FER分子筛中铝原子的受限落位

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

催化学报 ›› 2021, Vol. 42 ›› Issue (11): 2078-2087.DOI: 10.1016/S1872-2067(21)63884-6

• 论文 • 上一篇

FER分子筛中铝原子的受限落位

楚卫锋^a,†, 刘晓娜^b^,^d,†, 杨志强^c, Nakata Hiroya^e, 谭兴智^c, 刘雪斌^c, 徐龙伢^a, 郭鹏^b^,^$(), 李秀杰^a^,^#(), 朱向学^a^,^*()

^a中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连116023, 中国
^b中国科学院大连化学物理研究所, 洁净能源国家实验室, 甲醇制烯烃国家工程实验室, 国家能源低碳催化与工程研发中心, 辽宁大连116023, 中国
^c碧辟(中国)大连办公室, 能源创新实验室, 辽宁大连116023, 中国
^d中国科学院大学, 北京100049, 中国
^e京瓷株式会社, 先进材料与器件研究所, 京都, 日本

收稿日期:2021-04-07 修回日期:2021-04-07 出版日期:2021-11-18 发布日期:2021-08-18
通讯作者: 郭鹏,李秀杰,朱向学
作者简介:第一联系人：^†共同第一作者.
基金资助:
国家自然科学基金(21972136);国家自然科学基金(22008229);国家自然科学基金(21773233);国家自然科学基金(21991091);国家自然科学基金(U20A20120);中国科学院百人计划(Y706071202);中国科学院洁净能源创新研究院合作基金(DNL201908);兴辽英才计划(XLYC1908010);兴辽英才计划(XLYC1901006);碧辟能源创新实验室; STOE奖学金

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

摘要/Abstract

摘要：

分子筛是一类具有规则孔道或笼状结构的多孔材料, 因其独特的结构和可调的酸性而广泛用于石油化工、精细化学品合成、现代煤化工等诸多行业. 2006年Iglesia等在具有8元环孔道结构/侧口袋的FER和MOR分子筛上实现了无卤素添加、无贵金属存在条件下, 由二甲醚羰基化合成乙酸甲酯的反应. 乙酸甲酯通过进一步加氢可实现煤基乙醇的绿色生产. MOR分子筛通常具有较高的催化活性, 但失活迅速; FER分子筛表现出良好的催化稳定性, 但活性较低. 如何在保证FER分子筛稳定性的前提下, 进一步提升其羰基化活性是目前研究的热点. 前期理论和实验研究发现, 二甲醚羰基化反应活性与分子筛8元环孔道中的Brönsted酸位密度存在正相关. 因此, 通过优化合成条件, 选择性调控铝原子分布在“ferrierite”笼中, 可以提高FER分子筛的羰基化反应活性. 尽管研究者已在调节FER分子筛铝分布方面进行了大量研究, 但对于不同T位上Al原子的精准识别以及对应Brönsted酸位的可接触性还缺少系统和深入的认识.
