Activity of Cu-Al-oxo extra-framework clusters for selective methane oxidation on Cu exchanged zeolites

Lee, Insu; Lee, Mal Soon; Tao, Lei; Ikuno, Takaaki; Khare, Rachit; Jentys, Andreas; Huthwelker, Thomas; Borca, Camelia; Kalinko, Aleksandr; Gutierrez-Tinoco, Oliver Y.; Govind, Niranjan; Fulton, John L.; Hu, Jian Z.; Glezakou, Vassiliki-Alexandra; Rousseau, Roger J.; Sanchez-Sanchez, Maricruz; Lercher, Johannes A.

doi:10.1021/jacsau.1c00196

Title: Activity of Cu-Al-oxo extra-framework clusters for selective methane oxidation on Cu exchanged zeolites

Journal Article · Wed Jul 14 00:00:00 EDT 2021 · JACS Au

DOI:https://doi.org/10.1021/jacsau.1c00196· OSTI ID:1829498

Lee, Insu ^[1];

^[2]; Tao, Lei ^[1]; Ikuno, Takaaki ^[1]; Khare, Rachit ^[1]; Jentys, Andreas ^[1]; Huthwelker, Thomas ^[3]; Borca, Camelia ^[3]; Kalinko, Aleksandr ^[4];

^[2];

^[2]; Fulton, John L. ^[2];

^[2];

^[2]; Rousseau, Roger J. ^[2]; Sanchez-Sanchez, Maricruz ^[1];

^[2]

Technische Universitat Munchen
BATTELLE (PACIFIC NW LAB)
Paul Scherrer Institut
Photon Science DESY

Cu-zeolites are able to directly convert methane to methanol via a 3-step process using O2 as oxidant. Among the different zeolite topologies, Cu-exchanged mordenite (MOR) shows the highest methanol yields, attributed to a preferential formation of active Cu-oxo species in its 8-MR pores. The presence of extra-framework or partially detached Al species entrained in the micropores of MOR leads to the formation of nearly homotopic redox active Cu-Al-oxo nanoclusters with the ability to activate CH4. Studies of the activity of these sites together with characterization by 27Al NMR and IR spectroscopy leads to the conclusion that the active species are located in the 8-MR side pockets of MOR and it consists of two Cu ions and one Al linked by O. This Cu-Al oxo cluster shows an activity per Cu in methane oxidation significantly higher than of any previ-ously reported active Cu-oxo species. In order to determine unambiguously the structure of the active Cu-Al-oxo cluster, we combine experimental XANES of Cu K- and L- edges, Cu K-edge HERFD-XANES and Cu K-edge EXAFS with TDDFT and AIMD-assisted simulations. Our results provide evidence of a [Cu2AlO3]2+ cluster exchanged on MOR Al pairs that is able to oxidize up to two methane molecules per cluster at ambient pressure.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1829498

Report Number(s):: PNNL-SA-160856

Journal Information:: JACS Au, Vol. 1, Issue 9

Country of Publication:: United States

Language:: English

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