Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Elemental zoning enhances mass transport in zeolite catalysts for methanol to hydrocarbons

Nature Catalysis volume 6, pages 254–265 (2023)Cite this article

Subjects

Abstract

Mass transport limitations in zeolite catalysts pose major hurdles for their optimal performance in diverse chemical reactions. Most approaches to reduce these restrictions focus on the synthesis of either hierarchical or nanosized zeolites. Here we demonstrate that the existence of a siliceous, catalytically inactive exterior rim on ZSM-5 particles dramatically reduces the diffusion limitations, which leads to an enhanced catalyst lifetime for the methanol-to-hydrocarbon reaction. Our findings reveal that binary inorganic and organic structure-directing agents enable a one-pot synthesis of Si-zoned ZSM-5 catalysts with diffusion properties that are characteristic of particles with a much smaller size. Operando ultraviolet–visible light diffuse reflectance spectroscopy reveals a marked reduction in external coking among Si-zoned samples. Molecular dynamics simulations to assess the diffusion of methanol and benzene in siliceous pores and in those with Brønsted acids reveal substantially reduced transport limitations in zoned regions, consistent with the improved catalyst activity of Si-zoned zeolites relative to that of ZSM-5 with a homogeneous acid-site distribution.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Synthesis of zeolite ZSM-5 with elemental zoning.
Fig. 2: Crystal habit of the zeolite ZSM-5 samples under study.
Fig. 3: Characterization of zeolite ZSM-5 zoning and catalyst performance.
Fig. 4: Descriptor-based comparison of zeolite ZSM-5 catalyst performance.
Fig. 5: Tracking product evolution by operando UV–vis DR spectroscopy.
Fig. 6: FTIR spectroscopic characterization of zeolite ZSM-5 samples.
Fig. 7: Free energy barriers for methanol diffusion in MFI.

Data availability

Source data are provided with this paper. Data of main and extended data figures are available in the Supplementary Information, an online repository and upon request. Data from the molecular simulation studies are available in the online repository, including figure data, data from the USMD simulations (example input scripts for LAMMPS 12 December 2018 and PLUMED 2.4.3, initial and final configurations from the trajectories and BayesWHAM analysis scripts), and scripts and input files for evaluating the transmission coefficients using the effective positive flux method. Correspondence and request for materials should be addressed to J.D.R. or B.M.W.

References

  1. Choi, M. et al. Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts. Nature 461, 246–249 (2009).

    Article  CAS  PubMed  Google Scholar 

  2. Zhang, X. et al. Synthesis of self-pillared zeolite nanosheets by repetitive branching. Science 336, 1684–1687 (2012).

    Article  CAS  PubMed  Google Scholar 

  3. Fan, W. et al. Hierarchical nanofabrication of microporous crystals with ordered mesoporosity. Nat. Mater. 7, 984–991 (2008).

    Article  CAS  PubMed  Google Scholar 

  4. Lupulescu, A. I., Kumar, M. & Rimer, J. D. A facile strategy to design zeolite L crystals with tunable morphology and surface architecture. J. Am. Chem. Soc. 135, 6608–6617 (2013).

    Article  CAS  PubMed  Google Scholar 

  5. Chaikittisilp, W. et al. Formation of hierarchically organized zeolites by sequential intergrowth. Angew. Chem. Int. Ed. 52, 3355–3359 (2013).

    Article  CAS  Google Scholar 

  6. Awala, H. et al. Template-free nanosized faujasite-type zeolites. Nat. Mater. 14, 447–451 (2015).

    Article  CAS  PubMed  Google Scholar 

  7. Sachse, A. et al. Development of intracrystalline mesoporosity in zeolites through surfactant templating. Cryst. Growth Des. 17, 4289–4305 (2017).

    Article  CAS  Google Scholar 

  8. Willhammar, T. et al. Structure and catalytic properties of the most complex intergrown zeolite ITQ-39 determined by electron crystallography. Nat. Chem. 4, 188–194 (2012).

    Article  CAS  PubMed  Google Scholar 

  9. Na, K. et al. Pillared MFI zeolite nanosheets of a single-unit-cell thickness. J. Am. Chem. Soc. 132, 4169–4177 (2010).