本文选取了几种代表性模板剂, 分别在碱性和含氟体系下制备了系列FER分子筛样品, 利用Rietveld精修和模拟退火算法, 在原子水平揭示了模板剂种类以及合成介质变化对Al原子在不同T位分布的影响, 并结合二甲醚羰基化反应进行了结构和性能的关联. 首先选取不同尺寸大小的环状胺(环己胺、哌啶、吡啶、吡咯烷)和链状胺(乙二胺)合成了具有相似形貌、孔结构、酸密度的系列FER分子筛样品. 以CHA-Na-FER为例, PXRD精修结果显示, Na⁺(平衡35%的骨架负电荷)分布在10元环孔道中与O1形成氢键, 质子化的环己胺分布在“ferrierite”笼中, 并且环己胺上的N与O3形成氢键. 这说明与O1相连的T3位以及与O3相连的T1位都有可能是Al富集的位置. 为了进一步验证该结论, 本文还精修了吸附探针分子吡啶的样品CHA-Na-FER-Py-60h. 原粉以及吸附吡啶样品的精修结果表明, T1位和T3位是样品中铝富集的位置. 随后, 运用相同方法研究了Py-Na-FER, PI-Na-FER, En-Na-FER和Pyrr-HF-FER样品中的Al落位, 发现T1/T3位均是样品中Al富集的位置. 此外, 理论计算结果表明T1/T3位上Al原子的取代能较低, 说明Al优先取代T1/T3位上的Si, 这与精修结果相一致.
前期理论模拟结果表明, FER分子筛中T2-O5和T4-O7位点的CO插入反应能垒较低, 是二甲醚羰基化反应的活性位. 本文吡啶吸附实验、热重分析以及PXRD精修结果表明, FER分子筛中大部分Al富集在T1/T3位, 与T2/T4位相关的Brönsted酸约占18%~30%. 最后, 对各样品进行了二甲醚羰基化反应评价, 结果显示PI-Na-FER, Py-Na-FER, En-Na-FER和CHA-Na-FER催化剂的乙酸甲酯生成速率相近, 约为0.10 mol/(mol H⁺∙h). Pyrr-HF-FER催化剂的乙酸甲酯生成速率最高, 可达到0.16 mol/(mol H⁺∙h), 这可能是由于Pyrr-HF-FER催化剂具有更多T2/T4位相关的Brönsted酸. 虽然Pyrr-HF-FER催化剂的乙酸甲酯生成速率较其他四个催化剂有一定提升, 但其仍远低于MOR分子筛上乙酸甲酯生成速率(0.40 mol/(mol H⁺·h)).
综上, 有机模板剂的选择与合成介质的改变对FER分子筛中Al分布的调控作用是有限的, 即Al原子总是优先分布于T1/T3位. 而与T1和T3位相关的Brönsted酸位不是二甲醚羰基化反应的活性位点. 因此与MOR相比, FER分子筛在二甲醚羰基化反应中表现出较低的催化活性.

