Methane‐to‐Methanol on Mononuclear Copper(II) Sites Supported on Al 2 O 3 : Structure of Active Sites from Electron Paramagnetic Resonance**
| Autor: | Gina Noh, Jordan Meyet, Andrew D. Horton, Gunnar Jeschke, Christophe Copéret, Anton Ashuiev, Jeroen A. van Bokhoven, Daniel Klose, Alexander P. van Bavel, Mark A. Newton, Keith Searles |
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| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
chemistry.chemical_element General Chemistry 010402 general chemistry Photochemistry 01 natural sciences Copper Catalysis Methane 0104 chemical sciences law.invention chemistry.chemical_compound Monomer chemistry law Phase (matter) Reactivity (chemistry) Methanol Electron paramagnetic resonance Organometallic chemistry |
| Zdroj: | Angewandte Chemie International Edition. 60:16200-16207 |
| ISSN: | 1521-3773 1433-7851 |
| DOI: | 10.1002/anie.202105307 |
| Popis: | The selective conversion of methane to methanol remains one of the holy grails of chemistry, where Cu-exchanged zeolites have been shown promote this reaction under stepwise conditions. Over the years, several active sites have been proposed, ranging from mono-, di- to trimeric CuII . Herein, we report the formation of well-dispersed monomeric CuII species supported on alumina using surface organometallic chemistry and their reactivity towards the selective and stepwise conversion of methane to methanol. Extensive studies using various transition alumina supports combined with spectroscopic characterization, in particular electron paramagnetic resonance (EPR), show that the active sites are associated with specific facets, which are typically found in γ- and η-alumina phase, and that their EPR signature can be attributed to species having a tri-coordinated [(Al2 O)CuIIO(OH)]- T-shape geometry. Overall, the selective conversion of methane to methanol, a two-electron process, involves two monomeric CuII sites that play in concert. |
| Databáze: | OpenAIRE |
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