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Title: Pressure-induced polymerization of P(CN) 3

Abstract

Motivated to explore the formation of novel extended carbon-nitrogen solids via well-defined molecular precursor pathways, we studied the chemical reactivity of highly pure phosphorous tricyanide, P(CN) 3, under conditions of high pressure at room temperature. Raman and infrared (IR) spectroscopic measurements reveal a series of phase transformations below 10 GPa, and several low-frequency vibrational modes are reported for the first time. Synchrotron powder Xray diffraction (PXRD) measurements taken during compression show that molecular P(CN) 3 is highly compressible with a bulk modulus of 10.0±0.3 GPa and polymerizes into an amorphous solid above ~10.0 GPa. Raman and infrared (IR) spectra, together with first-principles molecular-dynamics simulations, show that the amorphization transition is associated with polymerization of the cyanide groups into CN bonds with predominantly sp 2 character, similar to known carbon nitrides, resulting in a novel PCN polymeric phase, which is recoverable to ambient pressure.

Authors:
ORCiD logo [1];  [2];  [2];  [1];  [1];  [1]
  1. Carnegie Inst. of Washington, Argonne, IL (United States). Geophysical Lab.
  2. Naval Research Lab. (NRL), Washington, DC (United States)
Publication Date:
Research Org.:
Carnegie Inst. of Science, Washington, DC (United States). Geophysical Lab.
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1338321
Alternate Identifier(s):
OSTI ID: 1228173
Grant/Contract Number:  
NA0002006; AC02-06CH11357; FG02-99ER45775; NA0001974
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gou, Huiyang, Yonke, Brendan L., Epshteyn, Albert, Kim, Duck Young, Smith, Jesse S., and Strobel, Timothy A. Pressure-induced polymerization of P(CN) 3. United States: N. p., 2015. Web. doi:10.1063/1.4919640.
Gou, Huiyang, Yonke, Brendan L., Epshteyn, Albert, Kim, Duck Young, Smith, Jesse S., & Strobel, Timothy A. Pressure-induced polymerization of P(CN) 3. United States. doi:10.1063/1.4919640.
Gou, Huiyang, Yonke, Brendan L., Epshteyn, Albert, Kim, Duck Young, Smith, Jesse S., and Strobel, Timothy A. Thu . "Pressure-induced polymerization of P(CN) 3". United States. doi:10.1063/1.4919640. https://www.osti.gov/servlets/purl/1338321.
@article{osti_1338321,
title = {Pressure-induced polymerization of P(CN) 3},
author = {Gou, Huiyang and Yonke, Brendan L. and Epshteyn, Albert and Kim, Duck Young and Smith, Jesse S. and Strobel, Timothy A.},
abstractNote = {Motivated to explore the formation of novel extended carbon-nitrogen solids via well-defined molecular precursor pathways, we studied the chemical reactivity of highly pure phosphorous tricyanide, P(CN)3, under conditions of high pressure at room temperature. Raman and infrared (IR) spectroscopic measurements reveal a series of phase transformations below 10 GPa, and several low-frequency vibrational modes are reported for the first time. Synchrotron powder Xray diffraction (PXRD) measurements taken during compression show that molecular P(CN)3 is highly compressible with a bulk modulus of 10.0±0.3 GPa and polymerizes into an amorphous solid above ~10.0 GPa. Raman and infrared (IR) spectra, together with first-principles molecular-dynamics simulations, show that the amorphization transition is associated with polymerization of the cyanide groups into CN bonds with predominantly sp2 character, similar to known carbon nitrides, resulting in a novel PCN polymeric phase, which is recoverable to ambient pressure.},
doi = {10.1063/1.4919640},
journal = {Journal of Chemical Physics},
number = 19,
volume = 142,
place = {United States},
year = {2015},
month = {5}
}

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Works referenced in this record:

Prediction of New Low Compressibility Solids
journal, August 1989


Low-Compressibility Carbon Nitrides
journal, January 1996


Experimental Realization of the Covalent Solid Carbon Nitride
journal, July 1993


Observation of crystalline C 3 N 4
journal, February 1994


Plasma chemical vapor deposition and properties of hard C 3 N 4 thin films
journal, November 1995

  • Vepr̆ek, S.; Weidmann, J.; Glatz, F.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 13, Issue 6
  • DOI: 10.1116/1.579613

Growth and composition of covalent carbon nitride solids
journal, June 1995

  • Zhang, Z. John; Fan, Shoushan; Lieber, Charles M.
  • Applied Physics Letters, Vol. 66, Issue 26
  • DOI: 10.1063/1.113794

Effect of ultraviolet light irradiation on amorphous carbon nitride films
journal, November 1997

