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Spongy chalcogels of non-platinum metals act as effective hydrodesulfurization catalysts

Abstract

Aerogels are low-density porous materials, made mostly of air, for which hundreds of applications have been found in recent years. Inorganic oxide-based aerogels have been known for a long time, carbon aerogels were discovered in the early 1990s and sulfur- and selenium-based aerogels (chalcogels) are the most recent additions to this family. Here we present new aerogels made of Co(Ni)–Mo(W)–S networks with extremely large surface areas and porosity. These systems are formed by the coordinative reactions of (MoS4)2− and (WS4)2− with Co2+ and Ni2+ salts in non-aqueous solvents. We show that these low-density sponge-like networks can absorb conjugated organic molecules and mercury ions, and preferentially adsorb CO2 over H2, which illustrates their high potential as gas-separation media. The chalcogels are shown to be twice as active as the conventional sulfided Co–Mo/Al2O3 catalyst for the hydrodesulfurization of thiophene.

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Figure 1: SEM and photographic images of chalcogels.
Figure 2: TEM images and STEM-XEDS spectra of aerogels.
Figure 3: Nitrogen adsorption–desorption isotherms, PDF analysis and adsorption of porphyrin I on chalcogel.
Figure 4: Adsorption isotherms of H2 and CO2 and measure of selectivity.
Figure 5: HDS-activity data for chalcogel-Co-1 as well as adsorption–desorption isotherms and XRD pattern for the tested material.

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Acknowledgements

These studies were supported primarily by the Nanoscale Science and Engineering Initiative of the National Science Foundation, and the HDS studies were supported by the National Science Foundation. We are thankful to P. J. Chupas for collection of the PDF data.

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S.B. and M.G.K. designed and conducted the research, HDS experiments were performed by A.F.G. and M.E.B., and S.B. and M.G.K. wrote the paper.

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Correspondence to Mercouri G. Kanatzidis.

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Bag, S., Gaudette, A., Bussell, M. et al. Spongy chalcogels of non-platinum metals act as effective hydrodesulfurization catalysts. Nature Chem 1, 217–224 (2009). https://doi.org/10.1038/nchem.208

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