关键词: FER分子筛, 铝落位, 结构表征, Brönsted酸位, 二甲醚羰基化

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

楚卫锋, 刘晓娜, 杨志强, Nakata Hiroya, 谭兴智, 刘雪斌, 徐龙伢, 郭鹏, 李秀杰, 朱向学. FER分子筛中铝原子的受限落位[J]. 催化学报, 2021, 42(11): 2078-2087.

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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图/表 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.

参考文献

[1]	P. Tian, Y. Wei, M. Ye, Z. Liu, ACS Catal., 2015, 5, 1922-1938.
[2]	Q. Zhang, J. Yu, A. Corma, Adv. Mater., 2020, 32, 2002927.
[3]	H. Ham, H. S. Jung, H. S. Kim, J. Kim, S. J. Cho, W. B. Lee, M. J. Park, J. W. Bae, ACS Catal., 2020, 10, 5135-5146.
[4]	K. Cao, D. Fan, L. Li, B. Fan, L. Wang, D. Zhu, Q. Wang, P. Tian, Z. Liu, ACS Catal., 2020, 10, 3372-3380.
[5]	J. Liu, H. Xue, X. Huang, P. Wu, S. Huang, S. Liu, W. Shen, Chin. J. Catal., 2010, 31, 729-738.
[6]	P. Cheung, A. Bhan, G. J. Sunley, E. Iglesia, Angew. Chem. Int. Ed., 2006, 45, 1617-1620.
[7]	F. E. Paulik, J. F. Roth, Chem. Commun., 1968, 1578-1578.
[8]	G. J. Sunley, D. J. Watson, Catal. Today, 2000, 58, 293-307.
[9]	A. Bhan, A. D. Allian, G. J. Sunley, D. J. Law, E. Iglesia, J. Am. Chem. Soc., 2007, 129, 4919-4924.
[10]	Y. Roman-Leshkov, M. Moliner, M. E. Davis, J. Phys. Chem. C, 2011, 115, 1096-1102.
[11]	A. B. Pinar, C. Marquez-Alvarez, M. Grande-Casas, J. Perez-Pariente, J. Catal., 2009, 263, 258-265.
[12]	J. Dedecek, M. J. Lucero, C. Li, F. Gao, P. Klein, M. Urbanova, Z. Tvaruzkova, P. Sazama, S. Sklenak, J. Phys. Chem. C, 2011, 115, 11056-11064.
[13]	S. Wang, L. Zhang, S. Li, Z. Qin, D. Shi, S. He, K. Yuan, P. Wang, T. Zhao, S. Fan, M. Dong, J. Li, W. Fan, J. Wang, J. Catal., 2019, 377, 81-97.
[14]	C. Marquez-Alvarez, A. B. Pinar, R. Garcia, M. Grande-Casas, J. Pérez-Pariente, Top. Catal., 2009, 52, 1281-1291.
[15]	W. Chu, X. Li, S. Liu, X. Zhu, S. Xie, F. Chen, Y. Wang, W. Xin, L. Xu, J. Mater. Chem. A, 2018, 6, 12244-12249.
[16]	P. Feng, X. Chen, X. Li, D. Zhao, S. Xie, L. Xu, G. He, Microporous Mesoporous Mater., 2017, 239, 354-362.
[17]	A. B. Pinar, L. Gomez-Hortigüela, L. B. McCusker, J. Perez-Pariente, Chem. Mater., 2013, 25, 3654-3661.
[18]	L. Wang, H. Xu, N. Yan, S. Correll, S. Xu, P. Guo, P. Tian, Z. Liu, CrystEngComm, 2018, 20, 699-702.
[19]	A. Martucci, A. Alberti, G. Cruciani, P. Radaelli, P. Ciambelli, M. Rapacciulo, Microporous Mesoporous Mater., 1999, 30, 95-101.
[20]	E. Artacho, E. Anglada, O. Dieguez, J. D. Gale, A. Garcia, J. Junquera, R. M. Martin, P. Ordejon, J. M. Pruneda, D. Sanchez-Portal, J. M. Soler, J. Phys.: Condens. Matter, 2008, 20, 064208.
[21]	M. Hammouri, S. K. Jha, I. Vasiliev, J. Phys. Chem. C, 2015, 119, 18719-18728.
[22]	N. Kaltsoyannis, J. E. McGrady, Principles and applications of density functional theory in inorganic chemistry II; Structure and bonding, Springer, Berlin,Heidelberg, 2004.
[23]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[24]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1997, 78, 1396-1396.
[25]	D. R. Hamann, M. Schluter, C. Chiang, Phys. Rev. Lett., 1979, 43, 1494-1497.
[26]	S. Grimme, J. Comput. Chem., 2006, 27, 1787-1799.
[27]	International Zeolite Association's Structure Commission http://www.iza-structure.org/index.htm.
[28]	D. E. Akporiaye, H. Fjellvag, E. N. Halvorsen, T. Haug, A. Karlsson, K. P. Lillerud, Chem. Commun., 1996, 1553-1554.
[29]	B. J. Campbell, A. K. Cheetham, G. Bellussi, L. Carluccio, G. Perego, R. Millini, D. E. Cox, Chem. Commun., 1998, 1725-1726.
[30]	X. Liu, Y. Cao, N. Yan, C. Ma, L. Cao, P. Guo, P. Tian, Z. Liu, Chin. J. Catal., 2020, 41, 1715-1722.
[31]	N. Yan, C. Ma, Y. Cao, X. Liu, L. Cao, P. Guo, P. Tian, Z. Liu, Small, 2020, 16, 2000902.
[32]	P. Feng, G. Zhang, X. Chen, K. Zang, X. Li, L. Xu, Appl. Catal. A, 2018, 557, 119-124.

FER分子筛中铝原子的受限落位

Constrained Al sites in FER-type zeolites

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