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Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes

Nature Chemistry volume 5, pages 537–543 (2013)Cite this article

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Abstract

Molecularly well-defined homogeneous catalysts are known for a wide variety of chemical transformations. The effect of small changes in molecular structure can be studied in detail and used to optimize many processes. However, many industrial processes require heterogeneous catalysts because of their stability, ease of separation and recyclability, but these are more difficult to control on a molecular level. Here, we describe the conversion of homogeneous cobalt complexes into heterogeneous cobalt oxide catalysts via immobilization and pyrolysis on activated carbon. The catalysts thus produced are useful for the industrially important reduction of nitroarenes to anilines. The ligand indirectly controls the selectivity and activity of the recyclable catalyst and catalyst optimization can be performed at the level of the solution-phase precursor before conversion into the active heterogeneous catalyst.

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Figure 1: Synthesis of an active cobalt oxide–nitrogen/carbon catalyst by pyrolysing a cobalt(II) acetate–phenanthroline complex on carbon.
Figure 2: Catalyst characterization.
Figure 3: Catalyst recycling and kinetic data of the hydrogenation of nitrobenzene catalysed by cobalt oxide.

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Acknowledgements

This research was supported by Federal Ministry of Education and Research (BMBF) and the state of Mecklenburg-Vorpommern.

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Authors and Affiliations

  1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock, 18059, Germany

    Felix A. Westerhaus, Rajenahally V. Jagadeesh, Gerrit Wienhöfer, Marga-Martina Pohl, Jörg Radnik, Annette-Enrica Surkus, Jabor Rabeah, Kathrin Junge, Henrik Junge, Martin Nielsen, Angelika Brückner & Matthias Beller

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  1. Felix A. Westerhaus
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Contributions

M.B., F.A.W. and R.V.J. planned and developed the project, F.A.W. performed and designed the experiments and co-wrote the paper, R.V.J. developed, designed and prepared the catalysts and was involved in writing the paper, G.W. conducted catalytic experiments and performed the analytics, M.N. was involved in discussions and contributed to the writing of the paper, K.J. participated in discussions and contributed to the writing of the paper, H.J. was involved in the development of the catalyst, A.E.S. performed electrochemical studies of the catalyst and was involved in the catalyst development, J. Radnik did the XPS experiments, M.M.P. performed the TEM experiments, J. Rabeah and A.B. were responsible for EPR experiments, M.B. directed the project, participated in the design of catalytic experiments and in the design of the catalyst, and co-wrote the paper.

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Correspondence to Matthias Beller.

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Westerhaus, F., Jagadeesh, R., Wienhöfer, G. et al. Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes. Nature Chem 5, 537–543 (2013). https://doi.org/10.1038/nchem.1645

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