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The effect of pyridinic- and pyrrolic-nitrogen in nitrogen-doped carbon nanotubes used as support for Pd-catalyzed nitroarene reduction: an experimental and theoretical study

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Abstract

Nitrogen-doped carbon nanotubes (N-CNTs) containing different nitrogen species were synthesized via a chemical vapour deposition technique. This was archived by use of ferrocene and ferrocenyl-2-(4-cyanophenyl)acrylonitrile as catalysts. The N-CNTs were acid-treated and then used as Pd nanoparticle supports (Pd/N-CNTs). Both N-CNTs and Pd/N-CNTs were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and other spectroscopic techniques. The selective reduction of nitroarenes to anilines was used as a model reaction to test the effect of pyridinic- and pyrrolic-nitrogen species on the catalytic performance of Pd/N-CNTs. A larger number of pyridinic-nitrogens in the N-CNTs increased nitroarene conversion and enhanced the selectivity towards anilines as opposed to the pyrrolic-nitrogens. Also, pyridinic-nitrogens favoured the nucleation of Pd nanoparticles with higher surface areas than those nucleated in the presence of pyrrolic-nitrogens. Density functional theory calculations were employed to determine the band-gap energy and optimal geometry of Pd complexed to pyridine and pyrrole ligands. These results showed that the pyridine complex had a lower band-gap energy (5.804 eV) than the pyrrole complex (6.406 eV) implying that the former complex is more reactive than the later. Thus, the inclusion of pyridinic-nitrogens in the N-CNTs, used as support, favours Pd-catalyzed nitroarene reductions.

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Acknowledgements

The authors wish to thank the University of KwaZulu-Natal and the National Research Foundation (NRF) for financial support. Dr. L.M. Ombaka is grateful for the award of doctoral bursary from the University of KwaZulu-Natal, College of Agriculture, Engineering and Science. We are grateful to Professor Bice Martincigh and Dr. R.S. Mwakubambanya for their insightful suggestions during the development of this manuscript and their assistance with proofreading.

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Authors and Affiliations

  1. School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban, 4000, South Africa

    Lucy M. Ombaka, Patrick G. Ndungu & Vincent O. Nyamori

  2. School of Physical Sciences and Technology, Technical University of Kenya, P.O. Box 52428-00200, Nairobi, Kenya

    Lucy M. Ombaka

  3. Department of Applied Chemistry, University of Johannesburg, Doornfontein Campus, P.O. Box 17011, Johannesburg, 2028, South Africa

    Patrick G. Ndungu

  4. Department of Chemistry, Egerton University, P.O. Box 536-20115, Njoro, Kenya

    Joshua Kibet

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  1. Lucy M. Ombaka
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Correspondence to Vincent O. Nyamori.

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Ombaka, L.M., Ndungu, P.G., Kibet, J. et al. The effect of pyridinic- and pyrrolic-nitrogen in nitrogen-doped carbon nanotubes used as support for Pd-catalyzed nitroarene reduction: an experimental and theoretical study. J Mater Sci 52, 10751–10765 (2017). https://doi.org/10.1007/s10853-017-1241-0

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