Rational Synthesis of Metastable Skutterudite Compounds Using Multilayer Precursors
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- 作者：Marc D. Hornbostel ; Edward J. Hyer ; James Thiel ; and David C. Johnson
- 刊名：Journal of the American Chemical Society
- 出版年：1997
- 出版时间：March 19, 1997
- 年：1997
- 卷：119
- 期：11
- 页码：2665 - 2668
- 全文大小：179K
- 年卷期：v.119,no.11(March 19, 1997)
- ISSN：1520-5126
文摘
A new metastable binary compound and a series of new, metastableternary crystalline compounds withthe skutterudite crystal structure have been prepared throughcontrolled crystallization of amorphous reactionintermediates formed by low-temperature interdiffusion of modulatedelemental reactants. Discussed in this paperareLa1-xFe4Sb12,FeSb3,Hf1-xFe4Sb12,andY1-xFe4Sb12.The amorphous reaction intermediate for each systemcrystallizes exothermically near 200 
C forming the desiredskutterudite structure. At temperatures above 500C,they decompose exothermically forming a thermodynamically more stablemixture of binary compounds and elementalcomponents. We propose that the desired compounds nucleate fromthe amorphous precursor because slow solidstate diffusion rates hinder disproportionation into the more stablemix of binary compounds and elements. Thisgeneral synthetic approach to prepare new metastable compounds givescontrol of both the composition andstructureof the product compounds.
C forming the desiredskutterudite structure. At temperatures above 500C,they decompose exothermically forming a thermodynamically more stablemixture of binary compounds and elementalcomponents. We propose that the desired compounds nucleate fromthe amorphous precursor because slow solidstate diffusion rates hinder disproportionation into the more stablemix of binary compounds and elements. Thisgeneral synthetic approach to prepare new metastable compounds givescontrol of both the composition andstructureof the product compounds.