Buta-1,3-diene hydrogenation and but-1-ene hydrogenation and isomerization were studied on low-loaded Pd/alpha-Al2O3 catalysts (0.1-0.3 wt.%) prepared from palladium acetylacetonate (Pd(C5H7O2)(2)). Deuterium tracer study, hydrogen chemisorption, transmission electron microscopy, and X-ray photoelectron spectroscopy analysis were used to establish the relationships between metal-support interactions, particle shapes, and buta-1,3-diene and but-1-ene hydrogenation and isomerization mechanisms. It was found that the hydrogenation reaction rates (turnover frequencies) are similar for buta-1,3-diene and but-1-ene, but 10 times lower for the 0.1% Pd catalyst compared to the 0.3% Pd catalyst. However, the 0.1% Pd catalyst has a high activity for the isomerization reaction which leads to 98% selectivity in isomers for the but-1-ene reaction. This unusual specific activity is explained considering that the 0.1% Pd catalyst contains flat particles in strong interaction with the support, as was deduced from several characterization methods, while the 0.3% Pd catalyst has more rugged bulk type particles after H-2 treatments because they are not interacting with the support.