Electrochemical Behavior and Shape Evolution of Structured Pd Nanoparticles in Alkaline Media─Influence of Electrochemically Absorbed Hydrogen.

We report on the electrochemical behavior and shape evolution of Pd nanocubes (Pd NCs) and Pd nanooctahedrons (Pd NOs) with an average size of 9.8 and 6.9 nm, respectively, in aqueous alkaline medium in the potential range of the underpotential deposition of H (UPD H) and H absorption. While the Pd NCs and Pd NOs remain stable in the potential region of the UPD H, H absorption and desorption of absorbed H (H) induce structural changes to the Pd NPs, as indicated by the results of electrochemical measurements and identical location-transmission electron microscopy (IL-TEM) analyses. Because both Pd NCs and Pd NOs are known to be stable in the potential region of H absorption and H desorption in acidic medium and maintain their structure, the irreversible structural changes are attributed to their interfacial interaction with the aqueous alkaline medium. In the alkaline medium, the nanoparticle surface/electrolyte interfacial structure plays an essential role in the mechanism of H desorption that is observed at higher potentials than that in the acidic medium. Hydrogen desorption is substantially hindered due to the structure of the water network adjacent to the Pd nanoparticles or the interaction between hydrated cations and adsorbed OH on the nanoparticle surface, resulting in the trapping of a small amount of H (incomplete H desorption). It is proposed that H trapping and associated structural strain lead to the deformation of the Pd nanoparticles and the loss of their initial structure.