andriy O.; Valle, Mario Accounts of Chemical Research, Vol. 44, Issue 3 https://doi.org/10.1021/ar1001318	journal	March 2011
Photodegradation Performance of g-C ₃ N ₄ Fabricated by Directly Heating Melamine Yan, S. C.; Li, Z. S.; Zou, Z. G. Langmuir, Vol. 25, Issue 17 https://doi.org/10.1021/la900923z	journal	September 2009
Anomalous piezoelectricity in two-dimensional graphene nitride nanosheets Zelisko, Matthew; Hanlumyuang, Yuranan; Yang, Shubin Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5284	journal	June 2014
A metal-free polymeric photocatalyst for hydrogen production from water under visible light Wang, Xinchen; Maeda, Kazuhiko; Thomas, Arne Nature Materials, Vol. 8, Issue 1 https://doi.org/10.1038/nmat2317	journal	November 2008
Polymorphic phases of sp ³ -hybridized superhard CN Wang, Xiaoli The Journal of Chemical Physics, Vol. 137, Issue 18 https://doi.org/10.1063/1.4765324	journal	November 2012
Electronegativity Identification of Novel Superhard Materials Li, Keyan; Wang, Xingtao; Zhang, Fangfang Physical Review Letters, Vol. 100, Issue 23 https://doi.org/10.1103/physrevlett.100.235504	journal	June 2008
Comment on “Hardness of Covalent and Ionic Crystals: First-Principle Calculations” Liu, Z. Y.; Guo, Xiaoju; He, Julong Physical Review Letters, Vol. 98, Issue 10 https://doi.org/10.1103/physrevlett.98.109601	journal	March 2007
Prediction of New Low Compressibility Solids Liu, A. Y.; Cohen, M. L. Science, Vol. 245, Issue 4920 https://doi.org/10.1126/science.245.4920.841	journal	August 1989
Evolutionary Crystal Structure Prediction as a Method for the Discovery of Minerals and Materials Oganov, A. R.; Ma, Y.; Lyakhov, A. O. Reviews in Mineralogy and Geochemistry, Vol. 71, Issue 1 https://doi.org/10.2138/rmg.2010.71.13	journal	January 2010
High-Pressure Synthesis of Crystalline Carbon Nitride Imide, C2N2(NH) Horvath-Bordon, Elisabeta; Riedel, Ralf; McMillan, Paul F. Angewandte Chemie International Edition, Vol. 46, Issue 9 https://doi.org/10.1002/anie.200603851	journal	February 2007
gt-C ₃ N ₄ -The First Stable Binary Carbon(IV) Nitride Kroke, Edwin Angewandte Chemie International Edition, Vol. 53, Issue 42 https://doi.org/10.1002/anie.201406427	journal	August 2014
Equation of state and phase stability of turbostratic carbon nitride Solozhenko, Vladimir L.; Solozhenko, Elena G.; Zinin, Pavel V. Journal of Physics and Chemistry of Solids, Vol. 64, Issue 8 https://doi.org/10.1016/S0022-3697(03)00111-2	journal	August 2003
A review of the preparation of carbon nitride films Muhl, Stephen; Méndez, Juan Manuel Diamond and Related Materials, Vol. 8, Issue 10 https://doi.org/10.1016/S0925-9635(99)00142-9	journal	October 1999
New developments in evolutionary structure prediction algorithm USPEX Lyakhov, Andriy O.; Oganov, Artem R.; Stokes, Harold T. Computer Physics Communications, Vol. 184, Issue 4 https://doi.org/10.1016/j.cpc.2012.12.009	journal	April 2013
Experimental study on the stability of graphitic C3N4 under high pressure and high temperature Fang, Leiming; Ohfuji, Hiroaki; Shinmei, Toru Diamond and Related Materials, Vol. 20, Issue 5-6 https://doi.org/10.1016/j.diamond.2011.03.034	journal	May 2011
A novel application of g-C3N4 thin film in photoelectrochemical anticorrosion Bu, Yuyu; Chen, Zhuoyuan; Yu, Jianqiang Electrochimica Acta, Vol. 88 https://doi.org/10.1016/j.electacta.2012.10.049	journal	January 2013
Modeling hardness of polycrystalline materials and bulk metallic glasses Chen, Xing-Qiu; Niu, Haiyang; Li, Dianzhong Intermetallics, Vol. 19, Issue 9 https://doi.org/10.1016/j.intermet.2011.03.026	journal	September 2011
Polymeric Graphitic Carbon Nitride for Heterogeneous Photocatalysis Wang, Xinchen; Blechert, Siegfried; Antonietti, Markus ACS Catalysis, Vol. 2, Issue 8 https://doi.org/10.1021/cs300240x	journal	July 2012
A Novel Superhard Tetragonal Carbon Mononitride Zhang, Meiguang; Wei, Qun; Yan, Haiyan The Journal of Physical Chemistry C, Vol. 118, Issue 6 https://doi.org/10.1021/jp409152t	journal	January 2014
Electronic and Structural Properties of Two-Dimensional Carbon Nitride Graphenes Deifallah, Malek; McMillan, Paul F.; Corà, Furio The Journal of Physical Chemistry C, Vol. 112, Issue 14 https://doi.org/10.1021/jp711483t	journal	March 2008
