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Title: Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba 8 M 24P 28+δ ( M =Cu/Zn)

Abstract

A new clathrate type has been discovered in the Ba/Cu/Zn/P system. The crystal structure of the Ba 8M 24P 28+δ (M=Cu/Zn) clathrate is composed of the pentagonal dodecahedra common to clathrates along with a unique 22-vertex polyhedron with two hexagonal faces capped by additional partially occupied phosphorus sites. This is the first example of a clathrate compound where the framework atoms are not in tetrahedral or trigonal-pyramidal coordination. In Ba 8M 24P 28+δ a majority of the framework atoms are five- and six-coordinated, a feature more common to electron-rich intermetallics. The crystal structure of this new clathrate was determined by a combination of X-ray and neutron diffraction and was confirmed with solid-state 31P NMR spectroscopy. Based on chemical bonding analysis, the driving force for the formation of this new clathrate is the excess of electrons generated by a high concentration of Zn atoms in the framework. The rattling of guest atoms in the large cages results in a very low thermal conductivity, a unique feature of the clathrate family of compounds.

Authors:
 [1];  [1];  [2];  [2]; ORCiD logo [1]
  1. Department of Chemistry, The University of California, Davis, One Shields Avenue Davis CA 95616 USA
  2. Department of Materials Science and Engineering, The University of California, Davis, One Shields Avenue Davis CA 95616 USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1345411
Resource Type:
Journal Article
Resource Relation:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 9
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE

