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.

  • Letter
  • Published:

A zeolite family with expanding structural complexity and embedded isoreticular structures

Nature volume 524, pages 74–78 (2015)Cite this article

Subjects

This article has been updated

Abstract

The prediction and synthesis of new crystal structures enable the targeted preparation of materials with desired properties. Among porous solids, this has been achieved for metal–organic frameworks1,2,3, but not for the more widely applicable zeolites4,5, where new materials are usually discovered using exploratory synthesis. Although millions of hypothetical zeolite structures have been proposed6,7, not enough is known about their synthesis mechanism to allow any given structure to be prepared. Here we present an approach that combines structure solution with structure prediction, and inspires the targeted synthesis of new super-complex zeolites. We used electron diffraction to identify a family of related structures and to discover the structural ‘coding’ within them. This allowed us to determine the complex, and previously unknown, structure of zeolite ZSM-25 (ref. 8), which has the largest unit-cell volume of all known zeolites (91,554 cubic ångströms) and demonstrates selective CO2 adsorption. By extending our method, we were able to predict other members of a family of increasingly complex, but structurally related, zeolites and to synthesize two more-complex zeolites in the family, PST-20 and PST-25, with much larger cell volumes (166,988 and 275,178 cubic ångströms, respectively) and similar selective adsorption properties. Members of this family have the same symmetry, but an expanding unit cell, and are related by hitherto unrecognized structural principles; we call these family members embedded isoreticular zeolite structures.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Figure 1: Structure determination of ZSM-25 using the strong reflections approach.
Figure 2: PXRD profiles and description of the structure of ZSM-25.
Figure 3: Comparison of the reflection distributions and framework structures of RHO-G3 to RHO-G6.
Figure 4: Gas adsorption properties of NaTEA-ZSM-25 and NaTEA-PST-20.

Similar content being viewed by others

Change history

  • 05 August 2015

    NaTEA-ZSM-25 was corrected to NaSrTEA-PST-20 in the Methods section.

References

  1. Yaghi, O. M. et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003)

    Article  CAS  PubMed  ADS  Google Scholar 

  2. Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002)

    Article  CAS  PubMed  ADS  Google Scholar 

  3. Deng, H. et al. Large-pore apertures in a series of metal-organic frameworks. Science 336, 1018–1023 (2012)

    Article  CAS  PubMed  ADS  Google Scholar 

  4. Davis, M. E. Ordered porous materials for emerging applications. Nature 417, 813–821 (2002)

    Article  CAS  PubMed  ADS  Google Scholar 

  5. Wang, Z., Yu, J. & Xu, R. Needs and trends in rational synthesis of zeolitic materials. Chem. Soc. Rev. 41, 1729–1741 (2012)

    Article  PubMed  Google Scholar 

  6. Foster, M. D. & Treacy, M. M. J. Atlas of Prospective Zeolite Structures http://www.hypotheticalzeolites.net/ (2010)

    Google Scholar 

  7. Deem, M. W. Deem Database http://www.hypotheticalzeolites.net/DATABASE/DEEM/index.php (2011)

    Google Scholar 

  8. Doherty, H. G., Plank, C. J. & Rosinski, E. J. Crystalline zeolite ZSM-25. US patent 4,247,416 (1981)

  9. Férey, G. Building units design and scale chemistry. J. Solid State Chem. 152, 37–48 (2000)

    Article  ADS  Google Scholar 

  10. Zou, X. D., Conradsson, T., Klingstedt, M., Dadachov, M. S. & O’Keeffe, M. A mesoporous germanium oxide with crystalline pore walls and its chiral derivative. Nature 437, 716–719 (2005)

    Article  CAS  PubMed  ADS  Google Scholar 

  11. Lin, H.-Y. et al. Crystalline inorganic frameworks with 56-ring, 64-ring, and 72-ring channels. Science 339, 811–813 (2013)

    Article  CAS  PubMed  ADS  Google Scholar 

  12. Willhammar, T., Yun, Y. F. & Zou, X. D. Structure determination: structural determination of ordered porous solids by electron crystallography. Adv. Funct. Mater. 24, 182–199 (2014)

    Article  CAS  Google Scholar 

  13. Zou, X. D., Hovmöller, S. & Oleynikov, P. Electron Crystallography: Electron Microscopy and Electron Diffraction Ch. 9 (Oxford Univ. Press, 2011)

