journal article·2020-10

Finned zeolite catalysts

Heng Dai, Yufeng Shen, Taimin Yang, Choongsze Lee, Donglong Fu, Ankur Agarwal, Thuy Thanh Le, Michael Tsapatsis, Jeremy C. Palmer, Bert M. Weckhuysen, Paul J. Dauenhauer, Xiaodong Zou, Jeffrey D. Rimer

Nature Materials· Volume 19· Issue 10
Publisher page

Abstract

There is growing evidence for the advantages of synthesizing nanosized zeolites with markedly reduced internal diffusion limitations for enhanced performances in catalysis and adsorption. Producing zeolite crystals with sizes less than 100 nm, however, is non-trivial, often requires the use of complex organics and typically results in a small product yield. Here we present an alternative, facile approach to enhance the mass-transport properties of zeolites by the epitaxial growth of fin-like protrusions on seed crystals. We validate this generalizable methodology on two common zeolites and confirm that fins are in crystallographic registry with the underlying seeds, and that secondary growth does not impede access to the micropores. Molecular modelling and time-resolved titration experiments of finned zeolites probe internal diffusion and reveal substantial improvements in mass transport, consistent with catalytic tests of a model reaction, which show that these structures behave as pseudo-nanocrystals with sizes commensurate to that of the fin. This approach could be extended to the rational synthesis of other zeolite and aluminosilicate materials.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Zeolite Catalysis and Synthesis · Catalytic Processes in Materials Science · Mesoporous Materials and Catalysis

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (39)

