Effect of Crystal Size on Framework Defects and Water Uptake in Fluoride Mediated Silicalite-1
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- 作者：Michelle E. Dose ; Ke Zhang ; Joshua A. Thompson ; Johannes Leisen ; Ronald R. Chance ; William J. Koros ; Benjamin A. McCool ; Ryan P. Lively
- 刊名：Chemistry of Materials
- 出版年：2014
- 出版时间：August 12, 2014
- 年：2014
- 卷：26
- 期：15
- 页码：4368-4376
- 全文大小：447K
- ISSN：1520-5002
文摘
The relationship between framework defects and crystal size in fluoride mediated silicalite-1 was investigated through nitrogen physisorption, X-ray diffraction, and vapor adsorption of ethanol and water on samples with crystal sizes ranging from 0.4 to 30 渭m in the b direction of the silicalite-1 crystals. X-ray diffraction reveals a shift in the lattice system from a predominantly monoclinic phase in smaller crystals to an orthorhombic phase in the larger crystals. 29Si MAS studies reveal minimal differences in framework silanol defect concentration. An H-4 type hysteresis in 77 K N2 adsorption isotherm and BdB-FHH pore size analysis reveal the presence of slit-like pores and a larger average pore size as well as a larger volume fraction of 鈥渕icrofissures鈥?in the larger crystals. Pure vapor adsorption measurements show more than a 2-fold increase in water uptake from 0.21 mmol/g to 0.51 mmol/g from the smallest to largest samples at 308 K near unit activity, while ethanol uptake remains on the order of 2.4 mmol/g for all samples. An increase in desorption hysteresis with crystal size and negligible differences in isosteric heats of adsorption of water lend support to the presence of microfissure defects in the larger samples. IAST predications for binary adsorption of ethanol and water in the silicalite-1 samples reveal a 2-fold ethanol/water selectivity enhancement for dilute (<5 wt % EtOH) solutions when crystal size is reduced. This systematic study of N2 physisorption, framework composition, and ethanol/water adsorption highlights the critical role that crystal size plays in the adsorption process, which can have significant implications for biofuel processes that produce dilute aqueous ethanol as a raw product.