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Cu-Exchanged Ferrierite Zeolite for the Direct CH4 to CH3OH Conversion: Insights on Cu Speciation from X-Ray Absorption Spectroscopy

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Abstract

The direct stepwise transformation of CH4 to CH3OH over Cu-exchanged zeolites has been an intensively researched reaction as it can provide a solution for the utilization of this abundant feedstock. Up to date a commercial process is far from realization, which is why an understanding of the Cu speciation in zeolites as a function of reaction conditions as well as the development of a mechanistic view of the reaction are necessary to further advance the field. Herein we study Cu-exchanged ferrierite zeolite for the direct CH4 to CH3OH conversion by utilizing X-ray absorption spectroscopy (XAS), in order to assess the local structure and electronic properties of Cu through the reaction. A Cu-FER sample with a Cu/Al = 0.20 and Si/Al = 11 was subjected to three reaction cycles yielding ultimately 96 µmol\(_{{{\text{C}}{{\text{H}}_3}{\text{OH}}}}/{{\text{g}}_{{\text{zeolite}}}}\). Normalized to the Cu loading, this accounts for 0.33 mol\(_{{{\text{C}}{{\text{H}}_3}{\text{OH}}}}\)/molCu, making the sample comparable to very active Cu-MOR materials reported in the literature. During O2 activation, a transient self-reduction regime of CuII to CuI ions was identified; eventually leading to mostly framework interacting CuII species. CH4 loading leads to a reduction of these CuII containing species; which are finally partially reoxidized during H2O-assisted CH3OH extraction. The speciation after CH4 activation as well as H2O-assisted CH3OH extraction was assessed via linear combination fitting analysis of the XAS data.

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Acknowledgements

This publication forms a part of the iCSI (industrial Catalysis Science and Innovation) Centre for Research-based Innovation, which receives financial support from the Research Council of Norway under contract no. 237922. EB acknowledges Innovation Fund Denmark (Industrial postdoc n. 5190-00018B). CL and AM acknowledge the Mega-grant of the Russian Federation Government to support scientific research at the Southern Federal University, No. 14.Y26.31.0001. We thank W. van Beek for the competent support during XAS experiments on the BM31 beamline of the ESRF. We are grateful to K. P. Lillerud for insightful discussions.

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Authors and Affiliations

  1. Center for Materials Science and Nanotechnology (SMN), Department of Chemistry, University of Oslo, 1033 Blindern, 0315, Oslo, Norway

    Dimitrios K. Pappas, Andrea Lazzarini, Emil S. Gutterød, Michael Dyballa, Silvia Bordiga, Unni Olsbye & Stian Svelle

  2. Haldor Topsøe A/S, Haldor Topsøes Allé 1, 2800, Kongens Lyngby, Denmark

    Elisa Borfecchia & Pablo Beato

  3. Department of Chemistry, NIS Centre and INSTM Reference Center, University of Turin, via P. Giuria 7, 10125, Turin, Italy

    Elisa Borfecchia, Gloria Berlier & Silvia Bordiga

  4. European Synchrotron Radiation Facility, 71 avenue des Martyrs, CS 40220, 38043, Grenoble, Cedex 9, France

    Kirill A. Lomachenko

  5. SINTEF Industry, Forskningsveien 1, 0373, Oslo, Norway

    Michael Dyballa & Bjørnar Arstad

  6. Smart Materials Research Institute, Southern Federal University, Sladkova Street 174/28, Rostov-on-Don, Russia, 344090

    Andrea Martini & Carlo Lamberti

  7. Department of Physics, INSTM Reference Center, CrisDi Interdepartmental Center, University of Turin, via P. Giuria 1, 10125, Turin, Italy

    Andrea Martini & Carlo Lamberti

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  1. Dimitrios K. Pappas
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  10. Carlo Lamberti
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Correspondence to Dimitrios K. Pappas, Silvia Bordiga or Pablo Beato.

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Pappas, D.K., Borfecchia, E., Lomachenko, K.A. et al. Cu-Exchanged Ferrierite Zeolite for the Direct CH4 to CH3OH Conversion: Insights on Cu Speciation from X-Ray Absorption Spectroscopy. Top Catal 62, 712–723 (2019). https://doi.org/10.1007/s11244-019-01160-7

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