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A mesoporous germanium oxide with crystalline pore walls and its chiral derivative

Nature volume 437, pages 716–719 (2005)Cite this article

Abstract

Microporous oxides are inorganic materials with wide applications in separations, ion exchange and catalysis1,2,3. In such materials, an important determinant of pore size is the number of M (where M = Si, Ge and so on) atoms in the rings delineating the channels1. The important faujasite structure exhibits 12-ring structures while those of zeolites4,5, germanates6,7,8 and other8 materials can be much larger. Recent attention has focused on mesoporous materials with larger pores of nanometre scale9,10,11; however, with the exception of an inorganic–organic hybrid12, these have amorphous pore walls, limiting many applications. Chiral porous oxides are particularly desirable for enantioselective sorption and catalysis13. However, they are very rare in microporous14,15 and mesoporous16 materials. Here we describe a mesoporous germanium oxide, SU-M, with gyroidal channels separated by crystalline walls that lie about the G (gyroid) minimal surface as in the mesoporous MCM-48 (ref. 9). It has the largest primitive cell and lowest framework density of any inorganic material and channels that are defined by 30-rings. One of the two gyroidal channel systems of SU-M can be filled with additional oxide, resulting in a mesoporous crystal (SU-MB) with chiral channels.

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Figure 1: Linkage of Ge 10 O 24 (OH) 3 clusters in SU-M.
Figure 2: Hierarchical description of the fcz net19.
Figure 3: The tiles of SU-M.
Figure 4
Figure 5: Cavities in SU-MB and faujasite.

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Acknowledgements

We thank S. Lidin for help and discussions, A. Chizmeshya for the volume data reported in Table 1, K. E. Christensen for checking ion-exchanged samples and A. Garcia-Bennett for the N2 isotherm. L. Q. Tang and E. Karlsson participated in the synthesis. The project is supported by the Swedish Science Research Council. M.O'K. acknowledges support from the US National Science Foundation. X.D.Z. is a Research Fellow of the Royal Swedish Academy of Sciences, supported by a grant from the Alice and Knut Wallenberg Foundation.

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Authors and Affiliations

  1. Structural Chemistry, Stockholm University, SE-106 91, Stockholm, Sweden

    Xiaodong Zou, Tony Conradsson & Miia Klingstedt

  2. Corpuscular Inc., 52 Papania Drive, New York, 10541, Mahopac, USA

    Mike S. Dadachov

  3. Department of Chemistry and Biochemistry, Arizona State University, Arizona, 85287, Tempe, USA

    Michael O'Keeffe

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Correspondence to Xiaodong Zou.

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Competing interests

The additional crystallographic data for SU-M (CCDC-278829) and SU-MB (CCDC-278830) can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif. Reprints and permissions information is available at npg.nature.com/reprintsandpermissions. The authors declare no competing financial interests.

Supplementary information

Supplementary Figures and Supplementary Tables

This file contains Supplementary Figures S1–S4 and Supplementary Tables S1–S4. (DOC 539 kb)

Supplementary Video S1

This movie shows the pore structures and gyroidal channels of SU-M (left) and SU-MB (right) in one unit cell. They are calculated from the structure factors of all reflections with d-values large than 12 Å (four unique ones for SU-M and 7 unique ones for SU-MB) obtained from the framework structures. The red side is towards the pore and the green side is towards the framework wall. In SU-M, two gyroidal channels with opposite chirality are present, whereas in SU-MB, one of them is filled. (GIF 4323 kb)

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Zou, X., Conradsson, T., Klingstedt, M. et al. A mesoporous germanium oxide with crystalline pore walls and its chiral derivative. Nature 437, 716–719 (2005). https://doi.org/10.1038/nature04097

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