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以选择性酸处理皂石为前驱体制备介孔二氧化硅及其表征

Synthesis and characterization of mesoporous silica from selectively acid-treated saponite as the precursors.

作者信息

Okada Kiyoshi, Yoshizaki Hisako, Kameshima Yoshikazu, Nakajima Akira, Madhusoodana Chengala D

机构信息

Department of Metallurgy and Ceramics Science, Tokyo Institute of Technology, O-okayama, Meguro, Tokyo 152-8552, Japan.

出版信息

J Colloid Interface Sci. 2007 Oct 1;314(1):176-83. doi: 10.1016/j.jcis.2007.05.036. Epub 2007 May 18.

Abstract

Mesoporous silicas were synthesized by hydrothermal treatment of selectively acid-treated saponite (an ideal structural formula: Na(1/3)Mg(3)(Si(11/3)Al(1/3))O(10)(OH)(2)), having a 2:1 type layered structure as the silica source and its porous properties were examined and compared with that from kaolinite (an ideal structural formula: Al(2)Si(2)O(5)(OH)(4)), having a 1:1 type layered structure. Synthetic saponite was selectively leached in H(2)SO(4) solutions with various concentrations (0.05-1 M) at 70 degrees C for 0.5 h. The resulting products (precursors) were mixed with cetyltrimethylammonium bromide (CTABr), NaOH and H(2)O, hydrothermally treated at 110 degrees C and removed the CTABr by calcining at 560 degrees C. A hexagonal mesoporous phase was obtained with higher Si/(Al(+Mg)) ratios of the resulting precursors. The XRD patterns of these products show the peaks assigned by a hexagonal lattice with a(0)=4.0-4.6 nm and the crystallinity becomes higher with higher Si/(Al(+Mg)) ratios of the precursors. The specific surface area (S(BET)) values of the present mesoporous silicas range from 800 to 1100 m(2)/g at CTABr/precursor=0.1 and although they are not as high as those from precursors prepared from calcining and acid-treatment of kaolinite (1420 m(2)/g), they are increased to 1400-1500 m(2)/g by increasing the ratio CTABr/precursor 0.2. The reason for the difference in the optimum preparation conditions between saponite and kaolinite may be attributed to the difference in the linkage of the SiO(4) tetrahedra in these precursors (i.e. layered or framework structures), which result in great differences in the selective leaching rates and structures of the resulting silica-rich products.

摘要

通过对选择性酸处理皂石(理想结构式:Na(1/3)Mg(3)(Si(11/3)Al(1/3))O(10)(OH)(2))进行水热处理来合成介孔二氧化硅,皂石具有2:1型层状结构作为硅源,并对其多孔性能进行了研究,并与具有1:1型层状结构的高岭土(理想结构式:Al(2)Si(2)O(5)(OH)(4))的多孔性能进行了比较。将合成皂石在70℃下于不同浓度(0.05 - 1M)的H(2)SO(4)溶液中选择性浸出0.5小时。将所得产物(前驱体)与十六烷基三甲基溴化铵(CTABr)、NaOH和H(2)O混合,在110℃下进行水热处理,并通过在560℃下煅烧除去CTABr。所得前驱体具有较高的Si/(Al + Mg)比时可获得六方介孔相。这些产物的XRD图谱显示出由六方晶格(a(0)=4.0 - 4.6nm)确定的峰,并且前驱体的Si/(Al + Mg)比越高,结晶度越高。在CTABr/前驱体 = 0.1时,本研究中的介孔二氧化硅的比表面积(S(BET))值在800至1100 m(2)/g范围内,尽管它们不如通过煅烧和酸处理高岭土制备的前驱体的比表面积高(1420 m(2)/g),但通过将CTABr/前驱体的比例增加到0.2,其比表面积可增加到1400 - 1500 m(2)/g。皂石和高岭土在最佳制备条件上存在差异的原因可能归因于这些前驱体中SiO(4)四面体的连接方式不同(即层状或骨架结构),这导致所得富硅产物的选择性浸出率和结构存在很大差异。

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