Abstract: It is generally acknowledged in heterogeneous catalysis that hydrogenation follows the so-called Horiuti-Polanyi (HP) mechanism. In this work, a thorough investigation of the mechanism of hydrogenation of hydroxyl groups and O catalyzed by a series of transition metals was carried out through density functional theory calculations, as surface hydroxyls and O are very common species in many catalytic systems. It is found that different metal catalysts exhibit different mechanisms. On some metal catalysts, the non-HP mechanism is preferred, whereas the classic HP mechanism is favored on other catalysts. Detailed analyses of the metal-dependent mechanism shows that the activity toward the dissociation of H₂ decides which mechanism is preferred. On active catalysts, such as Ni and Pt, H₂ prefers to dissociate with strong H adsorption energies, which lead to the classic HP mechanism being favored. On inactive surfaces, on the other hand, the adsorption of H is weak, which results in the non-HP mechanism being preferred. The parameter η, which is a structural descriptor, was defined to understand the different mechanisms.

Key words: Hydrogenation, Horiuti-Polanyi mechanism, Water formation, Transition metal, Density functional theory