Effect of Organic Template Agents on the Catalytic Performance of ZSM-11 Zeolite for Conversion of Methanol to Propene

doi:10.6023/A26050179

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (9): 1452-1463.DOI: 10.6023/A26050179 Previous Articles Next Articles

Article

有机模板剂对ZSM-11分子筛甲醇制丙烯催化性能的影响

原凯^a^,^*(), 李雨薇^a, 宋鑫鹏^a, 薛羽翔^a, 耿琰娜^a, 句宇廷^a, 樊升^b^,^*(), 贾翔宇^a^,^*()

^a 长治医学院药学院药物分子设计与新制剂长治市重点实验室山西长治 046000
^b 中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室山西太原 030001

投稿日期:2026-06-03 发布日期:2026-06-30
通讯作者: 原凯, 樊升, 贾翔宇
基金资助:
国家自然科学基金(22402012); 国家自然科学基金(22502224); 山西省基础研究计划青年基金(202403021222314); 山西省基础研究计划青年基金(202503021212409); 山西省高等学校科技创新基金(2024L272); 长治医学院博士启动基金(BS202302); 长治医学院博士启动基金(2025BS29)

Effect of Organic Template Agents on the Catalytic Performance of ZSM-11 Zeolite for Conversion of Methanol to Propene

Kai Yuan^a^,^*(), Yuwei Li^a, Xinpeng Song^a, Yuxiang Xue^a, Yanna Geng^a, Yuting Ju^a, Sheng Fan^b^,^*(), Xiangyu Jia^a^,^*()

^a Changzhi Key Laboratory of Drug Molecular Design and Innovative Pharmaceutics, School of Pharmacy, Changzhi Medical College, Changzhi, Shanxi 046000, China
^b State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China

Received:2026-06-03 Published:2026-06-30
Contact: Kai Yuan, Sheng Fan, Xiangyu Jia
Supported by:
The National Natural Science Foundation of China(22402012); The National Natural Science Foundation of China(22502224); The Fundamental Research Program of Shanxi province(202403021222314); The Fundamental Research Program of Shanxi province(202503021212409); The Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2024L272); The Doctoral Scientific Research Foundation of Changzhi Medical College(BS202302); The Doctoral Scientific Research Foundation of Changzhi Medical College(2025BS29)

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Abstract

Although ZSM-11 zeolite is an encouraging catalyst for converting methanol to propene (MTP), its inadequate catalytic durability hinders realistic application. Herein, three high-silica ZSM-11 zeolites, designated ZSM-11-DAO, ZSM-11-TBAOH and ZSM-11-TBABr, were synthesized hydrothermally using 1,8-octanediamine (DAO), tetrabutylammonium hydroxide (TBAOH) and tetrabutylammonium bromide (TBABr) as the organic template agents, respectively. The effect of organic template agents on the crystal size and acidic properties of ZSM-11 zeolite as well as its catalytic performance and reaction mechanism in MTP was systematically studied through comprehensive characterization techniques such as X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), scanning electron microscopy (SEM), isothermal adsorption of methanol vapor, inductively coupled plasma optical emission spectrometry (ICP-OES), temperature-programmed desorption of ammonia (NH₃-TPD), FT-IR spectra of pyridine adsorption (Py-IR), FT-IR spectra of 2,6-ditert-butylpyridine adsorption (dTBPy-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), ultraviolet-visible diffuse reflectance spectroscopy (DR UV-vis), gas chromatography-mass spectrometry (GC-MS) and ¹³C/²⁷Al/²⁹Si MAS NMR. The results indicate that although ZSM-11-DAO zeolite possesses a higher concentration of framework aluminum atoms (Al_F) situated within the straight channels, it features substantially larger crystal size. In contrast, both ZSM-11-TBAOH and ZSM-11-TBABr exhibit comparably smaller crystal size, but the latter contains a greater proportion of Al_F preferentially enriched in the straight channels relative to the former. The synergistic effect of reduced crystal size and preferential enrichment of Al_F within the straight channels effectively suppresses the formation of reactive aromatic intermediates and impedes their further condensation into coke precursors during MTP reaction; consequently, the propagation of the aromatic-based mechanism is significantly inhibited, and the relative contribution of alkene-based mechanism is improved. Compared to both ZSM-11-DAO and ZSM-11-TBAOH, ZSM-11-TBABr zeolite demonstrates higher selectivity to propene and better catalytic stability in MTP. This study not only presents an effective strategy for improving the catalytic performance of high-silica ZSM-11 zeolite in MTP but also unravels the effect of the crystal size and distribution of acid sites on the formation and evolution of active aromatic intermediates.

