期刊
CHEMISTRY OF MATERIALS
卷 25, 期 15, 页码 3137-3146出版社
AMER CHEMICAL SOC
DOI: 10.1021/cm401409s
关键词
swelling; exfoliation; titanate nanosheets; lepidocrocite; tetraalkylammonium cation
资金
- World Premier International Research Center Initiative on Materials Nanoarchitectonics (WPI-MANA)
- MEXT, Japan
- CREST of the Japan Science and Technology Agency (JST)
Osmotic swelling and exfoliation behaviors in a lepidocrocite-type titanate H1.07Ti1.73O4 center dot H2O were investigated upon reactions with tetramethylammonium (TMA(+)) and tetrabutylammonium (TBA(+)) cations. The reaction products in various physical states (suspension, wet aggregate, and deposited nanosheets) were characterized by several techniques, including X-ray diffraction under controlled humidity, small-angle X-ray scattering, particle size analysis, and atomic force microscopy. As the ratio of tetraalkylammonium ion in a solution to exchangeable proton in a solid decreased, the predominant product changed from the osmotically swollen phase, having an interlayer spacing d of several tens of nanometers, to the exfoliated nanosheets. The different behaviors of two cations in the osmotic swelling were evident from the slope and the transition point in the d versus C-1/2 plot, where C is the concentration of the cations. At a short reaction time, crystallites of a few stacks were obtained as a major product in the reaction with TMA(+). On the other hand, a mixture of those crystallites and a significant portion of unilamellar nanosheets were obtained in the reaction with TBA(+). In both cases, those stacks were ultimately thinned down at long reaction time to unilamellar nanosheets. The lateral size of the nanosheets could be controlled, depending on the type of the cations, the tetraalkylammonium-to-proton ratios, and the mode of the reaction (manual versus mechanical shaking). The nanosheets produced by TMA(+) had large lateral sizes up to tens of micrometers, and the suspension showed a distinctive silky appearance based on liquid crystallinity. Our work provides insights into the fundamentals of osmotic swelling and exfoliation, allowing a better understanding of the preparation of nanosheets, which are one of the most important building blocks in nanoarchitectonics.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据