Deciphering the reaction network for the acetoxylation of propylene to allyl acetate on PdCu catalysts combined DFT with kMC analysis

• Surface models of PdCu catalysts with different Cu segregations were constructed. • Reaction mechanism for propylene acetoxylation on PdCu catalysts was revealed. • The formation mechanism of byproduct CO 2 on PdCu catalysts was clarified. • The dominant paths for the formation of allyl acetate and CO 2 were investigated. • The effect of temperature on propylene acetoxylation to allyl acetate was studied. The acetoxylation of propylene to allyl acetate on PdCu catalysts is a critical step in the Lyondell method for BDO production. By combining Density Functional Theory and kinetic Monte Carlo simulations, the reaction network and the formation pathways of allyl acetate and CO 2 were systematically studied. Propylene and acetic acid were both activated by oxygen-assisted dehydrogenation to obtain CH 3 COO* and CH 2 CHCH 2 *, which would participate in the C-O coupling reaction to form allyl acetate, with the apparent activation energy of 0.64 eV. Besides, the dominant paths for the formation of CO 2 from the complete oxidation of propylene and acetic acid were identified with the apparent activation energy of 1.80 eV. As the temperature rises, the TOF of allyl acetate and CO 2 formation increase gradually, while the molar fraction of allyl acetate in the products decreases, indicating that temperature exerts a greater influence on the formation of CO 2 than allyl acetate.