Key words: ZSM-11 zeolite, organic template agent, crystal size, distribution of acid sites, methanol to propene

Cite this article

Kai Yuan, Yuwei Li, Xinpeng Song, Yuxiang Xue, Yanna Geng, Yuting Ju, Sheng Fan, Xiangyu Jia. Effect of Organic Template Agents on the Catalytic Performance of ZSM-11 Zeolite for Conversion of Methanol to Propene[J]. Acta Chimica Sinica, 2026, 84(9): 1452-1463.

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Fig. & Tab. 18

Figure 1. Schematic representation of pore architectures of ZSM-11 zeolite at the macroscopic (a) and microscopic (b) scales; the XRD patterns (c) and FT-IR spectra (d) in the region 1600~400 cm−1 of various ZSM-11 zeolites

Zeolites	Crystallinity/%	Surface area/ (m²•g⁻¹)		Pore volume/ (cm³•g⁻¹)
Zeolites	Crystallinity/%	total	micro	total	micro
ZSM-11-DAO	100	325	249	0.19	0.12
ZSM-11-TBAOH	100	353	256	0.22	0.12
ZSM-11-TBABr	98	368	268	0.22	0.12

Table 1. Relative crystallinity and textural properties of various ZSM-11 zeolites

Figure 2. The SEM images of various ZSM-11 zeolites (a) ZSM-11-DAO, (b) ZSM-11-TBAOH, (c) ZSM-11-TBABr

Figure 3. The N2 adsorption-desorption isotherms (a) and methanol vapor adsorption isotherms (b) of various ZSM-11 zeolites

Zeolites	Si/Al_bulk	NH₃-TPD (μmol•g⁻¹)			Py-IR (μmol•g⁻¹)		dTBPy-IR (μmol•g⁻¹)
Zeolites	Si/Al_bulk	strong	weak	total	Brønsted	Lewis	dTBPy-IR (μmol•g⁻¹)
ZSM-11-DAO	159	84	35	119	51	19	3
ZSM-11-TBAOH	177	74	29	103	34	16	5
ZSM-11-TBABr	178	72	29	101	33	17	2

Table 2. Elemental composition and acidic properties of various ZSM-11 zeolitesa

Zeolites	Si/Al_F	Q₃(Si(OAl)₁(OSi)₃) silicon/%	Q₄(Si(OSi)₄) silicon distribution/%
Zeolites	Si/Al_F	104	-109.6	-112.3	-113.7	-115.7
ZSM-11-DAO	165	2.4	5.7	25.4	38.8	27.7
ZSM-11-TBAOH	184	2.2	6.2	31.9	32.6	27.1
ZSM-11-TBABr	186	2.2	4.9	26.8	39.4	26.7

Table 3. Proportion of integrated peaks obtained by curve fitting of the 29Si MAS NMR spectra of various ZSM-11 zeolitesa

Figure 4. NH3-TPD profiles (a), Py-IR spectra (b), dTBPy-IR spectra (c) and Al 2p XPS spectra (d) of various ZSM-11 zeolites

Figure 5. 27Al MAS NMR spectra (a) as well as deconvoluted ones (b) of various ZSM-11 zeolites

Zeolites	Al_F/%	Al_EF/%	Aluminum distribution/%
Zeolites	Al_F/%	Al_EF/%	48.5	53.2	55.6	58.1
ZSM-11-DAO	100	0	6.7	45.9	30.2	17.2
ZSM-11-TBAOH	100	0	7.9	36.0	46.3	9.8
ZSM-11-TBABr	99	1	3.9	44.2	45.4	6.5

Table 4. Proportion of integrated peaks obtained by curve fitting of the 27Al MAS NMR spectra of various ZSM-11 zeolitesa

Figure 6. Deconvolution of the 29Si MAS NMR spectra of various ZSM-11 zeolites

Zeolites	Al_pairs/%	Al_single/%	Aluminum distribution/%
Zeolites	Al_pairs/%	Al_single/%	α	β	γ
ZSM-11-DAO	26.1	73.9	26.8	53.8	19.4
ZSM-11-TBAOH	63.2	36.8	16.4	62.9	20.7
ZSM-11-TBABr	63.4	36.6	28.4	54.8	16.8

Table 5. Proportion of different types of Al species in various Co(II)-ZSM-11 zeolitesa

Figure 7. DR UV-vis spectra of various Co(II)-ZSM-11 zeolites

Figure 8. Methanol conversion and product selectivity as a function of time on stream for MTP over ZSM-11-DAO (a), ZSM-11-TBAOH (b) and ZSM-11-TBABr (c); the (P－E)/E ratio (d) as a function of time on stream over the same three zeolites; TGA curves of various spent ZSM-11 zeolites (e). The reactions are performed at 430 ℃ and methanol WHSV of 2.9 h−1 under atmospheric pressure

