New mechanism of the direct pathway for formic acid oxidation on Pd(1 1 1)

By performing density functional theory calculations, we have evaluated the detailed mechanism of formic acid (HCOOH) oxidation process on Pd(1 1 1) surface, including geometric structures and energies of intermediates and transition states. Our calculations indicate that the co-adsorbed (H2O)2 or HCOOH plays an important role in influencing the initial adsorption configurations of HCOOH. For the first time, pathways of HCOOH decomposition in presence of (H2O)2 or HCOOH regarding the preference of CO2 formation are proposed.