CTAB on Synthesis and Pore Structure of Hierarchical Zeolite

doi:10.15541/jim20170340

Abstract

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

CLC Number:

TQ426

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.

Figures/Tables 8

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

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

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

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

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

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

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

Fig. 7 Adsorption properties of crystalline products to MB

References 20

[1]	NA K, CHOI M, PARK W,et al. Pillared MFI zeolite nanosheets of a single-unit-cell thickness. Journal of the American Chemical Society, 2010, 132(12): 4169-4177.
[2]	GUO YA-PING, WANG HAI-JIN, GUO YA-JUN,et al. Fabrication and characterization of hierarchical ZSM-5 zeolites by using organosilanes as additives. Chemical Engineering Journal, 2011, 166(1): 391-400.
[3]	SERRANO D P, SANZ R, PIZARRO P,et al. Synthesis of hierarchical TS-1 zeolite from silanized seeds. Topics in Catalysis, 2010, 53(19/20): 1319-1329.
[4]	CUI SHENG-HANG, ZHANG JUN-TAO, SHEN ZHI-BING.Hierarchical ZSM-5 zeolite: synthesis and catalytic applications.Chemical Industry and Engineering Progress, 2015, 34(9): 3331-3336.
[5]	TAO YOU-SHENG, KANOH H, ABRAMS L,et al. Mesopore- modified zeolites: preparation, characterization, and applications. Chemical Reviews, 2006, 37(21): 896-910.
[6]	CHAL R, GERARDIN C, BULUT M,et al. Overview and industrial assessment of synthesis strategies towards zeolites with mesopores. ChemCatChem., 2011, 3(1): 67-81.
[7]	DENG QIANG, ZHANG XIANG-WEN, WANG LI,et al. Catalytic isomerization and oligomerization of endo-dicyclopentadiene using alkali-treated hierarchical porous HZSM-5. Chemical Engineering Science, 2014, 135: 540-546.
[8]	XU YI-QUAN, FANG YE-SEN.Classification and designation of clay minerals.Silicate Bulletin, 1982, 3(1): 3-10, 16.
[9]	YANG DONG-HUA, LI JIAN-HUA, WANG XIN-BO,et al. Rapid synthesis and catalytic application of B-EU-1/ZSM-5 composite zeolite based on dual template. Journal of Inorganic Materials, 2016, 31(3): 248-256.
[10]	LU LEI, LI XING-YANG, LIU XIAO-QIN,et al. Enhancing hydrostability and catalytic performance of metal-organic frameworks by hybridizing with attapulgite, a natural clay. J. Mater. Chem., 2015, 3(13): 6998-7005.
[11]	ZHAO DENGSHAN, LI DENGHAO.Study on preparation of 4A zeolite molecular sieve from attapulgite clay.Non-Metallic Mines, 2008, 31(6): 7-9.
[12]	SHAO HUI, CHEN JING-JING, ZHONG JING,et al. Development of MeSAPO-5 molecular sieves from attapulgite for dehydration of carbohydrates. Industrial & Engineering Chemistry Research, 2015, 54(5): 1470-1477.
[13]	ZHENG SHU-QIN, GAN JIE, REN SHAO,et al. Synthesis of hierarchical catalytic materials from Si-Al gel and kaolin by hydrothermal crystallization. Acta Petroleisinica, 2014, 30(1): 32-37.
[14]	ZHOU XIAO-ZHAO, LIU YAN, MENG XIANG-JU,et al. Synthesis and catalytic cracking performance of Fe/Ti-ZSM-5 zeolite from attapulgite mineral. Chinese Journal of Catalysis, 2013, 34(8): 1504-1512.
[15]	FYFE C, LIN Z, TONG C,et al. Simple, efﬁcient synthesis of zeolite ZSM-11 (MEL) at temperatures below 100℃ using very dense gels. Microporous and Mesoporous Materials, 2012, 150(1): 7-13.
[16]	RUTKOWSKA M, PACIA I, BASAG S,et al. Catalytic performance of commercial Cu-ZSM-5 zeolite modiﬁed by desilication in NH3-SCR and NH3-SCO processes. Microporous and Mesoporous Materials, 2017, 246: 193-206.
[17]	ZHANG KE, LIU YUN-QI, ZHAO JIN-ZHONG,et al. Hierarchical porous ZSM-5 zeolite synthesized by in situ zeolitization and its coke deposition resistance in aromatization reaction. Chinese J. Chem, 2012, 30(3): 597-603.
[18]	THOMMES M, KANEKO K, NEIMARK A V,et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem., 2015, 87: 1051-1069.
[19]	BIEMELT T, SELZER C, SCHMIDT F,et al. Hierarchical porous zeolite ZSM-58 derived by desilication and desilication reassembly. Microporous and Mesoporous Materials, 2014, 187(3): 114-124.
[20]	YU QING-JU, CUI CHAOYUE, ZHANG QIANG,et al. Hierarchical ZSM-11 with intergrowth structures: synthesis, characterization and catalytic properties. Journal of Energy Chemistry, 2013, 22(5): 761-768.