ZSM-5催化甲醇制烯烃反应积碳贯穿孔道交联生长机理: 从分子结构、时空动态到催化剂失活

doi:10.1016/S1872-2067(25)64806-6

催化学报 ›› 2025, Vol. 78: 215-228.DOI: 10.1016/S1872-2067(25)64806-6

ZSM-5催化甲醇制烯烃反应积碳贯穿孔道交联生长机理: 从分子结构、时空动态到催化剂失活

王男^a, 吴一墨^a, 韩晶峰^a, 张亚楠^a^,^f, 王莉^b, 于洋^b, 张嘉兴^c, 熊昊^d, 陈晓^d, 周易达^a, 王韩丽新^e^,^f, 徐兆超^e, 徐舒涛^a, 郭新闻^c, 魏飞^d, 魏迎旭^a^,^*(), 刘中民^a^,^f^,^*()

^a中国科学院大连化学物理研究所, 低碳催化技术国家工程研究中心, 辽宁大连 116023
^b中国科学院大连化学物理研究所, 分析化学分离科学重点实验室, 辽宁大连 116023
^c大连理工大学化工学院, 精细化工国家重点实验室, 辽宁大连 116024
^d清华大学化学工程系, 绿色化学反应工程与技术北京市重点实验室, 北京 100084
^e中国科学院大连化学物理研究所, 分析化学分离科学重点实验室, 辽宁大连 116023
^f中国科学院大学, 北京 100049

收稿日期:2025-07-02 接受日期:2025-08-05 出版日期:2025-11-18 发布日期:2025-10-14
通讯作者: *电子信箱: weiyx@dicp.ac.cn (魏迎旭),
基金资助:
国家自然科学基金(22288101);国家自然科学基金(21991090);中国科学院杰出研究助理基金项目

Channel-passing growth mechanism of coke in ZSM-5 catalyzed methanol-to-hydrocarbons conversion: From molecular structure, spatiotemporal dynamics to catalyst deactivation

Nan Wang^a, Yimo Wu^a, Jingfeng Han^a, Yanan Zhang^a^,^f, Li Wang^b, Yang Yu^b, Jiaxing Zhang^c, Hao Xiong^d, Xiao Chen^d, Yida Zhou^a, Hanlixin Wang^e^,^f, Zhaochao Xu^e, Shutao Xu^a, Xinwen Guo^c, Fei Wei^d, Yingxu Wei^a^,^*(), Zhongmin Liu^a^,^f^,^*()

^aNational Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bDivision of Energy Research Resources, CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cState Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^dBeijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
^eCAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^fUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-07-02 Accepted:2025-08-05 Online:2025-11-18 Published:2025-10-14
Contact: *E-mail: weiyx@dicp.ac.cn (Y. Wei), liuzm@dicp.ac.cn (Z. Liu).
Supported by:
National Natural Science Foundation of China(22288101);National Natural Science Foundation of China(21991090);Distinguished Research Assistant Funding Project of Chinese Academy of Sciences(CAS)

摘要/Abstract

摘要：

分子筛催化剂在石油、煤、天然气化工及塑料、CO₂转化等领域具有重要应用, 但其快速积碳失活问题严重制约了工业催化过程高效、可持续发展. 尽管过去几十年对催化剂积碳的形成机制进行了大量研究, 但关于多环芳烃(PAHs)在分子筛孔道中的分子结构、空间落位及生长路径仍缺乏清晰认识. 尤其是在分子尺度上, PAHs在分子尺寸限域空间内的迁移和聚集行为如何影响催化剂的宏观性能尚不明确. 因此, 揭示积碳的分子结构及其在沸石孔道中的动态演化过程, 对于理解催化剂失活机制和设计抗积碳分子筛催化剂具有重要意义.

