Bis(μ-oxo) versus mono(μ-oxo)dicopper cores in a zeolite for converting methane to methanol: an in situ XAS and DFT investigation

Physical Chemistry Chemical Physics : PCCP
Evalyn M C AlayonJeroen A van Bokhoven

Abstract

Dicopper species have been identified as the active sites in converting methane to methanol in Cu-zeolites. To understand the formation of these copper cores in mordenite, we used in situ time-resolved X-ray absorption spectroscopy during heat treatment. Significant dehydration enabled the reduction of the copper cores, after which molecular oxygen was cleaved. The activated oxygen bridged two copper atoms to make the reactive precursor for the activation of methane. Even though the active bridging oxygen was detected, the XAS data were unable to distinguish a bis(μ-oxo)dicopper core from a mono(μ-oxo)dicopper core since XAS measures the average structure of the total copper population and the sample contains a mixture of copper species. We therefore used DFT calculations to understand the energetics of the formation of the active copper species and found that if a copper dimer exists in a zeolite, the mono(μ-oxo)dicopper species is an energetically plausible structure. This is in contrast to molecular dicopper cores where the bis(μ-oxo)dicopper core is preferentially formed.

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Citations

Mar 25, 2016·Angewandte Chemie·Patrick TomkinsJeroen A van Bokhoven
Apr 14, 2016·Journal of the American Chemical Society·Christopher PaolucciWilliam F Schneider
Jun 9, 2016·Annual Review of Chemical and Biomolecular Engineering·Carl Mesters
Jan 20, 2017·Chemical Reviews·Courtney E ElwellWilliam B Tolman
Mar 30, 2017·Chemical Communications : Chem Comm·Younhwa KimJongheop Yi
Mar 27, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Allen A C ReuleNatalia Semagina
Aug 8, 2018·Chemical Society Reviews·Elisa BorfecchiaSilvia Bordiga
Jun 24, 2017·Angewandte Chemie·Manoj RaviJeroen A van Bokhoven
Oct 5, 2018·Physical Chemistry Chemical Physics : PCCP·Zhenzhuo Lan, Shaama Mallikarjun Sharada
Sep 17, 2019·Chemical Communications : Chem Comm·Amy J KnorppJeroen A van Bokhoven
Jun 25, 2020·Physical Chemistry Chemical Physics : PCCP·Andrea MartiniSilvia Bordiga
May 6, 2017·Science·Vitaly L SushkevichJeroen A van Bokhoven
Feb 24, 2021·Physical Chemistry Chemical Physics : PCCP·Xi YuShenggang Li
Apr 1, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Olajumoke Adeyiga, Samuel O Odoh
Jun 15, 2021·Chemical Science·Vitaly L SushkevichJeroen A van Bokhoven
Sep 26, 2017·Journal of the American Chemical Society·Dimitrios K PappasPablo Beato
Feb 6, 2017·Accounts of Chemical Research·Patrick TomkinsJeroen A van Bokhoven
Jun 15, 2017·Journal of the American Chemical Society·Takaaki IkunoJohannes A Lercher
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Feb 23, 2019·Journal of Chemical Theory and Computation·Yuri Alexandre AotoAndreas Köhn
Dec 12, 2018·Journal of the American Chemical Society·Jayeon BaekOmar M Yaghi
Sep 15, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Dipak PanthiSamuel O Odoh
Sep 29, 2021·Angewandte Chemie·Gabriele DeplanoSilvia Bordiga

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