    Article  CAS  PubMed  Google Scholar 

  10. Dai, H. et al. Finned zeolite catalysts. Nat. Mater. 19, 1074–1080 (2020).

    Article  CAS  PubMed  Google Scholar 

  11. Schmidt, J. E. et al. Coke formation in a zeolite crystal during the methanol-to-hydrocarbons reaction as studied with atom probe tomography. Angew. Chem. Int. Ed. 55, 11173–11177 (2016).

    Article  CAS  Google Scholar 

  12. Kunieda, T., Kim, J. H. & Niwa, M. Source of selectivity of p-xylene formation in the toluene disproportionation over HZSM-5 zeolites. J. Catal. 188, 431–433 (1999).

    Article  CAS  Google Scholar 

  13. Qin, W., Zhou, Y. & Rimer, J. D. Deleterious effects of non-framework Al species on the catalytic performance of ZSM-5 crystals synthesized at low temperature. React. Chem. Eng. 4, 1957–1968 (2019).

    Article  CAS  Google Scholar 

  14. Wang, C. et al. Maximizing sinusoidal channels of HZSM-5 for high shape-selectivity to p-xylene. Nat. Commun. 10, 4348 (2019).

    Article  PubMed  PubMed Central  Google Scholar 

  15. Aramburo, L. R. et al. The porosity, acidity, and reactivity of dealuminated zeolite ZSM‐5 at the single particle level: the influence of the zeolite architecture. Chem. Eur. J. 17, 13773–13781 (2011).

    Article  CAS  PubMed  Google Scholar 

  16. Kim, K., Ryoo, R., Jang, H.-D. & Choi, M. Spatial distribution, strength, and dealumination behavior of acid sites in nanocrystalline MFI zeolites and their catalytic consequences. J. Catal. 288, 115–123 (2012).

    Article  CAS  Google Scholar 

  17. Yang, D.J. Process for coating crystalline silica polymorphs. European Patent 4452909 (1982).

  18. Rodewald, P.G. Silica-modified zeolite catalysts. US patent 4402867A (1981).

  19. Von Ballmoos, R. & Meier, W. M. Zoned aluminium distribution in synthetic zeolite ZSM-5. Nature 289, 782–783 (1981).

    Article  Google Scholar 

  20. Althoff, R., Schulz-Dobrick, B., Schüth, F. & Unger, K. Controlling the spatial distribution of aluminum in ZSM-5 crystals. Micropor. Mater. 1, 207–218 (1993).

    Article  CAS  Google Scholar 

  21. Groen, J. C. et al. Creation of hollow zeolite architectures by controlled desilication of Al-zoned ZSM-5 crystals. J. Am. Chem. Soc. 127, 10792–10793 (2005).

    Article  CAS  PubMed  Google Scholar 

  22. Danilina, N., Krumeich, F., Castelanelli, S. A. & van Bokhoven, J. A. Where are the active sites in zeolites? Origin of aluminum zoning in ZSM-5. J. Phys. Chem. C. 114, 6640–6645 (2010).

    Article  CAS  Google Scholar 

  23. Ristanović, 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).

    Article  Google Scholar 

  24. Kim, J. H., Ishida, A., Okajima, M. & Niwa, M. Modification of HZSM-5 by CVD of various silicon compounds and generation of para-selectivity. J. Catal. 161, 387–392 (1996).

    Article  CAS  Google Scholar 

  25. Zheng, S., Heydenrych, H. R., Jentys, A. & Lercher, J. A. Influence of surface modification on the acid site distribution of HZSM-5. J. Phys. Chem. B 106, 9552–9558 (2002).

    Article  CAS  Google Scholar 

  26. Jae, J. et al. Investigation into the shape selectivity of zeolite catalysts for biomass conversion. J. Catal. 279, 257–268 (2011).

    Article  CAS  Google Scholar 

  27. Ennaert, T. et al. Potential and challenges of zeolite chemistry in the catalytic conversion of biomass. Chem. Soc. Rev. 45, 584–611 (2016).

    Article  CAS  PubMed  Google Scholar 

  28. Zheng, S., Heydenrych, H. R., Röger, H. P., Jentys, A. & Lercher, J. A. On the enhanced selectivity of HZSM-5 modified by chemical liquid deposition. Top. Catal. 22, 101–106 (2003).

    Article  CAS  Google Scholar 

  29. Cheng, Y.-T., Zhuopeng, W., Gilbert, C. J., Wei, F. & Huber, G. W. Production of p-xylene from biomass by catalytic fast pyrolysis using ZSM-5 catalysts with reduced pore openings. Angew. Chem. Int. Ed. 51, 11097–11100 (2012).