本研究以工业上广泛应用的ZSM-5沸石为模型催化剂, 通过结合高分辨基质辅助激光解吸电离傅里叶变换离子回旋共振质谱与多维度化学成像技术和理论手段, 首次在原子分辨率和单晶尺度上揭示了甲醇制烃类(MTH)反应中积碳贯穿孔道交联生长机理. 研究团队开发了多尺度光谱工具箱, 包括红外显微光谱、结构光照明显微镜、飞行时间二次离子质谱和原子分辨的积分差分相位衬度-扫描透射电子显微技术, 实现了对PAHs分子结构、空间定位及动态演化的全面解析-实验结果表明, PAHs在ZSM-5孔道中通过孔道交叉处连接形成多核链状结构, 其生长受沸石分子尺度受限微环境的模板效应驱动. 高分辨质谱结合同位素标记分析显示, PAHs的质量分布呈现离散分段特征, 表明其通过孔道贯穿的生长模式, 即芳烃分子核在相邻孔道交叉处通过C4或苯、萘单元逐步连接. 结合同位素标记和理论计算, 研究确定了PAHs的具体分子构型, 发现其优先沿ZSM-5直孔道排列, 形成热力学稳定的链状结构. 此外, 原子分辨成像直接观测到PAHs分子在孔道中的填充行为及空间落位, 证实了其与沸石骨架的紧密相互作用. 更重要的是, PAHs的通道传递生长机制具有普适性, 在ZSM-22(1D孔道)和ZSM-35(2D孔道)等其他孔道、笼结构沸石中同样存在. 这一机制揭示了PAHs在受限空间中普遍的动态演化路径, 从初始的可溶性芳烃到最终的不溶性多核链状焦炭, 逐步导致催化剂孔道堵塞和失活. 建立的失活模型更新了对积碳失活的认识, 积碳-分子筛互锁相的传热、传质、电子/质子传输、亲/疏水性质发生改变是催化剂失活的本质.

综上, 本文首次从分子尺度揭示了ZSM-5催化MTH反应中积碳贯穿孔道交联生长机理, 建立了积碳结构-落位-演变路径的完整机理模型, 为理解沸石催化剂失活提供了新视角. 研究提出的多尺度失活模型不仅解决了长期困扰学术界的积碳形成难题, 还为设计抗积碳沸石催化剂提供了理论依据和全新思路. 此外, 本研究发展的多尺度表征方法也为其他分子尺寸、纳米尺度受限体系的主客体化学研究提供了重要参考.

关键词: 分子筛, 甲醇制烃类, 积碳表征, 失活, 反应机理

Abstract:

Coke formation is the primary cause of zeolite deactivation in industrial catalysis, yet the structural identity, spatial location and molecular routes of polycyclic aromatic hydrocarbons (PAHs) within confined zeolite pores remain elusive. Here, by coupling matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry with multi-dimensional chemical imaging, we unveil a channel-passing growth mechanism for PAHs in ZSM-5 zeolites during methanol conversion through identifying the molecular fingerprints of larger PAHs, pinpointing and visualizing their 3D location and spatiotemporal evolution trajectory with atomic resolution and at both channel and single-crystal scales. Confined aromatic entities cross-link with each other, culminating in multicore PAH chains as the both thermodynamically favorable and kinetically trapped host-guest entanglement wrought and templated by the defined molecular-scale constrained microenvironments of zeolite. The mechanistic concept proves general across both channel- and cage-structured zeolite materials. Our multiscale deactivating model based on the full-picture coke structure-location correlations—spanning atom, molecule, channel/cage and single crystal scales—would shed new light on the intertwined chemical and physical processes in catalyst deactivation. This work not only resolves long-standing puzzles in coke formation but also provides design principles for coke-resistant zeolites. The methods and insights would rekindle interest in confinement effects and host-guest chemistry across broader chemistry fields beyond catalysis and carbon materials.

