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Renewable ethylene can be obtained by dehydration of bio‐ethanol and used for production of vinyl acetate (VAM) through reaction with acetic acid (AcOH), using Pd−Cu catalysts. In the present manuscript, structural characterizations of Pd−Cu/ZrO2 catalysts show that these systems present cubic structure with different spatial distributions. Particularly, it is shown that combustion of ethylene and acetic acid can be inhibited below 180 °C, maximizing the rates of VAM formation, when the catalysts are modified with Ti+4. The effects of AcOH concentration on rates of VAM formation show that higher AcOH concentrations favor the formation of undesired byproducts, while lower AcOH concentrations favor effects related to O2 mobility, which can lead to surface decomposition. VAM formation is favored, with selectivities ranging from 0.8 to 1.0. XPS results indicate the existence of metallic Pd, CuO species and Zr species, in agreement with IR results. DRIFTS results also show that different Pd‐acetate intermediates can be present, depending on the electronic effects associated to Pd−Cu and Zr species. Order in the court: PdCu alloys over ZrO2 based catalysts were studied for Vinyl acetate synthesis. Interesting results were found, showing a structure feasible for acetoxidation process. Ligand effects were achieved at ZrO2 interphase with PdCu particles, promoting VAM desorption, due to the H spillover and surface hydroxyl recovery; However, the orientation of alloys suggest that ordered PdCu over ZrO2−Ti+4, enables efficiently the dehydrogenation step. [ABSTRACT FROM AUTHOR]

• Preparation of Pd-Cu catalysts over ZrO2 incorporating Al+3 and Ti+4 like promoters. • The Pd-Cu nanoarrays influence the O2 mobility in VAM synthesis. • The presence of Cu+2 in the lattice explains the promotion of Vinyl acetate monomer. • Statistical analyses were performed to find the main correlations of the products. • Microkinetical model was achieved from directions of fluctuations for Vinyl acetate. Catalytic oxidation is a suitable route for the production of oxygenated compounds from lignocellulose biomass, whose processing produce ethylene and AcOH like subproducts in first-generation ethanol production. Furthermore, the development of routes to convert green ethylene from renewable sources, have been motivating other possibles applications like green monomers, fuels, and fine chemicals. In this work we prepared Pd-Cu catalysts over ZrO 2 mixed oxides incorporating Al+3 and Ti+4 like promoters. The catalysts were characterized by XRD-in situ, BET, H 2 chemisorption and HRTEM. Catalytic tests were performed through experimental planning. Statistical analyses allowed to find the main correlations of the products. The PCA coefficients revealed that Vinyl acetate monomer formation was influenced by the AcOH and O 2 consumption at low ethylene coverage. Acetaldehyde emerged as an important intermediate for Vinyl acetate monomer synthesis. XRD results showed that the Pd-Cu catalyst exhibit tetragonal/orthorhombic nature with differences in the lattice position. The presence of Cu+2 in the lattice explains the promotion of Vinyl acetate monomer formation due to acetaldehyde formation, AcOH hydrogenation and posterior H 2 spillover, releasing the hydroxyl groups during Vinyl acetate monomer dehydrogenation from the active site. A microkinetical model was achieved from directions of fluctuations, indicating ethylene coupling and AcOH hydrogenation to produce Vinyl acetate monomer (VAM). [ABSTRACT FROM AUTHOR]