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Title: Synthesis, Structure, and Pressure-Induced Polymerization of Li 3 Fe(CN) 6 Accompanied with Enhanced Conductivity

Abstract

By providing a new route to synthesize inorganic/organic conductors with tunable composition and properties, pressure-induced polymerization of charged triple-bond monomers like acetylide and cyanide could lead to formation of a conductive metal–carbon network composite. The industry application of this promising synthetic method is mainly limited by the reaction pressure needed, which is often too high to be reached for gram amounts of sample. Here we successfully synthesized highly conductive Li3Fe(CN)6 at maximum pressure around 5 GPa and used in situ diagnostic tools to follow the structural and functional transformations of the sample, including in situ X-ray and neutron diffraction and Raman and impedance spectroscopy, along with the neutron pair distribution function measurement on the recovered sample. The cyanide anions start to react around 1 GPa and bond to each other irreversibly at around 5 GPa, which are the lowest reaction pressures in all known metal cyanides and within the technologically achievable pressure range for industrial production. Moreover, the conductivity of the polymer is above 10–3 S·cm–1, which reaches the range of conductive polymers. Our investigation suggests that the pressure-induced polymerization route is practicable for synthesizing some types of functional conductive materials for industrial use, and further research like doping andmore » heating can hence be motivated to synthesize novel materials under lower pressure and with better performances.« less

Authors:
 [1];  [1];  [2];  [2];  [3];  [3];  [3];  [3];  [4];  [1]
+ Show Author Affiliations
  1. Center for High Pressure Science and Technology Advanced Research, Beijing (China); Carnegie Inst. of Washington, Washington, DC (United States)
  2. Japan Atomic Energy Agency, Ibaraki (Japan)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Center for High Pressure Science and Technology Advanced Research, Beijing (China); Carnegie Inst. of Washington, Argonne, IL (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); 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:
1265900
Grant/Contract Number:  
AC05-00OR22725; SC0001057
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 23; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Li, Kuo, Zheng, Haiyan, Hattori, Takanori, Sano-Furukawa, Asami, Tulk, Christopher A., Molaison, Jamie, Feygenson, Mikhail, Ivanov, Ilia N., Yang, Wenge, and Mao, Ho-kwang. Synthesis, Structure, and Pressure-Induced Polymerization of Li 3 Fe(CN) 6 Accompanied with Enhanced Conductivity. United States: N. p., 2015. Web. doi:10.1021/acs.inorgchem.5b01851.
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Li, Kuo, Zheng, Haiyan, Hattori, Takanori, Sano-Furukawa, Asami, Tulk, Christopher A., Molaison, Jamie, Feygenson, Mikhail, Ivanov, Ilia N., Yang, Wenge, & Mao, Ho-kwang. Synthesis, Structure, and Pressure-Induced Polymerization of Li 3 Fe(CN) 6 Accompanied with Enhanced Conductivity. United States. https://doi.org/10.1021/acs.inorgchem.5b01851
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Li, Kuo, Zheng, Haiyan, Hattori, Takanori, Sano-Furukawa, Asami, Tulk, Christopher A., Molaison, Jamie, Feygenson, Mikhail, Ivanov, Ilia N., Yang, Wenge, and Mao, Ho-kwang. Tue . "Synthesis, Structure, and Pressure-Induced Polymerization of Li 3 Fe(CN) 6 Accompanied with Enhanced Conductivity". United States. https://doi.org/10.1021/acs.inorgchem.5b01851. https://www.osti.gov/servlets/purl/1265900.
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@article{osti_1265900,
title = {Synthesis, Structure, and Pressure-Induced Polymerization of Li 3 Fe(CN) 6 Accompanied with Enhanced Conductivity},
author = {Li, Kuo and Zheng, Haiyan and Hattori, Takanori and Sano-Furukawa, Asami and Tulk, Christopher A. and Molaison, Jamie and Feygenson, Mikhail and Ivanov, Ilia N. and Yang, Wenge and Mao, Ho-kwang},
abstractNote = {By providing a new route to synthesize inorganic/organic conductors with tunable composition and properties, pressure-induced polymerization of charged triple-bond monomers like acetylide and cyanide could lead to formation of a conductive metal–carbon network composite. The industry application of this promising synthetic method is mainly limited by the reaction pressure needed, which is often too high to be reached for gram amounts of sample. Here we successfully synthesized highly conductive Li3Fe(CN)6 at maximum pressure around 5 GPa and used in situ diagnostic tools to follow the structural and functional transformations of the sample, including in situ X-ray and neutron diffraction and Raman and impedance spectroscopy, along with the neutron pair distribution function measurement on the recovered sample. The cyanide anions start to react around 1 GPa and bond to each other irreversibly at around 5 GPa, which are the lowest reaction pressures in all known metal cyanides and within the technologically achievable pressure range for industrial production. Moreover, the conductivity of the polymer is above 10–3 S·cm–1, which reaches the range of conductive polymers. Our investigation suggests that the pressure-induced polymerization route is practicable for synthesizing some types of functional conductive materials for industrial use, and further research like doping and heating can hence be motivated to synthesize novel materials under lower pressure and with better performances.},
doi = {10.1021/acs.inorgchem.5b01851},
journal = {Inorganic Chemistry},
number = 23,
volume = 54,
place = {United States},
year = {Tue Nov 17 00:00:00 EST 2015},
month = {Tue Nov 17 00:00:00 EST 2015}
}
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    From Molecules to Carbon Materials—High Pressure Induced Polymerization and Bonding Mechanisms of Unsaturated Compounds
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