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Research article2021Peer reviewedOpen access

Investigation of the Deactivation and Reactivation Mechanism of a Heterogeneous Palladium(II) Catalyst in the Cycloisomerization of Acetylenic Acids by In Situ XAS

Yuan, Ning; Gudmundsson, Arnar; Gustafson, Karl P. J.; Oschmann, Michael; Tai, Cheuk-Wai; Persson, Ingmar; Zou, Xiaodong; Verho, Oscar; Bajnoczi, Eva G.; Backvall, Jan-E

Abstract

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

Keywords

X-ray absorption spectroscopy; cycloisomerization; deactivation/reactivation; heterogeneous; palladium catalysis

Published in

ACS Catalysis
2021, Volume: 11, number: 5, pages: 2999-3008
Publisher: AMER CHEMICAL SOC

      SLU Authors

        • UKÄ Subject classification

        Physical Chemistry

        More information

        Correction in ACS Catalysis, 2022, 12, (6), 3410. https://doi.org/10.1021/acscatal.2c00853

        Publication identifier

        DOI: https://doi.org/10.1021/acscatal.0c04374

        Permanent link to this page (URI)

        https://res.slu.se/id/publ/111516