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Methane to methanol: structure-activity relationships for Cu-CHA

Abstract

Cu-exchanged zeolites possess active sites that are able to cleave the C–H bond of methane at temperatures ≤200 °C, enabling its selective partial oxidation to methanol. Herein we explore this process over Cu-SSZ-13 materials. We combine activity tests and X-ray absorption spectroscopy (XAS) to thoroughly investigate the influence of reaction parameters and material elemental composition on the productivity and Cu speciation during the key process steps. We find that the CuII moieties responsible for the conversion are formed in the presence of O2 and that high temperature together with prolonged activation time increases the population of such active sites. We evidence a linear correlation between the reducibility of the materials and their methanol productivity. By optimizing the process conditions and material composition, we are able to reach a methanol productivity as high as 0.2 mol CH3OH/mol Cu (125 μmol/g), the highest value reported to date for Cu-SSZ-13. Our results clearly demonstrate that high populations of 2Al Z2CuII sites in 6r, favored at low values of both Si:Al and Cu:Al ratios, inhibit the material performance by being inactive for the conversion. Z[CuIIOH] complexes, although shown to be inactive, are identified as the precursors to the methane-converting active sites. By critical examination of the reported catalytic and spectroscopic evidence, we propose different possible routes for active-site formation.
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Category

Academic article

Language

English

Author(s)

  • Dimitrios Pappas
  • Elisa Borfecchia
  • Michael Martin Dyballa
  • Ilia A. Pankin
  • Kirill A. Lomachenko
  • Andrea Martini
  • Matteo Signorile
  • Shewangizaw Teketel
  • Bjørnar Arstad
  • Gloria Berlier
  • Carlo Lamberti
  • Silvia Bordiga
  • Unni Olsbye
  • Karl Petter Lillerud
  • Stian Svelle
  • Pablo Beato

Affiliation

  • SINTEF Industry / Process Technology
  • Haldor Topsoe A/S
  • European Synchrotron Radiation Facility
  • University of Turin
  • Southern Federal University
  • University of Oslo

Date

25.09.2017

Year

2017

Published in

Journal of the American Chemical Society

ISSN

0002-7863

Volume

139

Issue

42

Page(s)

14961 - 14975

View this publication at Norwegian Research Information Repository