CTAB对多级孔分子筛合成及孔道层次结构影响

doi:10.15541/jim20170340

无机材料学报 ›› 2018, Vol. 33 ›› Issue (6): 629-634.DOI: 10.15541/jim20170340 CSTR: 32189.14.10.15541/jim20170340

CTAB对多级孔分子筛合成及孔道层次结构影响

李红玑^1,2, 周孝德¹, 张建民², 杨靖², 王发良², 王向阳²

1. 西安理工大学水利水电学院, 西安 710048;
2. 西安工程大学环境与化学工程学院, 西安 710048;

收稿日期:2017-07-17 修回日期:2017-10-26 出版日期:2018-06-20 网络出版日期:2018-05-24
基金资助:
国家自然科学基金(21573171);陕西省重点研发计划(2017GY-121);陕西省教育厅专项科研计划(17JK0327);陕西省大学生创新创业计划(1715, 1731)

CTAB on Synthesis and Pore Structure of Hierarchical Zeolite

LI Hong-Ji^1,2, ZHOU Xiao-De¹, ZHANG Jian-Min², YANG Jing², WANG Fa-Liang², WANG Xiang-Yang²

1. Faculty of Water Resources and Hydraulic Power, Xi’an University of Technology, Xi’an 710048, China;
2. School of Environment and Chemistry Engineering, Xi’an Polytechnic University, Xi’an 710048, China;

Received:2017-07-17 Revised:2017-10-26 Published:2018-06-20 Online:2018-05-24
Supported by:
National Natural Science Foundation of China (21573171); Shaanxi Province Key Research and Development Plan (2017GY-121); Shaanxi Provincial Natural Science Foundation (17JK0327); Research and Innovation Training Project for Graduate in General Universities of Shaanxi Province (1715, 1731)

摘要/Abstract

摘要：

以预处理后的凹凸棒石(Si-ATP)为前驱体, 采用双模板剂一步法合成了多级孔分子筛, 研究了结构导向剂十六烷基三甲基溴化铵(CTAB)用量对分子筛孔道层次结构和种类的影响。结果表明：当CTAB用量为0.01~0.03 g 或0.05~0.07 g时, 孔道层次结构因子(HF)与CTAB用量呈线性相关; XRD结果显示, 当CTAB用量为0.03~0.05 g时, 分子筛从ZSM-5型向(H)ZSM-11型转变, 这说明在利用此方法制备多级孔分子筛时, 可通过调变CTAB用量定向调控分子筛微介孔比例。CTAB用量为0.05 g, 合成的(H)ZSM-11分子筛比表面积(S_BET)为432.02 m²/g, 总孔体积(V_tot)为0.40 cm³/g, 亚甲基蓝(MB)的吸附容量为366.45 mg/g, 说明CTAB导向构筑的介孔孔道有利于吸附大分子物质。

关键词: Si-ATP, CTAB, 多级孔分子筛, 孔道层次结构因子

Abstract:

Hierarchical zeolite was successfully synthesized with pretreated attapulgite (Si-ATP) by dual-template in one pot. Influence of the amount of structure-directing agent, hexadecyl trimethyl ammonium bromide (CTAB), on hierarchical pore structure and crystal morphology was systematically investigated. The results showed that the hierarchy factor (HF) had a good linear dependence on CTAB amount when it was between 0.01 and 0.03 g or 0.05 and 0.07 g. XRD revealed that the crystal morphology transferred from ZSM-5 to (H)ZSM-11 when CTAB amount ranged from 0.03 to 0.05 g. These results indicated that the ratio of micropore and mesopore could be controlled by CTAB amount when preparing hierarchical zeolites by this method. (H)ZSM-11 zeolites, prepared with 0.05 g of CTAB, exhibited a high specific surface area (S_BET=432.02 m²/g), a large total volume (V_tot=0.40 cm³/g), and an adsorption capacity of methylene blue (MB) (366.45 mg/g). Therefore, the mesoporous pore built by CTAB is beneficial for adsorbing of macromolecules.

Key words: Si-ATP, CTAB, hierarchical zeolite, hierarchical factor

中图分类号:

TQ426

李红玑, 周孝德, 张建民, 杨靖, 王发良, 王向阳. CTAB对多级孔分子筛合成及孔道层次结构影响[J]. 无机材料学报, 2018, 33(6): 629-634.

LI Hong-Ji, ZHOU Xiao-De, ZHANG Jian-Min, YANG Jing, WANG Fa-Liang, WANG Xiang-Yang. CTAB on Synthesis and Pore Structure of Hierarchical Zeolite[J]. Journal of Inorganic Materials, 2018, 33(6): 629-634.

图/表 8

图1 ATP、Si-ATP和CTAB0.05晶化产物的FT-IR谱图

Fig. 1 Infrared spectra of ATP, Si-ATP and crystalline product with 0.05 g CTAB

图2 ATP、Si-ATP及不同CTAB用量条件下晶化产物的XRD图谱

Fig. 2 XRD patterns of ATP, Si-ATP and crystalline products with different CTAB additions

图3 不同CTAB用量条件下晶化产物SEM照片

Fig. 3 SEM images of crystalline products with different CTAB additions

图4 不同CTAB用量条件下晶化产物N2吸附-脱附曲线

Fig. 4 N2 adsorption-desorption isotherms of crystalline products with different CTAB additions

图5 不同CTAB用量条件下晶化产物孔径分布图

Fig. 5 Pore size distribution of crystalline products with different CTAB additions

表1 不同CTAB用量条件下晶化产物质构特性

Table 1 Textural properties of crystalline products with different CTAB additions

Sample	S_BET/ (m²•g^-1)	S_mic/ (m²•g^-1)	S_mes/ (m²•g^-1)	V_tot/ (cm³•g^-1)	V_mic/ (cm³•g^-1)	V_mes/ (cm³•g^-1)	HF
CTAB0.01	324.73	132.34	192.39	0.20	0.07	0.13	0.21
CTAB0.02	321.85	118.35	203.50	0.21	0.07	0.14	0.20
CTAB0.03	301.06	177.49	123.57	0.21	0.10	0.11	0.21
CTAB0.04	313.20	112.75	200.45	0.16	0.06	0.10	0.24
CTAB0.05	432.02	165.65	266.37	0.40	0.08	0.32	0.12
CTAB0.06	372.38	189.08	183.30	0.34	0.11	0.23	0.18
CTAB0.07	300.28	212.81	87.47	0.19	0.12	0.07	0.16

图6 不同CTAB用量条件下晶化产物层次因子分布

Fig. 6 Hierarchy factor of crystalline products with different CTAB additions

图7 晶化产物对MB的吸附性能

Fig. 7 Adsorption properties of crystalline products to MB

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CTAB对多级孔分子筛合成及孔道层次结构影响

CTAB on Synthesis and Pore Structure of Hierarchical Zeolite

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