Impregnation of KOAc on PdAu/SiO causes Pd-acetate formation and metal restructuring

Potassium-promoted, oxide-supported PdAu is catalytically active for the gas-phase acetoxylation of ethylene to form vinyl acetate monomer (VAM), in which the potassium improves long-term activity and VAM selectivity. The alkali metal is incorporated into the catalyst via wet impregnation of its salt solution, and it is generally assumed that this common catalyst preparation step has no effect on the catalyst structure. However, in this work, we report evidence to the contrary. We synthesized a silica-supported PdAu (PdAu/SiO 2 , 8 wt% Pd, 4 wt% Au) model catalyst containing Pd-rich PdAu alloy and pure Au phases. Impregnation with potassium acetate (KOAc) aqueous solution and subsequent drying did not cause XRD-detectible changes to the bimetal structure. However, DRIFTS indicated the presence of Pd 3 (OAc) 6 species, which is correlated to up to 2% Pd loss after washing of the dried KOAc-promoted PdAu/SiO 2 . Carrying out the impregnation step with an AcOH-only solution and subsequent drying caused significant enlargement of the pure Au grain size and generated a smaller amount of Pd 3 (OAc) 6 . During co-impregnation of AcOH and KOAc, grain sizes were enlarged slightly, and substantial amounts of K 2 Pd 2 (OAc) 6 and Pd 3 (OAc) 6 were detected by DRIFTS and correlated to up to 32% Pd loss after washing. Synchrotron XAS analysis showed that approximately half the Pd atoms were oxidized, corroborating the presence of the Pd-acetate species. These results indicate wet-impregnation-induced metal leaching can occur and be substantial during catalyst preparation. During catalyst preparation, the simple wet impregnation of KOAc on bimetallic PdAu/SiO 2 catalysts forms various Pd-acetate complexes, particularly at increasing concentrations of KOAc and AcOH, causing Pd leaching and metal restructuring.