Figure 9. Product selectivity and (P－E)/E ratio for MTP over various ZSM-11 zeolites under conditions of 380  ℃ and low methanol conversion (≈6%) after 30 min on stream

Figure 10. GC-MS chromatogram of the CH2Cl2 soluble fraction of the retained organic species extracted from various carbon-deposited ZSM-11 zeolites after methanol reaction for 30 min at 380 ℃ and with a WHSV of 2.9 h−1

Figure 11. The 13C MAS NMR spectra of various carbon-deposited ZSM-11 zeolites after methanol reaction for 30 min at 380 ℃ and with a WHSV of 2.9 h−1

Figure 12. The UV-vis spectra of various carbon-deposited ZSM-11 zeolites after methanol reaction for 30 min at 380 ℃ and with a WHSV of 2.9 h−1 (a), together with the integrated areas of the characteristic absorption bands derived from peak deconvolution (b)

Figure 13. The content of carbonaceous species over various ZSM-11 zeolites after methanol reaction for varying durations at 430 ℃ and with a WHSV of 2.9 h−1

References 47

[1]	Tian P.; Wei Y. X.; Ye M.; Liu Z. M. ACS Catal. 2015, 5, 1922. doi: 10.1021/acscatal.5b00007
[2]	Paunović V.; Liesche G.; Sundmacher K.; Bokhoven J. A. V. Nat. Catal. 2026, 9, 348. doi: 10.1038/s41929-026-01506-x
[3]	Lin S. F.; Li H.; Tian P.; Wei Y. X.; Ye M.; Liu Z. M. J. Am. Chem. Soc. 2025, 147, 11585. doi: 10.1021/jacs.4c12145
[4]	Yarulina I.; Chowdhury A. D.; Meirer F.; Weckhuysen B. M.; Gascon J. Nat. Catal. 2018, 1, 398. doi: 10.1038/s41929-018-0078-5
[5]	Dokania A.; Gong X.; Abou-Hamad E.; Dikhtiarenko A.; Shoinkhorova T.; Ye Y. R.; Patarroyo J.; Wehbe N.; Chowdhury A. D.; Gascon J. Chem. Catal. 2025, 5, 101168.
[6]	Shen Y. F.; Le T. T.; Fu D. L.; Schmidt J. E.; Filez M.; Weckhuysen B. M.; Rimer J. D. ACS Catal. 2018, 8, 11042. doi: 10.1021/acscatal.8b02274
[7]	Wang S.; Wang P. F.; Qin Z. F.; Chen Y. Y.; Dong M.; Li J. F.; Zhang K.; Liu P.; Wang J. G.; Fan W. B. ACS Catal. 2018, 8, 5485. doi: 10.1021/acscatal.8b01054
[8]	Yuan K.; Jia X. Y.; Wang S.; Fan S.; He S. P.; Wang P. F.; Dong M.; Qin Z. F.; Fan W. B.; Wang J. G. J. Fuel Chem. Technol. 2023, 51, 1652. doi: 10.1016/S1872-5813(23)60361-5
[9]	Yuan K.; Jia X. Y.; Wang S.; Fan S.; He S. P.; Wang P. F.; Qin Z. F.; Dong M.; Fan W. B.; Wang J. G. Microporous Mesoporous Mater. 2022, 341, 112051. doi: 10.1016/j.micromeso.2022.112051
[10]	Dyballa M.; Becker P.; Trefz D.; Klemm E.; Fischer A.; Jakob H.; Hunger M. Appl. Catal. A: Gen. 2016, 510, 233. doi: 10.1016/j.apcata.2015.11.017
[11]	Ding J.; Zhang Z. Q.; Meng C.; Zhao G. F.; Liu Y.; Lu Y. Catal. Today 2020, 347, 10. doi: 10.1016/j.cattod.2018.02.058
[12]	Wang S.; Zhang L.; Li S. Y.; Qin Z. F.; Shi D. Z.; He S. P.; Yuan K.; Wang P. F.; Zhao T. S.; Fan S. B.; Dong M.; Li J. F.; Fan W. B.; Wang J. G. J. Catal. 2019, 377, 81. doi: 10.1016/j.jcat.2019.07.028
