Dynamic behavior of molecular Pd-acetate trimers and dimers in heterogeneous vinyl acetate synthesis
Vinyl acetate monomer (VAM) is a crucial intermediate in the production of various polymers. While molecular Pd-acetate trimers and dimers, such as Pd<sub>3</sub>(OAc)<sub>6</sub> and K<sub>2</sub>Pd<sub>2</sub>(OAc)<sub>6</sub>, are known to form on potassium acetate (KOAc)-promoted PdAu catalysts during heterogeneous VAM synthesis, their mechanistic role remains unclear. Here, we study the dynamics of different Pd-acetate species by utilizing in situ and operando crystallographic and spectroscopic characterizations combined with computational modeling on monometallic Pd model catalysts. The promoter-free catalyst expectedly shows low catalytic activity and VAM selectivity, corresponding to the complete reduction of Pd<sub>n</sub>(OAc)<sub>2n</sub> species to form Pd<sup>0</sup> and PdC<sub>x</sub> nanoparticles. Conversely, noticeable quantities of K<sub>n</sub>Pd<sub>2</sub>(OAc)<sub>n+4</sub> species remain on the KOAc-promoted catalyst, leading to smaller nanoparticle formation with 10 times the activity and double the selectivity for VAM. This study reveals that molecular Pd-acetate trimers and dimers are significant indicators of catalytic performance and highlights their structurally dynamic nature in heterogeneous vinyl acetate chemistry.
Authors
- Laiyuan Chen
- Alexandre C. Foucher (ORCID: https://orcid.org/0000-0001-5042-4002)
- Jeffrey T. Miller (ORCID: https://orcid.org/0000-0002-6269-0620)
- Byeong Jun (ORCID: https://orcid.org/0000-0002-8703-2309)
- Michael S. Wong (ORCID: https://orcid.org/0000-0002-3652-3378)
- Sean G. Mueller
- Kimberly N. Heck (ORCID: https://orcid.org/0000-0001-6676-9881)
- Justin J. Dodson
- Thomas P. Senftle (ORCID: https://orcid.org/0000-0002-5889-5009)
- Jacob Arredondo (ORCID: https://orcid.org/0000-0001-5052-5807)
- Welman C. Elias (ORCID: https://orcid.org/0000-0002-9792-7392)
- Hunter P. Jacobs (ORCID: https://orcid.org/0000-0001-6190-874X)
- Christian Sandoval‐Pauker (ORCID: https://orcid.org/0000-0002-7831-331X)
- Shan Jiang (ORCID: https://orcid.org/0000-0002-1314-2695)
- Steven Alexander
Institutions
- Seoul National University of Science and Technology (KR)
- Oak Ridge National Laboratory (US)
- Celanese (United States) (US)
- Purdue University West Lafayette (US)
- Rice University (US)
Publication Details
- Journal
- Nature Communications
- Published
- 2025-12-08
- DOI
- https://doi.org/10.1038/s41467-025-66820-7
- Citations
- 1
- Primary Topic
- Catalysis for Biomass Conversion
- Type
- article
- Field-Weighted Citation Impact
- 0.67
Funders
- U.S. Department of Energy
- Office of Science
- Oak Ridge National Laboratory
- Brookhaven National Laboratory
- National Renewable Energy Laboratory