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<p>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><i>n</i></sub>(OAc)<sub>2<i>n</i></sub> species to form Pd<sup>0</sup> and PdC<sub><i>x</i></sub> nanoparticles. Conversely, noticeable quantities of K<sub><i>n</i></sub>Pd<sub>2</sub>(OAc)<sub><i>n</i>+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.</p>

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Dynamic behavior of molecular Pd-acetate trimers and dimers in heterogeneous vinyl acetate synthesis

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年12月8日

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  • Hunter P. Jacobs,
  • Welman C. Elias,
  • Kimberly N. Heck,
  • Shan Jiang,
  • Justin J. Dodson,
  • Christian Sandoval-Pauker,
  • Alexandre C. Foucher,
  • Byeong Jun Cha,
  • Jacob H. Arredondo,
  • Laiyuan Chen,
  • Sean G. Mueller,
  • Steven R. Alexander,
  • Thomas P. Senftle,
  • Jeffrey T. Miller,
  • Michael S. Wong

摘要

Vinyl acetate monomer (VAM) is a crucial intermediate in the production of various polymers. While molecular Pd-acetate trimers and dimers, such as Pd3(OAc)6 and K2Pd2(OAc)6, 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 Pdn(OAc)2n species to form Pd0 and PdCx nanoparticles. Conversely, noticeable quantities of KnPd2(OAc)n+4 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.