We show that methanol can be produced on copper (II) exchanged small-pore (i.e. 8-membered ring) zeolites including SSZ-13 (CHA), SSZ-16 (AFX) and SSZ-39 (AEI) at a temperature of 200 °C with yields as high as 39 µmol methanol/gzeolite and methanol/Cu ratios up to 0.09 (which are the largest reported to date). Previously, medium and large pore zeolites (MFI, MOR, FER) ion-exchanged with copper were shown to selectively convert methane to methanol with a methanol/Cu ratio of 0.03 and below.1 The reactive copper species on Cu-ZSM-5 was found to be a mono-μ-oxo-dicopper complex ([Cu—O—Cu]2+) based on an absorption feature at 22,700 cm-1 in UV–vis spectra1-2 and several unique features in resonance-enhanced Raman spectra.3 No evidence of mono-μ-oxo-dicopper species was found in the UV–vis spectra of Cu-SSZ-13, Cu-SSZ-16 and Cu-SSZ-39, however extra-framework Cu—O vibrations that cannot be assigned to mono-μ-oxo-dicopper species were detected in Raman spectra of Cu-SSZ-13 and Cu-SSZ-39 zeolites. We conclude that mono-μ-oxo-dicopper is not the reactive copper species on the small-pore zeolites that have been investigated, and we report evidence of a copper-oxygen complex that yet has to be identified. References: 1 E. M. Alayon, M. Nachtegaal, M. Ranocchiari, J. A. van Bokhoven, Chemm. Commun. 2012 48, 404 2 P. J. Smeets, M. H. Groothaert, R. A. Schoonheydt, Catal. Today 2005, 110, 303 3 J. S. Woertink, P. J. Smeets, M. H. Groothaert , M. A. Vance, B. F. Sels , R. A. Schoonheydt, E. I. Solomon, PNAS 2009 106, 18908

Methane to methanol conversion on copper-containing small-pore aeolites

249th National Meeting (2015)

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