Abstract
Cryptomelane-type manganese oxide (OMS-2) has been widely used to explore the semiconducting and catalytic properties of molecular sieves with mixed-valent frameworks. Selective synthesis of patterned thin films of OMS-2 with hierarchical nanostructures and oriented crystals is challenging owing to difficulties in preserving the mixed valence, porosity and crystalline phase. Here, we report that pulsed-laser ablation of OMS-2 in an oxygen-rich medium produces a three-dimensional nanostructured array of parallel and inclined OMS-2 fibres on bare substrates of (001) single-crystal strontium titanate. Both parallel and inclined OMS-2 fibres elongate along the [001]OMS-2 direction. The parallel fibres interact strongly with the substrate and grow epitaxially along 〈110〉STO with lattice misfits of less than 4%, whereas the inclined fibres are oriented with (301) parallel to the substrate surface. The spontaneous orientation of the crystalline OMS-2 domains over the STO surface opens up a new avenue in lattice-engineered synthesis of multilayer materials.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Corma, A. From microporous to mesoporous molecular sieve materials and their use in catalysis. Chem. Rev. 97, 2373–2419 (1997).
Davis, M. E. Ordered porous materials for emerging applications. Nature 417, 813–821 (2002).
Lai, Z. et al. Microstructural optimization of a zeolite membrane for organic vapour separation. Science 300, 456–460 (2003).
Dong, J., Lin, Y. S., Kanezashi, M. & Tang, Z. Microporous inorganic membranes for high temperature hydrogen purification. J. Appl. Phys. 104, 121301 (2008).
Li, Y., Sasaki, T., Shimizu, Y. & Koshizaki, N. Hexagonal-close-packed, hierarchical amorphous TiO2 nanocolumn arrays: Transferability, enhanced photocatalytic activity, and superamphiphilicity without ultraviolet irradiation. J. Am. Chem. Soc. 130, 14755–14762 (2008).
Okubo, T. et al. Heteroepitaxial growth of a zeolite. Angew. Chem. Int. Ed. 40, 1069–1071 (2001).
Wakihara, T., Yamakita, S., Iezumi, K. & Okubo, T. Heteroepitaxial growth of a zeolite film with a patterned surface-texture. J. Am. Chem. Soc. 125, 12388–12389 (2003).
Xiong, C., Coutinho, D. & Balkus, K. J. Jr Fabrication of hollow spheres composed of nanosized ZSM-5 crystals via laser ablation. Micropor. Mesopor. Mater. 86, 14–22 (2005).
Muñoz, T. Jr & Balkus, K. J. Preparation of oriented zeolite UTD-1 membranes via pulsed laser ablation. J. Am. Chem. Soc. 121, 139–146 (1999).
Pisklak, T. J. & Balkus, K. J. Preparation and characterization of UTD-12/ZSM-48 thin films via pulsed-laser deposition. Micropor. Mesopor. Mater. 81, 125–134 (2005).
Washmon-Kriel, L. & Balkus, K. J. Preparation and characterization of oriented MAPO-39 membranes. Micropor. Mesopor. Mater. 38, 107–121 (2000).
Balkus, K. J. Jr & Scott, A. S. Zeolite coatings on three-dimensional objects via laser ablation. Chem. Mater. 11, 189–191 (1999).
Mohaddes-Ardabili, L. et al. Self-assembled single-crystal ferromagnetic iron nanowires formed by decomposition. Nature Mater. 3, 533–538 (2004).
Suib, S. L. Porous manganese oxide octahedral molecular sieves and octahedral layered materials. Acc. Chem. Res. 41, 479–487 (2008).
Tian, Z. R. et al. Manganese oxide mesoporous structures: Mixed-valent semiconducting catalysts. Science 276, 926–930 (1997).
Suib, S. L. Structure, porosity, and redox in porous manganese oxide octahedral layer and molecular sieve materials. J. Mater. Chem. 18, 1623–1631 (2008).
Vrejoiu, I., Alexe, M., Hesse, D. & Goesele, U. Functional perovskites—from epitaxial films to nanostructured arrays. Adv. Funct. Mater. 18, 3892–3906 (2008).
Chrisey, D. B. & Hubler, G. K. Pulsed Laser Deposition of Thin Films (Wiley, 1994).
Li, W.-N. et al. Hydrothermal synthesis of structure- and shape-controlled manganese oxide octahedral molecular sieve nanomaterials. Adv. Funct. Mater. 16, 1247–1253 (2006).
Yuan, J., Li, W.-N., Gomez, S. & Suib, S. L. Shape-controlled synthesis of manganese oxide octahedral molecular sieve three-dimensional nanostructures. J. Am. Chem. Soc. 127, 14184–14185 (2005).
Yuan, J. et al. Superwetting nanowire membranes for selective absorption. Nature Nanotech. 3, 332–336 (2008).
Liu, J., Makwana, V., Cai, J., Suib, S. L. & Aindow, M. Effects of alkali metal and ammonium cation templates on nanofibrous cryptomelane-type manganese oxide octahedral molecular sieves (OMS-2). J. Phys. Chem. B 107, 9185–9194 (2003).
Isber, S. et al. Study of manganese oxide thin films grown by pulsed laser deposition. Thin Solid Films 517, 1592–1595 (2009).
Abràmoff, M. D., Magalhães, P. J. & Ram, S. J. Image processing with ImageJ. Biophoton. Int. 11, 36–41 (2004).
Holland, T. J. B. & Redfern, S. A. T. UNITCELL: A nonlinear least-squares program for cell-parameter refinement implementing regression and deletion diagnostics. J. Appl. Crystallogr. 30, 84 (1997).
Kilaas, R. & O’Keefe, M. A. in Computer Simulation of Electron Microscope Diffraction and Images (eds Krakow, E. W. & O’Keefe, M. A.) (TMS, 1989).
Acknowledgements
We thank the US Department of Energy (DOE), Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science and NSF award number DMR-0907197, for financial support. We would like to thank R. Ristau for preparing cross-section samples on the FIB-TEM and J. Romanow for helping acquiring secondary-electron SEM images. X. Shen and F. Galasso were very helpful with suggestions and encouragement.
Author information
Authors and Affiliations
Contributions
A.E.E., C.-H.C. and S.L.S conceived and designed the experiments. A.E.E., Y.N. and B.O.W. carried out PLD experiments. A.E.E collected crystal structure data and SEM images and analysed them along with L.E., R.J. and S.L.S. L.Z. and M.A. collected the TEM data and analysed the orientation relationships. A.M. prepared the OMS-2 target material. A.E.E., L.E, L.Z., M.A. and S.L.S. co-wrote the paper. All authors discussed the results and commented on the manuscript.
Corresponding author
Supplementary information
Supplementary Information
Supplementary Information (PDF 921 kb)
Rights and permissions
About this article
Cite this article
Espinal, A., Zhang, L., Chen, CH. et al. Nanostructured arrays of semiconducting octahedral molecular sieves by pulsed-laser deposition. Nature Mater 9, 54–59 (2010). https://doi.org/10.1038/nmat2567
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nmat2567