    Google Scholar 

  14. Gramm, F. et al. Complex zeolite structure solved by combining powder diffraction and electron microscopy. Nature 444, 79–81 (2006)

    Article  CAS  PubMed  ADS  Google Scholar 

  15. Baerlocher, C. et al. Structure of the polycrystalline zeolite catalyst IM-5 solved by enhanced charge flipping. Science 315, 1113–1116 (2007)

    Article  CAS  PubMed  ADS  Google Scholar 

  16. Baerlocher, C. et al. Ordered silicon vacancies in the framework structure of the zeolite catalyst SSZ-74. Nature Mater. 7, 631–635 (2008)

    Article  CAS  ADS  Google Scholar 

  17. Zhang, D. L., Oleynikov, P., Hovmöller, S. & Zou, X. D. Collecting 3D electron diffraction data by the rotation method. Z. Kristallogr. 225, 94–102 (2010)

    Article  CAS  Google Scholar 

  18. Wan, W., Sun, J. L., Su, J., Hovmöller, S. & Zou, X. D. Three-dimensional rotation electron diffraction: software RED for automated data collection and data processing. J. Appl. Crystallogr. 46, 1863–1873 (2013)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

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

    Article  CAS  ADS  Google Scholar 

  20. Martínez-Franco, R. et al. Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents. Proc. Natl Acad. Sci. USA 110, 3749–3754 (2013)

    Article  PubMed  PubMed Central  ADS  Google Scholar 

  21. Hua, W. et al. A germanosilicate structure with 11×11×12‐ring channels solved by electron crystallography. Angew. Chem. Int. Edn 53, 5868–5871 (2014)

    Article  CAS  Google Scholar 

  22. Zhang, H., Zou, X. D., Oleynikov, P. & Hovmöller, S. Structure relations in real and reciprocal space of hexagonal phases related to i-ZnMgRE quasicrystals. Phil. Mag. 86, 543–548 (2006)

    Article  CAS  ADS  Google Scholar 

  23. Hong, S. B. et al. Synthesis and characterization of zeolite ZSM-25. Stud. Surf. Sci. Catal. 135, 186 (2001)

    Article  Google Scholar 

  24. Baerlocher, Ch. & McCusker, L. B. Database of Zeolite Structures http://www.iza-structure.org/databases/ (2007)

    Google Scholar 

  25. Karle, J. & Karle, I. L. The symbolic addition procedure for phase determination for centrosymmetric and non-centrosymmetric crystals. Acta Crystallogr. 21, 849–859 (1966)

    Article  CAS  Google Scholar 

  26. Vaughan, D. E. W. & Strohmaier, K. G. Synthesis of ECR-18—a synthetic analog of paulingite. Micropor. Mesopor. Mat. 28, 233–239 (1999)

    Article  CAS  Google Scholar 

  27. Blatov, V. A., Ilyushin, G. D., Lapshin, A. E. & Golubeva, O. Yu. Structure and chemical composition of the new zeolite ISC-1 from the data of nanocluster modeling. Glass Phys. Chem. 36, 663–672 (2010)

    Article  CAS  Google Scholar 

  28. Rochelle, G. T. Amine scrubbing for CO2 capture. Science 325, 1652–1654 (2009)

    Article  CAS  PubMed  ADS  Google Scholar 

  29. Shang, J. et al. Discriminative separation of gases by a “molecular trapdoor” mechanism in chabazite zeolites. J. Am. Chem. Soc. 134, 19246–19253 (2012)

    Article  CAS  PubMed  Google Scholar 

  30. Lozinska, M. M. et al. Cation gating and relocation during the highly selective “trapdoor” adsorption of CO2 on univalent cation forms of zeolite Rho. Chem. Mater. 26, 2052–2061 (2014)

    Article  CAS  Google Scholar 

  31. Totktarev, A., Harris, T., Kibby, C., Ione, K. & O'Rear, D. Studies on ZSM-25. In Proc. 12th Int. Zeolite Conf. Vol. 1 (eds Treacy, M. M. J. et al.) 2023–2030 (Materials Research Society, Cambridge Univ. Press, 1999)

    Google Scholar 

  32. Chatelain, T. et al. Synthesis and characterization of high-silica zeolite RHO prepared in the presence of 18-crown-6 ether as organic template. Microporous Mater. 4, 231–238 (1995)

    Article  CAS  Google Scholar 

  33. Coe, C. G., Gaffney, T. R. & Srinivasan, R. S. Chabazite for gas separation. US patent 4,925,460 (1990)

  34. Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. A64, 112–122 (2008)