Citation Formats

Dolyniuk, Juli-Anna, Zaikina, Julia V., Kaseman, Derrick C., Sen, Sabyasachi, and Kovnir, Kirill. Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn). United States: N. p., 2017. Web. doi:10.1002/anie.201611510.
Dolyniuk, Juli-Anna, Zaikina, Julia V., Kaseman, Derrick C., Sen, Sabyasachi, & Kovnir, Kirill. Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn). United States. doi:10.1002/anie.201611510.
Dolyniuk, Juli-Anna, Zaikina, Julia V., Kaseman, Derrick C., Sen, Sabyasachi, and Kovnir, Kirill. Wed . "Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn)". United States. doi:10.1002/anie.201611510.
@article{osti_1345411,
title = {Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn)},
author = {Dolyniuk, Juli-Anna and Zaikina, Julia V. and Kaseman, Derrick C. and Sen, Sabyasachi and Kovnir, Kirill},
abstractNote = {A new clathrate type has been discovered in the Ba/Cu/Zn/P system. The crystal structure of the Ba8M24P28+δ (M=Cu/Zn) clathrate is composed of the pentagonal dodecahedra common to clathrates along with a unique 22-vertex polyhedron with two hexagonal faces capped by additional partially occupied phosphorus sites. This is the first example of a clathrate compound where the framework atoms are not in tetrahedral or trigonal-pyramidal coordination. In Ba8M24P28+δ a majority of the framework atoms are five- and six-coordinated, a feature more common to electron-rich intermetallics. The crystal structure of this new clathrate was determined by a combination of X-ray and neutron diffraction and was confirmed with solid-state 31P NMR spectroscopy. Based on chemical bonding analysis, the driving force for the formation of this new clathrate is the excess of electrons generated by a high concentration of Zn atoms in the framework. The rattling of guest atoms in the large cages results in a very low thermal conductivity, a unique feature of the clathrate family of compounds.},
doi = {10.1002/anie.201611510},
journal = {Angewandte Chemie (International Edition)},
number = 9,
volume = 56,
place = {United States},
year = {Wed Jan 18 00:00:00 EST 2017},
month = {Wed Jan 18 00:00:00 EST 2017}
}
  • Order–disorder–order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu–Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16-xZnxP30 with 0 < x < 1.6 (10% Zn/Mtotal), but vanishes at greater substitution concentrations. Higher Zn concentrations (up to 35% Zn/Mtotal) resulted in themore » additional substitution of Zn for P in Ba8M16+yP30-y (M = Cu, Zn) with 0 ≤ y ≤ 1. This causes the formation of Cu–Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm[3 with combining macron]n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba–Cu–Zn–P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu–Zn bonds. For the compounds with the highest Zn content, a disorder–order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu–Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30.« less
  • Here, the high pressure properties of the novel tetrel-free clathrate, Ba 8Cu 13.1Zn 3.3P 29.6, were investigated using synchrotron powder X-ray diffraction. The pressure was applied using a diamond anvil cell. No structural transitions or decomposition were detected in the studied pressure range of 0.1–7 GPa. The calculated bulk modulus for Ba 8Cu 13.1Zn 3.3P 29.6 using a third-order Birch-Murnaghan equation of state is 65(6) GPa at 300 K. This bulk modulus is comparable to the bulk moduli of Ge- and Sn-based clathrates, like A 8Ga 16Ge 30 (A = Sr, Ba) and Sn 19.3Cu 4.7P 22I 8, but lowermore » than those for the transition metal-containing silicon-based clathrates, Ba 8 T xSi46–x, T = Ni, Cu; 3 ≤ x ≤ 5.« less
  • According to cluster calculations, the electronic structures of compounds based on Y{sub 1}Ba{sub 2}Cu{sub 3}O{sub 7} and Y{sub 1}Ba{sub 2}Cu{sub 4}O{sub 8} with isoelectronically substituted barium have some qualitative distinctions. These compounds behave differently upon barium substitution by other elements due to differences in the character of their highest occupied and lowest unoccupied molecular orbitals. Substitution of barium by radium is expected to lead to an increase in oxygen stability without a significant decrease in the critical temperature of superconduction transition T{sub s}. In order to raise T{sub s}, it is of interest to study the systems YBa{sub 2-m}(Be ormore » Mg){sub m}Cu{sub 3}O{sub x} and YBa{sub 2-m}(Ca, Sr){sub m}Cu{sub 3}O{sub x}. On partial substitution of barium by calcium in YBa{sub 2}Cu{sub 4}O{sub 8}, the mechanism of T{sub s} elevation may involve contraction of the forbidden band due to oxygen sublattice distortions in the vicinity of Ba centers.« less
  • Three series of vacancy-free quaternary clathrates of type I, Ba{sub 8}Zn{sub x}Ge{sub 46-x-y}Si{sub y}, Ba{sub 8}(Zn,Cu){sub x}Ge{sub 46-x}, and Ba{sub 8}(Zn,Pd){sub x}Ge{sub 46-x}, have been prepared by reactions of elemental ingots in vacuum sealed quartz at 800 {sup o}C. In all cases cubic primitive symmetry (space group Pm3n, a{approx}1.1 nm) was confirmed for the clathrate phase by X-ray powder diffraction and X-ray single crystal analyses. The lattice parameters show a linear increase with increase in Ge for Ba{sub 8}Zn{sub x}Ge{sub 46-x-y}Si{sub y}. M atoms (Zn, Pd, Cu) preferably occupy the 6d site in random mixtures. No defects were observed formore » the 6d site. Site preference of Ge and Si in Ba{sub 8}Zn{sub x}Ge{sub 46-x-y}Si{sub y} has been elucidated from X-ray refinement: Ge atoms linearly substitute Si in the 24k site whilst a significant deviation from linearity is observed for occupation of the 16i site. A connectivity scheme for the phase equilibria in the 'Ba{sub 8}Ge{sub 46}' corner at 800 {sup o}C has been derived and a three-dimensional isothermal section at 800 {sup o}C is presented for the Ba-Pd-Zn-Ge system. Studies of transport properties carried out for Ba{sub 8{l_brace}}Cu,Pd,Zn{r_brace}{sub x}Ge{sub 46-x} and Ba{sub 8}Zn{sub x}Si{sub y}Ge{sub 46-x-y} evidenced predominantly electrons as charge carriers and the closeness of the systems to a metal-to-insulator transition, fine-tuned by substitution and mechanical processing of starting material Ba{sub 8}Ge{sub 43}. A promising figure of merit, ZT {approx}0.45 at 750 K, has been derived for Ba{sub 8}Zn{sub 7.4}Ge{sub 19.8}Si{sub 18.8}, where pricey germanium is exchanged by reasonably cheap silicon. - Graphical abstract: Quaternary phase diagram of Ba-Pd-Zn-Ge system at 800 {sup o}C.« less