Thermodynamics of the hybrid interaction of hydrogen with palladium nanoparticles

Palladium-hydrogen is a prototypical metal-hydrogen system. It is therefore not at all surprising that a lot of attention has been devoted to the absorption and desorption of hydrogen in nanosized palladium particles. Several seminal articles on the interaction of H with Pd nanocubes and nanoparticles have recently been published. Although each article provides for the first time detailed data on specific aspects of hydrogen in nanoparticles, they individually do not contain enough information to draw firm conclusions about the involved mechanisms. Here, we show that the large body of data available so far in literature exhibits general patterns that lead to unambiguous conclusions about the processes involved in H absorption and desorption in Pd nanoparticles. On the basis of a remarkably robust scaling law for the hysteresis in absorption-desorption isotherms, we show that hydrogen absorption in palladium nanoparticles is consistent with a coherent interface model and is thus clearly different from bulk Pd behaviour. However, H desorption occurs fully coherently only for small nanoparticles (typically smaller than 50 nm) at temperatures sufficiently close to the critical temperature. For larger particles it is partially incoherent, as in bulk, where dilute α-PdHx and high concentration β-PdHx phases coexist.