Elucidating the mechanism of heterogeneous Wacker oxidation over Pd-Cu/zeolite Y by transient XAS

The heterogenization of Wacker catalysts using chloride-free systems can potentially be a good alternative for the commercial homogeneous Wacker oxidation of ethylene, which utilizes excessive aqueous chloride solvents. However, the mechanism of the heterogeneous system has not been clarified, preve...

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Bibliographic Details
Published in:Nature communications 2020-02, Vol.11 (1), p.1118-1118, Article 1118
Main Authors: Imbao, Jerick, van Bokhoven, Jeroen A., Clark, Adam, Nachtegaal, Maarten
Format: Article
Language:English
Subjects:
140/58
147/137
639/638/440/950
639/638/77/885
639/638/77/887
Carbon dioxide
Catalysts
Chlorides
Copper
Humanities and Social Sciences
multidisciplinary
Oxidation
Redox reactions
Science
Science (multidisciplinary)
X ray absorption
Zeolites
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Summary:The heterogenization of Wacker catalysts using chloride-free systems can potentially be a good alternative for the commercial homogeneous Wacker oxidation of ethylene, which utilizes excessive aqueous chloride solvents. However, the mechanism of the heterogeneous system has not been clarified, preventing the rational design of better catalysts. Here, we report a transient X-ray absorption spectroscopic (XAS) investigation of the heterogeneous Wacker oxidation over Pd-Cu/zeolite Y coupled with kinetic studies and chemometric analysis. Insight is obtained by operando quickXAS allowing the quantitative determination of rates and thereby revealing a rapid redox reaction involving copper. Our work demonstrates that copper is not only the site of oxygen activation, but is also involved in the formation of undesired carbon dioxide. Without detecting the presence of Cu(0) and Pd(I), our results suggest that two one-electron transfers to two Cu(II) ions to reoxidize Pd(0) is at work in this heterogeneous Wacker catalyst. Unlike the homogeneous Wacker process, understanding of the mechanism of the heterogeneous system remains superficial. Here, the authors investigate the mechanism of heterogeneous Wacker oxidation over Pd-Cu/zeolite Y through the synergistic combination of kinetic, spectroscopic and chemometric studies.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-020-14982-x