    Article  CAS  Google Scholar 

  30. Foster, A. J., Jae, J., Cheng, Y.-T., Huber, G. W. & Lobo, R. F. Optimizing the aromatic yield and distribution from catalytic fast pyrolysis of biomass over ZSM-5. Appl. Catal. A 423–424, 154–161 (2012).

    Article  Google Scholar 

  31. Yan, Z. et al. On the acid-dealumination of USY zeolite: a solid state NMR investigation. J. Mol. Catal. A 194, 153–167 (2003).

    Article  CAS  Google Scholar 

  32. Le, T. T., Chawla, A., & Rimer, J. D. Impact of acid site speciation and spatial gradients on zeolite catalysis. J. Catal. 391, 56–68 (2020).

    Article  CAS  Google Scholar 

  33. Knott, B. C. et al. Consideration of the aluminum distribution in zeolites in theoretical and experimental catalysis research. ACS Catal. 8, 770–784 (2017).

    Article  Google Scholar 

  34. Ravi, M., Sushkevich, V. L. & van Bokhoven, J. A. Towards a better understanding of Lewis acidic aluminium in zeolites. Nat. Mater. 19, 1047–1056 (2020).

    Article  CAS  PubMed  Google Scholar 

  35. Persson, A. E., Schoeman, B. J., Sterte, J. & Ottesstedt, J. E. The synthesis of discrete colloidal particles of TPA–silicalite-1. Zeolites 14, 557–567 (1994).

    Article  CAS  Google Scholar 

  36. Dai, F. Y., Suzuki, M., Takahashi, H. & Saito, I. Mechanism of zeolite crystallization without using template reagents of organic bases. Stud. Surf. Sci. Catal. 28, 223–230 (1986).

    Article  CAS  Google Scholar 

  37. Chawla, A. et al. Cooperative effects of inorganic and organic structure-directing agents in ZSM-5 crystallization. Mol. Syst. Des. Eng. 3, 159–170 (2018).

    Article  CAS  Google Scholar 

  38. Meng, L. et al. A dual-templating synthesis strategy to hierarchical ZSM-5 zeolites as efficient catalysts for the methanol-to-hydrocarbons reaction. J. Catal. 361, 135–142 (2018).

    Article  CAS  Google Scholar 

  39. Mores, D. et al. Core–shell H-ZSM-5/silicalite-1 composites: Brønsted acidity and catalyst deactivation at the individual particle level. Phys. Chem. Chem. Phys. 13, 15985–15994 (2011).

    Article  CAS  PubMed  Google Scholar 

  40. 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).

    Article  CAS  PubMed  Google Scholar 

  41. Vonballmoos, R. & Meier, W. M. Zoned aluminum distribution in synthetic zeolite ZSM-5. Nature 289, 782–783 (1981).

    Article  CAS  Google Scholar 

  42. Li, T., Krumeich, F., Chen, M., Ma, Z. & van Bokhoven, J. A. Defining aluminum zoning during synthesis of ZSM-5 zeolites. Phys. Chem. Chem. Phys. 734, 734–739 (2020).

    Article  Google Scholar 

  43. Li, T. et al. Variation of aluminium distribution in small‐sized ZSM‐5 crystals during desilication. Chem. Eur. J. 25, 15879–15886 (2019).

    Article  CAS  PubMed  Google Scholar 

  44. Li, T., Krumeich, F. & van Bokhoven, J. A. Where does the zeolite ZSM-5 nucleation and growth start? The effect of aluminum. Cryst. Growth Des. 19, 2548–2551 (2019).

    Article  CAS  Google Scholar 

  45. Shen, Y. et al. Deconvoluting the competing effects of zeolite framework topology and diffusion path length on methanol to hydrocarbons reaction. ACS Catal. 8, 11042–11053 (2018).

    Article  CAS  Google Scholar 

  46. 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).

    Article  CAS  Google Scholar 

  47. Cavalcante, C. L. Jr & Ruthven, D. M. Adsorption of branched and cyclic paraffins in silicalite. 2. Kinetics. Ind. Eng. Chem. Res. 34, 185–191 (1995).

    Article  CAS  Google Scholar 

  48. Gao, M. B. et al. Direct quantification of surface barriers for mass transfer in nanoporous crystalline materials. Commun. Chem. 2, 43–52 (2019).