Key words: Zeolites, Methanol-to-hydrocarbons, Coke characterization, Deactivation, Reaction mechanisms

王男, 吴一墨, 韩晶峰, 张亚楠, 王莉, 于洋, 张嘉兴, 熊昊, 陈晓, 周易达, 王韩丽新, 徐兆超, 徐舒涛, 郭新闻, 魏飞, 魏迎旭, 刘中民. ZSM-5催化甲醇制烯烃反应积碳贯穿孔道交联生长机理: 从分子结构、时空动态到催化剂失活[J]. 催化学报, 2025, 78: 215-228.

Nan Wang, Yimo Wu, Jingfeng Han, Yanan Zhang, Li Wang, Yang Yu, Jiaxing Zhang, Hao Xiong, Xiao Chen, Yida Zhou, Hanlixin Wang, Zhaochao Xu, Shutao Xu, Xinwen Guo, Fei Wei, Yingxu Wei, Zhongmin Liu. Channel-passing growth mechanism of coke in ZSM-5 catalyzed methanol-to-hydrocarbons conversion: From molecular structure, spatiotemporal dynamics to catalyst deactivation[J]. Chinese Journal of Catalysis, 2025, 78: 215-228.

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图/表 6

Fig. 1. An overview of the micro-spectroscopic toolbox utilized in this work to study aromatic spatiotemporal migration-agglomeration evolution and dynamic PAH-zeolite guest-host interplay at the single crystal level. Schematics of the zeolite crystal for infrared micro-spectroscopy imaging (b), structured illumination microscopy imaging (e, images were acquired by focusing on the middle z-plane of crystals to exclude external surface interference) and time-of-flight secondary ion mass spectrometry depth profiling (g). (a) The optical photograph of the capsule Z5@SiO2 (L) crystals. (c) Time-resolved 2D IR intensity maps of a Z5@SiO2 (L) crystal recorded in real time through custom-developed RQSI approach during methanol conversion at 475 °C for the 1615 cm-1 (aromatic species) vibrational bands. (d) 1D line-scan concentration plots of aromatic guests. (f) Supper-resolution spatiotemporal distribution of carbonaceous species obtained from SIM in Z5@SiO2 (L) crystals with time on stream (TOS). MTH reaction performance of Z5@SiO2 (L) at 475? °C and WHSV of 10 h-1 was presented in Fig. S9. The fluorescence intensities of the selected lines are also displayed. The SIM images are the fluorescence originating from the overlap of four curves with different laser excitations of 405?nm (detection at 435-485?nm, blue), 488?nm (detection at 500-545?nm, green), 561?nm (detection at 570-640?nm, yellow) and 640?nm (detection at 663-738?nm, magenta). (h) Nanoscale 3D reconstruction of 13C+ secondary ion depth profile of the Z5@SiO2 (L) crystal after 4 h of methanol conversion.

Fig. 2. (a) Schematic illustration of aromatic migration-agglomeration dynamics in molecular-scale zeolite confined space and spatiotemporal evolution within single crystal, taking methanol conversion over channel-structured ZSM-5 (3D MFI topology) as a prototypical system. (b) MTH reaction performance over Z5@SiO2 (20) at 475? °C and WHSV of 4 h-1. (c) Operando FTIR spectra for tracking the surface species evolution over Z5@SiO2 (L) crystals at 400 °C and detailed surface C1 species evolution routes with infrared signals attribution. (d) Time-evolving chromatograms of soluble coke extracted from the spent up-layer Z5@SiO2 (20) catalysts after HF digestion. See layered catalyst bed in Fig. S12. (e) Time-of-flight mass spectrogram after comprehensive two-dimensional gas chromatography of the soluble coke at 197 min of the reaction.

Fig. 3. The mass spectra of the liberated carbonaceous deposits obtained from the spent upper-layer Z5@SiO2 (20) catalysts by HF dissolution-CCl4 extraction after MTH reaction with WHSV of 4 h-1 at 475? °C for 5 min for illustrative purposes (a), at 475? °C for different durations (5-133 min) (b), at different temperatures (350-475? °C) and from the bottom-layer of H-ZSM-5 (105) with lower density of acidity (c).