  • Zhang, Mei; Nakayama, Yoshikazu
  • Journal of Applied Physics, Vol. 82, Issue 10
  • DOI: 10.1063/1.366356

Synthesis of carbon nitride films at low temperatures
journal, January 1997

  • Hammer, P.; Baker, M. A.; Lenardi, C.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 15, Issue 1
  • DOI: 10.1116/1.580481

A graphitic carbon nitride
journal, December 1990

  • Sekine, T.; Kanda, H.; Bando, Y.
  • Journal of Materials Science Letters, Vol. 9, Issue 12
  • DOI: 10.1007/BF00721588

Triazine-based Carbon Nitrides for Visible-Light-Driven Hydrogen Evolution
journal, January 2013

  • Schwinghammer, Katharina; Tuffy, Brian; Mesch, Maria B.
  • Angewandte Chemie International Edition, Vol. 52, Issue 9
  • DOI: 10.1002/anie.201206817

Triazine-Based Graphitic Carbon Nitride: a Two-Dimensional Semiconductor
journal, May 2014

  • Algara-Siller, Gerardo; Severin, Nikolai; Chong, Samantha Y.
  • Angewandte Chemie International Edition, Vol. 53, Issue 29
  • DOI: 10.1002/anie.201402191

FORMATION OF C 3 N 4 CLUSTERS BY LASER ABLATION OF NITRIDED GRAPHITE
journal, February 1996


Influence of RF plasma properties on the deposited PACVD CNx layers
journal, December 1997


Experimental study on the stability of graphitic C3N4 under high pressure and high temperature
journal, May 2011


High-Pressure Bulk Synthesis of Crystalline C 6 N 9 H 3 ·HCl:  A Novel C 3 N 4 Graphitic Derivative
journal, August 2001

  • Zhang, Zhihong; Leinenweber, Kurt; Bauer, Matt
  • Journal of the American Chemical Society, Vol. 123, Issue 32
  • DOI: 10.1021/ja0103849

Synthesis of a bulk crystalline phase of carbon nitride
journal, September 1998

  • Dymont, V. P.; Nekrashevich, E. M.; Starchenko, I. M.
  • Journal of Experimental and Theoretical Physics Letters, Vol. 68, Issue 6
  • DOI: 10.1134/1.567896

Synthesis of carbon nitride crystals at high pressures and temperatures
journal, December 1998

  • He, D. W.; Zhang, F. X.; Zhang, X. Y.
  • Journal of Materials Research, Vol. 13, Issue 12
  • DOI: 10.1557/JMR.1998.0471

Synthesis of nanocrystalline nitrogen-rich carbon nitride powders at high pressure
journal, December 2002


High-pressure pyrolysis study of C 3 N 6 H 6 : a route to preparing bulk C 3 N 4
journal, October 2002


Structure and stability of carbon nitride under high pressure and high temperature up to 125GPa and 3000K
journal, October 2013


High-Pressure Synthesis of Crystalline Carbon Nitride Imide, C2N2(NH)
journal, February 2007

  • Horvath-Bordon, Elisabeta; Riedel, Ralf; McMillan, Paul F.
  • Angewandte Chemie International Edition, Vol. 46, Issue 9
  • DOI: 10.1002/anie.200603851

Novel Synthetic Routes to Carbon Nitride
journal, July 1995

  • Todd, M.; Kouvetakis, J.; Groy, T. L.
  • Chemistry of Materials, Vol. 7, Issue 7
  • DOI: 10.1021/cm00055a023

Theoretical Tracing of a Novel Route from Molecular Precursors through Polymers to Dense, Hard C 3 N 4 Solids
journal, May 1999

  • Kroll, Peter; Hoffmann, Roald
  • Journal of the American Chemical Society, Vol. 121, Issue 19
  • DOI: 10.1021/ja984406b

Identification of new pillared-layered carbon nitride materials at high pressure
journal, July 2013

  • Salamat, Ashkan; Deifallah, Malek; Cabrera, Raul Quesada
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02122

Phosphorus-Doped Carbon Nitride Solid: Enhanced Electrical Conductivity and Photocurrent Generation
journal, May 2010

  • Zhang, Yuanjian; Mori, Toshiyuki; Ye, Jinhua
  • Journal of the American Chemical Society, Vol. 132, Issue 18
  • DOI: 10.1021/ja101749y

Unique Electronic Structure Induced High Photoreactivity of Sulfur-Doped Graphitic C 3 N 4
journal, August 2010

  • Liu, Gang; Niu, Ping; Sun, Chenghua
  • Journal of the American Chemical Society, Vol. 132, Issue 33
  • DOI: 10.1021/ja103798k

Synthesis of Molecular Precursors to Carbon−Nitrogen−Phosphorus Polymeric Systems
journal, February 1998