Tri-s-triazine derivatives. Part I. From trichloro-tri-s-triazine to graphitic C3N4 structuresPart II: Alkalicyamelurates M3[C6N7O3], M = Li, Na, K, Rb, Cs, manuscript in preparation. Kroke, Edwin; Schwarz, Marcus; Horath-Bordon, Elisabeth New Journal of Chemistry, Vol. 26, Issue 5 https://doi.org/10.1039/b111062b	journal	April 2002
Shock synthesis and characterization of new diamond-like carbon nitrides Komatsu, Tamikuni Physical Chemistry Chemical Physics, Vol. 6, Issue 5 https://doi.org/10.1039/b315695h	journal	January 2004
Corrugated layered heptazine-based carbon nitride: the lowest energy modifications of C3N4 ground state Gracia, J.; Kroll, P. Journal of Materials Chemistry, Vol. 19, Issue 19 https://doi.org/10.1039/b821568e	journal	January 2009
A novel low compressible and superhard carbon nitride: Body-centered tetragonal CN2 Li, Quan; Liu, Hanyu; Zhou, Dan Physical Chemistry Chemical Physics, Vol. 14, Issue 37 https://doi.org/10.1039/c2cp41694h	journal	January 2012
Synthesis of superhard cubic BC2N Solozhenko, Vladimir L.; Andrault, Denis; Fiquet, Guillaume Applied Physics Letters, Vol. 78, Issue 10 https://doi.org/10.1063/1.1337623	journal	March 2001
Predicting hardness of dense C3N4 polymorphs He, Julong; Guo, Licong; Guo, Xiaoju Applied Physics Letters, Vol. 88, Issue 10 https://doi.org/10.1063/1.2182109	journal	March 2006
Crystal structure prediction using ab initio evolutionary techniques: Principles and applications Oganov, Artem R.; Glass, Colin W. The Journal of Chemical Physics, Vol. 124, Issue 24 https://doi.org/10.1063/1.2210932	journal	June 2006
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Density-functional theory investigation of hardness, stability, and electron-energy-loss spectra of carbon nitrides with C 11 N 4 stoichiometry Mattesini, M.; Matar, S. F. Physical Review B, Vol. 65, Issue 7 https://doi.org/10.1103/PhysRevB.65.075110	journal	January 2002
Symmetry-general least-squares extraction of elastic data for strained materials from ab initio calculations of stress Le Page, Yvon; Saxe, Paul Physical Review B, Vol. 65, Issue 10 https://doi.org/10.1103/PhysRevB.65.104104	journal	February 2002
Strain dependent bonding in solid C 3 N 4 : High elastic moduli but low strength Zhang, Yi; Sun, Hong; Chen, Changfeng Physical Review B, Vol. 73, Issue 6 https://doi.org/10.1103/PhysRevB.73.064109	journal	February 2006
Most likely phase of superhard BC 2 N by ab initio calculations Zhou, Xiang-Feng; Sun, Jian; Fan, Ya-Xian Physical Review B, Vol. 76, Issue 10 https://doi.org/10.1103/PhysRevB.76.100101	journal	September 2007
First-principles calculations of the ferroelastic transition between rutile-type and CaCl 2 -type SiO 2 at high pressures Togo, Atsushi; Oba, Fumiyasu; Tanaka, Isao Physical Review B, Vol. 78, Issue 13 https://doi.org/10.1103/PhysRevB.78.134106	journal	October 2008
Superhard semiconducting C 3 N 2 compounds predicted via first-principles calculations Tian, Fubo; Wang, Jinhua; He, Zhi Physical Review B, Vol. 78, Issue 23 https://doi.org/10.1103/PhysRevB.78.235431	journal	December 2008
Evolutionary search for superhard materials: Methodology and applications to forms of carbon and TiO 2 Lyakhov, Andriy O.; Oganov, Artem R. Physical Review B, Vol. 84, Issue 9 https://doi.org/10.1103/PhysRevB.84.092103	journal	September 2011
Strong excitonic effects in the optical properties of graphitic carbon nitride g -C 3 N 4 from first principles Wei, Wei; Jacob, Timo Physical Review B, Vol. 87, Issue 8 https://doi.org/10.1103/PhysRevB.87.085202	journal	February 2013
Electronegativity Identification of Novel Superhard Materials Li, Keyan; Wang, Xingtao; Zhang, Fangfang Physical Review Letters, Vol. 100, Issue 23 https://doi.org/10.1103/PhysRevLett.100.235504	journal	June 2008
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Hardness of Covalent Crystals Gao, Faming; He, Julong; Wu, Erdong Physical Review Letters, Vol. 91, Issue 1 https://doi.org/10.1103/PhysRevLett.91.015502	journal	July 2003
Hardness of Covalent and Ionic Crystals: First-Principle Calculations Šimůnek, Antonín; Vackář, Jiří Physical Review Letters, Vol. 96, Issue 8 https://doi.org/10.1103/PhysRevLett.96.085501	journal	March 2006
Low-Compressibility Carbon Nitrides Teter, D. M.; Hemley, R. J. Science, Vol. 271, Issue 5245 https://doi.org/10.1126/science.271.5245.53	journal	January 1996
Metastable host-guest structure of carbon Zhu, Q.; Feya, O. D.; Boulfelfel, S. E. Journal of Superhard Materials, Vol. 36, Issue 4 https://doi.org/10.3103/S1063457614040030	journal	July 2014

