Selective hydride interstitials induced in a high-entropy lanthanide oxyhydride
Year:2024DOI:10.1021/acs.chemmater.4c01617
Extra Information
Yuvraj Vaishnav, Rohit K. Rai, Walid Al Maksoud, Fumitaka Takeiri, Shusaku Hayama, Samy Ould-Chikh, Marcell Toth, Raza U.S. Baccha, Bambar Davaasuren, Maxim Avdeev, Genki Kobayashi, Yoji Kobayashi. Chemistry of Materials, 2024, 36(21), 10504-10513. ☞ Congratulations Yuvraj! First KAUST-native student paper from the group, on high entropy materials! Thanks to our collaborators at Riken (Genki Kobayashi group) and ANSTO (Max Avdeev) for impedance and neutron measurements.
Abstract
High-entropy materials have gained significant interest in many applications, but structural investigations of the effect on anions in the crystal structure are still scarce. Here, we study the effect of multicomponent cation disorder in the case of mixed-anion compounds. The distribution of mixed anions among various coordination sites is important given their implications for properties such as ionic conductivity and bulk diffusion in catalysis. Structural analysis in the fluorite-type (La,Ce,Pr,Nd,Y)H1.5O0.75 reveals that the disordered cationic effects create new interstitial sites, occupied selectively by hydride despite oxide and hydride disorder in other compositions and sites. In contrast, single-lanthanide oxyhydrides of analogous anion content, such as LaH1.5O0.75, or SmH2O0.5 lack the complex interstitial structure. Hydride ion conductivity measurements and bond valence sum energy maps show a considerably low activation energy of hydride migration due to the additional interstitial sites induced by high entropy. Such interstitials can be crucial in applications that involve hydride ion diffusion, such as ammonia synthesis catalysis and solid-state ionics, as further high-entropy compositions are explored.