Detecting different oxygen-ion jump pathways in Bi2WO6 with 1-and 2-dimensional 17O MAS NMR spectroscopy

被引:111
作者
Kim, N
Vannier, RN
Grey, CP [1 ]
机构
[1] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11794 USA
[2] Univ Sci & Technol Lille, CNRS, UMR 8012, ENSCL,Lab Cristallochim & Physicochim Solide, F-59652 Villeneuve Dascq, France
关键词
D O I
10.1021/cm048388a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Bismuth tungsten oxide (Bi2WO6) is an in = 1 Aurivillius phase and some of its doped compounds show moderately high oxygen ion conductivity. These materials are structurally related to the more disordered bismuth vanadium oxide Aurivillius phases (or BIMEVOXes), which exhibit extremely high conductivities. We demonstrate that a combination of one- and two-dimensional, variable-temperature, O-17 MAS NMR spectroscopy may be used to probe ionic motion in the Nb5+-doped bismuth tungstates and resolve different oxide-ion conduction mechanisms that occur over a very wide range of different time scales (10(-1) to 10(-1) s). The use of O-17 two-dimensional exchange spectroscopy dramatically increases the range of oxide-ion conductors that can be investigated by MAS NMR. Motion commences in the perovskite layers, with slow exchange between the Bi2O22+ and (WO4)(n)(2n-) layers occurring at higher temperatures, as detected by 2D NMR. Simulation of the 1D O-17 NMR spectra of Bi2W1-xNbxO6 with x = 0.05 and 0. 1 shows an increase in ionic conductivity from x = 0.05 to 0.1 consistent with the anionic conductivity of these materials measured by ac impedance spectroscopy.
引用
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页码:1952 / 1958
页数:7
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