RESUMO
The research on the functional properties of medium- and high-entropy alloys (MEAs and HEAs) has been in the spotlight recently. Many significant discoveries have been made lately in hydrogen-based economy-related research where these alloys may be utilized in all of its key sectors: water electrolysis, hydrogen storage, and fuel cell applications. Despite the rapid development of MEAs and HEAs with the ability to reversibly absorb hydrogen, the research is limited to transition-metal-based alloys that crystallize in body-centered cubic solid solution or Laves phase structures. To date, no study has been devoted to the hydrogenation of rare-earth-element (REE)-based MEAs or HEAs, as well as to the alloys crystallizing in face-centered-cubic (FCC) or hexagonal-close-packed structures. Here, we elucidate the formation and hydrogen storage properties of REE-based ScYNdGd MEA. More specifically, we present the astounding stabilization of the single-phase FCC structure induced by the hydrogen absorption process. Moreover, the measured unprecedented high storage capacity of 2.5 H/M has been observed after hydrogenation conducted under mild conditions that proceeded without any phase transformation in the material. The studied MEA can be facilely activated, even after a long passivation time. The results of complementary measurements showed that the hydrogen desorption process proceeds in two steps. In the first, hydrogen is released from octahedral interstitial sites at relatively low temperatures. In the second, high-temperature process, it is associated with the desorption of hydrogen atoms stored in tetrahedral sites. The presented results may impact future research of a novel group of REE-based MEAs and HEAs with adaptable hydrogen storage properties and a broad scope of possible applications.
RESUMO
Ammonia synthesis holds significant importance for both agricultural fertilizer production and emerging green energy applications. Here, we present a comprehensive characterization of a catalyst for mechanochemical ammonia synthesis, based on Cs-promoted Fe. The study sheds light on the catalyst's dynamic evolution under reaction conditions and the origin of deactivation. Initially, elemental Cs converts to CsH, followed by partial CsOH formation due to trace oxygen impurities on the surface of the Fe metal and the equipment. Concurrently, the mechanical milling process comminutes Fe, exposing fresh metallic Fe surfaces. This comminution correlates with an induction period observed during ammonia formation. Critical to the study, degradation of active Cs promoter species (CsH and CsNH2) into inactive CsOH emerged as the primary deactivation mechanism. By increasing the Cs content from 2.2â mol % to 4.2â mol %, we achieved stable, continuous ammonia synthesis for nearly 90â hours, showcasing one of the longest-running mechanocatalytic gas phase reactions. Studies of the temperature dependence of the reaction revealed negligible bulk temperature influence in the range of -10 °C to 100 °C, highlighting the dominance of mechanical action over bulk thermal effects. This study offers insights into the complex interplay between mechanical processing, reactive species, and deactivation mechanisms in mechanocatalytic ammonia synthesis.
RESUMO
Nanocomposites of complex metal hydrides and oxides are promising solid state electrolytes. The interaction of the metal hydride with the oxide results in a highly conducting interface layer. Up until now it has been assumed that the interface chemistry is independent of the nanoconfinement method. Using 29Si solid state NMR and LiBH4/SiO2 as a model system, we show that the silica surface chemistry differs for nanocomposites prepared via melt infiltration or ball milling. After melt infiltration, a Si···H···BH3 complex is present on the interface, together with silanol and siloxane groups. However, after ball milling, the silica surface consists of Si- H sites, and silanol and siloxane groups. We propose that this change is related to a redistribution of silanol groups on the silica surface during ball milling, where free silanol groups are converted to mutually hydrogen-bonded silanol groups. The results presented here help to explain the difference in ionic conductivity between nanocomposites prepared via ball milling and melt infiltration.