期刊
CHEMISTRY OF MATERIALS
卷 19, 期 7, 页码 1808-1815出版社
AMER CHEMICAL SOC
DOI: 10.1021/cm062039u
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The formation process of novel tungstate-based inorganic-organic hybrid nanobelts/nanotubes with lamellar mesostructures has been investigated, with an emphasis on monitoring the morphological and microstructural changes of the products during the reactions of H2W2O7 center dot xH(2)O (x = 3.49) with n-alkylamines (CmH2m+1NH2, 4 <= m <= 14) in a system of heptane/n-alkylamine/H2W2O7 center dot xH(2)O (n-alkylamine:H2W2O7 center dot xH(2)O molar ratio of about 30) under ambient conditions. The results indicate that normal intercalation occurrs in the early stage to form intercalation compounds with double-octahedral W-O layers, which are then dissolved in the highly alkaline aqueous solutions confined in the reverse-micelle-like media, where the dissolved species recrystallize to form hybrid nanobelts/nanotubes with single-octahedral W-O layers. Both the intercalation compounds obtained after a short reaction time (e.g., 30 min) and the hybrid nanobelts/nanotubers formed after a long reaction time (e.g., 5 days) possess a bilayered arrangement of n-alkyl chains, but their tilt angle in the intercalation compounds (42 degrees) is much smaller than that in the hybrid nanobelts/nanotubes (71 degrees). The interlayer water released from H2W2O7 center dot xH(2)O upon intercalation of n-alkylamine reacts with excess n-alkylamine molecules to form highly alkaline aqueous solutions, which have vital effects on the subsequent dissolution of the double-octahedral W-O layers to be single-octahedral layers. In addition, the high molar n-alkylamine:H2W2O7 center dot xH(2)O ratios (e.g., 30) are necessary to form tungstate-based inorganic-organic nanobelts/nanotubes, and the nonpolar solvents not only facilitate the reactions between n-alkylamines and H2W2O7 center dot xH(2)O but also favor the formation of belt/tubelike morphology.
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