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EPR and DFT study of the ethylene reaction with O− radicals on the surface of nanocrystalline MgO

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Abstract

Different radical forms of oxygen (O−, O −2 and O −3 ) on the surface of nanocrystalline MgO are well known. It was earlier demonstrated that EPR-silent species with properties very similar to those of O− radicals exist on the surface of magnesium oxide in addition to the O− radicals observed by EPR. In this study we characterized the reactivity of these two types of O− radicals in reaction with ethylene. It was demonstrated that this reaction yields different products for observable and unobservable O− radicals. Conventional \({\text{O}}_{{3{\text{C}}}}^{ - }\) radicals generated by MgO illumination with UV light at room temperature in the presence of oxygen initiate hydrogen atom abstraction from ethylene to form secondary radicals H2C=C− with hyperfine splitting A 1 = 59 G, A 2 = 6 G. The \({\text{O}}_{{4{\text{C}}}}^{ - }\) radicals not observed directly by EPR were synthesized by MgO illumination in the presence of oxygen at 163 K followed by evacuation at 203 K. They were shown to react with ethylene to form an addition product with two groups of two equivalent protons with isotropic hyperfine constants A 1 = 38 G and A 2 = 23 G. Such radicals were obtained for the first time by reaction of O− radicals with ethylene on the MgO surface. Their concentration was approximately equal to the concentration of [\({\text{O}}_{{4{\text{C}}}}^{ - }\)·O2] complexes observed by EPR before the oxygen desorption. The structures of both radicals were simulated by DFT, and a good match between the experimental and computational results was obtained.

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Acknowledgments

This work was supported in part by Russian Foundation for Basic Research (Grants 14-03-01110-a and 15-03-08070-a).

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Authors and Affiliations

  1. Boreskov Institute of Catalysis SB RAS, Prospekt Lavrentieva 5, Novosibirsk, Russia, 630090

    Alexander M. Volodin, Vasilii I. Avdeev, Sergei E. Malykhin & Alexander F. Bedilo

  2. Novosibirsk Institute of Technology, Moscow State University of Design and Technology Branch, Krasny Prospekt 35, Novosibirsk, Russia, 630099

    Alexander F. Bedilo

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  1. Alexander M. Volodin
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  2. Vasilii I. Avdeev
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Correspondence to Alexander F. Bedilo.

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Volodin, A.M., Avdeev, V.I., Malykhin, S.E. et al. EPR and DFT study of the ethylene reaction with O− radicals on the surface of nanocrystalline MgO. Res Chem Intermed 43, 1047–1061 (2017). https://doi.org/10.1007/s11164-016-2682-9

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