Cited By (11)

Cubic C3N: A New Superhard Phase of Carbon-Rich Nitride Wei, Qun; Zhang, Quan; Yan, Haiyan Materials, Vol. 9, Issue 10 https://doi.org/10.3390/ma9100840	journal	October 2016
Investigation on the Stability of Derivative Melam from Melamine Pyrolysis under High Pressure Yuan, Xiaohong; Luo, Kun; Wu, Yingju Nanomaterials, Vol. 8, Issue 3 https://doi.org/10.3390/nano8030172	journal	March 2018
Nitrogen oxides under pressure stability, ionization, polymerization, and superconductivity Li, Dongxu; Oganov, Artem R.; Dong, Xiao arXiv https://doi.org/10.48550/arxiv.1506.08362	preprint	January 2015
(L) ₂ C ₂ P ₂ : Dicarbondiphosphide Stabilized by N-Heterocyclic Carbenes or Cyclic Diamido Carbenes Li, Zhongshu; Chen, Xiaodan; Andrada, Diego M. Angewandte Chemie, Vol. 129, Issue 21 https://doi.org/10.1002/ange.201612247	journal	April 2017
(L) ₂ C ₂ P ₂ : Dicarbondiphosphide Stabilized by N-Heterocyclic Carbenes or Cyclic Diamido Carbenes Li, Zhongshu; Chen, Xiaodan; Andrada, Diego M. Angewandte Chemie International Edition, Vol. 56, Issue 21 https://doi.org/10.1002/anie.201612247	journal	April 2017
Ferroelectricity and Elasticity of Rhombohedral BiFeO ₃ Under Uniaxial Stress Dong, Huafeng; Wu, Zhigang; Wu, Fugen physica status solidi (RRL) - Rapid Research Letters, Vol. 12, Issue 4 https://doi.org/10.1002/pssr.201700431	journal	February 2018
Pharaoh's Serpents: New Insights into a Classic Carbon Nitride Material: Pharaoh's Serpents: New Insights into a Classic Carbon Nitride Material Miller, Thomas S.; d'Aleo, Anita; Suter, Theo Zeitschrift für anorganische und allgemeine Chemie, Vol. 643, Issue 21 https://doi.org/10.1002/zaac.201700268	journal	October 2017
Alkaline-earth metal (Mg) polynitrides at high pressure as possible high-energy materials Wei, Shuli; Li, Da; Liu, Zhao Physical Chemistry Chemical Physics, Vol. 19, Issue 13 https://doi.org/10.1039/c6cp08771j	journal	January 2017
Carbon nitrides: synthesis and characterization of a new class of functional materials Miller, T. S.; Jorge, A. Belen; Suter, T. M. Physical Chemistry Chemical Physics, Vol. 19, Issue 24 https://doi.org/10.1039/c7cp02711g	journal	January 2017
One step synthesis of efficient photocatalysts by TCAP doped g-C ₃ N ₄ for enhanced visible-light photocatalytic activity Wu, Hao; Huo, Yaoxing New Journal of Chemistry, Vol. 44, Issue 3 https://doi.org/10.1039/c9nj05270d	journal	January 2020
Ground-state structures, physical properties and phase diagram of carbon-rich nitride C ₅ N Wu, Qinghua; Hu, Qianku; Hou, Yiming Journal of Physics: Condensed Matter, Vol. 30, Issue 38 https://doi.org/10.1088/1361-648x/aada2c	journal	August 2018

Similar Records

Hydrazone-Linked Heptazine Polymeric Carbon Nitrides for Synergistic Visible-Light-Driven Catalysis

Journal Article · Mon Jun 01 20:00:00 EDT 2020 · Chemistry - A European Journal · OSTI ID:1632322

Advanced processing and properties of superhard materials

Book · Thu Jun 01 00:00:00 EDT 1995 · OSTI ID:55363

Synthesis of Ultra‐Incompressible and Recoverable Carbon Nitrides Featuring CN ₄ Tetrahedra

Journal Article · Sat Dec 09 19:00:00 EST 2023 · Advanced Materials · OSTI ID:2580525

Related Subjects

36 MATERIALS SCIENCE

The phase diagram and hardness of carbon nitrides

Citation Formats

References (46)

Cited By (11)

Similar Records

Related Subjects