Layered CeSO and LiCeSO Oxide Chalcogenides Obtained via Topotactic Oxidative and Reductive Transformations

被引：9

作者：

Cassidy, Simon J. ^{[1
]}

Pitcher, Michael J. ^{[1
]}

Lim, Jared J. K. ^{[1
]}

Hadermann, Joke ^{[2
]}

Allen, Jeremy P. ^{[3
,4
]}

Watson, Graeme W. ^{[3
,4
]}

Britto, Sylvia ^{[5
]}

Chong, Elena J. ^{[1
]}

Free, David G. ^{[1
]}

Grey, Clare P. ^{[5
]}

Clarke, Simon J. ^{[1
]}

机构：

[1] Univ Oxford, Dept Chem, Inorgan Chem Lab, South Parks Rd, Oxford OX1 3QR, England

[2] Univ Antwerp, Electron Microscopy Mat Sci EMAT, Groenenborgerlaan 171, B-2020 Antwerp, Belgium

[3] Trinity Coll Dublin, Sch Chem, Dublin 2, Ireland

[4] Trinity Coll Dublin, CRANN, Dublin 2, Ireland

[5] Univ Cambridge, Dept Chem, Lensfield Rd, Cambridge CB2 1EW, England

来源：

INORGANIC CHEMISTRY | 2019年 / 58卷 / 06期

基金：

英国工程与自然科学研究理事会; 爱尔兰科学基金会;

关键词：

LITHIUM INSERTION; PHYSICAL-PROPERTIES; OXYSULFIDES; ZIRCONIUM; DISORDER; MODEL;

D O I：

10.1021/acs.inorgchem.8b03485

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The chemical accessibility of the Celv oxidation state enables redox chemistry to be performed on the naturally coinagemetal -deficient phases CeM1-xSO (M = Cu, Ag). A metastable black compound with the PbFC1 structure type (space group P4/nmm: a = 3.8396(1) angstrom, c = 6.607(4) angstrom, V = 97.40(6) angstrom(3)) and a composition approaching CeSO is obtained by deintercalation of Ag from CeAg0.8SO. High-resolution transmission electron microscopy reveals the presence of large defect-free regions in CeSO, but stacking faults are also evident which can be incorporated into a quantitative model to account for the severe peak anisotropy evident in all the highresolution X-ray and neutron diffractograms of bulk CeSO samples; these suggest that a few percent of residual Ag remains. A strawcolored compound with the filled PbFCI (i.e., ZrSiCuAs- or HfCuSi2type) structure (space group P4/nmm: a = 3.98171(1) angstrom, c = 8.70913(5) angstrom, V = 138.075(1) angstrom 3) and a composition close to LiCeSO, but with small amounts of residual Ag, is obtained by direct reductive lithiation of CeAga8S0 or by insertion of Li into CeSO using chemical or electrochemical means. Computation of the band structure of pure, stoichiometric CeSO predicts it to be a Ce' compound with the 4f-states lying approximately 1 eV above the sulfide-dominated valence band maximum. Accordingly, the effective magnetic moment per Ce ion measured in the CeSO samples is much reduced from the value found for the Ce3+-containing LiCeSO, and the residual paramagnetism corresponds to the Ce3+ ions remaining due to the presence of residual Ag, which presumably reflects the difficulty of stabilizing Ce' in the presence of sulfide (S2-). Comparison of the behavior of CeCu0.8SO with that of CeCu0.8SO reveals much slower reaction kinetics associated with the Cu,_xS layers, and this enables intermediate CeCui LixSO phases to be isolated.

引用

页码：3838 / 3850

页数：13

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