Impact of Zeolite Framework Composition and Flexibility on Methanol-To-Olefins Selectivity: Confinement or Diffusion?

This is the peer reviewed version of the following article: P. Ferri, C. Li, R. Millán, J. Martínez-Triguero, M. Moliner, M. Boronat, A. Corma, Angew. Chem. Int. Ed. 2020, 59, 19708, which has been published in final form at https://doi.org/10.1002/anie.202007609. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] The methanol-to-olefins reaction catalyzed by small-pore cage-based acid zeolites and zeotypes produces a mixture of short chain olefins, whose selectivity to ethene, propene and butene varies with the cavity architecture and with the framework composition. The product distribution of aluminosilicates and silicoaluminophosphates with the CHA and AEI structures (H-SSZ-13, H-SAPO-34, H-SSZ-39 and H-SAPO-18) has been experimentally determined, and the impact of acidity and framework flexibility on the stability of the key cationic intermediates involved in the mechanism and on the diffusion of the olefin products through the8rwindows of the catalysts has been evaluated by means of periodic DFT calculations and ab initio molecular dynamics simulations. The preferential stabilization by confinement of fully methylated hydrocarbon pool intermediates favoring the paring pathway is the main factor controlling the final olefin product distribution.This work has been supported by the European Union through ERC-AdG-2014-671093 (SynCatMatch), Spanish Government through "Severo Ochoa" (SEV-2016-0683, MINECO), MAT2017-82288-C2-1-P (AEI/FEDER, UE) and RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE), and by Generalitat Valenciana through AICO/2019/060. The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization. Red Espanola de Supercomputacion (RES) and Servei d'Informatica de la Universitat de Valencia (SIUV) are acknowledged for computational resources and technical support. P.F. and R.M. thank ITQ for their contracts. C.L. acknowledges China Scholarship Council (CSC) for a Ph.D fellowship.Ferri-Vicedo, P.; Li, C.; Millán-Cabrera, R.; Martínez-Triguero, J.; Moliner Marin, M.; Boronat Zaragoza, M.; Corma Canós, A. (2020). Impact of Zeolite Framework Composition and Flexibility on Methanol-To-Olefins Selectivity: Confinement or Diffusion?. Angewandte Chemie International Edition. 59(44):19708-19715. https://doi.org/10.1002/anie.20200760919708197155944Olah, G. A. (2005). Beyond Oil and Gas: The Methanol Economy. Angewandte Chemie International Edition, 44(18), 2636-2639. doi:10.1002/anie.200462121Olah, G. A. (2005). Jenseits von Öl und Gas: die Methanolwirtschaft. Angewandte Chemie, 117(18), 2692-2696. doi:10.1002/ange.200462121Tian, P., Wei, Y., Ye, M., & Liu, Z. (2015). Methanol to Olefins (MTO): From Fundamentals to Commercialization. ACS Catalysis, 5(3), 1922-1938. doi:10.1021/acscatal.5b00007Haw, J. F., Song, W., Marcus, D. M., & Nicholas, J. B. (2003). The Mechanism of Methanol to Hydrocarbon Catalysis. Accounts of Chemical Research, 36(5), 317-326. doi:10.1021/ar020006oOlsbye, U., Svelle, S., Bjørgen, M., Beato, P., Janssens, T. V. W., Joensen, F., … Lillerud, K. P. (2012). Conversion of Methanol to Hydrocarbons: How Zeolite Cavity and Pore Size Controls Product Selectivity. Angewandte Chemie International Edition, 51(24), 