Fig. 4. MALDI FT-ICR mass spectra of the extracts from the spent Z5@SiO2 (20) after 5?min reaction at 475? °C for comparing the feeding of 13C-methanol (a) and D-methanol (b) with normal methanol. (c) 13C MAS NMR spectroscopy of the isolated insoluble coke from Z5@SiO2 (20). (d) The identified conceivable PAH molecular structures and their channel-resolved spatial location in MFI pore network. (e) Full molecular picture of PAHs evolution routes and aromatic migration-agglomeration dynamic trajectory in molecular-scale zeolite confined space. PAH agglomerates evolve from long chain olefins and light polymethylbenzenes (“seeding”) to one-/two-ring PAHs behaving as building units for aromatic cluster formation (“growing”) and eventually to channel-passing aromatic agglomerates (“agglomerating”). Primary coking seeds mature from C4 to polymethylbenzenes and naphthalene in a dynamic manner. Direct atomic-resolution iDPC-STEM image of the coke-loaded short b-axis ZSM-5 crystals (~30 nm thickness) after MTH reaction at 475 °C with WHSV of 10 h-1 for 10 h from the (010) projection (f, left). Structural model of the MFI framework filled by channel-passing PAH molecules (f, right). Magnified iDPC-STEM images of an empty straight channel before reaction (h, top) and filled by a PAHs molecule after reaction (g, left). Corresponding structures of the MFI framework before (h, bottom) and after (g, right) the filling of channel-passing PAH molecules. The orange ellipses present the shapes of straight channels and the blue belts present the orientation of sinusoidal channels.

Fig. 5. MALDI FT-ICR mass spectra for extracts obtained from other channel-structured zeolites (ZSM-35@SiO2 and ZSM-22@SiO2) and the deduced possible molecular structure of PAHs. The indicated molecular structures are representative examples of possible structures. Lower signal-to-noise ratio observed in 1-D TON signifies a lower PAHs intensity.

Fig. 6. MALDI FT-ICR mass spectra for extracts obtained from other channel-structured zeolites (ZSM-35@SiO2 and ZSM-22@SiO2) and the deduced possible molecular structure of PAHs. The indicated molecular structures are representative examples of possible structures. Lower signal-to-noise ratio observed in 1-D TON signifies a lower PAHs intensity.

