Solid-State Ion-Exchanged Cu/Mordenite Catalysts for the Direct Conversion of Methane to Methanol

http://pubs.acs.org/doi/abs/10.1021/acscatal.6b02372

Ha V. Le†, Samira Parishan‡, Anton Sagaltchik§, Caren Göbel∥, Christopher Schlesiger⊥, Wolfgang Malzer⊥, Annette Trunschke# , Reinhard Schomäcker‡, and Arne Thomas*† 

† Institute of Chemistry−Functional Materials, Technische Universität Berlin, BA2, Hardenbergstraße 40, 10623 Berlin, Germany

‡ Institute of Chemistry−Technical Chemistry, Technische Universität Berlin, TC8, Straße des 17. Juni 124, 10623 Berlin, Germany

§ BasCat−UniCat BASF Joint Lab, Technische Universität Berlin, EW K 01, Hardenbergstraße 36, 10623 Berlin, Germany

∥ Institute of Chemistry, Technische Universität Berlin, TK01, Straße des 17. Juni 135, 10623 Berlin, Germany

⊥ Institute of Optics and Atomic Physics, Technische Universität Berlin, Hardenbergstraße 36, 10623 Berlin, Germany

# Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany

ACS Catal., 2017, 7, pp 1403–1412

DOI: 10.1021/acscatal.6b02372

The selective oxidation of methane to methanol is a highly challenging target, which is of considerable interest to gain value-added chemicals directly from fuel gas. Copper-containing zeolites, such as Cu/mordenite, have been currently reported to be the most efficient catalysts for this reaction. In this work, it is shown that solid-state ion-exchanged Cu/mordenites exhibit a significantly higher activity for the partial oxidation of methane to methanol than comparable reference catalysts, i.e., Cu/mordenites prepared by the conventional liquid-phase ion exchange procedure. The efficiency of these Cu/mordenites remained unchanged over several successive cycles. From temperature-programmed reduction (TPR) measurements, it can be concluded that the solid-state protocol accelerates Cu exchange at the small pores of mordenite: those are positions where the most active Cu species are presumably located. In situ ultraviolet–visible (UV-vis) spectroscopy furthermore indicates that different active clusters including dicopper- and tricopper-oxo complexes are formed in the catalyst upon oxygen treatment. Notably after activation of methane, different methoxy intermediates seem to be generated at the Cu sites from which one is preferably transformed to methanol by reaction with water. It is furthermore described that the applied reaction conditions have considerable influence on the finally observed methanol production from methane.

Keywords: 

methane hydroxylation; methane monooxygenase; microporous; mordenite; selective oxidation; zeolites