5810-5831. doi:10.1002/anie.201103657Olsbye, U., Svelle, S., Bjørgen, M., Beato, P., Janssens, T. V. W., Joensen, F., … Lillerud, K. P. (2012). Umwandlung von Methanol in Kohlenwasserstoffe: Wie Zeolith-Hohlräume und Porengröße die Produktselektivität bestimmen. Angewandte Chemie, 124(24), 5910-5933. doi:10.1002/ange.201103657Van Speybroeck, V., De Wispelaere, K., Van der Mynsbrugge, J., Vandichel, M., Hemelsoet, K., & Waroquier, M. (2014). First principle chemical kinetics in zeolites: the methanol-to-olefin process as a case study. Chem. Soc. Rev., 43(21), 7326-7357. doi:10.1039/c4cs00146jYarulina, I., Chowdhury, A. D., Meirer, F., Weckhuysen, B. M., & Gascon, J. (2018). Recent trends and fundamental insights in the methanol-to-hydrocarbons process. Nature Catalysis, 1(6), 398-411. doi:10.1038/s41929-018-0078-5Moliner, M., Martínez, C., & Corma, A. (2013). Synthesis Strategies for Preparing Useful Small Pore Zeolites and Zeotypes for Gas Separations and Catalysis. Chemistry of Materials, 26(1), 246-258. doi:10.1021/cm4015095McCann, D. M., Lesthaeghe, D., Kletnieks, P. W., Guenther, D. R., Hayman, M. J., Van Speybroeck, V., … Haw, J. F. (2008). A Complete Catalytic Cycle for Supramolecular Methanol‐to‐Olefins Conversion by Linking Theory with Experiment. Angewandte Chemie International Edition, 47(28), 5179-5182. doi:10.1002/anie.200705453McCann, D. M., Lesthaeghe, D., Kletnieks, P. W., Guenther, D. R., Hayman, M. J., Van Speybroeck, V., … Haw, J. F. (2008). A Complete Catalytic Cycle for Supramolecular Methanol‐to‐Olefins Conversion by Linking Theory with Experiment. Angewandte Chemie, 120(28), 5257-5260. doi:10.1002/ange.200705453Wang, C.-M., Wang, Y.-D., Xie, Z.-K., & Liu, Z.-P. (2009). Methanol to Olefin Conversion on HSAPO-34 Zeolite from Periodic Density Functional Theory Calculations: A Complete Cycle of Side Chain Hydrocarbon Pool Mechanism. The Journal of Physical Chemistry C, 113(11), 4584-4591. doi:10.1021/jp810350xIlias, S., & Bhan, A. (2012). Mechanism of the Catalytic Conversion of Methanol to Hydrocarbons. ACS Catalysis, 3(1), 18-31. doi:10.1021/cs3006583De Wispelaere, K., Hemelsoet, K., Waroquier, M., & Van Speybroeck, V. (2013). Complete low-barrier side-chain route for olefin formation during methanol conversion in H-SAPO-34. Journal of Catalysis, 305, 76-80. doi:10.1016/j.jcat.2013.04.015Hemelsoet, K., Van der Mynsbrugge, J., De Wispelaere, K., Waroquier, M., & Van Speybroeck, V. (2013). Unraveling the Reaction Mechanisms Governing Methanol-to-Olefins Catalysis by Theory and Experiment. ChemPhysChem, 14(8), 1526-1545. doi:10.1002/cphc.201201023Li, J., Wei, Y., Chen, J., Tian, P., Su, X., Xu, S., … Liu, Z. (2011). Observation of Heptamethylbenzenium Cation over SAPO-Type Molecular Sieve DNL-6 under Real MTO Conversion Conditions. Journal of the American Chemical Society, 134(2), 836-839. doi:10.1021/ja209950xXu, S., Zheng, A., Wei, Y., Chen, J., Li, J., Chu, Y., … Liu, Z. (2013). Direct Observation of Cyclic Carbenium Ions and Their Role in the Catalytic Cycle of the Methanol-to-Olefin Reaction over Chabazite Zeolites. Angewandte Chemie International Edition, 52(44), 11564-11568. doi:10.1002/anie.201303586Xu, S., Zheng, A., Wei, Y., Chen, J., Li, J., Chu, Y., … Liu, Z. (2013). Direct Observation of Cyclic Carbenium Ions and Their Role in the Catalytic Cycle of the Methanol-to-Olefin Reaction over Chabazite Zeolites. Angewandte Chemie, 