参考文献

[1]	A. Corma, Chem. Rev., 1995, 95, 559-614.
[2]	Y. Li, J. Yu, Nat. Rev. Mater., 2021, 6, 1156-1174.
[3]	A. Corma, S. Iborra, A. Velty, Chem. Rev., 2007, 107, 2411-2502.
[4]	B. Smit, T. L. M. Maesen, Nature, 2008, 451, 671-678.
[5]	B. M. Weckhuysen, J. Yu, Chem. Soc. Rev., 2015, 44, 7022-7024.
[6]	E. M. Gallego, M. T. Portilla, C. Paris, A. León-Escamilla, M. Boronat, M. Moliner, A. Corma, Science, 2017, 355, 1051-1054.
[7]	M. Dusselier, M. E. Davis, Chem. Rev., 2018, 118, 5265-5329.
[8]	C. Li, C. Paris, J. Martínez-Triguero, M. Boronat, M. Moliner, A. Corma, Nat. Catal., 2018, 1, 547-554.
[9]	P. Ferri, C. Li, C. Paris, A. Vidal-Moya, M. Moliner, M. Boronat, A. Corma, ACS Catal., 2019, 9, 11542-11551.
[10]	U. Olsbye, S. Svelle, M. Bjørgen, P. Beato, T. V. W. Janssens, F. Joensen, S. Bordiga, K. P. Lillerud, Angew. Chem. Int. Ed., 2012, 51, 5810-5831.
[11]	F. Schmidt, C. Hoffmann, F. Giordanino, S. Bordiga, P. Simon, W. Carrillo-Cabrera, S. Kaskel, J. Catal., 2013, 307, 238-245.
[12]	C. Wang, A. Brenig, J. Xu, F. Deng, V. Paunović, J. A. van Bokhoven, J. Am. Chem. Soc., 2024, 146, 34279-34284.
[13]	K. Stanciakova, B. Ensing, F. Göltl, R. E. Bulo, B. M. Weckhuysen, ACS Catal., 2019, 9, 5119-5135.
[14]	P. Tian, Y. Wei, M. Ye, Z. Liu, ACS Catal., 2015, 5, 1922-1938.
[15]	I. Yarulina, A. D. Chowdhury, F. Meirer, B. M. Weckhuysen, J. Gascon, Nat. Catal., 2018, 1, 398-411.
[16]	C. Vogt, B. M. Weckhuysen, Nat. Rev. Chem., 2022, 6, 89-111.
[17]	J. Zhou, M. Gao, J. Zhang, W. Liu, T. Zhang, H. Li, Z. Xu, M. Ye, Z. Liu, Nat. Commun., 2021, 12, 17.
[18]	C. Wang, L. Yang, M. Gao, X. Shao, W. Dai, G. Wu, N. Guan, Z. Xu, M. Ye, L. Li, J. Am. Chem. Soc., 2022, 144, 21408-21416.
[19]	A. Corma, L. Sauvanaud, E. Doskocil, G. Yaluris, J. Catal., 2011, 279, 183-195.
[20]	C. H. Bartholomew, Catal. Rev., 1982, 24, 67-112.
[21]	C. H. Bartholomew, Appl. Catal. A, 2001, 212, 17-60.
[22]	M. Guisnet, F. R. Ribeiro, Deactivation and Regeneration of Zeolite Catalysts, Imperial College Press, 2011.
[23]	H. Schulz, Catal. Lett., 2018, 148, 1263-1280.
[24]	A. J. Martín, S. Mitchell, C. Mondelli, S. Jaydev, J. Pérez-Ramírez, Nat. Catal., 2022, 5, 854-866.
[25]	E. T. C. Vogt, D. Fu, B. M. Weckhuysen, Angew. Chem. Int. Ed., 2023, 62, e202300319.
[26]	Y. Wei, J. Li, C. Yuan, S. Xu, Y. Zhou, J. Chen, Q. Wang, Q. Zhang, Z. Liu, Chem. Commun., 2012, 48, 3082.
[27]	S. Müller, Y. Liu, M. Vishnuvarthan, X. Sun, A. C. van Veen, G. L. Haller, M. Sanchez-Sanchez, J. A. Lercher, J. Catal., 2015, 325, 48-59.
