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Hydrazine decomposition on a small platinum cluster: the role of N2H5 intermediate

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Abstract

This work presents a comprehensive DFT study on the interaction between hydrazine derivatives with a platinum catalyst surface, which is represented by a tetrahedral Pt4 cluster model. Three separate reaction pathways were investigated; two of which are related to possible pathways of NH3 formation. The first pathway describes the intramolecular transfer of one hydrogen atom in the hydrazine molecule forming the NHNH3 intermediate, then dissociating into NH and NH3. The second describes the addition of one external hydrogen atom to hydrazine forming N2H5, followed by its dissociation to NH2 and NH3. The third reaction pathway involves the formation of N2H3 by means of hydrogen abstraction by an external hydrogen. The reactions were studied in both the absence and the presence of a Pt4 cluster. We find that the assistance of the Pt4 cluster lacks a systematic effect on the reactions barrier heights. It is also shown that the ammonia formation can possibly proceed through the formation of the N2H5 intermediate, leading to more exothermic intermediate steps in the presence of the Pt4 cluster.

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Acknowledgments

The authors acknowledge the continuous research and fellowship support of the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Grants 302,408/2014-2, 303259/2012-4, and 304914/2013-4, Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), and the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP), Grants 2012/50666-2, 2011/07623-8, and 2014/24155-6. We also wish to thank Dr. Corey A. Petty for his kind attention in revising this manuscript.

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Authors and Affiliations

  1. Divisão de Ensino, Academia da Força Aérea, Pirassununga, São Paulo, 13643-000, Brazil

    Marina Pelegrini

  2. Núcleo de Pesquisa em Ciências Exatas e Tecnológicas, Universidade de Franca, Franca, SP, 14404-600, Brazil

    Renato L. T. Parreira & Eder H. da Silva

  3. Departamento de Química, Instituto Tecnológico de Aeronáutica, São José Dos Campos, São Paulo, 12228-900, Brazil

    Luiz F. A. Ferrão, Jose A. F. F. Rocco & Francisco B. C. Machado

  4. Departamento de Química, Universidade Federal de Santa Catarina, Campus Universitário Trindade, CP 476, Florianópolis, SC, 88040-900, Brazil

    Giovanni F. Caramori & Alexandre O. Ortolan

  5. Divisão de Aerotermodinâmica e Hipersônica, Instituto de Estudos Avançados, São José Dos Campos, São Paulo, 12228-840, Brazil

    Orlando Roberto-Neto

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  1. Marina Pelegrini
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Correspondence to Marina Pelegrini, Luiz F. A. Ferrão or Francisco B. C. Machado.

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Pelegrini, M., Parreira, R.L.T., Ferrão, L.F.A. et al. Hydrazine decomposition on a small platinum cluster: the role of N2H5 intermediate. Theor Chem Acc 135, 58 (2016). https://doi.org/10.1007/s00214-016-1816-x

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