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

Journal Article · · ACS Catalysis
 [1];  [2];  [3];  [4];  [2];  [5];  [2];  [6];  [7];  [8]
  1. Stockholm Univ. (Sweden). Arrhenius Lab. Dept. of Materials and Environmental Chemistry; Swedish Univ. of Agricultural Sciences, Uppsala (Sweden). Dept. of Molecular Sciences; OSTI
  2. Stockholm Univ. (Sweden). Arrhenius Lab. Dept. of Materials and Environmental Chemistry
  3. Stockholm Univ. (Sweden). Arrhenius Lab. Dept. of Materials and Environmental Chemistry; Stockholm Univ. (Sweden). Arrhenius Lab. Dept. of Organic Chemistry
  4. Stockholm Univ. (Sweden). Arrhenius Lab. Dept. of Organic Chemistry
  5. Swedish Univ. of Agricultural Sciences, Uppsala (Sweden). Dept. of Molecular Sciences
  6. Stockholm Univ. (Sweden). Arrhenius Lab. Dept. of Organic Chemistry; Swedish Univ. of Agricultural Sciences, Uppsala (Sweden). Dept. of Molecular Sciences; Uppsala Univ. (Sweden). Uppsala Biomedical Centre. Dept. of Medicinal Chemistry
  7. Swedish Univ. of Agricultural Sciences, Uppsala (Sweden). Dept. of Molecular Sciences; Wigner Research Centre for Physics, Budapest (Hungary)
  8. Stockholm Univ. (Sweden). Arrhenius Lab. Dept. of Organic Chemistry; Mid Sweden Univ., Sundsvall (Sweden). Dept. of Natural Sciences
+ Show Author Affiliations
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.
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1816328
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 5 Vol. 11; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
X-ray absorption spectroscopy
cycloisomerization
deactivation/reactivation
heterogeneous
palladium catalysis