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

Juli Anna Dolyniuk; Jian Wang; Maxwell A.T. Marple; Sabyasachi Sen; Yongqiang Cheng; Anibal J. Ramirez-Cuesta; Kirill Kovnir

doi:10.1021/acs.chemmater.8b00966

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

Juli Anna Dolyniuk, Jian Wang, Maxwell A.T. Marple, Sabyasachi Sen, Yongqiang Cheng, Anibal J. Ramirez-Cuesta, Kirill Kovnir

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

Quaternary clathrate-I phases with an overall composition of Ba₈M_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 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.

Original language	English
Pages (from-to)	3419-3428
Number of pages	10
Journal	Chemistry of Materials
Volume	30
Issue number	10
DOIs	https://doi.org/10.1021/acs.chemmater.8b00966
State	Published - May 22 2018

Funding

*E-mail: [email protected]. ORCID Jian Wang: 0000-0003-1326-4470 Sabyasachi Sen: 0000-0002-4504-3632 Kirill Kovnir: 0000-0003-1152-1912 Funding This research was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-SC0008931. J.D. acknowledges the DOE-SCGSR fellowship for time spent at the Oak Ridge National Laboratory. This research used resources at the Spallation Neutron Source operated by the Oak Ridge National Laboratory, which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. The computing resources were made available through the VirtuES project, funded by the Laboratory Directed Research and Development (LDRD) program at ORNL. Notes The authors declare no competing financial interest.

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title = "Chemical Bonding and Transport Properties in Clathrates-I with Cu-Zn-P Frameworks",

abstract = "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.",

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AU - Sen, Sabyasachi

AU - Cheng, Yongqiang

AU - Ramirez-Cuesta, Anibal J.

AU - Kovnir, Kirill

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N2 - 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.

AB - 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.

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

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