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Cobalt-based nanocatalysts for green oxidation and hydrogenation processes

A Corrigendum to this article was published on 30 December 2015

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Abstract

This protocol describes the preparation of cobalt-based nanocatalysts and their applications in environmentally benign redox processes for fine chemical synthesis. The catalytically active material consists of nanoscale Co3O4 particles surrounded by nitrogen-doped graphene layers (NGrs), which have been prepared by pyrolysis of phenanthroline-ligated cobalt acetate on carbon. The resulting materials have been found to be excellent catalysts for the activation of both molecular oxygen and hydrogen; in all tested reactions, water was the only by-product. By applying these catalysts, green oxidations of alcohols and hydrogenation of nitroarenes for the synthesis of nitriles, esters and amines are demonstrated. The overall time required for catalyst preparation and for redox reactions is 35 h and 10–30 h, respectively.

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Figure 1: TEM images with an inset image showing the position of the nitrogen-doped graphene layers of Co3O4/NGr@C catalyst.
Figure 2: Co3O4/NGr@C-catalyzed synthesis of nitriles.
Figure 3: Gram-scale reactions: Co3O4/NGr@C-catalyzed synthesis of nitriles.
Figure 4: Hydrogenation of nitroarenes to anilines catalyzed by Co3O4/NGr@C-catalysts.
Figure 5: Gram-scale reactions for the hydrogenation of nitroarenes catalyzed by Co3O4/NGr@C catalysts.
Figure 6: Reductive amination of aldehydes with nitro compounds.
Figure 7: Reuse of the Co3O4/NGr@C-catalyst after recycling.
Figure 8
Figure 9: Impregnation of cobalt-phenanthroline complex on carbon.
Figure 10: Grinding of the dried catalyst (left) and the crucible with lid that is used for pyrolysis (right).
Figure 11
Figure 12
Figure 13: Reaction glass vial and autoclave.
Figure 14: Equipment setup for hydrogenation and oxidation reactions.

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Change history

  • 16 September 2015

     In the version of this article initially published, Box 1 had the incorrect title; the correct title is 'Catalyst recycling experiments with nitrobenzene: 30 h.' The error has been corrected (for both the Box itself and the corresponding entry in the Timing section) in the HTML and PDF versions of the article.

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Acknowledgements

The German Federal Ministry of Education and Research (BMBF) and the State of Mecklenburg-Vorpommern are gratefully acknowledged for their general support.

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Authors and Affiliations

Authors

Contributions

M. Beller, R.V.J. and T.S. planned the project. R.V.J. and T.S. developed and prepared the catalysts. R.V.J., T.S. and M. Beller wrote the paper. A.-E.S., M. Beller, K.J. and H.J. were involved in the development of this class of catalysts. M.-M.P., J.R., M. Bauer and A.B. performed the characterization of the catalyst.

Corresponding author

Correspondence to Matthias Beller.

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Competing interests

A German patent application has been filed in 2012 for the preparation and use of the Co catalysts. This patent has been transferred in 2013 to Evonik Industries. They are doing currently an upscaling of the catalyst for commercial purposes.

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Jagadeesh, R., Stemmler, T., Surkus, AE. et al. Cobalt-based nanocatalysts for green oxidation and hydrogenation processes. Nat Protoc 10, 916–926 (2015). https://doi.org/10.1038/nprot.2015.049

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