Zeolites are crystalline solids, usually aluminosilicates, with ordered microporosity, for which more than two hundred different structures are known. They play a crucial role in present-day society; for instance, as catalysts in the oil refining and petrochemical industry.1 In future energy systems conductive porous carbon materials are expected to play a key role, as battery electrode materials, supercapacitors, and in fuel cells and electrolyzers.2, 3 However, preparing well-defined ordered microporous carbon materials has been a long-standing challenge. Prof Ryoo and his team describe in Nature a new strategy to prepare these materials with unprecedented precision.4
Carbon mesostructures can be prepared by filling the ordered mesopores (diameter larger than 2 nm) of silica scaffolds, and removing the silica afterwards.5 However, common carbon precursors such as sucrose or furfuryl alcohol are too large to easily diffuse in the 0.5–1.3 nm-sized pores of zeolites. Smaller precursor molecules such as ethylene decompose only at high temperatures, resulting in incomplete pore filling and carbon structures being formed outside the zeolite pores. Ryoo et al.5 demonstrate that the use of lanthanum, yttrium or calcium catalysts lowers the decomposition temperature of ethylene by 200 °C. Although the exact catalytic mechanism remains unclear, this results in carbon formation exclusively inside the zeolite pores in which the catalyst is present (see Figure 1). After zeolite removal, a well-defined, ordered and interconnected microporous carbon structure is obtained.
The same strategy is applied to several different zeolite structures, with pores down to 0.71 nm. Three-dimensional open zeolite porosity leads to interconnected carbon networks. Interestingly, also well-defined carbon quantum dots with intriguing optical properties can be formed. The materials are prepared on the scale of several grams, and are electronically conducting, very important for application as energy materials. However, the limited mechanical robustness seems to be a great disadvantage. Structures faithfully replicating zeolite micropores are intrinsically fragile, but perhaps this problem might be circumvented by introducing additional mesopores in the zeolites, resulting in a robust nanoscale carbon backbone after templating.
In short, the exciting findings reported in this paper enable the preparation of ordered microporous carbon materials with a wide range of structures, and will hopefully be followed by a series of papers providing more insight into the catalytic mechanism and exploring the wide range of new functional materials and their optical and electronic properties.
References
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Gong, K., Du, F., Xia, Z., Durstock, M. & Dai, L. Nitrogen-doped carbon nanotubbe arrays with high electrocatalytic activity for oxygen reduction. Science 323, 760 (2009).
Kim, K., Lee, T., Kwon, Y., Seo, Y., Song, J., Park, J. K., Lee, H., Park, J. Y., Ihee, H., Cho, S. J. & Ryoo, R. Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template. Nature 535, 131 (2016).
Ryoo, R., Joo, S. H. & Jun, S. Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation. J. Phys. Chem. B 103, 7743 (1999).
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de Jongh, P. Miniature structures meticulously replicated in carbon. NPG Asia Mater 9, e339 (2017). https://doi.org/10.1038/am.2016.188
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DOI: https://doi.org/10.1038/am.2016.188