[28]	N. Wang, Y. Zhi, Y. Wei, W. Zhang, Z. Liu, J. Huang, T. Sun, S. Xu, S. Lin, Y. He, A. Zheng, Z. Liu, Nat. Commun., 2020, 11, 1079.
[29]	D. Mores, J. Kornatowski, U. Olsbye, B. M. Weckhuysen, Chem. Eur. J., 2011, 17, 2874-2884.
[30]	D. Fu, O. van der Heijden, K. Stanciakova, J. E. Schmidt, B. M. Weckhuysen, Angew. Chem. Int. Ed., 2020, 59, 15502-15506.
[31]	R. Y. Brogaard, B. M. Weckhuysen, J. K. Nørskov, J. Catal., 2013, 300, 235-241.
[32]	M. Guisnet, P. Magnoux, Appl. Catal., 1989, 54, 1-27.
[33]	T. Liang, J. Chen, Z. Qin, J. Li, P. Wang, S. Wang, G. Wang, M. Dong, W. Fan, J. Wang, ACS Catal., 2016, 6, 7311-7325.
[34]	D. Rojo-Gama, M. Signorile, F. Bonino, S. Bordiga, U. Olsbye, K. P. Lillerud, P. Beato, S. Svelle, J. Catal., 2017, 351, 33-48.
[35]	I. Yarulina, K. De Wispelaere, S. Bailleul, J. Goetze, M. Radersma, E. Abou-Hamad, I. Vollmer, M. Goesten, B. Mezari, E. J. M. Hensen, J. S. Martínez-Espín, M. Morten, S. Mitchell, J. Perez-Ramirez, U. Olsbye, B. M. Weckhuysen, V. Van Speybroeck, F. Kapteijn, J. Gascon, Nat. Chem., 2018, 10, 804-812.
[36]	S. Lee, M. Choi, J. Catal., 2019, 375, 183-192.
[37]	P. Rzepka, D. Sheptyakov, C. Wang, J. A. van Bokhoven, V. Paunović, ACS Catal., 2024, 14, 5593-5604.
[38]	D. Mores, E. Stavitski, M. Kox, J. Kornatowski, U. Olsbye, B. Weckhuysen, Chem. Eur. J., 2008, 14, 11320-11327.
[39]	E. Stavitski, B. M. Weckhuysen, Chem. Soc. Rev., 2010, 39, 4615-4625.
[40]	J. E. Schmidt, J. D. Poplawsky, B. Mazumder, Ö. Attila, D. Fu, D. A. Matthijs de Winter, F. Meirer, S. R. Bare, B. M. Weckhuysen, Angew. Chem. Int. Ed., 2016, 55, 11173-11177.
[41]	A. M. Beale, S. D. M. Jacques, B. M. Weckhuysen, Chem. Soc. Rev., 2010, 39, 4656-4672.
[42]	F. Meirer, B. M. Weckhuysen, Nat. Rev. Mater., 2018, 3, 324-340.
[43]	S. Das, R. Pashminehazar, S. Sharma, S. Weber, T. L. Sheppard, Chem. Ing. Tech., 2022, 94, 1591-1610.
[44]	J. T. C. Wennmacher, S. Mahmoudi, P. Rzepka, S. Sik Lee, T. Gruene, V. Paunović, J. A. van Bokhoven, Angew. Chem. Int. Ed., 2022, 61, e202205413.
[45]	B. Weckhuysen, Angew. Chem. Int. Ed., 2009, 48, 4910-4943.
[46]	I. L. C. Buurmans, B. M. Weckhuysen, Nat. Chem., 2012, 4, 873-886.
[47]	S. Mitchell, N.-L. Michels, K. Kunze, J. Pérez-Ramírez, Nat. Chem., 2012, 4, 825-831.
[48]	K. Kim, T. Lee, Y. Kwon, Y. Seo, J. Song, J. K. Park, H. Lee, J. Y. Park, H. Ihee, S. J. Cho, R. Ryoo, Nature, 2016, 535, 131-135.
[49]	S. Shao, H. Zhang, R. Xiao, X. Li, Y. Cai, J. Anal. Appl. Pyrolysis, 2017, 127, 258-268.
[50]	X. Wu, S. Xu, Y. Wei, W. Zhang, J. Huang, S. Xu, Y. He, S. Lin, T. Sun, Z. Liu, ACS Catal., 2018, 8, 7356-7361.