  • McMurran, Jeff; Kouvetakis, J.; Nesting, David C.
  • Chemistry of Materials, Vol. 10, Issue 2
  • DOI: 10.1021/cm9705799

Synthesis of LiBC 4 N 4 , BC 3 N 3 , and Related C−N Compounds of Boron:  New Precursors to Light Element Ceramics
journal, August 2000

  • Williams, Darrick; Pleune, Brett; Kouvetakis, J.
  • Journal of the American Chemical Society, Vol. 122, Issue 32
  • DOI: 10.1021/ja0006752

Structural and electronic properties of C3N4−nPn (n=0,1,2,3,4)
journal, August 2004


Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts
journal, January 2008

  • Thomas, Arne; Fischer, Anna; Goettmann, Frederic
  • Journal of Materials Chemistry, Vol. 18, Issue 41
  • DOI: 10.1039/b800274f

A metal-free polymeric photocatalyst for hydrogen production from water under visible light
journal, November 2008

  • Wang, Xinchen; Maeda, Kazuhiko; Thomas, Arne
  • Nature Materials, Vol. 8, Issue 1
  • DOI: 10.1038/nmat2317

Graphitic carbon nitride materials: controllable synthesis and applications in fuel cells and photocatalysis
journal, January 2012

  • Zheng, Yao; Liu, Jian; Liang, Ji
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee03479d

Ueber eine Verbindung des Cyans mit Phosphor
journal, January 1863


Ueber den Cyanphosphor
journal, January 1864


The crystal and molecular structure of phosphorus tricyanide
journal, September 1964


Das Schwingungsspektrum des Phosphortricyanids
journal, August 1961

  • Goubeau, J.; Haeberle, H.; Ulmer, H.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 311, Issue 1-2
  • DOI: 10.1002/zaac.19613110115

Infrared and Raman spectra of P(CN)3 and As(CN)3
journal, April 1965


The Raman spectra of phosphorus and arsenic tricyanides, P(CN)3 and As(CN)3
journal, January 1976

  • Edwards, H. G. M.; Ingman, J. S.; Long, D. A.
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 32, Issue 4
  • DOI: 10.1016/0584-8539(76)80141-9

Vibrational frequencies and structural determination of phosphorous tricyanide
journal, September 2004

  • Jensen, James O.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 60, Issue 11
  • DOI: 10.1016/j.saa.2003.12.032

The infrared and Raman spectra of ClC(CN)3 and the [C(CN)3]− ion
journal, January 1963


The Raman and i.r. spectra of methyl phosphorus dicyanide and methyl arsenic dicyanide
journal, January 1976

  • Edwards, H. G. M.; Ingman, J. S.; Long, D. A.
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 32, Issue 4
  • DOI: 10.1016/0584-8539(76)80142-0

Phase Transitions and Thermodynamic Properties of Rubidium and Cesium Cyanides
journal, August 1968

  • Sugisaki, Masayasu; Matsuo, Takasuke; Suga, Hiroshi
  • Bulletin of the Chemical Society of Japan, Vol. 41, Issue 8
  • DOI: 10.1246/bcsj.41.1747

Neutron diffraction study of KCN III and KCN IV at high pressure
journal, October 1974


Crystal structure of rubidium cyanide at 4 K determined by neutron powder diffraction
journal, February 1984


High-pressure behavior of the alkali cyanides KCN and NaCN
journal, July 1999


High‐pressure Raman and x‐ray studies of the alkali cyanides up to 27 GPa
journal, September 1985

  • Strössner, K.; Hochheimer, H. D.; Hönle, W.
  • The Journal of Chemical Physics, Vol. 83, Issue 5
  • DOI: 10.1063/1.449289

Physical and chemical transformations of sodium cyanide at high pressures
journal, October 2009

  • Chen, Jing-Yin; Yoo, Choong-Shik
  • The Journal of Chemical Physics, Vol. 131, Issue 14
  • DOI: 10.1063/1.3245861

Phosphorus-carbon nuclear magnetic coupling constants in phosphorus(III) cyanides
journal, January 1990


Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions
journal, January 1986

  • Mao, H. K.; Xu, J.; Bell, P. M.
  • Journal of Geophysical Research, Vol. 91, Issue B5, p. 4673-4676
  • DOI: 10.1029/JB091iB05p04673

Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408

XRDA 3.1 - a program for X-ray diffraction analysis on a PC
journal, February 1998


Phonons and related crystal properties from density-functional perturbation theory
journal, July 2001

  • Baroni, Stefano; de Gironcoli, Stefano; Dal Corso, Andrea
  • Reviews of Modern Physics, Vol. 73, Issue 2
  • DOI: 10.1103/RevModPhys.73.515