    Article  MATH  ADS  Google Scholar 

  35. Gordon, E. K., Samson, S. & Kamb, W. B. Crystal structure of the zeolite paulingite. Science 154, 1004–1007 (1966)

    Article  CAS  PubMed  ADS  Google Scholar 

  36. Palatinus, L. & Chapuis, G. SUPERFLIP – a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions. J. Appl. Crystallogr. 40, 786–790 (2007)

    Article  CAS  Google Scholar 

  37. Palatinus, L., Prathapa, S. J. & van Smaalen, S. EDMA: a computer program for topological analysis of discrete electron densities. J. Appl. Crystallogr. 45, 575–580 (2012)

    Article  CAS  Google Scholar 

  38. Young R. A., (ed.) The Rietveld Method (Oxford Univ. Press, 1995)

    Google Scholar 

  39. Le Bail, A., Duroy, H. & Fourquet, J. L. Ab-initio structure determination of LiSbWO6 by X-ray powder diffraction. Mater. Res. Bull. 23, 447–452 (1988)

    Article  CAS  Google Scholar 

  40. Larson, A. C. & Von Dreele, R. B. General Structure Analysis System (GSAS). Report No. LAUR 86-748 (Los Alamos National Laboratory, 2004)

    Google Scholar 

  41. Henson, N. J., Cheetham, A. K. & Gale, J. D. Theoretical calculations on silica frameworks and their correlation with experiment. Chem. Mater. 6, 1647–1650 (1994)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We acknowledge financial support from the Swedish Research Council (VR), the Swedish Governmental Agency for Innovation Systems (VINNOVA), the Röntgen-Ångström Cluster through the project grant MATsynCELL, the Knut and Alice Wallenberg Foundation through the project grant 3DEM-NATUR, the NCRI (2012R1A3A-2048833) and BK 21-plus programmes through the National Research Foundation of Korea, and the UK EPSRC (EP/J02077X/1). We acknowledge the ESRF, Grenoble (ID31, A. N. Fitch; ID22, C. Drathen) and the PAL, Pohang (9B, D. Ahn) for synchrotron X-ray beam time. We thank L. B. McCusker and C. Baerlocher for suggestions about the Rietveld refinement. The TEM was financed by the Knut and Alice Wallenberg Foundation.

Author information

Author notes

  1. Peng Guo and Jiho Shin: These authors contributed equally to this work.

  2. Suk Bong Hong, Paul A. Wright and Xiaodong Zou: These authors jointly supervised this work.

Authors and Affiliations

  1. Department of Materials and Environmental Chemistry, Inorganic and Structural Chemistry, Stockholm University, Stockholm, SE-106 91, Sweden

    Peng Guo, Jie Su, Leifeng Liu & Xiaodong Zou

  2. Berzelii Centre EXSELENT on Porous Materials, Stockholm University, Stockholm, SE-106 91, Sweden

    Peng Guo, Jie Su, Leifeng Liu & Xiaodong Zou

  3. Centre for Ordered Nanoporous Materials Synthesis, School of Environmental Science and Engineering, POSTECH, Pohang, 790-784, South Korea

    Jiho Shin, Jung Gi Min, Hyun June Choi & Suk Bong Hong

  4. EaStCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK

    Alex G. Greenaway & Paul A. Wright

  5. School of Pharmacy and Biomedical Sciences, University of Portsmouth, Portsmouth, PO1 2DT, UK

    Paul A. Cox

Authors
  1. Peng Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jiho Shin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Alex G. Greenaway
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jung Gi Min
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jie Su
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Hyun June Choi
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Leifeng Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Paul A. Cox
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Suk Bong Hong
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Paul A. Wright
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Xiaodong Zou
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

S.B.H. and P.A.W. identified and initiated the research project, which was developed and brought to a conclusion jointly by S.B.H., P.A.W. and X.Z. J.Sh., J.G.M., H.J.C. and S.B.H. carried out the zeolite synthesis and gas sorption work. P.G. conducted the TEM work. P.G., L.L. and X.Z. carried out the structure solution and structure prediction work. P.G., A.G.G., J.Su, P.A.W. and X.Z. made the Rietveld refinements. P.A.C. did the molecular modelling and energy calculations. P.G., J.Sh., S.B.H., P.A.W. and X.Z. wrote and corrected the manuscript.

