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Title: Chemical Bonding and Transport Properties in Clathrates-I with Cu–Zn–P Frameworks

Here quaternary clathrate-I phases with an overall composition of Ba 8 M 16+yP 30-y (M = Cu,Zn) exhibit complex structural chemistry. Characterization of the electronic structures and chemical bonding using quantum-chemical calculations and 31P solid state NMR spectroscopy demonstrated that the Cu–Zn–P framework is flexible and able to accommodate up to six Zn atoms per formula unit via bonding rearrangements, such as partial Zn/P substitution and the formation of Cu–Zn bonds. Such perturbations of the framework’s bonding affect the thermal and charge transport properties. The overall thermoelectric figure-of-merit, ZT, of Ba 8Cu 14Zn 2P 30 is 0.62 at 800 K, which is 9 times higher than the thermoelectric performance of the ternary parent phase Ba 8Cu 16P 30. Through a combination of inelastic neutron scattering and single crystal X-ray diffraction experiments at 10 K, low-energy rattling of the Ba guest atoms inside the large tetrakaidecahedral cages are shown to be the reason for the low thermal conductivities observed for the studied clathrates.
Authors:
 [1] ; ORCiD logo [2] ;  [1] ; ORCiD logo [1] ; ORCiD logo [3] ; ORCiD logo [3] ; ORCiD logo [2]
  1. Univ. of California, Davis, CA (United States)
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 10; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1474850

Dolyniuk, Juli -Anna, Wang, Jian, Marple, Maxwell A. T., Sen, Sabyasachi, Cheng, Yongqiang, Ramirez-Cuesta, Anibal J., and Kovnir, Kirill. Chemical Bonding and Transport Properties in Clathrates-I with Cu–Zn–P Frameworks. United States: N. p., Web. doi:10.1021/acs.chemmater.8b00966.
Dolyniuk, Juli -Anna, Wang, Jian, Marple, Maxwell A. T., Sen, Sabyasachi, Cheng, Yongqiang, Ramirez-Cuesta, Anibal J., & Kovnir, Kirill. Chemical Bonding and Transport Properties in Clathrates-I with Cu–Zn–P Frameworks. United States. doi:10.1021/acs.chemmater.8b00966.
Dolyniuk, Juli -Anna, Wang, Jian, Marple, Maxwell A. T., Sen, Sabyasachi, Cheng, Yongqiang, Ramirez-Cuesta, Anibal J., and Kovnir, Kirill. 2018. "Chemical Bonding and Transport Properties in Clathrates-I with Cu–Zn–P Frameworks". United States. doi:10.1021/acs.chemmater.8b00966. https://www.osti.gov/servlets/purl/1474850.
@article{osti_1474850,
title = {Chemical Bonding and Transport Properties in Clathrates-I with Cu–Zn–P Frameworks},
author = {Dolyniuk, Juli -Anna and Wang, Jian and Marple, Maxwell A. T. and Sen, Sabyasachi and Cheng, Yongqiang and Ramirez-Cuesta, Anibal J. and Kovnir, Kirill},
abstractNote = {Here quaternary clathrate-I phases with an overall composition of Ba8M16+yP30-y (M = Cu,Zn) exhibit complex structural chemistry. Characterization of the electronic structures and chemical bonding using quantum-chemical calculations and 31P solid state NMR spectroscopy demonstrated that the Cu–Zn–P framework is flexible and able to accommodate up to six Zn atoms per formula unit via bonding rearrangements, such as partial Zn/P substitution and the formation of Cu–Zn bonds. Such perturbations of the framework’s bonding affect the thermal and charge transport properties. The overall thermoelectric figure-of-merit, ZT, of Ba8Cu14Zn2P30 is 0.62 at 800 K, which is 9 times higher than the thermoelectric performance of the ternary parent phase Ba8Cu16P30. Through a combination of inelastic neutron scattering and single crystal X-ray diffraction experiments at 10 K, low-energy rattling of the Ba guest atoms inside the large tetrakaidecahedral cages are shown to be the reason for the low thermal conductivities observed for the studied clathrates.},
doi = {10.1021/acs.chemmater.8b00966},
journal = {Chemistry of Materials},
number = 10,
volume = 30,
place = {United States},
year = {2018},
month = {4}
}