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


Chemical and phase transformations of cyanogen at high pressures
journal, December 1986

  • Yoo, Choong Shik; Nicol, Malcolm
  • The Journal of Physical Chemistry, Vol. 90, Issue 25
  • DOI: 10.1021/j100283a028

Pressure-induced phase transition and polymerization of tetracyanoethylene (TCNE)
journal, March 2013

  • Tomasino, Dane; Chen, Jing-Yin; Kim, Minesob
  • The Journal of Chemical Physics, Vol. 138, Issue 9
  • DOI: 10.1063/1.4793710

K 3 Fe(CN) 6 : Pressure-Induced Polymerization and Enhanced Conductivity
journal, November 2013

  • Li, Kuo; Zheng, Haiyan; Ivanov, Ilia N.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 46
  • DOI: 10.1021/jp407429z

Raman spectroscopic study of high-pressure behavior of Ag 3 [Co(CN) 6 ]
journal, August 2011


Large negative linear compressibility of Ag3[Co(CN)6]
journal, November 2008

  • Goodwin, A. L.; Keen, D. A.; Tucker, M. G.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 48
  • DOI: 10.1073/pnas.0804789105

Solid state polymerization of cyanoacetylene into conjugated linear chains under pressure
journal, July 1989

  • Aoki, K.; Kakudate, Y.; Yoshida, M.
  • The Journal of Chemical Physics, Vol. 91, Issue 2
  • DOI: 10.1063/1.457130

Optical modes of t r a n s ‐polyacetylene
journal, January 1981

  • Schügerl, F. B.; Kuzmany, H.
  • The Journal of Chemical Physics, Vol. 74, Issue 2
  • DOI: 10.1063/1.441151

Graphitic network models of ‘‘diamondlike’’ carbon
journal, January 1990

  • Tamor, M. A.; Wu, C. H.
  • Journal of Applied Physics, Vol. 67, Issue 2
  • DOI: 10.1063/1.345808

Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon
journal, July 2001


Modeling studies of amorphous carbon
journal, July 1984


Symmetry breaking in nitrogen-doped amorphous carbon: Infrared observation of the Raman-active G and D bands
journal, June 1989


Superhard and Elastic Carbon Nitride Thin Films Having Fullerenelike Microstructure
journal, August 1995


Role of nitrogen in the formation of hard and elastic CN x thin films by reactive magnetron sputtering
journal, February 1999

  • Hellgren, Niklas; Johansson, Mats P.; Broitman, Esteban
  • Physical Review B, Vol. 59, Issue 7
  • DOI: 10.1103/PhysRevB.59.5162

Ultraviolet and visible Raman studies of nitrogenated tetrahedral amorphous carbon films
journal, May 2000


Triggering dynamics of the high-pressure benzene amorphization
journal, December 2006

  • Ciabini, Lucia; Santoro, Mario; Gorelli, Federico A.
  • Nature Materials, Vol. 6, Issue 1
  • DOI: 10.1038/nmat1803

High-pressure polymerization of phenylacetylene and of the benzene and acetylene moieties
journal, January 2003

  • Santoro, Mario; Ciabini, Lucia; Bini, Roberto
  • Journal of Raman Spectroscopy, Vol. 34, Issue 7-8
  • DOI: 10.1002/jrs.1024

Molecules under extreme conditions: Chemical reactions at high pressure
journal, January 2003

  • Schettino, Vincenzo; Bini, Roberto
  • Physical Chemistry Chemical Physics, Vol. 5, Issue 10
  • DOI: 10.1039/b301381b

Benzene bridges under pressure
journal, January 2007


Calculated high‐pressure properties of solid acetylene and possible polymerization paths
journal, February 1987

  • LeSar, R.
  • The Journal of Chemical Physics, Vol. 86, Issue 3
  • DOI: 10.1063/1.452238

Revisiting the Electronic Structure of Phosphazenes
journal, November 2005

  • Chaplin, Adrian B.; Harrison, John A.; Dyson, Paul J.
  • Inorganic Chemistry, Vol. 44, Issue 23
  • DOI: 10.1021/ic0511266

Structure and Conformation of the Medium-Sized Chlorophosphazene Rings
journal, August 2014

  • Bowers, David J.; Wright, Brian D.; Scionti, Vincenzo
  • Inorganic Chemistry, Vol. 53, Issue 17
  • DOI: 10.1021/ic500272b

Synthesis of a New Class of Fused Cyclotetraphosphazene Ring Systems
journal, December 2014

  • Beşli, Serap; Mutlu, Ceylan; İbişoğlu, Hanife
  • Inorganic Chemistry, Vol. 54, Issue 1
  • DOI: 10.1021/ic5025235

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