TY - JOUR
T1 - Dynamic behavior of molecular Pd-acetate trimers and dimers in heterogeneous vinyl acetate synthesis
AU - Jacobs, Hunter P.
AU - Elias, Welman C.
AU - Heck, Kimberly N.
AU - Jiang, Shan
AU - Dodson, Justin J.
AU - Sandoval-Pauker, Christian
AU - Foucher, Alexandre C.
AU - Cha, Byeong Jun
AU - Arredondo, Jacob H.
AU - Chen, Laiyuan
AU - Mueller, Sean G.
AU - Alexander, Steven R.
AU - Senftle, Thomas P.
AU - Miller, Jeffrey T.
AU - Wong, Michael S.
N1 - Publisher Copyright:
© The Author(s) 2025.
PY - 2026/12
Y1 - 2026/12
N2 - 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.
AB - 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.
UR - https://www.scopus.com/pages/publications/105026888980
U2 - 10.1038/s41467-025-66820-7
DO - 10.1038/s41467-025-66820-7
M3 - Article
C2 - 41354743
AN - SCOPUS:105026888980
SN - 2041-1723
VL - 17
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 127
ER -