Hydride formation pressures and kinetics in individual Pd nanoparticles with systematically varied levels of plastic deformation.

Abstract

Pd nanoparticles, together with bulk and thin film Pd, constitute the archetype model system for metal-hydrogen interactions. The density of defects in Pd nanoparticles, such as grain boundaries and dislocations, combined with their size, shape, composition and lattice strain, dictate their hydrogen sorption kinetics and thermodynamics. Despite decades of research and its relevance in applications, such as solid-state hydrogen storage, hydrogen sensors, hydrogen embrittlement, and hydrogen separation membranes, a coherent picture of the intricate interplay between defects, strain and Pd nanoparticle hydrogen sorption properties is missing. Here, we employ a combination of single particle nanocompression, single particle plasmonic nanoimaging and high-resolution cross-sectional single particle TEM imaging to investigate hydrogen absorption kinetics and hydride phase formation pressures in a nanofabricated array of Pd nanoparticles on sapphire substrate with systematically varied levels of plastic deformation - and thus defects and strain. We not only show a clear deformation-level dependent trend of both the kinetics and the hydride formation pressure, but also reveal their complex evolution upon hydrogen cycling. We discuss how these results provide a quantitative view of the impact of plastic deformation on nanoscale metal hydrides, and how they reveal the surface and bulk morphology of Pd nanoparticles upon repeated hydrogen cycling.