125(44), 11778-11782. doi:10.1002/ange.201303586Li, J., Wei, Y., Chen, J., Xu, S., Tian, P., Yang, X., … Liu, Z. (2014). Cavity Controls the Selectivity: Insights of Confinement Effects on MTO Reaction. ACS Catalysis, 5(2), 661-665. doi:10.1021/cs501669kZhang, W., Chen, J., Xu, S., Chu, Y., Wei, Y., Zhi, Y., … Liu, Z. (2018). Methanol to Olefins Reaction over Cavity-type Zeolite: Cavity Controls the Critical Intermediates and Product Selectivity. ACS Catalysis, 8(12), 10950-10963. doi:10.1021/acscatal.8b02164Song, W., Fu, H., & Haw, J. F. (2001). Supramolecular Origins of Product Selectivity for Methanol-to-Olefin Catalysis on HSAPO-34. Journal of the American Chemical Society, 123(20), 4749-4754. doi:10.1021/ja0041167Svelle, S., Olsbye, U., Joensen, F., & Bjørgen, M. (2007). Conversion of Methanol to Alkenes over Medium- and Large-Pore Acidic Zeolites: Steric Manipulation of the Reaction Intermediates Governs the Ethene/Propene Product Selectivity. The Journal of Physical Chemistry C, 111(49), 17981-17984. doi:10.1021/jp077331jHwang, A., Johnson, B. A., & Bhan, A. (2019). Mechanistic study of methylbenzene dealkylation in methanol-to-olefins catalysis on HSAPO-34. Journal of Catalysis, 369, 86-94. doi:10.1016/j.jcat.2018.10.022Bhawe, Y., Moliner-Marin, M., Lunn, J. D., Liu, Y., Malek, A., & Davis, M. (2012). Effect of Cage Size on the Selective Conversion of Methanol to Light Olefins. ACS Catalysis, 2(12), 2490-2495. doi:10.1021/cs300558xKang, J. H., Walter, R., Xie, D., Davis, T., Chen, C.-Y., Davis, M. E., & Zones, S. I. (2018). Further Studies on How the Nature of Zeolite Cavities That Are Bounded by Small Pores Influences the Conversion of Methanol to Light Olefins. ChemPhysChem, 19(4), 412-419. doi:10.1002/cphc.201701197Kang, J. H., Alshafei, F. H., Zones, S. I., & Davis, M. E. (2019). Cage-Defining Ring: A Molecular Sieve Structural Indicator for Light Olefin Product Distribution from the Methanol-to-Olefins Reaction. ACS Catalysis, 9(7), 6012-6019. doi:10.1021/acscatal.9b00746Li, C., Paris, C., Martínez-Triguero, J., Boronat, M., Moliner, M., & Corma, A. (2018). Synthesis of reaction‐adapted zeolites as methanol-to-olefins catalysts with mimics of reaction intermediates as organic structure‐directing agents. Nature Catalysis, 1(7), 547-554. doi:10.1038/s41929-018-0104-7Ferri, P., Li, C., Paris, C., Vidal-Moya, A., Moliner, M., Boronat, M., & Corma, A. (2019). Chemical and Structural Parameter Connecting Cavity Architecture, Confined Hydrocarbon Pool Species, and MTO Product Selectivity in Small-Pore Cage-Based Zeolites. ACS Catalysis, 9(12), 11542-11551. doi:10.1021/acscatal.9b04588Chen, J., Li, J., Yuan, C., Xu, S., Wei, Y., Wang, Q., … Liu, Z. (2014). Elucidating the olefin formation mechanism in the methanol to olefin reaction over AlPO-18 and SAPO-18. Catalysis Science & Technology, 4(9), 3268. doi:10.1039/c4cy00551aDusselier, M., Deimund, M. A., Schmidt, J. E., & Davis, M. E. (2015). Methanol-to-Olefins Catalysis with Hydrothermally Treated Zeolite SSZ-39. ACS Catalysis, 5(10), 6078-6085. doi:10.1021/acscatal.5b01577Martín, N., Li, Z., Martínez-Triguero, J., Yu, J., Moliner, M., & Corma, A. (2016). Nanocrystalline SSZ-39 zeolite as an efficient catalyst for the methanol-to-olefin (MTO) process. Chemical Communications, 52(36), 6072-6075. doi:10.1039/c5cc09719cMartínez-Franco, R., Li, Z., Martínez-Triguero, J., Moliner, M., & Corma, A. (2016). Improving the catalytic performance of SAPO-18 for the methanol-to-olefins (MTO) reaction by controlling the Si distribution and crystal size. Catalysis Science & Technology, 6(8), 2796-2806. doi:10.1039/c5cy02298cBleken, F., Bjørgen, M., Palumbo, L., Bordiga, S., Svelle, S., Lillerud, K.