Atomic-scale selectivity of hydrogen for storage sites in Pd nanoparticles at atmospheric pressure

Hydrogen-storage materials are important carriers for a viable hydrogen economy. Despite palladium being the most studied storage material, the hydrogen-storage mechanism of Pd remains ambiguous owing to the lack of atomic-scale evidence of the diffusion and storage of H atoms in its lattice. In the study reported here, this classical process was investigated on the atomic scale using an in situ transmission electron microscope equipped with an atmospheric-pressure sample holder. The expansion of the Pd interplanar spacings was found to comprise three distinct stages during the diffusion of H atoms. Moreover, the expansion in d-spacing of Pd{111} was markedly different from that of Pd{220}. First-principles calculations indicate that H atoms mainly occupy the centers of the tetrahedral cages in the Pd unit cells during the diffusion stage, and they eventually occupy the octahedral cage centers in the equilibrium state. Moreover, H atoms were detected in substantially high densities in defects such as stacking faults and twin boundaries. These observations on the preferred hydrogen-storage domains can help clarify the hydrogen-storage mechanism and offer guidelines on the future design of higher-capacity hydrogen-storage materials.