[51]	A. Janda, A. T. Bell, J. Am. Chem. Soc., 2013, 135, 19193-19207.
[52]	S. M. Campbell, X.-Z. Jiang, R. F. Howe, Microporous Mesoporous Mater., 1999, 29, 91-108.
[53]	T. R. Forester, R. F. Howe, J. Am. Chem. Soc., 1987, 109, 5076-5082.
[54]	I. B. Minova, S. K. Matam, A. Greenaway, C. R. A. Catlow, M. D. Frogley, G. Cinque, P. A. Wright, R. F. Howe, ACS Catal., 2019, 9, 6564-6570.
[55]	J. D. Mosley, J. W. Young, J. Agarwal, H. F. Schaefer III, P. V. R. Schleyer, M. A. Duncan, Angew. Chem. Int. Ed., 2014, 53, 5888-5891.
[56]	J. W. Niemantsverdriet, in: Spectroscopy in Catalysis, Wiley-VCH Verlag GmbH & Co. KGaA, 2007, 85-119.
[57]	J. S. Fletcher, J. C. Vickerman, Anal. Chem., 2013, 85, 610-639.
[58]	K. Hemelsoet, Q. Qian, T. De Meyer, K. De Wispelaere, B. De Sterck, B. M. Weckhuysen, M. Waroquier, V. Van Speybroeck, Chem. Eur. J., 2013, 19, 16595-16606.
[59]	V. Van Speybroeck, K. Hemelsoet, K. De Wispelaere, Q. Qian, J. Van der Mynsbrugge, B. De Sterck, B. M. Weckhuysen, M. Waroquier, ChemCatChem, 2013, 5, 173-184.
[60]	G. T. Whiting, N. Nikolopoulos, I. Nikolopoulos, A. D. Chowdhury, B. M. Weckhuysen, Nat. Chem., 2019, 11, 23-31.
[61]	M. Gao, H. Li, W. Liu, Z. Xu, S. Peng, M. Yang, M. Ye, Z. Liu, Nat. Commun., 2020, 11, 3641.
[62]	A. Feller, J.-O. Barth, A. Guzman, I. Zuazo, J. A. Lercher, J. Catal., 2003, 220, 192-206.
[63]	L. Pinard, S. Hamieh, C. Canaff, F. Ferreira Madeira, I. Batonneau-Gener, S. Maury, O. Delpoux, K. Ben Tayeb, Y. Pouilloux, H. Vezin, J. Catal., 2013, 299, 284-297.
[64]	N. Chaouati, A. Soualah, M. Chater, M. Tarighi, L. Pinard, J. Catal., 2016, 344, 354-364.
[65]	P. Andy, N. S. Gnep, M. Guisnet, E. Benazzi, C. Travers, J. Catal., 1998, 173, 322-332.
[66]	B. Tian, Y. Qiao, L. Bai, F. Liu, Y. Tian, K. Xie, Fuel Process. Technol., 2017, 159, 386-395.
[67]	Y.-G. Wang, X.-Y. Wei, R.-L. Xie, F.-J. Liu, P. Li, Z.-M. Zong, Energy Fuels, 2015, 29, 595-601.
[68]	A. D. Chowdhury, K. Houben, G. T. Whiting, S.-H. Chung, M. Baldus, B. M. Weckhuysen, Nat. Catal., 2018, 1, 23-31.
[69]	N. Wang, W. Sun, Y. Hou, B. Ge, L. Hu, J. Nie, W. Qian, F. Wei, J. Catal., 2018, 360, 89-96.
[70]	G. D. Price, J. J. Pluth, J. V. Smith, J. M. Bennett, R. L. Patton, J. Am. Chem. Soc., 1982, 104, 5971-5977.
[71]	J. R. Agger, N. Hanif, C. S. Cundy, A. P. Wade, S. Dennison, P. A. Rawlinson, M. W. Anderson, J. Am. Chem. Soc., 2003, 125, 830-839.
[72]	M. B. J. Roeffaers, R. Ameloot, M. Baruah, H. Uji-i, M. Bulut, G. De Cremer, U. Müller, P. A. Jacobs, J. Hofkens, B. F. Sels, D. E. De Vos, J. Am. Chem. Soc., 2008, 130, 5763-5772.
