Hydrogen Generation from Water Splitting by 3H₂O + Pd₁₃ → 3H₂ + Pd₁₃O₃ Reaction

Abstract The Pd clusters are widely concerned because of their outstanding catalytic capacity. Here such a candidate of Pd₁₃ cluster with the icosahedron symmetry and multiple active sites is shown. The first‐principles calculations reveal that this cluster can maximally catalyze the water‐splitting reaction to generate three H₂ from three H₂O molecules. The geometrical structures of the reactants, transition states, and products are optimized, and their stabilities are confirmed by the frequency analysis. The intrinsic reaction coordinates are constructed to confirm the rationality of the reaction. Firstly, one H₂O is adsorbed on atop sites of the Pd₁₃ cluster and releases an H₂ through a reaction of H₂O@Pd₁₃ → H₂@[O+Pd₁₃]. Then, the remained O+Pd₁₃ cluster can continually split H₂O and generate additional H₂, and the obtained 2O+Pd₁₃ cluster can also dissociate H₂O to generate H₂. However, it is found that the 3O+Pd₁₃ cluster cannot continue the splitting reaction. It is also observed that the O+Pd₁₃ cluster can adsorb two molecules at the same time and split them one by one. These findings support that the Pd₁₃ cluster, O+Pd₁₃, and 2O+Pd₁₃ are promising candidates for efficient generation of H₂ from H₂O splitting reaction.