Show source-provided references
1. Gallego, E. M. et al. ‘Ab initio’ synthesis of zeolites for preestablished catalytic reactions. Science 355, 1051–1054 (2017).10.1126/science.aal0121 ↗
2. Paolucci, C. et al. Dynamic multinuclear sites formed by mobilized copper ions in NOx selective catalytic reduction. Science 357, 898–903 (2017).10.1126/science.aan5630 ↗
3. Cychosz, K. A., Guillet-Nicolas, R., Garcia-Martinez, J. & Thommes, M. Recent advances in the textural characterization of hierarchically structured nanoporous materials. Chem. Soc. Rev. 46, 389–414 (2017).10.1039/C6CS00391E ↗
4. Varoon, K. et al. Dispersible exfoliated zeolite nanosheets and their application as a selective membrane. Science 333, 72–75 (2011).10.1126/science.1208891 ↗
5. Rangnekar, N., Mittal, N., Elyassi, B., Caro, J. & Tsapatsis, M. Zeolite membranes—a review and comparison with MOFs. Chem. Soc. Rev. 44, 7128–7154 (2015).10.1039/C5CS00292C ↗
6. Karwacki, L. et al. Morphology-dependent zeolite intergrowth structures leading to distinct internal and outer-surface molecular diffusion barriers. Nat. Mater. 8, 959–965 (2009).10.1038/nmat2530 ↗
7. Hwang, A. et al. Effects of diffusional constraints on lifetime and selectivity in methanol-to-olefins catalysis on HSAPO-34. J. Catal. 369, 122–132 (2019).10.1016/j.jcat.2018.10.031 ↗
8. Awala, H. et al. Template-free nanosized faujasite-type zeolites. Nat. Mater. 14, 447–451 (2015).10.1038/nmat4173 ↗
9. Choi, M. et al. Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts. Nature 461, 246–249 (2009).10.1038/nature08288 ↗
10. Na, K. et al. Directing zeolite structures into hierarchically nanoporous architectures. Science 333, 328–332 (2011).10.1126/science.1204452 ↗
11. Zhang, X. et al. Synthesis of self-pillared zeolite nanosheets by repetitive branching. Science 336, 1684–1687 (2012).10.1126/science.1221111 ↗
12. Mintova, S. et al. Nanosized microporous crystals: emerging applications. Chem. Soc. Rev. 44, 7207–7233 (2015).10.1039/C5CS00210A ↗
13. Gallego, E. M. et al. Simple organic structure directing agents for synthesizing nanocrystalline zeolites. Chem. Sci 8, 8138–8149 (2017).10.1039/C7SC02858J ↗
14. Vicente, J. et al. Direct synthesis of nano-ferrierite along the 10-ring-channel direction boosts their catalytic behavior. Angew. Chem. Int. Ed. 57, 3459–3463 (2018).10.1002/anie.201711418 ↗
15. Li, K., Valla, J. & Garcia-Martinez, J. Realizing the commercial potential of hierarchical zeolites: new opportunities in catalytic cracking. ChemCatChem 6, 46–66 (2014).10.1002/cctc.201300345 ↗
16. Perez-Ramirez, J., Christensen, C. H., Egeblad, K., Christensen, C. H. & Groen, J. C. Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design. Chem. Soc. Rev. 37, 2530–2542 (2008).10.1039/b809030k ↗
17. Liu, Y. et al. Steam-stable aluminosilicate mesostructures assembled from zeolite type Y seeds. J. Am. Chem. Soc. 122, 8791–8792 (2000).10.1021/ja001615z ↗
18. Park, D. H. et al. Selective petroleum refining over a zeolite catalyst with small intracrystal mesopores. Angew. Chem. Int. Ed. 48, 7645–7648 (2009).10.1002/anie.200901551 ↗
19. Shen, Y. et al. Deconvoluting the competing effects of framework topology and diffusion path length on methanol-to-hydrocarbons reactions. ACS Catal. 8, 11042–11053 (2018).10.1021/acscatal.8b02274 ↗
20. Ristanovic, Z. et al. Intergrowth structure and aluminium zoning of a zeolite ZSM-5 crystal as resolved by synchrotron-based micro X-Ray diffraction imaging. Angew. Chem. Int. Ed. 52, 13382–13386 (2013).10.1002/anie.201306370 ↗
21. Ding, K. et al. Constructing hierarchical porous zeolites via kinetic regulation. J. Am. Chem. Soc. 137, 11238–11241 (2015).10.1021/jacs.5b06791 ↗
22. De Yoreo, J. J. et al. Crystallization by particle attachment in synthetic, biogenic, and geologic environments. Science 349, aaa6760 (2015).10.1126/science.aaa6760 ↗
23. Lupulescu, A. I. & Rimer, J. D. In situ imaging of silicalite-1 surface growth reveals the mechanism of crystallization. Science 344, 729–732 (2014).10.1126/science.1250984 ↗
24. Zhu, H., Liu, Z., Kong, D., Wang, Y. & Xie, Z. Synthesis and catalytic performances of mesoporous zeolites templated by polyvinyl butyral gel as the mesopore directing agent. J. Phys. Chem. C 112, 17257–17264 (2008).10.1021/jp805766m ↗
25. Zhang, H. et al. Seeding bundlelike MFI zeolite mesocrystals: A dynamic, nonclassical crystallization via epitaxially anisotropic growth. Chem. Mater. 29, 9247–9255 (2017).10.1021/acs.chemmater.7b03121 ↗
26. Kim, S., Park, G., Woo, M. H., Kwak, G. & Kim, S. K. Control of hierarchical structure and framework–Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on methanol conversion. ACS Catal. 9, 2880–2892 (2019).10.1021/acscatal.8b04493 ↗
27. Ghorbanpour, A., Gumidyala, A., Grabow, L. C., Crossley, S. P. & Rimer, J. D. Epitaxial growth of ZSM-5@silicalite-1: a core-shell zeolite designed with passivated surface acidity. ACS Nano 9, 4006–4016 (2015).10.1021/acsnano.5b01308 ↗
28. Ilias, S. & Bhan, A. Mechanism of the catalytic conversion of methanol to hydrocarbons. ACS Catal. 3, 18–31 (2013).10.1021/cs3006583 ↗
29. Khare, R., Millar, D. & Bhan, A. A mechanistic basis for the effects of crystallite size on light olefin selectivity in methanol-to-hydrocarbons conversion on MFI. J. Catal. 321, 23–31 (2015).10.1016/j.jcat.2014.10.016 ↗
30. Nordvang, E. C., Borodina, E., Ruiz-Martinez, J., Fehrmann, R. & Weckhuysen, B. M. Effects of coke deposits on the catalytic performance of large zeolite H-ZSM-5 crystals during alcohol-to-hydrocarbon reactions as investigated by a combination of optical spectroscopy and microscopy. Chem. Eur. J. 21, 17324–17335 (2015).10.1002/chem.201503136 ↗
31. Kolokathis, P. D. et al. Dimensionality reduction of free energy profiles of benzene in silicalite-1: calculation of diffusion coefficients using transition state theory. Mol. Simul. 40, 80–100 (2014).10.1080/08927022.2013.840895 ↗
32. Ruthven, D. M., Eic, M. & Richard, E. Diffusion of C8 aromatic hydrocarbons in silicalite. Zeolites 11, 647–653 (1991).10.1016/S0144-2449(05)80166-6 ↗
33. Góra-Marek, Kinga, Tarach, Karolina & Choi, Minkee 2,6-Di-tert-butylpyridine sorption approach to quantify the external acidity in hierarchical zeolites. J. Phys. Chem. C 118, 12266–12274 (2014).10.1021/jp501928k ↗
34. Shen, Y., Le, T. T., Li, R. & Rimer, J. D. Optimized synthesis of ZSM-11 catalysts using 1,8-diaminooctane as a structure-directing agent. ChemPhysChem 19, 529–537 (2018).10.1002/cphc.201700968 ↗
35. International Zeolite Association (IZA) Structure Database. IZA http://www.iza-structure.org/databases/ (2017).
36. Borodina, E. et al. Influence of the reaction temperature on the nature of the active and deactivating species during methanol to olefins conversion over H-SSZ-13. ACS Catal. 5, 992–1003 (2015).10.1021/cs501345g ↗
37. Yarulina, I. et al. Structure-performance descriptors and the role of Lewis acidity in the methanol-to-propylene process. Nat. Chem. 10, 804–812 (2018).10.1038/s41557-018-0081-0 ↗
38. Laloué, N., Laroche, C., Jobic, H. & Methivier, A. Kinetic Monte Carlo study of binary diffusion in silicalite. Adsorption 13, 491–500 (2007).10.1007/s10450-007-9067-8 ↗
39. Forester, T. R. & Smith, W. Bluemoon simulations of benzene in silicalite-1 - Prediction of free energies and diffusion coefficients. J. Chem. Soc. Faraday Trans. 93, 3249–3257 (1997).10.1039/a702063e ↗