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Varied pore organization in mesostructured semiconductors based on the [SnSe4]4- anion

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Abstract

Open framework metal chalcogenide solids, with pore sizes in the nano- and mesoscale, are of potentially broad technological and fundamental interest in research areas ranging from optoelectronics to the physics of quantum confinement1,2. Although there have been significant advances in the design and synthesis of mesostructured silicas3,4, the construction of their non-oxidic analogues still remains a challenge. Here we describe a synthetic strategy that allows the preparation of a large class of mesoporous materials based on supramolecular assembly of tetrahedral Zintl anions [SnSe4]4- with transition metals in the presence of cetylpyridinium (CP) surfactant molecules. These mesostructured semiconducting selenide materials are of the general formulae (CP)4-2xMxSnSe4 (where 1.0 < x < 1.3; M=Mn, Fe, Co, Zn, Cd, Hg). The resulting materials are open framework chalcogenides and form mesophases with uniform pore size (with spacings between 35 and 40 Å). The pore arrangement depends on the synthetic conditions and metal used, and include disordered wormhole, hexagonal and even cubic phases. All compounds are medium bandgap semiconductors (varying between 1.4 and 2.5 eV). We expect that such semiconducting porous networks could be used for optoelectronic, photosynthetic and photocatalytic applications.

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Figure 1: X-ray scattering of mesostructured chalcogenides.
Figure 2: Transmission electron microscope images of mesostructured chalcogenides.
Figure 3: 119Sn Mössbauer spectra (85 K) with derived δ/ΔEq parameters.
Figure 4: Thermogravimetric data and optical absorption spectra.

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Acknowledgements

This work made use of the SEM and TEM facilities of the Center for Advanced Microscopy at Michigan State University. Financial support from the National Science Foundation is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Michigan State University, East Lansing, 48824, Michigan, USA

    Pantelis N. Trikalitis, K. Kasthuri Rangan & Mercouri G. Kanatzidis

  2. Department of Physics, University of Ionnina, Ioannina, 45110, Greece

    Thomas Bakas

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  1. Pantelis N. Trikalitis
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  2. K. Kasthuri Rangan
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  3. Thomas Bakas
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  4. Mercouri G. Kanatzidis
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Correspondence to Mercouri G. Kanatzidis.

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Trikalitis, P., Rangan, K., Bakas, T. et al. Varied pore organization in mesostructured semiconductors based on the [SnSe4]4- anion. Nature 410, 671–675 (2001). https://doi.org/10.1038/35070533

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