Direct and cluster-assisted dehydrogenation of methane by Nb+ and Ta+: a theoretical investigation

文献情報

出版日 2017-05-24

DOI 10.1039/C7CP01833A

インパクトファクター 3.676

著者

Emilia Sicilia, Gloria Mazzone, Adriana Pérez-González, Jenny Pirillo, Annia Galano, Thomas Heine, Nino Russo

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要旨

DFT calculations have been performed to examine both direct and cluster-assisted methane C–H bond activation by Nb+ and Ta+ cations. The commonly accepted dehydrogenation pathways, that are oxidative addition and reductive elimination, have been studied in detail for methane ligated clusters M(CH4)n+ (M = Nb, Ta and n = 1–4). For the second H atom transfer to the metal in the presence of additional CH4 molecules (n > 1) two alternative routes have been explored. Energy profiles for ground quintet and excited triplet and singlet spin states of both Nb+ and Ta+ cations have been calculated. Spin crossings occur for all the examined pathways. Clustering of methane ligands appears to favorably affect the process stabilizing all the intercepted minima and transition states and bringing all the calculated PESs below the reference energy of the separated reactants. The direct activation of methane (n = 1) can proceed efficiently only for Ta+, whereas dehydrogenation is endothermic for Nb+ by 9.0 kcal mol−1. When assisted by additional methane ligands, the dehydrogenation process becomes exothermic for both cations whatever the number of coordinated molecules.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Direct and cluster-assisted dehydrogenation of methane by Nb+ and Ta+: a theoretical investigation

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Physical Chemistry Chemical Physics

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