    Article  Google Scholar 

  49. Khare, R., Liu, Z. H., Han, Y. & Bhan, A. A mechanistic basis for the effect of aluminum content on ethene selectivity in methanol-to-hydrocarbons conversion on HZSM-5. J. Catal. 348, 300–305 (2017).

    Article  CAS  Google Scholar 

  50. Olsbye, U. et al. The formation and degradation of active species during methanol conversion over protonated zeotype catalysts. Chem. Soc. Rev. 44, 7155–7176 (2015).

    Article  CAS  PubMed  Google Scholar 

  51. Yarulina, I., Chowdhury, A. D., Meirer, F., Weckhuysen, B. W. & Gascon, J. Recent trends and fundamental insights in the methanol-to-hydrocarbons process. Nat. Catal. 1, 398–411 (2018).

    Article  CAS  Google Scholar 

  52. Remi, J. C. S. et al. The role of crystal diversity in understanding mass transfer in nanoporous materials. Nat. Mater. 15, 401–406 (2016).

    Article  CAS  Google Scholar 

  53. 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 (2018).

    Article  Google Scholar 

  54. 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).

    Article  CAS  PubMed  Google Scholar 

  55. Fu, D., van der Heijden, O., Stanciakova, K., Schmidt, J. E. & Weckhuysen, B. M. Disentangling reaction processes of zeolites within single-oriented channels. Angew. Chem. Int. Ed. 59, 15502–15506 (2020).

    Article  CAS  Google Scholar 

  56. Goetze, J. et al. Insights into the activity and deactivation of the methanol-to-olefins process over different small-pore zeolites as studied with operando UV–vis spectroscopy. ACS Catal. 7, 4033–4046 (2017).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  57. 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).

    Article  CAS  Google Scholar 

  58. Barbera, K., Bonino, F., Bordiga, S., Janssens, T. V. W. & Beato, P. Structure–deactivation relationship for ZSM-5 catalysts governed by framework defects. J. Catal. 280, 196–205 (2011).

    Article  CAS  Google Scholar 

  59. Qin, Z. et al. Comparative study of nano-ZSM-5 catalysts synthesized in OH– and F– media. Adv. Func. Mater. 24, 257–264 (2014).

    Article  CAS  Google Scholar 

  60. Paul, G. et al. Combined solid-state NMR, FT-IR and computational studies on layered and porous materials. Chem. Soc. Rev. 47, 5684–5739 (2018).

    Article  CAS  PubMed  Google Scholar 

  61. Ghorbanpour, A., Rimer, J. D. & Grabow, L. C. Periodic, vdW-corrected density functional theory investigation of the effect of Al siting in H-ZSM-5 on chemisorption properties and site-specific acidity. Catal. Commun. 52, 98–102 (2014).

    Article  CAS  Google Scholar 

  62. Smit, B. & Maesen, T. L. M. Molecular simulations of zeolites: adsorption, diffusion, and shape selectivity. Chem. Rev. 108, 4125–4184 (2008).

    Article  CAS  PubMed  Google Scholar 

  63. Kolokathis, P. D., Kali, G., Jobic, H. & Theodorou, D. N. Diffusion of aromatics in silicalite-1: experimental and theoretical evidence of entropic barriers. J. Phys. Chem. C. 120, 21410–21426 (2016).

    Article  CAS  Google Scholar 

  64. Peters, B. Reaction Rate Theory and Rare Events (Elsevier, 2017).

  65. Teixeira, A. R. et al. Dominance of surface barriers in molecular transport through silicalite-1. J. Phys. Chem. C 117, 25545–25555 (2013).

    Article  CAS  Google Scholar 

  66. Hibbe, F. et al. The nature of surface barriers on nanoporous solids explored by microimaging of transient guest distributions. J. Am. Chem. Soc. 133, 2804–2807 (2011).

    Article  CAS  PubMed  Google Scholar 

  67. Sastre, G., Karger, J. & Ruthven, D. M. Surface barriers and symmetry of adsorption and desorption processes. Adsorption 27, 777–785 (2021).

    Article  CAS  Google Scholar 

  68. Wang, R. et al. Art of architecture: efficient transport through solvent-filled metal–organic frameworks regulated by topology. Chem. Mater. 33, 6832–6840 (2021).

    Article  CAS  Google Scholar 

  69. Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).