Corresponding authors

Correspondence to Suk Bong Hong, Paul A. Wright or Xiaodong Zou.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

The Crystallography Information Files (CIFs) are deposited at the Cambridge Crystallographic Data Centre (CCDC, http://www.ccdc.cam.ac.uk) with CCDC numbers: 1031577 for as-made NaTEA-ZSM-25, 1057085 for calcined NaTEA-ZSM-25, 1057832 for as-made NaSrTEA-PST-20 and 1039878 for Na+-exchanged NaSrTEA-PST-20.

Extended data figures and tables

Extended Data Figure 1 Characterization of ZSM-25 and PST-20 zeolites.

a, b, PXRD patterns (left panels), 27Al (middle panels) and 29Si (right panels) magic-angle spinning NMR spectra of as-made (bottom plots within each panel) and calcined (top plots within each panel) ZSM-25 (a) and PST-20 (b).

Extended Data Figure 2 Reconstructed 3D reciprocal lattice from the RED data.

a–c, NaTEA-ZSM-25 and d–f, NaSrTEA-PST-20. a, d, The 3D reciprocal lattice with the crystal inset. b, c, e, f, 2D slices cut from the reconstructed 3D reciprocal lattice showing the (hk0) plane (b, e), (hkh) (c) and (f) reciprocal plane. The distributions of the strong reflections for NaTEA-ZSM-25 and NaSrTEA-PST-20 are similar to that of PAU.

Extended Data Figure 3 Structure factor amplitudes and phases calculated from the structure models of RHO-G1 to RHO-G6.

The reflections are shown. Reflections in red and blue have phases of 0° and 180°, respectively. The red, green and blue circles correspond to d-spacings of 1.0 Å, 1.6 Å and 3.0 Å, respectively. The frameworks are idealized in the pure SiO2 forms.

Extended Data Figure 4 PXRD profiles for the Rietveld refinement of as-made and Na+-exchanged NaSrTEA-PST-20.

Top, as-made NaSrTEA-PST-20. Bottom, Na+-exchanged NaSrTEA-PST-20 (denoted NaTEA-PST-20). The observed, calculated and difference curves are shown in blue, red and black, respectively. The good agreement of observed and calculated data at high angles (inset) indicates that the framework structure is correct. The slight differences at lower angles are due to incomplete determination of the positions of all guest molecules/cations (X-ray wavelength λ = 0.40091 Å).

Extended Data Figure 5 The prediction of the RHO-family members RHO-G1 to RHO-G6 from the structure of PAU (RHO-G3).

The arrows indicate how the structures were predicted from their nearest generations. The 3D electron-density map of RHO-Gn (n = 4–6) was generated using the structure factors of strong reflections from RHO-G(n − 1), which allowed a 3D structure model of RHO-Gn to be built. The structures of RHO-G1 and RHO-G2 were obtained from RHO-G3 by model building.

Extended Data Figure 6 Tile representations of the structures of RHO-G1 to RHO-G6 in the RHO family.

The structure expansion operates at two levels: first, a pair of pau and d8r cages is inserted along each unit-cell edge (top) resulting in isoreticular expansion of the scaffold; and second, other cages are embedded (middle) in the inter-scaffold space. The resulting frameworks are denoted as ‘embedded isoreticular zeolite structures’ (bottom).

Extended Data Table 1 Structure factor amplitudes and phases used for structure solution of ZSM-25
Full size table
Extended Data Table 2 Room-temperature CO2/CH4 and CO2/N2 selectivities
Full size table

Supplementary information

Supplementary Information

This file contains Supplementary Discussion (including the location of TEA+ cations in NaTEA-ZSM-25 by computational modelling), Supplementary Figures 1–9 and Supplementary Tables 1–17. (PDF 2843 kb)

Supplementary Data 1

This file contains crystallographic information for as-made NaTEA-ZSM-25, calcined NaTEA-ZSM-25, as-made NaSrTEA-PST-20 and Na+-exchanged NaSrTEA-PST-20. (CIF 2951 kb)

Supplementary Data 2

This file contains crystallographic information for hypothetical RHO-G1 to RHO-G6. (CIF 61 kb)

PowerPoint slides

Source data

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Guo, P., Shin, J., Greenaway, A. et al. A zeolite family with expanding structural complexity and embedded isoreticular structures. Nature 524, 74–78 (2015). https://doi.org/10.1038/nature14575

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature14575

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

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