-P., & Olsbye, U. (2009). The Effect of Acid Strength on the Conversion of Methanol to Olefins Over Acidic Microporous Catalysts with the CHA Topology. Topics in Catalysis, 52(3), 218-228. doi:10.1007/s11244-008-9158-0Wang, C.-M., Wang, Y.-D., Du, Y.-J., Yang, G., & Xie, Z.-K. (2015). Similarities and differences between aromatic-based and olefin-based cycles in H-SAPO-34 and H-SSZ-13 for methanol-to-olefins conversion: insights from energetic span model. Catalysis Science & Technology, 5(9), 4354-4364. doi:10.1039/c5cy00483gGallego, E. M., Li, C., Paris, C., Martín, N., Martínez-Triguero, J., Boronat, M., … Corma, A. (2018). Making Nanosized CHA Zeolites with Controlled Al Distribution for Optimizing Methanol-to-Olefin Performance. Chemistry - A European Journal, 24(55), 14631-14635. doi:10.1002/chem.201803637Chen, D., Moljord, K., & Holmen, A. (2012). A methanol to olefins review: Diffusion, coke formation and deactivation on SAPO type catalysts. Microporous and Mesoporous Materials, 164, 239-250. doi:10.1016/j.micromeso.2012.06.046Wang, C., Li, B., Wang, Y., & Xie, Z. (2013). Insight into the topology effect on the diffusion of ethene and propene in zeolites: A molecular dynamics simulation study. Journal of Energy Chemistry, 22(6), 914-918. doi:10.1016/s2095-4956(14)60272-2Ghysels, A., Moors, S. L. C., Hemelsoet, K., De Wispelaere, K., Waroquier, M., Sastre, G., & Van Speybroeck, V. (2015). Shape-Selective Diffusion of Olefins in 8-Ring Solid Acid Microporous Zeolites. The Journal of Physical Chemistry C, 119(41), 23721-23734. doi:10.1021/acs.jpcc.5b06010Cnudde, P., Demuynck, R., Vandenbrande, S., Waroquier, M., Sastre, G., & Speybroeck, V. V. (2020). Light Olefin Diffusion during the MTO Process on H-SAPO-34: A Complex Interplay of Molecular Factors. Journal of the American Chemical Society, 142(13), 6007-6017. doi:10.1021/jacs.9b10249“Structure Commission of the International Zeolite Association (IZA-SC) Database of Zeolite structures ” can be found underhttp://www.iza-structure.org/databases/ n.d.Olson, D. H., Camblor, M. A., Villaescusa, L. A., & Kuehl, G. H. (2004). Light hydrocarbon sorption properties of pure silica Si-CHA and ITQ-3 and high silica ZSM-58. Microporous and Mesoporous Materials, 67(1), 27-33. doi:10.1016/j.micromeso.2003.09.025Ruthven, D. M., & Reyes, S. C. (2007). Adsorptive separation of light olefins from paraffins. Microporous and Mesoporous Materials, 104(1-3), 59-66. doi:10.1016/j.micromeso.2007.01.005Hedin, N., DeMartin, G. J., Roth, W. J., Strohmaier, K. G., & Reyes, S. C. (2008). PFG NMR self-diffusion of small hydrocarbons in high silica DDR, CHA and LTA structures. Microporous and Mesoporous Materials, 109(1-3), 327-334. doi:10.1016/j.micromeso.2007.05.007Li, Z., Martínez-Triguero, J., Concepción, P., Yu, J., & Corma, A. (2013). Methanol to olefins: activity and stability of nanosized SAPO-34 molecular sieves and control of selectivity by silicon distribution. Physical Chemistry Chemical Physics, 15(35), 14670. doi:10.1039/c3cp52247