硅酸盐学报

季铵盐-高岭石系列插层复合物的制备及结构表征

作者：刘钦甫王定郭鹏张帅程宏飞李晓光张士龙

关键词：高岭石季铵盐碳链长度纳米卷

分类号：P 578.964；TQ 324.4

出版年,卷(期):页码：2015,43(2):222-230

DOI：10.14062/j.issn.0454-5648.2015.02.14

摘要：

通过多次置换插层反应，以高岭石/甲醇插层复合物为中间体，将不同链长季铵盐分子插入高岭石层间，对其结构、形貌和插层机理进行了探讨。结果表明：季铵盐分子在高岭石层间主要以全反转式构形存在，季铵盐碳链长度对其插层复合体的结构和形貌具有明显控制作用。碳原子数小于8的季铵盐在高岭石层间以单层平卧形式存在，其形成的高岭石插层复合体晶形仍为片状；碳原子数大于等于8的季铵盐在高岭石层间呈石蜡型倾斜双层形式排列，且碳链与高岭石(001)晶面的夹角随碳原子数增大而减小。碳原子数大于等于8的季铵盐进入高岭石层间，将导致高岭石晶层的卷曲，形成纳米卷或管，且随季铵盐碳链长度增加，高岭石片层卷曲程度加深，纳米卷的数量增多。

Kaolinite intercalation compounds with series quaternary ammonium salt prepared through displacement intercalation were characterized.The intercalation mechanism, the arrangement of quaternary ammonium salts between kaolinite layers and the thermal stability and morphology of intercalation complexes were investigated. The results show that the quaternary ammonium salts between kaolinite layers mainly arrange as all-trans configuration, and their carbon chain length has a significant effect on the structure and morphology of intercalation complexes. The quaternary ammonium slats with short carbon chains (i.e., the carbon number was <8) mainly form a monolayer structure in kaolinite interlayer, and the morphology of intercalation complexes remains flat. When the quaternary ammonium salts with relative longer carbon chains (i.e., the carbon number was 8) mainly arrange in a paraffin-type bilayer structure, the angle between the carbon chain and (001) plane of kaolinite gradually decreases with the increase of the carbon number. In addition, kaolinite platelet beginsto crimp and even develops to nanoscroll when the quaternary ammonium salts with the relative longer carbon chains were intercalated into kaolinite,and the degree of crimp and number of nano-tubes increase with the increase of the quaternary carbon chain length.

基金项目：

基金项目：国家自然科学基金重点项目(51034006)；北京市共建项目(20121141301)。

作者简介：

第一作者：刘钦甫(1964—)，男，博士，教授。

参考文献：

参考文献:

[1] KOMORI Y, SUGAHARA Y. Intercalation of alkylamines and water into kaolinite with methanol kaolinite as an intermediate [J]. Appl Clay Sci, 1999, 15: 241−252.

[2] SINGH B, GILKES R J. An electron optical investigation of the alteration of kaolinite to hallosite [J]. Clays Clay Miner, 1992, 40: 212−229.

[3] KOMORI Y, SUGAHARA Y, KURODA K. A kaolinite-NMF- methanol intercalation compound as a versatile intermediate for further intercalation reaction of kaolinite [J] J Mater Res, 1998, 13: 930−934.

[4] ELBOKL T A, DRTELLIER C. Intercalation of cyclic imides in kaolinite[J]. J Colloid Interface Sci, 2008, 323: 338−348.

[5] LETAIEF S, TONLE I K, DIACO T, et al. Nanohybrid materials from interlayer functionalization of kaolinite: Application to the electrochemical preconcentration of cyanide [J]. Appl Clay Sci, 2008, 42: 95−101.

[6] 宋海明, 张宝述, 孙红娟, 等. 烷基季铵阳离子改性制备有机粘土的研究及应用进展[J]. 中国非金属矿工业导刊, 2007(04): 7−10.

SONG Haiming, ZHANG Baoshu, SUN Hongjuan, et al. China Non-Metall Min Ind Herald (in Chinese), 2007(04): 7−10.

[7] BOTANA Adrian, MOLLO Mariana, EISENBERG Patricia, et al. Effect of modified montmorillonite on biodegradable PHB nanocomposite [J]. Appl Clay Sci, 2010, 47(3/4): 263−270.

[8] MA Yuehong, ZHU Jianxi, HE Hongping, et al. Infrared investigation of organo-montmorillonites prepared from different surfactants [J]. Spectrochim Acta, Part A: Mol Biomol Spectrosc, 2010, 76(2): 122−129.

[9] 李伟东, 黄建国, 许承晃. 高岭土-二甲基亚砜夹层复合物的形成机理[J]. 华侨大学学报: 自然科学版, 1994, 15(1): 48−52.

LI Weidong, HUANG Jianguo, XU Chenghuang. J Huaqiao Univ: Nat Sci (in Chinese), 1994, 15(1): 48−52.

[10] KOMORI Y, ENOTO H, TAKENAWA R. Modification of the interlayer surface of kaolinite with methoxy groups [J]. Langrnuir, 2000, 16: 5506−5508.

[11] LIN H P, CHENG S F, MOU C Y. Mesoporous molecular sieves MCM-41 with a hollow tubular morphology [J]. Chem Mater, 1998, 10(2): 581−589.

[12] 周公度. 无机结构化学[M]. 北京: 科学出版社, 1984: 118−119.

[13] LAGALY G. Characterization of clays by organic compounds [J]. Clay Miner, 1981, 16: 1−21.

[14] BENEKE K, LAGALY G. The brittle mica-like KNiAsO4 and its organic derivatives [J]. Clay Miner, 1982, 17: 175−183.

[15] TOMASZ K, MACIEJ H, KATARZYNA S, et al. Adsorption isotherms of homologous alkyldimethylbe-nzylauunonium bromides on sodium montmorillonite [J]. J Colloid Interface Sci, 2003, 264: 14−19.

[16] BRINDLEY G W, MOLL W F. Complexes of natural and synthetic Ca-montmorillonites with fatty acids [J]. Am Miner, 1965, 50: 1355−1370.

[17] VAIA R A, TEUKOLSKY R K, GIANNELIS E P. Interlayer structure and molecular environment of alkylammonium layered silicates [J]. Chem Mater, 1994(6): 1017−1022.

[18] VENKATARAMAN N. V, VASUDEVAN S. Conformation of methylene chains in an intercalated surfactant bilayer [J]. J Phys Chem B, 2001, 105: 1805−1812.

[19] 朱建喜. HDTMA+十柱撑蒙脱石层间域内有机离子的排列、演化模式及构型变化[D]. 中国科学院广州地球化学研究所, 2003.

ZHU Jianxi. Arrangement models, evolution and conformation of alkylammonium-cations in the interlayers of HDTMA+ pillared montmorillonite(in Chinese, dissertation). Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, 2003.

服务与反馈：

【文章下载】【加入收藏】