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Direct access to thermally stable and highly crystalline mesoporous transition-metal oxides with uniform pores

Abstract

Even after a decade or so of research, the direct synthesis of highly crystalline mesoporous transition-metal oxides that are thermally stable and well ordered still constitutes a major challenge. Although various soft- and hard-templating approaches have been developed in the past, they usually suffer from multiple, tedious steps and often result in poor structure control. For many applications including power generation and energy conversion, however, high crystallinity and controlled mesoporosity are a prerequisite. To this end, here we report on an approach established for group-IV (titanium) and group-V (niobium) oxides, with potential applications to photovoltaic cells and fuel cells, respectively, which overcomes previous limitations. It gives direct access to the desired materials in a ‘one-pot’ synthesis using block copolymers with an sp2-hybridized carbon-containing hydrophobic block as structure-directing agents which converts to a sturdy, amorphous carbon material under appropriate heating conditions. This in situ carbon is sufficient to act as a rigid support keeping the pores of the oxides intact while crystallizing at temperatures as high as 1,000 C.

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Figure 1: Schematic representation of CASH method.
Figure 2: Materials characterization by X-ray.
Figure 3: Materials characterization by electron microscopy.
Figure 4: Materials characterization by nitrogen physisorption.
Figure 5: Experimental evidence of in situ carbon formation.
Figure 6: Electron diffraction from crystalline materials.

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Acknowledgements

This work was supported by grants from the Department of Energy (DE-FG02 87ER45298) and the National Science Foundation (DMR-0605856). The work was further supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2005-214-D00298). Cornell High Energy Synchrotron Source (CHESS) is a national user facility supported by the National Science Foundation and the National Institute of General Medical Sciences. We thank A. Burns for help with the graphics and figures.

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Correspondence to Ulrich Wiesner.

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Lee, J., Christopher Orilall, M., Warren, S. et al. Direct access to thermally stable and highly crystalline mesoporous transition-metal oxides with uniform pores. Nature Mater 7, 222–228 (2008). https://doi.org/10.1038/nmat2111

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