    Article  CAS  Google Scholar 

  70. Tribello, G. A., Bonomi, M., Branduardi, D., Camilloni, C. & Bussi, G. PLUMED 2: new feathers for an old bird. Comput. Phys. Commun. 185, 604–613 (2014).

    Article  CAS  Google Scholar 

  71. Bai, C., Liu, L. & Sun, H. Molecular dynamics simulations of methanol to olefin reactions in HZSM-5 zeolite using a ReaxFF force field. J. Phys. Chem. C 116, 7029–7039 (2012).

    Article  CAS  Google Scholar 

  72. Nastase, S. A. F. et al. Mechanistic insight into the framework methylation of H-ZSM-5 for varying methanol loadings and Si/Al ratios using first-principles molecular dynamics simulations. ACS Catal. 10, 8904–8915 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  73. Database of Zeolite Structures (International Zeolite Association Structure Commission, accessed 2023); http://www.iza-structure.org/databases/

  74. Parrinello, M. & Rahman, A. Polymorphic transitions in single crystals: a new molecular dynamics method. J. Appl. Phys. 52, 7182–7190 (1981).

    Article  CAS  Google Scholar 

  75. Zheng, S. & Pfaendtner, J. Enhanced sampling of chemical and biochemical reactions with metadynamics. Mol. Simul. 41, 55–72 (2015).

    Article  CAS  Google Scholar 

  76. Ferguson, A. L. BayesWHAM: a Bayesian approach for free energy estimation, reweighting, and uncertainty quantification in the weighted histogram analysis method. J. Comput. Chem. 38, 1583–1605 (2017).

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

J.D.R. acknowledges support primarily from the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award no. DE-SC0014468. Additional support was provided by the Welch Foundation (Award E-1794 to J.D.R. and Award E-1882 to J.C.P.). This work is supported by the NWO Gravitation program, Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC) and a European Research Council (ERC) Advanced Grant (no. 321140). This research used resources of the National Synchrotron Light Source II, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. We thank J. E. Schmidt (Utrecht University) for useful discussions. We also thank A. Bhan (University of Minnesota) and Z. Shi (University of Minnesota) for their help with diffusivity measurements and technical guidance. M.E. Davis (Caltech) is acknowledged for assistance with TGA measurements. Computational resources were generously provided by the Hewlett Packard Enterprise Data Science Institute at the University of Houston and the Texas Advanced Computing Center at the University of Texas at Austin.

Author information

Author notes

  1. These authors contributed equally: Thuy T. Le, Wei Qin.

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Houston, Houston, TX, USA

    Thuy T. Le, Wei Qin, Ankur Agarwal, Matthew D. Patton, Jeremy C. Palmer & Jeffrey D. Rimer

  2. Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Faculty of Science, Utrecht University, Utrecht, the Netherlands

    Nikolaos Nikolopoulos, Donglong Fu & Bert M. Weckhuysen

  3. Materials Measurement Science Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA

    Conan Weiland

  4. SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Simon R. Bare

Authors
  1. Thuy T. Le
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wei Qin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ankur Agarwal
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Nikolaos Nikolopoulos
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Donglong Fu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Matthew D. Patton
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Conan Weiland
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Simon R. Bare
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Jeremy C. Palmer
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Bert M. Weckhuysen
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Jeffrey D. Rimer
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.D.R., W.Q. and T.T.L. conceived the project and designed the experiments. T.T.L., W.Q., N.N., D.F. and M.D.P. were primarily responsible for the data collection and analysis. B.M.W. was responsible for the operando UV–vis DR measurements and also discussed the project concept and related experiments with J.D.R. and T.T.L. C.W. and S.R.B. were responsible for the VKE–XPS measurements and data analysis. J.D.R. was responsible for the zeolite synthesis, characterization and catalytic testing. J.C.P. and A.A. were responsible for the molecular dynamics simulations and discussions of the mechanistic interpretations. J.D.R. and T.T.L. wrote the manuscript and prepared the figures with help from the other coauthors. All the authors contributed to scientific discussions and the preparation as well as the revisions of the manuscript and Supplementary Information materials.

Corresponding authors

Correspondence to Bert M. Weckhuysen or Jeffrey D. Rimer.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Catalysis thanks Svetlana Mintova and the other, anonymous, reviewers for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 Surface permeability of zoned and homogeneous zeolite samples.

Surface permeability, α, from fitting early uptake data in Supplementary Fig. 9 with a spherical particle model, plotted against the Al surface-to-bulk ratio of the following samples: Si-zoned (red symbols), homogeneous (purple symbols), and Al-zoned (blue symbol) zeolites.

