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The ITQ-37 mesoporous chiral zeolite

Abstract

The synthesis of crystalline molecular sieves with pore dimensions that fill the gap between microporous and mesoporous materials is a matter of fundamental and industrial interest1,2,3. The preparation of zeolitic materials with extralarge pores and chiral frameworks would permit many new applications. Two important steps in this direction include the synthesis4 of ITQ-33, a stable zeolite with 18 × 10 × 10 ring windows, and the synthesis5 of SU-32, which has an intrinsically chiral zeolite structure and where each crystal exhibits only one handedness. Here we present a germanosilicate zeolite (ITQ-37) with extralarge 30-ring windows. Its structure was determined by combining selected area electron diffraction (SAED) and powder X-ray diffraction (PXRD) in a charge-flipping algorithm6. The framework follows the SrSi2 (srs) minimal net7 and forms two unique cavities, each of which is connected to three other cavities to form a gyroidal channel system. These cavities comprise the enantiomorphous srs net of the framework. ITQ-37 is the first chiral zeolite with one single gyroidal channel. It has the lowest framework density (10.3 T atoms per 1,000 Å3) of all existing 4-coordinated crystalline oxide frameworks, and the pore volume of the corresponding silica polymorph would be 0.38 cm3 g-1.

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Figure 1: Structure of SDA2 used for synthesizing the ITQ–37 zeolite.
Figure 2: Observed (blue), calculated (red) and difference (black) PXRD profiles for the Rietveld refinement of the as-synthesized ITQ-37 ( λ = 1.5406 Å).
Figure 3: Electron density map derived by the charge-flipping algorithm and the obtained structure model, both are viewed along the c axis.
Figure 4: The framework and corresponding nets of ITQ-37.
Figure 5: Tiling of ITQ-37.

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Acknowledgements

This project is supported by the CICYT (Project MAT 2006-14274-C02-01 and Prometeo 2008 GV), the Swedish Research Council (VR) and the Swedish Governmental Agency for Innovation Systems (VINNOVA). J.S. and C.B. are supported by post-doctoral grants from the Carl-Trygger and Wenner-Gren foundations respectively. M.M. thanks ITQ for a scholarship.

Author Contributions D.Z. and M.L. carried out the TEM work. J.S. solved and refined the structures. C.B. did the topological analysis. M.M., M.J.D.-C. and A.C. carried out the zeolite synthesis work. Á.C. synthesized the organic structure directing agents. J.S., C.B., A.C. and X.Z. wrote and corrected the manuscript.

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Correspondence to Avelino Corma or Xiaodong Zou.

Supplementary information

Supplementary Information

This file contains Supplementary Figures S1-S12 with Legends and Supplementary Tables S1-S4. (PDF 929 kb)

Supplementary Information

This file contains Crystallographic Information of ITQ-37. (TXT 4 kb)

Supplementary Framework Structure Movie

This movie shows the framework structure of ITQ-37. Only the Si-Si connections are shown. (MOV 20518 kb)

Supplementary Channel Structure Movie

This movie shows the structure of extra-large pores in ITQ-37 in tiling representation. Only framework tiles are represented (green and gold). The green tiles correspond to the D4Rs. (MOV 4528 kb)

Supplementary Cage Structure Movie

This movie shows the structure of an extra-large cage with three pore-openings in ITQ-37 in tiling representation. Only framework tiles are represented (green and gold). The green tiles correspond to the D4Rs. (MOV 5113 kb)

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Sun, J., Bonneau, C., Cantín, Á. et al. The ITQ-37 mesoporous chiral zeolite. Nature 458, 1154–1157 (2009). https://doi.org/10.1038/nature07957

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