Pure hydrogen is not only one of the key ingredients in chemistry industries, but also the future fuel sources for proton-exchange membrane fuel cells and especially controlled fusion reactors. Pd and Pd−based membranes are the only commercial products for H separation and purification, which are influenced by various point defects, including vacancies and substitutional atoms. In this work, the design rationale for H diffusion process in Pd−based membranes is elucidated by intentionally modulating the electronic interaction between vacancy and H. Adding (removing) one itinerant electron in the Pd-Vacancy system strengthens (weakens) the directional bonding between H and Pd, thus facilitating (impeding) H diffusion in Pd. Extra condition is supplemented to the Hume-Rothery rules for the design of solid-solution Pd−based membranes for faster H diffusion, that is a lower-electronegativity (χ) element accelerates H diffusion by providing extra bonding electrons, while a higher one has opposite effect. Solute elements Ag (χ = 1.93), Ir (2.20), and W (2.36) in Pd (2.20) are chosen to demonstrate our design principle in real Pd-based membranes. The good agreement between experimental and theoretical results confirms the effectiveness and soundness of this new rationale, and also sheds insights into the physical picture of the complex interaction between point defects.
Read full abstract