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Non-aqueous supramolecular assembly of mesostructured metal germanium sulphides from (Ge4S10)4− clusters

Nature volume 397, pages 681–684 (1999)Cite this article

Abstract

Microporous materials have found extensive application as catalysts, ion-exchange media and sorbents1,2. The discovery of mesoporous silica3 has opened the path to selective catalysis and separation of large molecules and to the synthesis of inorganic–organic composite materials, polymer mesofibres and semiconducting quantum dots4,5,6,7. Various oxide-based mesoporous materials, such as TiO2, ZrO2, SnO2, Al2O3, Nb2O5 and GeO2, have been reported8,9,10,11,12,13. A challenge for materials research is now to expand the scope of mesoporous materials beyond the oxides. Only a few non-oxide mesostructured composites, such as CdS, SnS2 and CdSe, have been reported; they are usually synthesized by ad hoc hydrothermal methods or from aqueous solutions containing ill-defined species, and are often not well characterized14,15,16. Herewe report the rational synthesis of a new family of metal germanium sulphide mesostructured materials prepared by a non-aqueous surfactant-templated assembly of adamantanoid [Ge4S10]4− cluster precursors. In the presence of quaternary alkylammonium surfactants, [Ge4S10]4− anions in formamide solution self-organize with metal cations (Co2+, Ni2+, Cu+ and Zn2+) to create well ordered hexagonal metal germanium sulphide mesostructures, some having fibre-like morphologies with channels running down the long axis of the fibre. Materials of this genre could prove effective in applications as diverse as detoxification of heavy metals in polluted water streams, sensing of sulphurous vapours, and the formation of semiconductor quantum ‘anti-dot’ devices.

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Figure 1: X-ray diffraction and TEM results.
Figure 2: Raman spectra.
Figure 3: NMR and thermogravimetry results.
Figure 4: Proposed architecture of the mesostructured material.

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Acknowledgements

We thank R. L. Bedard for helpful discussions, critical reading of the manuscript and elemental analyses of the materials. We thank E. Chomski for creative and technical assistance with Fig. 4. G.A.O. acknowledges the Killam Foundation for the award of an Isaac Walton Killam research fellowship (1995–97). M.J.M. is indebted to NSERC for a post-graduate scholarship (1995–99). This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC) and UOP.

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  1. Department of Chemistry, Materials Chemistry Research Group, 80 St George Street, M5S 3H6, Toronto, Canada

    Mark J. MacLachlan, Neil Coombs & Geoffrey A. Ozin

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  1. Mark J. MacLachlan
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  3. Geoffrey A. Ozin
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Correspondence to Geoffrey A. Ozin.

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MacLachlan, M., Coombs, N. & Ozin, G. Non-aqueous supramolecular assembly of mesostructured metal germanium sulphides from (Ge4S10)4− clusters. Nature 397, 681–684 (1999). https://doi.org/10.1038/17776

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