[73]	M. B. J. Roeffaers, R. Ameloot, A.-J. Bons, W. Mortier, G. De Cremer, R. de Kloe, J. Hofkens, D. E. De Vos, B. F. Sels, J. Am. Chem. Soc., 2008, 130, 13516-13517.
[74]	L. Karwacki, M. H. F. Kox, D. A. Matthijs de Winter, M. R. Drury, J. D. Meeldijk, E. Stavitski, W. Schmidt, M. Mertens, P. Cubillas, N. John, A. Chan, N. Kahn, S. R. Bare, M. Anderson, J. Kornatowski, B. M. Weckhuysen, Nat. Mater., 2009, 8, 959-965.
[75]	G. Sastre, P. M. Viruela, A. Corma, Chem. Phys. Lett., 1997, 264, 565-572.
[76]	F. Márquez, H. García, E. Palomares, L. Fernández, A. Corma, J. Am. Chem. Soc., 2000, 122, 6520-6521.
[77]	G. Li, C. Foo, X. Yi, W. Chen, P. Zhao, P. Gao, T. Yoskamtorn, Y. Xiao, S. Day, C. C. Tang, G. Hou, A. Zheng, S. C. E. Tsang, J. Am. Chem. Soc., 2021, 143, 8761-8771.
[78]	W. Chen, J. Han, Y. Wei, A. Zheng, Angew. Chem. Int. Ed., 2022, 61, e202116269.
[79]	M. Li, Y. Ye, B. Bai, C. Liu, H. Wang, Z. Xu, J. Xiao, F. Jiao, X. Pan, X. Bao, J. Am. Chem. Soc., 2025, 147, 15747-15754.
[80]	D. Kiani, I. E. Wachs, ACS Catal., 2024, 14, 16770-16784.
[81]	Y. Ma, L. Huang, Y. Tan, H. An, Q. Zhang, C. Xu, B. Shen, Fuel, 2025, 390, 134659.
[82]	N. Wang, L. Wang, Y. Zhi, J. Han, C. Zhang, X. Wu, J. Zhang, L. Wang, B. Fan, S. Xu, Y. Zheng, S. Lin, R. Wu, Y. Wei, Z. Liu, J. Energy Chem., 2023, 76, 105-116.
[83]	R. Xu, K. Wang, G. Chen, W. Yan, Natl. Sci. Rev., 2019, 6, 191-194.
[84]	T. Hartman, R. G. Geitenbeek, G. T. Whiting, B. M. Weckhuysen, Nat. Catal., 2019, 2, 986-996.
[85]	Y. Tian, M. Gao, H. Xie, S. Xu, M. Ye, Z. Liu, J. Am. Chem. Soc., 2024, 146, 4958-4972.
[86]	K. De Wispelaere, C. S. Wondergem, B. Ensing, K. Hemelsoet, E. J. Meijer, B. M. Weckhuysen, V. Van Speybroeck,, J. Ruiz-Martı́nez, ACS Catal., 2016, 6, 1991-2002.
[87]	H. Wang, Y. Hou, W. Sun, Q. Hu, H. Xiong, T. Wang, B. Yan, W. Qian, ACS Catal., 2020, 10, 5288-5298.
[88]	C. Zhang, X. Wu, Y. Zhang, L. Wang, Y. Jin, M. Gao, M. Ye, Y. Wei, Z. Liu, ACS Catal., 2025, 15, 1553-1562.
[89]	C. Wang, Y. Chu, D. Xiong, H. Wang, M. Hu, Q. Wang, J. Xu, F. Deng, Angew. Chem. Int. Ed., 2024, 63, e202480361.
[90]	C. Wang, M. Zheng, M. Hu, W. Cai, Y. Chu, Q. Wang, J. Xu, F. Deng, J. Am. Chem. Soc., 2024, 146, 8688-8696.

ZSM-5催化甲醇制烯烃反应积碳贯穿孔道交联生长机理: 从分子结构、时空动态到催化剂失活

Channel-passing growth mechanism of coke in ZSM-5 catalyzed methanol-to-hydrocarbons conversion: From molecular structure, spatiotemporal dynamics to catalyst deactivation

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