Source data

Extended Data Fig. 2 Conversion and selectivity of zoned and homogeneous zeolite catalysts.

a, Conversion of methanol and dimethyl ether as a function of time-on-stream for the Al-zoned sample A-4 (blue cross), homogeneous samples H1-3 (purple circles) and H2-6 (purple triangles), and Si-zoned samples S1-1 (red squares), S2-1 (red inverted triangles), and S3-2 (red diamonds). All reactions were performed at 350 °C using a space velocity of 0.18–0.30 mol MeOH mol−1 H+ s−1. b, Selectivity profile (left y-axis) at sub-100% conversion (initial data point after 20 min induction period) and the ratio of ethene to the sum of 2-methylbutane and 2-methylbutene (symbols, right y-axis).

Source data

Extended Data Fig. 3 Relationship between turnover number and coke accumulation in zoned and homogeneous zeolite catalysts.

Turnover number (TON) of each tested catalyst plotted against the coke content in dry zeolite samples (listed in Supplementary Table 7).

Source data

Extended Data Fig. 4 Molecular dynamics simulations of methanol and benzene diffusion in zeolite MFI.

a, Free energy profile at 350 °C (potential of mean force, in units of the thermal energy kBT ≈ 0.0537 eV at T = 350 °C) for internal diffusion of methanol in the high loading limit (that is, 16 methanol per unit cell) through the straight channel (b-direction) of MFI with: aluminium sites (Si/Al = 23) occupied by methoxy groups (purple, MFI-CH3) and a purely siliceous material (orange, MFI). b, Free energy profile for internal diffusion of benzene in the low loading limit through the straight channel of MFI with: aluminum sites occupied by methoxy groups (purple, MFI-CH3) and Brønsted acids (blue, MFI-H), and purely siliceous material (orange, MFI). c, d, Images of benzene from Supplementary Movie 3 diffusing through a straight channel populated with methoxy groups. e, Image of benzene from Supplementary Movie 4 diffusing through a straight channel with Brønsted acid sites. Atom coloring is as follows: Si (yellow), O (red), H on acidic groups (blue), Al (green), C (black), and H on guest species (white).

Source data

Supplementary information

Supplementary Information

Supplementary Methods, Tables 1–9, Discussion, Figs. 1–17 and References.

A 7 ns SMD trajectory in which methanol is pulled along the straight channel of an MFI framework with a methoxy group attached to O17 (Supplementary Fig. 17). The view is along [100], and the horizontal direction aligned to [010]. Atom coloring is as follows: Si (yellow), O (red), H on acidic groups (blue), Al (green), C (black), and H on guest species (white).

A 7 ns SMD trajectory in which methanol is pulled along the straight channel of an MFI framework with a Brønsted acid site attached to O17 (Supplementary Fig. 17). The view is along [100], and the horizontal direction aligned to [010]. Atom coloring is as follows: Si (yellow), O (red), H on acidic groups (blue), Al (green), C (black), and H on guest species (white).

A 7 ns SMD trajectory in which benzene is pulled along the straight channel of an MFI framework with a methoxy group attached to O17 (Supplementary Fig. 17). The view is along [100], and the horizontal direction aligned to [010]. Atom coloring is as follows: Si (yellow), O (red), H on acidic groups (blue), Al (green), C (black), and H on guest species (white).

A 7 ns SMD trajectory in which benzene is pulled along the straight channel of an MFI framework with a Brønsted acid site attached to O17 (Supplementary Fig. 17). The view is along [100], and the horizontal direction aligned to [010]. Atom coloring is as follows: Si (yellow), O (red), H on acidic groups (blue), Al (green), C (black), and H on guest species (white).

Source data

Source Data Figs. 1, 3, 4, 5, 6 and 7.

Source Data for Figs. 1c-d, 3a-c, 4a-d, 5b-d, 6a-b and 7a,f.

Source Data Extended Data Figs. 1, 2, 3 and 4

Source Data for Extended Data Figs. 1, 2a, 3 and 4a,b.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Le, T.T., Qin, W., Agarwal, A. et al. Elemental zoning enhances mass transport in zeolite catalysts for methanol to hydrocarbons. Nat Catal 6, 254–265 (2023). https://doi.org/10.1038/s41929-023-00927-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41929-023-00927-2

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing