Dynamic behavior of molecular Pd-acetate trimers and dimers in heterogeneous vinyl acetate synthesis #MMPMID41354743
Jacobs HP; Elias WC; Heck KN; Jiang S; Dodson JJ; Sandoval-Pauker C; Foucher AC; Cha BJ; Arredondo JH; Chen L; Mueller SG; Alexander SR; Senftle TP; Miller JT; Wong MS
Nat Commun 2025[Dec]; ? (?): ? PMID41354743show ga
Vinyl acetate monomer (VAM) is a crucial intermediate in the production of various polymers. While molecular Pd-acetate trimers and dimers, such as Pd(3)(OAc)(6) and K(2)Pd(2)(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 Pd(n)(OAc)(2n) species to form Pd(0) and PdC(x) nanoparticles. Conversely, noticeable quantities of K(n)Pd(2)(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.
Nat+Commun 2025 ; ? (?): ?
