中孔FAU型沸石的合成及孔结构表征

doi:10.15541/jim20140135

无机材料学报 ›› 2014, Vol. 29 ›› Issue (11): 1173-1178.DOI: 10.15541/jim20140135 CSTR: 32189.14.10.15541/jim20140135

中孔FAU型沸石的合成及孔结构表征

冯春峰, 马丽, 马静红, 李瑞丰

(太原理工大学精细化工研究所, 太原030024)

收稿日期:2014-03-19 修回日期:2014-05-23 出版日期:2014-11-20 网络出版日期:2014-10-24
作者简介:冯春峰(1990–), 女, 硕士研究生. E-mail: 1541325445@qq.com
基金资助:
国家自然科学基金 (51272169);National Natural Science Foundation of China (51272169)

Synthesis and Pore Structure of Mesozeolite FAU

FENG Chun-Feng, MA Li, MA Jing-Hong, LI Rui-Feng

(Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, China)

Received:2014-03-19 Revised:2014-05-23 Published:2014-11-20 Online:2014-10-24
About author:FENG Chun-Feng. E-mail: 1541325445@qq.com

摘要/Abstract

摘要：

本研究采用有机硅烷偶联剂二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵(TPOAC)作为中孔模板剂, 在水热条件下合成了具有FAU结构的中孔X和Y型沸石, 并用X射线衍射、扫描电镜、透射电镜、氮气吸附/脱附和热重分析技术对合成样品进行了结构表征。结果表明, 在该沸石合成体系中TPOAC的加入使沸石晶粒纳米化, 同时可在沸石晶粒内部创造丰富的直径为5~6 nm的中孔, 并且改变了沸石晶体的外观形貌。从而获得了不仅保持沸石固有微孔、同时具有晶内中孔和晶间中孔的介孔FAU沸石。

关键词: FAU沸石, 多级孔沸石, 中孔模板剂

Abstract:

Mesoporous zeolites X and Y with FAU structure were hydrothermally synthesized using an organos-ilane surfactant (TPOAC) as mesopore-generating agent, which was added into the conventional synthesis system of the crystalline microporous aluminosilicates. X-ray diffraction, scanning electron microscope, high-resolution transmission electron microscope, N₂ adsorption-desorption isotherms and thermogravimetric analysis were used to characterize their structural and textural features. The results showed that the presence of TPOAC led to nanoscale zeolite crystals and abundant intracrystal mesopores at diameter of 5~6 nm, forming the meso-zeolites X and Y with micropores, intra- and inter-mesopores. Both mesoporous zeolite X and Y displayed not only inherent topological and microporous structure of zeolite FAU, but also different morphology from conventional zeolite FAU crystals.

Key words: zeolite FAU, hierarchical zeolite, mesoporous templates

中图分类号:

TQ174

冯春峰, 马丽, 马静红, 李瑞丰. 中孔FAU型沸石的合成及孔结构表征[J]. 无机材料学报, 2014, 29(11): 1173-1178.

FENG Chun-Feng, MA Li, MA Jing-Hong, LI Rui-Feng. Synthesis and Pore Structure of Mesozeolite FAU[J]. Journal of Inorganic Materials, 2014, 29(11): 1173-1178.

图/表 7

图 1 NaX、MNaX(a)和NaY、MNaY(b)的XRD图谱

Fig. 1 XRD patterns of NaX, MNaX (a) and NaY, MNaY (b)

图 2 NaX(a)和MNaX(b)沸石的SEM照片

Fig. 2 SEM images of NaX (a) and MNaX (b)

图 3 NaY(a)和MNaY(b)沸石的SEM照片

Fig. 3 SEM images of NaY (a) and MNaY (b)

图 4 MNaX(a)和MNaY(b)型沸石的HRTEM照片

Fig. 4 HRTEM images of MNaX (a) and MNaY (b) zeolites

图 5 NaX和MNaX(a)及NaY和MNaY(b) FAU沸石的N2吸附/脱附等温线以及相应的DFT孔径分布图(c, d)

Fig. 5 N2 adsorption-desorption isotherms NaX and MNaX(a); NaY and MNaY (b) and relative DFT pore size distribution (c, MNaX; d, MNaY) of zeolites with FAU structure, respectively

