Constrained Al sites in FER-type zeolites

doi:10.1016/S1872-2067(21)63884-6

Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (11): 2078-2087.DOI: 10.1016/S1872-2067(21)63884-6

Constrained Al sites in FER-type zeolites

Weifeng Chu^a,†, Xiaona Liu^b^,^d,†, Zhiqiang Yang^c, Hiroya Nakata^e, Xingzhi Tan^c, Xuebin Liu^c, Longya Xu^a, Peng Guo^b^,^$(), Xiujie Li^a^,^#(), Xiangxue Zhu^a^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bNational Engineering Laboratory for Methanol to Olefins, State Energy Low Carbon Catalysis and Engineering R&D Center, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cEnergy Innovation Laboratory, BP (China) Dalian Office, Dalian 116023, Liaoning, China
^dUniversity of Chinese Academy of Sciences, Beijing 100049, China
^eResearch Institute for Advanced Materials and Devices, Kyocera Corporation, Kyoto 619-0237, Japan

Received:2021-04-07 Revised:2021-04-07 Online:2021-11-18 Published:2021-08-18
Contact: Peng Guo,Xiujie Li,Xiangxue Zhu
About author:^$Tel: +86-411-84379149; Fax: +86-411-84379289; E-mail: pguo@dicp.ac.cn
^#Tel/Fax: +86-411-84379279; E-mail: xiujieli@dicp.ac.cn;
^*Tel/Fax: +86-411-84379279; E-mail: zhuxx@dicp.ac.cn;
First author contact:^†These authors contributed equally.
Supported by:
National Natural Science Foundation of China(21972136);National Natural Science Foundation of China(22008229);National Natural Science Foundation of China(21773233);National Natural Science Foundation of China(21991091);National Natural Science Foundation of China(U20A20120);CAS Pioneer Hundred Talents Program(Y706071202);Dalian National Laboratory for Clean Energy Cooperation Fund, Chinese Academy of Sciences(DNL201908);Liaoning Revitalization Talents Program(XLYC1908010);Liaoning Revitalization Talents Program(XLYC1901006);BP Energy Innovation Laboratory, and Scholarship from STOE

Abstract

Abstract:

Crystallographic sites of Brönsted acids (Si-OH-Al) in zeolites, which are closely associated with the Al sites, play a significant and unique role in the catalytic application, especially when they are distributed in open channel systems or confined in cavities with small pore openings. In this article, we unraveled constrained Al crystallographic sites in FER-type zeolites containing the distinct local environments (10-ring channels and ferrierite cavities) by Rietveld refinement against the powder X-ray diffraction data. Final refinement demonstrates that regardless of the types of structure-directing agents and synthetic medium utilized, T1 and/or T3 are Al-rich positions, which are further confirmed by theoretical calculations. This new finding of constrained Al sites in the FER-type zeolite can well explain its limited catalytic activity in the DME carbonylation reaction.

Key words: FER-type zeolite, Aluminum siting, Structural characterization, Brönsted acid site;, DME carbonylation

Weifeng Chu, Xiaona Liu, Zhiqiang Yang, Hiroya Nakata, Xingzhi Tan, Xuebin Liu, Longya Xu, Peng Guo, Xiujie Li, Xiangxue Zhu. Constrained Al sites in FER-type zeolites[J]. Chinese Journal of Catalysis, 2021, 42(11): 2078-2087.

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Figures/Tables 7

Fig. 1. (a) FER-type zeolite framework. For better understanding, the 10-ring channels and ferrierite cavities are highlighted in blue and yellow, respectively. Atom color: blue: T, red: O. (b) PXRD patterns of FER- and MOR-type zeolites; (c) SEM images of sample CHA-Na-FER, PI-Na-FER, Py-Na-FER, En-Na-FER, Pyrr-HF-FER, and MOR-type zeolite.

Table 1 XRF results, textural properties, and acid amounts of FER-type and MOR-type zeolites.

Sample	SAR ^a	Na/Al ^a	Surface area (m²/g)			Pore volume (cm³/g)		Acid amount ^c (mmol/g)	Number of Py ^d	Percentage of T2 and/or T4^e
Sample	SAR ^a	Na/Al ^a	S_BET	S_micro	S_ext^b	V_micro^b	V_meso	Acid amount ^c (mmol/g)	Number of Py ^d	Percentage of T2 and/or T4^e
PI-Na-FER	12.6	0.11	384	338	46	0.130	0.094	1.10	2.2	18%
CHA-Na-FER	13.2	0.36	397	340	57	0.131	0.218	1.03	2.0	20%
Py-Na-FER	13.2	0.80	390	344	46	0.131	0.114	1.03	2.0	20%
En-Na-FER	10.9	0.03	395	333	62	0.128	0.238	1.22	2.3	20%
Pyrr-HF-FER	13.0	—	392	334	58	0.128	0.163	1.11	1.8	30%
MOR	12.4	0.72	566	505	61	0.193	0.088	0.96	—	—

Fig. 2. (a) NH3-TPD profiles of proton-form FER- and MOR-type zeolites; (b) 27Al MAS NMR spectra of proton-form CHA-Na-FER, PI-Na-FER, Py-Na-FER, En-Na-FER, and Pyrr-HF-FER.

Fig. 3. Rietveld refinement results of CHA-Na-FER and CHA-Na-FER-Py-60h samples. (a) Final Rietveld refinement plot of CHA-Na-FER. The observed, calculated, and difference curves are in blue, red, and black, respectively. The vertical bars indicate the positions of Bragg peaks. The insert is enlarged high angle part. (b,c) Na+ and CHA locate in the 10-ring channels and ferrierite cavities of CHA-Na-FER, respectively. (d-f) For CHA-Na-FER-Py-60h sample, the protonated Py is occluded in the 10-ring channels and ferrierite cavities. Atom color: blue: Si or Al, red: O, yellow: Na+, saddle brown: N, navy blue: C, misty rose: H.

Fig. 4. Schematic illustration of interactions between Py and FER-type zeolites. (a) T3 site is Al-rich position. (b) There are two Al atoms locating in T1 sites. For better understanding, the 10-ring channels and ferrierite cavities are highlighted in blue and yellow, respectively. Atom color: blue: Si, purple: Al, red: O, saddle brown: N, navy blue: C, misty rose: H.

Fig. 5. Optimized structures and the calculated ∆Einteraction of Py locating in 10-ring channels and ferrierite cavities. (a-c) T3 sites are Al-rich positions; (d-h) T1 sites are Al-rich positions. Atom color: blue: Si, purple: Al, red: O, saddle brown: N, navy blue: C, misty rose: H.

Fig. 6. MA synthesis rate per H+ over MOR- and a variety of FER-type zeolites. Reaction conditions: 160 °C, 3.0 MPa, GHSV = 3000 h-1, DME/CO/N2 = 4/91/5, TOS = 50 h.

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Constrained Al sites in FER-type zeolites

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