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 Pd 13 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 H 2 from three H 2 O 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 H 2 O is adsorbed on atop sites of the Pd 13 cluster and releases an H 2 through a reaction of H 2 O@Pd 13 → H 2 @[O+Pd 13 ]. Then, the remained O+Pd 13 cluster can continually split H 2 O and generate additional H 2 , and the obtained 2O+Pd 13 cluster can also dissociate H 2 O to generate H 2 . However, it is found that the 3O+Pd 13 cluster cannot continue the splitting reaction. It is also observed that the O+Pd 13 cluster can adsorb two molecules at the same time and split them one by one. These findings support that the Pd 13 cluster, O+Pd 13 , and 2O+Pd 13 are promising candidates for efficient generation of H 2 from H 2 O splitting reaction.