Copolymerization of CO and N2 to Extended CON2 Framework Solid at High Pressures

Yoo, Choong-Shik; Kim, Minseob; Lim, Jinhyuk; Ryu, Young Jay; Batyrev, Iskander G.

doi:10.1021/acs.jpcc.8b03415

Title: Copolymerization of CO and N₂ to Extended CON₂ Framework Solid at High Pressures

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Abstract

Synthesis of novel extended forms of nitrogen and nitrogen-rich materials has been a topic of interest in development of high-energy-density materials. Here, we present the formation of high-density (3.983 g/cm³) copolymer CON₂, formed in crystalline form by laser heating of CO–N₂ mixtures above 1700 K and 45 GPa—a substantially lower pressure–temperature condition than those required for converting pure nitrogen (above 110 GPa and 2000 K). It can be made even at lower pressures ~20 GPa at ambient temperature for amorphous solid. According to the refined structure, the crystalline polymer is made of nitrogen-hybridized, eight-membered rings of singly bonded CON₂ in a three-dimensional framework structure in the space group of P4₃, as one of the previously predicted structures. Furthermore, unlike the predicted structures, the present P4₃ solid converts back to ε-N₂-like and δ-N₂-like molecular phases as pressure unloads to 20 and 10 GPa, respectively.

Authors:

^[1]; Kim, Minseob ^[1]; Lim, Jinhyuk ^[1];

^[2];

^[3]

Washington State Univ., Pullman, WA (United States)
Washington State Univ., Pullman, WA (United States); Univ. of Chicago, IL (United States)
Army Research Lab., Aberdeen Proving Ground, MD (United States)

Publication Date:: 2018-06-06

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA); NSF-DMR; ARO; Defense Advanced Research Projects Agency (DARPA)

OSTI Identifier:: 1463722

Grant/Contract Number:: NA0001974; NA0003342; 1701360; W911NF-17-1-0468; W31P4Q-12-1-0009

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 24; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: ENGLISH

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; mixtures; chemical structure; physical and chemical processes; nitrogen; polymers

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                    Yoo, Choong-Shik, Kim, Minseob, Lim, Jinhyuk, Ryu, Young Jay, and Batyrev, Iskander G. Copolymerization of CO and N2 to Extended CON2 Framework Solid at High Pressures.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcc.8b03415.

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                    Yoo, Choong-Shik, Kim, Minseob, Lim, Jinhyuk, Ryu, Young Jay, & Batyrev, Iskander G. Copolymerization of CO and N2 to Extended CON2 Framework Solid at High Pressures.  United States.  https://doi.org/10.1021/acs.jpcc.8b03415

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                    Yoo, Choong-Shik, Kim, Minseob, Lim, Jinhyuk, Ryu, Young Jay, and Batyrev, Iskander G. Wed .  
"Copolymerization of CO and N2 to Extended CON2 Framework Solid at High Pressures".  United States.  https://doi.org/10.1021/acs.jpcc.8b03415.  https://www.osti.gov/servlets/purl/1463722.

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@article{osti_1463722,

  title        = {Copolymerization of CO and N2 to Extended CON2 Framework Solid at High Pressures},

  author       = {Yoo, Choong-Shik and Kim, Minseob and Lim, Jinhyuk and Ryu, Young Jay and Batyrev, Iskander G.},

  abstractNote = {Synthesis of novel extended forms of nitrogen and nitrogen-rich materials has been a topic of interest in development of high-energy-density materials. Here, we present the formation of high-density (3.983 g/cm3) copolymer CON2, formed in crystalline form by laser heating of CO–N2 mixtures above 1700 K and 45 GPa—a substantially lower pressure–temperature condition than those required for converting pure nitrogen (above 110 GPa and 2000 K). It can be made even at lower pressures ~20 GPa at ambient temperature for amorphous solid. According to the refined structure, the crystalline polymer is made of nitrogen-hybridized, eight-membered rings of singly bonded CON2 in a three-dimensional framework structure in the space group of P43, as one of the previously predicted structures. Furthermore, unlike the predicted structures, the present P43 solid converts back to ε-N2-like and δ-N2-like molecular phases as pressure unloads to 20 and 10 GPa, respectively.},

  doi          = {10.1021/acs.jpcc.8b03415},

  journal      = {Journal of Physical Chemistry. C},

  number       = 24,

  volume       = 122,

  place        = {United States},

  year         = {2018},

  month        = {6}

}

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Title: Copolymerization of CO and N2 to Extended CON2 Framework Solid at High Pressures

Abstract

Citation Formats

Title: Copolymerization of CO and N₂ to Extended CON₂ Framework Solid at High Pressures