Langmuir-Blodgett法制备b-轴取向MFI型分子筛膜

doi:10.15541/jim20150478

无机材料学报 ›› 2016, Vol. 31 ›› Issue (4): 377-382.DOI: 10.15541/jim20150478

Langmuir-Blodgett法制备b-轴取向MFI型分子筛膜

年佩^1,2, 鱼婷^{2, 3}, 苏美慧^1,2, 王政^1,2, 张斌兴^1,2, 李山^1,2, 宋智^1,2, 马强^1,2

(宁夏大学1. 化学化工学院; 2. 能源化工重点实验室, 省部共建天然气转化国家重点实验室培育基地; 3. 新华学院, 银川 750021)

收稿日期:2015-10-08 修回日期:2015-11-18 出版日期:2016-04-20 网络出版日期:2016-03-25
作者简介:年佩(1989–), 女, 硕士研究生. E-mail: Nian_528@163.com
基金资助:
国家自然科学基金(21066011;21366026)

Fabrication of b-oriented MFI Film via Langmuir-Blodgett Technique

NIAN Pei^1,2, YU Ting^2,3, SU Mei-Hui^1,2, WANG Zheng^1,2, ZHANG Bin-Xing^1,2, LI Shan^1,2, SONG Zhi^1,2, MA Qiang^1,2

(1. Institute of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China; 2. Key Laboratory of Energy Resources and Chemical Engineering, Ningxia University, Yinchuan 750021, China; 3. Xinhua college, Ningxia University, Yinchuan 750021, China)

Received:2015-10-08 Revised:2015-11-18 Published:2016-04-20 Online:2016-03-25
About author:NIAN Pei. E-mail: Nian_528@163.com
Supported by:
National Natural Science Foundation of China(21066011;21366026)

摘要/Abstract

摘要：

实验利用Langmuir-Blodgett(LB)技术大面积有序组装分子筛晶粒, 进而制备连续致密且高度b-轴取向MFI型分子筛膜。首先, 采用LB技术在表面性质不同的不锈钢载体和铂电极载体上实现了b-轴取向MFI分子筛晶粒的高度有序组装; 其次, 采用合成液预处理法对LB法制备的高度b-轴取向的MFI晶种层进行二次合成。XRD和SEM表征结果显示: 采用合成液预处理法可以有效抑制分子筛晶粒在二次生长过程中生成孪晶, 进而获得高度b-轴取向MFI分子筛膜; 最后, 电化学测试结果证实采用LB技术制备的b-轴取向MFI分子筛膜致密, 无缺陷。

关键词: Langmuir-Blodgett技术, 分子筛膜, 取向分子筛膜

Abstract:

A compact and highly b-oriented MFI-type zeolite monolayer was fabricated by assembling anisotropic zeolite micro-crystals extending over the centimeter scale by Langmuir-Blodgett (LB) method. The LB monolayer was subsequently employed as a seed layer for the secondary growth of highly b-oriented and defect-free MFI zeolite films. Firstly, LB technique was used to assemble a highly b-oriented MFI type zeolite monolayer on stainless steel substrates and platinum electrodes at an optimum target pressure of 20 mN/m constantly. Secondly, the precursor pretreatment method for preparing highly b-oriented MFI films was proved to be achievable. The crystal intergrowth and orientation of the MFI films were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The experimental results confirmed that the precursor pretreatment method was an effective route to suppress the undesired a-oriented twin growth during the secondary growth step. Finally, the highly b-oriented MFI-type zeolite film modified platinum electrodes were further tested as the working electrodes in an aqueous solution including [Fe(CN)₆]^3- with a diameter of 0.72 nm. Cyclic voltammetry experimental results demonstrated that the b-oriented MFI films fabricated by the Langmuir-Blodgett method were defect-free.

Key words: Langmuir-Blodgett technique, zeolite film, oriented zeolite film

中图分类号:

O611

年佩, 鱼婷, 苏美慧, 王政, 张斌兴, 李山, 宋智, 马强. Langmuir-Blodgett法制备b-轴取向MFI型分子筛膜[J]. 无机材料学报, 2016, 31(4): 377-382.

NIAN Pei, YU Ting, SU Mei-Hui, WANG Zheng, ZHANG Bin-Xing, LI Shan, SONG Zhi, MA Qiang. Fabrication of b-oriented MFI Film via Langmuir-Blodgett Technique[J]. Journal of Inorganic Materials, 2016, 31(4): 377-382.

图/表 7

图1 LB法组装b-轴取向分子筛晶粒层示意图

Fig. 1 Schematic diagram of b-oriented monolayer assembled by LB technique

图2 不同醇改性MFI分子筛晶种的π-A曲线

Fig. 2 Pressure-area isotherms for modified MFI microcrystals prepared using (a) aqueous, (b) methanol, (c) ethanol, and (d) sec-butanol modified MFI microcrystals

图3 不同载体上组装的MFI分子筛晶种层的SEM照片和XRD图谱

Fig. 3 SEM images and XRD patterns of MFI monolayer assembled on different substrates (a,b) Stainless-steel; (c,d) Platinum plates

图4 在不同载体上制备的MFI分子筛晶种层光学照片

Fig. 4 Optical photographs of the MFI monolayer on various substrates (a) Glass and silicon wafer; (b) Stainless-steel

图5 合成液预晶化法(a~c)和直接水热法(d~f)二次生长过程制备的MFI分子筛膜的SEM照片

Fig. 5 SEM images of the MFI films synthesized with precursor pretreatment method (a-c) and without precursor pretreatment method (d-f)

图6 合成液预晶化(a)1.5h和(b)3h制备的MFI分子筛膜的XRD图谱

Fig. 6 XRD patterns of the MFI films synthesized with precursor pretreatment method for (a) 1.5 h and (b) 3 h Inset is the enlarged images around (0100) peaks

图7 MFI分子筛膜修饰Pt电极的循环伏安曲线

Fig. 7 Cyclic voltammograms of [Fe(CN)6]3- on (a) the bare Pt electrode and (b) the b-oriented MFI film-modified Pt electrode

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Langmuir-Blodgett法制备b-轴取向MFI型分子筛膜

Fabrication of b-oriented MFI Film via Langmuir-Blodgett Technique

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