表 1 FAU沸石的孔结构参数

Table 1 Pore structure parameters of zeolites with FAU structure

Sample	S_BET/(m²·g^-1)	S_ext/(m²·g^-1)	S_mic/(m²·g^-1)	V_mic/(cm³·g^-1)	V_meso/(cm³·g^-1)	d_p/nm
NaX	943	26	917	0.35	0.04	-
MNaX	872	141	731	0.27	0.21	5.9
NaY	945	28	917	0.35	0.06	-
MNaY	971	177	794	0.29	0.19	5.5

图 6 NaX、MNaX (a)和NaY、MNaY (b)的TG曲线

Fig. 6 TG curves of NaX, MNaX (a) and NaY, MNaY (b)

参考文献 18

[1]	徐如人,庞文琴. 分子筛与多孔材料化学. 北京: 科学出版社, 2004: 69-148.
[2]	THOMAS F. DEGNAN JR.Applications of zeolites in petroleum refining. Topics in Catalysis, 2000, 13(4): 349-356.
[3]	VERMEIREN W, GILSON J P. Impact of zeolites on the petroleum and petrochemical industry. Topics in Catalysis, 2009, 52(9): 1131-1161.
[4]	CORMA A. From microporous to mesoporous molecular sieve materials and their use in catalysis. Chemical Reviews, 1997, 97(6): 2373-2420.
[5]	KORTUNOV P, VASENKOV S, KÄRGER J, et al. The role of mesopores in intracrystalline transport in USY zeolite: PFG NMR diffusion study on various length scales. Journal of the American Chemical Society, 2005, 127(37): 13055-13059.
[6]	MÖLLER K, BEIN T. Mesoporosity-a new dimension for zeolites. Chemical Society Reviews, 2013, 42(9): 3689-3707.
[7]	VERBOEKEND D, PEREZ‐RAMIREZ J. Desilication mechanism revisited: highly mesoporous all-silica zeolites enabled through pore-directing agents. Chemistry-A European Journal, 2011, 17(4): 1137-1147.
[8]	GROEN J C, MOULIJN J A, PÉREZ-RAMÍREZ J. Desilication: on the controlled generation of mesoporosity in MFI zeolites. Journal of Materials Chemistry, 2006, 16(22): 2121-2131.
[9]	JACOBSEN C J H, MADSEN C, HOUZVICKA J, et al. Mesoporous zeolite single crystals. Journal of the American Chemical Society, 2000, 122(29): 7116-7117.
[10]	TAO Y, KANOH H, KANEKO K. Uniform mesopore-donated zeolite Y using carbon aerogel templating. The Journal of Physical Chemistry B, 2003, 107(40): 10974-10976.
[11]	WANG L, ZHANG Z, YIN C, et al. Hierarchical mesoporous zeolites with controllable mesoporosity templated from cationic poly-mers. Microporous and Mesoporous Materials, 2010, 131(1): 58-67.
[12]	WANG H, PINNAVAIA T J. MFI zeolite with small and uniform intracrystal mesopores. Angewandte Chemie International Edition, 2006, 45(45): 7603-7606.
[13]	XUE Z, MA J, HAO W, et al. Synthesis and characterization of ordered mesoporous zeolite LTA with high ion exchange ability. Journal of Materials Chemistry, 2012, 22(6): 2532-2538.
[14]	CHO K, CHO H S, DE MENORVAL L C, et al. Generation of mesoporosity in LTA zeolites by organosilane surfactant for rapid molecular transport in catalytic application. Chemistry of Materials, 2009, 21(23): 5664-5673.
[15]	INAYAT A, KNOKE I, SPIECKER E, et al. Assemblies of mesoporous FAU-type zeolite nanosheets. Angewandte Chemie International Edition, 2012, 51(8): 1962-1965.
[16]	LIU B, CHEN F, ZHENG L, et al. Synthesis and structural properties of hierarchically structured aluminosilicates with zeolite Y (FAU) frameworks. RSC Advances, 2013, 3(35): 15075-15084.
[17]	LIU S, CAO X, LI L, et al. Preformed zeolite precursor route for synthesis of mesoporous X zeolite. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2008, 318(1):269-274.
[18]	XUE Z, MA J, ZHENG J, et al. Hierarchical structure and catalytic properties of a microspherical zeolite with intracrystalline mespores. Acta Materialia, 2012, 60(16): 5712-5722.

中孔FAU型沸石的合成及孔结构表征

Synthesis and Pore Structure of Mesozeolite FAU

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 18

相关文章 1

编辑推荐

Metrics

本文评价