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Gas-Phase Mechanism of O.-/Ni2+-Mediated Methane Conversion to Formaldehyde

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Li,  Yake
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig;
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Green Catalysis Center and College of Chemistry, Zhengzhou University;

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Müller,  Fabian
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig;
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Institut für Chemie, Humboldt-Universität zu Berlin;

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Schöllkopf,  Wieland
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Citation

Li, Y., Müller, F., Schöllkopf, W., Asmis, K., & Sauer, J. (2022). Gas-Phase Mechanism of O.-/Ni2+-Mediated Methane Conversion to Formaldehyde. Angewandte Chemie International Edition, e202202297. doi:10.1002/anie.202202297.


Cite as: http://hdl.handle.net/21.11116/0000-000A-AB9B-7
Abstract
The gas-phase reaction of NiAl2O4+ with CH4 is studied by mass spectrometry in combination with vibrational action spectroscopy and density functional theory (DFT). Two product ions, NiAl2O4H+ and NiAl2O3H2+, are identified in the mass spectra. The DFT calculations predict that the global minimum-energy isomer of NiAl2O4+ contains Ni in the +II oxidation state and features a terminal Al−O.- oxygen radical site. They show that methane can react along two competing pathways leading to formation of either a methyl radical (CH3⋅) or formaldehyde (CH2O). Both reactions are initiated by hydrogen atom transfer from methane to the terminal O.- site, followed by either CH3⋅ loss or CH3⋅ migration to an O2- site next to the Ni2+ center. The CH3⋅ attaches as CH3+ to O2- and its unpaired electron is transferred to the Ni-center reducing it to Ni+. The proposed mechanism is experimentally confirmed by vibrational spectroscopy of the reactant and two different product ions.