在水热体系中研究了以阳离子表面活性剂为主，阴离子表面活性剂、非离子表面活性剂、中性伯胺等为辅的混合表面活性剂对合成锆掺杂介孔分子筛的影响，考察了水/SiO2摩尔比、晶化温度、晶化时间及混合表面活性剂/SiO2摩尔比对所制分子筛结构的影响，对优化条件下合成的样品进行了表征. 结果表明，锆掺杂介孔分子筛的最佳合成体系为阴阳离子表面活性剂混合体系，最佳合成配方为水/SiO2摩尔比58，混合表面活性剂/SiO2摩尔比0.15, 100℃下晶化48 h. 最佳条件下合成的样品在小角区域有一个明显的衍射峰，表明其具有一定的长程有序性，晶面间距d=9.71 nm，平均孔径为5.55 nm，壁厚4.16 nm，具有三维蠕虫状孔道结构，吸附亚甲基蓝、罗丹明B与甲基橙的混合溶液时，对亚甲基蓝的吸附选择性较好，吸附率达90.24%.
The rapid economic development has also brought many environmental problems while providing people with a high quality of life. In particular, a large number of industrial solid wastes have become increasingly prominent. This facilitates the synthesis of highly active and doped mesoporous molecular sieves inexpensively because some industrial solid wastes contain both silicon species and transition metal elements. In this paper we used mixed surfactants system as template and the industrial silicon slag with zirconium as raw material for the synthesis process of zirconium substituted mesoporous molecular sieve. In the synthesis process, cationic surfactants (cetyltrimethylammonium bromide CTAB was used in this paper) were mainly used, and other surfactants (such as nonionic surfactant polyphenol vinyl ether-10, OP-10; neutral primary amine dodecylamine, DDA, and anionic surfactant sodium dodecyl benzene sulfonate, SDBS and sodium dodecyl sulfate SDS) supplemented, the effect of different mixed surfactants systems on the synthesis of zirconium substituted mesoporous molecular sieves in hydrothermal system were studied. In order to improve the synthesis repeatability, the effects of various factors on the proprietary of zirconium substituted mesoporous molecular sieves, such as the molar ratios of water to silicon and mixed surfactants to SiO2, crystallization temperature and crystallization time were also studied. The sample obtained under optimum conditions were characterized with different methods. The results showed that the optimized synthesis system was the mixed anionic and cationic surfactants (CTAB and SDBS), the suitable mole ratios of surfactant/SiO2 and H2O/SiO2 were 0.15 and 58, respectively. The optimized crystallization temperature and time were 100℃ and 48 h. The zirconium substituted mesoporous molecular sieves had a clear diffraction peak in the low angle region, indicating that the sample had a certain long-range order. The interplanar spacing d was 9.71 nm, the average pore diameter was 5.55 nm and the wall thickness was 4.16 nm. The zirconium substituted sample had a three-dimensional worm-like pore structure. For the mixed dyes solution of methylene blue, rhodamine B and methyl orange, the sample showed a good selective adsorption ability to methylene blue, the adsorption rate was 90.31%.
[1] Kresge, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C., Beck, J. S.. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism [J]. Nature, 1992, 359: 710-712.
[2] 刘红，王志刚，李浩. Fe-MSU-1介孔分子筛的合成及其催化苯酚羟基化性能[J].催化学报, 2007,28(3): 222-228.
LIU H, WANG Z G, LI H. Synthesis of Fe-MSU-1 and Its Catalytic Properties for Hydroxylation of Phenol [J]. Chinese Journal of Catalysis, 2007, 28(3): 222-228.
[3] 吴美玲，周灵杰，陈玮娜. Ti—MSU分子筛的合成、表征及其催化性能研究[J]. 石油炼制与化工, 2014,45(5): 50-53.
Wu M L，Zhou L J，Chen W N. SYNTHESIS AND CHARACTERIZATION OF Ti-MSU MESOPOROUS MOLECULAR SIEVES AND THEIR CATALYTIC PERFORMANCE [J]. PETROLEUM PROCESSING AND PETROCHEMICALS, 2014,45(5): 50-53.
[4] 朱金红，刘靖，赵文江，等. Al-MSU-S介孔及介孔-微孔分子筛的合成、表征及其催化性能[J].催化学报,2004, 25(9): 741-747.
Zhu J H , LIU J , Zhao W J, et al. Synthesis and Characterization of Al-MSU-S Mesoporous and Meso-Microporous Molecular Sieves and Their Catalytic Performance [J]. Chinese Journal of Catalysis, 2004, 25(9): 741-747.
[5] 杜丽，刘军民，廖世军.金属掺杂中孔分子筛的合成及其研究[J].石油学报(石油加工),2006?,?22?(s1)?:210-213.
Du L, Liu J M, Liao Sh J. INVESTIGATIoN oF METAL EMBEDDED MSU—V MESOPoROUS MATERIALS[J]. Acta Petrolei Sinica(Petroleum Processing Section),2006?,?22?(s1)?:210-213.
[6] Huo Qisheng, D.I., Margolese, Galen D. Stucky. Surfactant Control of Phases in the Synthesis of Mesoporous Silica-Based Materials[J]. Chem. Mater, 1996. 8: 1147-1160.
[7] Chen Fengxi, Huang Liming, Li Quanzhi. Synthesis of MCM-48 Using Mixed Cationic-Anionic Surfactants as Templates [J]. Chem. Mater, 1997. 9: 2685-2686.
[8] 王静静，鲁金明，杨建华，等. 阴阳离子表面活性剂混合表面活性剂合成介孔MCM-48分子筛[J]. 石油化工, 2013, 42(5): 506-511.
Wang J J, Lu J M, Yang J H, et al. Synthesis of Mesoporous MCM-48 Molecular Sieves with Cationic and Anionic Mixed Surfactant System as Template[J]. Petrochemical Technology, 2013, 42(5): 506-511.
[9]赵伟，姚建东，李全芝,等. 以混合非离子-阳离子表面活性剂为模板合成中孔MCM-48[J].科学通报,2001, 46(13):1089-1091.
Zhao W, Yao J D, Li Q Zh, et al. A Mixed Nonionic-Cationic Surfactant Templating Pathway to Cubic Mesoporous Molecular Sieves MCM-48[J].CHINESE SCIENCE BULLETIN,2001, 46(13):1089-1091.
[10]颜学武，陈海鹰，李全芝. 以混合中性-阳离子表面活性剂为模板合成MCM-48[J].化学学报,1998,56:1214-1217.
Yan X W, Chen H Y, Li Q Zh. A Mixed Neutral-Cationic Surfactant Templating Pathway to Cubic Mesoporous Molecular Sieves[J].ACTA CHIMICA SINICA,1998,56:1214-1217.
[11] 张雪莲，廖世军，刘军民，等.高含锆量的中孔分子筛Zr-MSU-V的合成与表征[J].分子催化学报,2001.20(5):417
Zhang X L, Liao S J, Liu J M, et al. Synthesis and Characterization of Mesoporous Zeolite Zr-with High Zirconium Composition[J]. JOURNAL OF MOLECULAR CATALYSIS (CH INA), 2001.20(5):417.
[12] 赵伟. 含和不含杂原子MCM-48中孔分子筛的合成、功能化及其催化性能[D]. 上海市杨浦区邯郸路220号(上海)：复旦大学. 2002：46.
[13] 安群利. 介孔分子筛MCM-41的合成及性能研究[D]. 西安市雁塔路58号(西安)：西安科技大学. 2005:18-25.