[13]	Yuan K.; Jia X. Y.; Wang S.; Fan S.; He S. P.; Wang P. F.; Qin Z. F.; Dong M.; Fan W. B.; Wang J. G. Chem Synth. 2023, 4, 31. doi: 10.20517/cs
[14]	Wu Q. H.; Ji Z.; Zhang J. H.; Jiao Q. R.; Wang Z. X.; Liu Y.; Dai W. J.; Wang Y.; Li W. L.; Zheng J. J.; Li R. F. Catal. Sci. Technol. 2026, 16, 480. doi: 10.1039/D5CY01063B
[15]	Li M.; Yuan E. H.; Dai W. J.; Wang Y.; Zhou A. N.; Liu Z. W. Chem. Eng. J. 2025, 521, 167044. doi: 10.1016/j.cej.2025.167044
[16]	Olsbye U.; Svelle S.; Lillerud K. P.; Wei Z. H.; Chen Y. Y.; Li J. F.; Wang J. G.; Fan W. B. Chem. Soc. Rev. 2015, 44, 7155. doi: 10.1039/c5cs00304k pmid: 26185806
[17]	Wang S.; Qin Z. F.; Dong M.; Wang J. G.; Fan W. B. Chem. Catal. 2022, 2, 1657.
[18]	Yaripour F.; Shariatinia Z.; Sahebdelfar S.; Irandoukht A. J. Nat. Gas. Sci. Eng. 2015, 22, 260.
[19]	Zhang Y. M.; Zu Y.; Yan K.; Zhu Y.; Luo Y. B.; Xing E. H.; Li Q.; Song L. J.; Li T.; Mei Y.; Shu X. T. Appl. Catal. B: Environ. Energy. 2024, 357, 124292.
[20]	Álvaro-Muñoz T.; Márquez-Álvarez C.; Sastre E. Catal. Today 2012, 179, 27. doi: 10.1016/j.cattod.2011.07.038
[21]	Ma Y.; Tang X. M.; Hu J. Y.; Ma Y. H.; Chen W.; Liu Z. Q.; Han S. C.; Xu C.; Wu Q. M.; Zheng A. M.; Zhu L. F.; Meng X. J.; Xiao F. S. J. Am. Chem. Soc. 2022, 144, 6270. doi: 10.1021/jacs.1c12338
[22]	Yuan K.; Ju Y. T.; Lu N. Y.; Shi J.; Wang P. F. Acta Chim. Sinica 2025, 83, 1184 (in Chinese). doi: 10.6023/A25060240
	(原凯, 句宇廷, 路宁悦, 师晶, 王鹏飞, 化学学报, 2025, 83, 1184.)
[23]	Guo Y. X.; Wang S.; Geng R.; Wang P. F.; Li S. Y.; Dong M.; Qin Z. F.; Wang J. G.; Fan W. B. iScience 2023, 26, 107748. doi: 10.1016/j.isci.2023.107748
[24]	Li Y.; Yu M.; Cai K.; Wang M. Y.; Lv J.; Howe R. F.; Huang S. Y.; Ma X. B. Phys. Chem. Chem. Phys. 2020, 22, 11374. doi: 10.1039/D0CP00850H
[25]	Ke Q. L.; Khalil I.; Smeyers B.; Li Z.; Oliveira-Silva R. D.; Sels B.; Sakellariou D.; Dusselier M. Angew. Chem. Int. Ed. 2021, 60, 24189. doi: 10.1002/anie.202109163 pmid: 34478216
[26]	Liu P.; Ren J.; Sun Y. H. Microporous Mesoporous Mater. 2008, 114, 365. doi: 10.1016/j.micromeso.2008.01.022
[27]	Martínez-Franco R.; Li Z. B.; Martínez-Triguero J.; Moliner M.; Corma A. Catal. Sci. Technol. 2016, 6, 2796. doi: 10.1039/C5CY02298C
[28]	Yu B. Y.; Wang Y. N.; Xie S. J.; Chen F. C.; Liu W.; Li X. J.; Zhu X. X.; Xu L. Y. Fuel 2024, 371, 131953. doi: 10.1016/j.fuel.2024.131953
[29]	Molino A.; Łukaszuk K. A.; Rojo-Gama D.; Lillerud K. P.; Olsbye U.; Bordiga S.; Svelle S.; Beato P. Chem. Commun. 2017, 53, 6816. doi: 10.1039/C6CC10118F
[30]	Yu Q. J.; Cui C. Y.; Zhang Q.; Chen J.; Li Y.; Sun J. P.; Li C. Y.; Cui Q. K.; Yang C. H.; Shan H. H. J. Energy Chem. 2013, 22, 761. doi: 10.1016/S2095-4956(13)60101-1
[31]	Shen Y. F.; Le T. T.; Li R.; Rimer J. D. ChemPhysChem 2018, 19, 529. doi: 10.1002/cphc.v19.4
