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Title: Pressure induced polymerization of acetylide anions in CaC 2 and 10 7 fold enhancement of electrical conductivity

Abstract

Transformation between different types of carbon–carbon bonding in carbides often results in a dramatic change of physical and chemical properties. Under external pressure, unsaturated carbon atoms form new covalent bonds regardless of the electrostatic repulsion. It was predicted that calcium acetylide (also known as calcium carbide, CaC2) polymerizes to form calcium polyacetylide, calcium polyacenide and calcium graphenide under high pressure. In this work, the phase transitions of CaC2 under external pressure were systematically investigated, and the amorphous phase was studied in detail for the first time. Polycarbide anions like C66– are identified with gas chromatography-mass spectrometry and several other techniques, which evidences the pressure induced polymerization of the acetylide anions and suggests the existence of the polyacenide fragment. Additionally, the process of polymerization is accompanied with a 107 fold enhancement of the electrical conductivity. As a result, the polymerization of acetylide anions demonstrates that high pressure compression is a viable route to synthesize novel metal polycarbides and materials with extended carbon networks, while shedding light on the synthesis of more complicated metal organics.

Authors:
 [1];  [1];  [2];  [3];  [1];  [4];  [1];  [5];  [6];  [6];  [7];  [6];  [8];  [9];  [10];  [2];  [11]
+ Show Author Affiliations
  1. Center for High Pressure Science and Technology Advanced Research (HPSTAR), PO Box 8009, Beijing, 100088, China
  2. Center for High Pressure Science and Technology Advanced Research (HPSTAR), PO Box 8009, Beijing, 100088, China, Geophysical Laboratory, Carnegie Institution of Washington, Washington DC, 20015, USA
  3. COFCO Nutrition & Health Research Institute, Beijing Key Laboratory of Nutrition Health and Food Safety, Beijing 100209, China
  4. Agilent Technologies (China) Co., Ltd., Wangjingbei Road, Chaoyang District, Beijing 100102, China
  5. Department of Chemistry, Durham University, South Road, Durham, DH1 3 LE, UK
  6. Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, TN 37830, USA
  7. Centre for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
  8. Center for High Pressure Science and Technology Advanced Research (HPSTAR), PO Box 8009, Beijing, 100088, China, Geophysical Laboratory, Carnegie Institution of Washington, Washington DC, 20015, USA, HPSynC, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, IL 60439, USA
  9. Geophysical Laboratory, Carnegie Institution of Washington, Washington DC, 20015, USA
  10. Dept. of Physics, Southern University of Science and Technology, ShenZhen, China.
  11. Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China, Collaborative Innovation Centre of Quantum Matter, Beijing, China
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research in Extreme Environments (EFree)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
2217403
Alternate Identifier(s):
OSTI ID: 1311295
Grant/Contract Number:  
AC02-06CH11357; FG02-99ER45775; NA0001974; SC0001057; AC05-00OR22725
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 8 Journal Issue: 1; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zheng, Haiyan, Wang, Lijuan, Li, Kuo, Yang, Youyou, Wang, Yajie, Wu, Jiajia, Dong, Xiao, Wang, Chun-Hai, Tulk, Christopher A., Molaison, Jamie J., Ivanov, Ilia N., Feygenson, Mikhail, Yang, Wenge, Guthrie, Malcolm, Zhao, Yusheng, Mao, Ho-Kwang, and Jin, Changqing. Pressure induced polymerization of acetylide anions in CaC 2 and 10 7 fold enhancement of electrical conductivity. United Kingdom: N. p., 2016. Web. doi:10.1039/C6SC02830F.
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Zheng, Haiyan, Wang, Lijuan, Li, Kuo, Yang, Youyou, Wang, Yajie, Wu, Jiajia, Dong, Xiao, Wang, Chun-Hai, Tulk, Christopher A., Molaison, Jamie J., Ivanov, Ilia N., Feygenson, Mikhail, Yang, Wenge, Guthrie, Malcolm, Zhao, Yusheng, Mao, Ho-Kwang, & Jin, Changqing. Pressure induced polymerization of acetylide anions in CaC 2 and 10 7 fold enhancement of electrical conductivity. United Kingdom. https://doi.org/10.1039/C6SC02830F
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Zheng, Haiyan, Wang, Lijuan, Li, Kuo, Yang, Youyou, Wang, Yajie, Wu, Jiajia, Dong, Xiao, Wang, Chun-Hai, Tulk, Christopher A., Molaison, Jamie J., Ivanov, Ilia N., Feygenson, Mikhail, Yang, Wenge, Guthrie, Malcolm, Zhao, Yusheng, Mao, Ho-Kwang, and Jin, Changqing. Mon . "Pressure induced polymerization of acetylide anions in CaC 2 and 10 7 fold enhancement of electrical conductivity". United Kingdom. https://doi.org/10.1039/C6SC02830F.
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@article{osti_2217403,
title = {Pressure induced polymerization of acetylide anions in CaC 2 and 10 7 fold enhancement of electrical conductivity},
author = {Zheng, Haiyan and Wang, Lijuan and Li, Kuo and Yang, Youyou and Wang, Yajie and Wu, Jiajia and Dong, Xiao and Wang, Chun-Hai and Tulk, Christopher A. and Molaison, Jamie J. and Ivanov, Ilia N. and Feygenson, Mikhail and Yang, Wenge and Guthrie, Malcolm and Zhao, Yusheng and Mao, Ho-Kwang and Jin, Changqing},
abstractNote = {Transformation between different types of carbon–carbon bonding in carbides often results in a dramatic change of physical and chemical properties. Under external pressure, unsaturated carbon atoms form new covalent bonds regardless of the electrostatic repulsion. It was predicted that calcium acetylide (also known as calcium carbide, CaC2) polymerizes to form calcium polyacetylide, calcium polyacenide and calcium graphenide under high pressure. In this work, the phase transitions of CaC2 under external pressure were systematically investigated, and the amorphous phase was studied in detail for the first time. Polycarbide anions like C66– are identified with gas chromatography-mass spectrometry and several other techniques, which evidences the pressure induced polymerization of the acetylide anions and suggests the existence of the polyacenide fragment. Additionally, the process of polymerization is accompanied with a 107 fold enhancement of the electrical conductivity. As a result, the polymerization of acetylide anions demonstrates that high pressure compression is a viable route to synthesize novel metal polycarbides and materials with extended carbon networks, while shedding light on the synthesis of more complicated metal organics.},
doi = {10.1039/C6SC02830F},
journal = {Chemical Science},
number = 1,
volume = 8,
place = {United Kingdom},
year = {Mon Dec 19 00:00:00 EST 2016},
month = {Mon Dec 19 00:00:00 EST 2016}
}
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Publisher's Version of Record
https://doi.org/10.1039/C6SC02830F
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