[32]	Park J. W.; Kim S. J.; Seo M.; Kim S. Y.; Sugi Y.; Seo G. Appl. Catal. A: Gen. 2008, 349, 76. doi: 10.1016/j.apcata.2008.07.006
[33]	Ji Y. J.; Zhang B.; Zhang K.; Xu L.; Peng H. G.; Wu P. Acta Chim. Sinica 2013, 71, 371 (in Chinese). doi: 10.6023/A12110980
	(纪永军, 张斌, 张坤, 徐乐, 彭洪根, 吴鹏, 化学学报, 2013, 71, 371.)
[34]	Zhang J.; Ding X. N.; Liu H. C.; Fan D.; Xu S. T.; Wei Y. X.; Liu Z. M. Acta Chim. Sinica 2022, 80, 590 (in Chinese). doi: 10.6023/A22010014
	(张瑾, 丁湘浓, 刘红超, 樊栋, 徐舒涛, 魏迎旭, 刘中民, 化学学报, 2022, 80, 590.)
[35]	Dědeček J.; Sobalík Z.; Wichterlová B. Catal. Rev.: Sci. Eng. 2012, 54, 135. doi: 10.1080/01614940.2012.632662
[36]	He S. P.; Fan S.; Yuan K.; Guo S. J.; Wang S.; Qin Z. F.; Dong M.; Fan W. B.; Wang J. G. Appl. Catal. A: Gen. 2022, 637, 118604. doi: 10.1016/j.apcata.2022.118604
[37]	Svelle S.; Joensen F.; Nerlov J.; Olsbye U.; Lillerud K. P.; Kolboe S.; Bjørgen M. J. Am. Chem. Soc. 2006, 128, 14770. doi: 10.1021/ja065810a pmid: 17105263
[38]	Bjørgen M.; Svelle S.; Joensen F.; Nerlov J.; Kolboe S.; Bonino F.; Palumbo L.; Bordiga S.; Olsbye U. J. Catal. 2007, 249, 195. doi: 10.1016/j.jcat.2007.04.006
[39]	Xue Y. F.; Li J. F.; Wang P. F.; Cui X. J.; Zheng H. Y.; Niu Y. L.; Dong M.; Qin Z. F.; Wang J. G.; Fan W. B. Appl. Catal. B: Environ. 2021, 280, 119391. doi: 10.1016/j.apcatb.2020.119391
[40]	Fan S.; Wang H.; Wang P. F.; Jiao W. Y.; Wang S.; Qin Z. F.; Dong M.; Wang J. G.; Fan W. B. Chem Catal. 2024, 4, 100927.
[41]	Fan S.; Wang H.; Wang S.; Dong M.; Fan W. B. Sci China Chem. 2024, 67, 3934. doi: 10.1007/s11426-024-2078-4
[42]	Wang C.; Wang Q.; Xu J.; Qi G. D.; Gao P.; Wang W. Y.; Zou Y. Y.; Feng N. D.; Liu X. L.; Deng F. Angew. Chem. Int. Ed. 2016, 55, 2507. doi: 10.1002/anie.v55.7
[43]	Wang J. B.; Wei Y. X.; Li J. Z.; Xu S. T.; Zhang W. N.; He Y. L.; Chen J. R.; Zhang M. Z.; Zheng A. M.; Deng F.; Guo X. W.; Liu Z. M. Catal. Sci. Technol. 2016, 6, 89. doi: 10.1039/C5CY01420D
[44]	Mores D.; Stavitski E.; Verkleij S. P.; Lombard A.; Cabiac A.; Rouleau L.; Patarin J.; Simon-Masseron A.; Weckhuysen B. M. Phys. Chem. Chem. Phys. 2011, 13, 15985. doi: 10.1039/c1cp21324e
[45]	Fu D. L.; Schmidt J. E.; Ristanović Z.; Chowdhury A. D.; Meirer F.; Weckhuysen B. M. Angew. Chem. Int. Ed. 2017, 56, 11217. doi: 10.1002/anie.v56.37
[46]	Yang L.; Yan T. T.; Wang C. M.; Dai W. L.; Wu G. J.; Hunger M.; Fan W. B.; Xie Z. K.; Guan N. J.; Li L. D. ACS Catal. 2019, 9, 6491. doi: 10.1021/acscatal.9b00641
[47]	Burkett S. L.; Davis M. E. Chem. Mater. 1995, 7, 1453. doi: 10.1021/cm00056a009

有机模板剂对ZSM-11分子筛甲醇制丙烯催化性能的影响

Effect of Organic Template Agents on the Catalytic Performance of ZSM-11 Zeolite for Conversion of Methanol to Propene

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