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Perovskite-type oxhydrides such as BaTiO3−xHy exhibit mixed hydride ion and electron conduction and are an attractive class of materials for developing energy storage devices. However, the underlying mechanism of electric conductivity and its relation to the composition of the material remains unclear. Here we report detailed insights into the hydride local environment, the electronic structure and hydride conduction dynamics of barium titanium oxyhydride. We demonstrate that DFT-assisted solid-state NMR is an excellent tool for differentiating between the different feasible electronic structures in these solids. Our results indicate that upon reduction of BaTiO3 the introduced electrons are delocalized among all Ti atoms forming a bandstate. Furthermore, each vacated anion site is reoccupied by at most a single hydride, or else remains vacant. This single occupied bandstate structure persists at different hydrogen concentrations (y = 0.13−0.31) and a wide range of temperatures (∼ 100−300 K).

Perovskite-type oxyhydrides, BaTiO3−xHx, represent a novel class of hydride ion conducting materials of interest for several electrochemical applications, but fundamental questions surrounding the defect chemistry and hydride ion transport mechanism remain unclear. Here we report results from powder X-ray diffraction, thermal gravimetric analysis, nuclear magnetic resonance spectroscopy, inelastic neutron scattering (INS), and density functional theory (DFT) simulations on three metal hydride reduced BaTiO3 samples characterized by the simultaneous presence of hydride ions and oxygen vacancies. The INS spectra are characterized by two predominating bands at around 114 (ω⊥) and 128 (ω∥) meV, assigned as fundamental Ti–H vibrational modes perpendicular and parallel to the Ti–H–Ti bond direction, respectively, and four additional, weaker, bands at around 99 (ω1), 110 (ω2), 137 (ω3) and 145 (ω4) meV that originate from a range of different local structures associated with different configurations of the hydride ions and oxygen vacancies in the materials. Crucially, the combined analyses of INS and DFT data confirm the presence of both nearest and next-nearest neighbouring oxygen vacancies to the hydride ions. This supports previous findings from quasielastic neutron scattering experiments, that the hydride ion transport is governed by jump diffusion dynamics between neighbouring and next-nearest neighbouring hydride ion–oxygen vacancy local structures. Furthermore, the investigation of the momentum transfer dependence of the INS spectrum is used to derive the mean square displacement of the hydride ions, which is shown to be in excellent agreement with the calculations. Analysis of the mean square displacement confirms that the hydrogen vibrational motions are localized in nature and only very weakly affected by the dynamics of the surrounding perovskite structure. This insight motivates efforts to identify alternative host lattices that allow for a less localization of the hydride ions as a route to higher hydride ion conductivities.

We investigated the hydride reduction of tetragonal BaTiO

The hydrogenation of the Zintl phase NdGa was studied by in situ neutron powder diffraction. We find a compositional range of 0.1 < x < 0.8 in NdGaH1+x. Hydrogen atoms are located in two diff ...

Perovskite-type oxyhydrides, BaTiO3–xHx, have been recently shown to exhibit hydride-ion (H–) conductivity at elevated temperatures, but the underlying mechanism of hydride-ion conduction and how it depends on temperature and oxygen vacancy concentration remains unclear. Here, we investigate, through the use of quasielastic neutron scattering techniques, the nature of the hydride-ion dynamics in three metal hydride-reduced BaTiO3 samples that are characterized by the simultaneous presence of hydride ions and oxygen vacancies. Measurements of elastic fixed window scans upon heating reveal the presence of quasielastic scattering due to hydride-ion dynamics for temperatures above ca. 200 K. Analyses of quasielastic spectra measured at low (225 and 250 K) and high (400–700 K) temperature show that the dynamics can be adequately described by established models of jump diffusion. At low temperature, ≤250 K, all of the models feature a characteristic jump distance of about 2.8 A, thus of the order of the distanc...

Mesoporous silica SBA-15 (with ∼6 nm pore size and ∼6 nm wall thickness) was exposed to a hydrothermal environment at 2 and 5 GPa. The p,T quenched products were investigated by powder X-ray diffraction and transmission electron microscopy. Infrared spectroscopy and thermogravimetric analysis of a sample subjected to 5 GPa at room temperature suggests functionalization of both inner and outer pore surface by silanol. Partial transformation to nano-sized (20–50 nm) coesite crystals with nonfaceted morphology was observed during short equilibration times of 2 h at 125°C, which is significantly below the melting point of water (∼250°C). Untransformed SBA-15 maintained intact pore structure. At 175°C and during 8 h, SBA-15 transformed completely into faceted coesite crystals with dimensions 100–300 nm, suggesting Ostwald ripening and thus significant mass transport in the solid water environment. At 2 GPa the melting point of water is near 70°C. Partial transformation to nano-sized α-quartz was observ...

Journal of solid state chemistry 277, 37 - 45 (2019). doi:10.1016/j.jssc.2019.05.033, Hydrides Eu3Si4H2+x were obtained by exposing the Zintl phase Eu3Si4 to a hydrogen atmosphere at a pressure of 30 bar and temperatures from 25 to 300 °C. Structural analysis using powder X-ray diffraction (PXRD) data suggested that hydrogenations in a temperature range 25–200 °C afford a uniform hydride phase with an orthorhombic structure (Immm, a ≈ 4.40 Å, b ≈ 3.97 Å, c ≈ 19.8 Å), whereas at 300 °C mixtures of two orthorhombic phases with c ≈ 19.86 and ≈ 19.58 Å were obtained. The assignment of a composition Eu3Si4H2+x is based on first principles DFT calculations, which indicated a distinct crystallographic site for H in the Eu3Si4 structure. In this position, H atoms are coordinated in a tetrahedral fashion by Eu atoms. The resulting hydride Eu3Si4H2 is stable by −0.46 eV/H atom with respect to Eu3Si4 and gaseous H2. Deviations between the lattice parameters of the DFT optimized Eu3Si4H2 structure and the ones extracted from PXRD patterns pointed to the presence of additional H in interstitials also involving Si atoms. Subsequent DFT modeling of compositions Eu3Si4H3 and Eu3Si4H4 showed considerably better agreement to the experimental unit cell volumes. It was then concluded that the hydrides of Eu3Si4 have a composition Eu3Si4H2+x (x, Published by Academic Press, Orlando, Fla.

Hydrides GdGaH were obtained by exposing the Zintl phase GdGa with the CrB structure to a hydrogen atmosphere at pressures from 1.5 to 50 bar and temperatures from 50 to 500 degrees C. Structural a ...

The Zintl phase CaSi2 commonly occurs in the 6R structure where puckered hexagon layers of Si atoms are stacked in an AA′BB′CC′ fashion. In this study we show that sintering of CaSi2 in a hydrogen atmosphere (30 bar) at temperatures between 200 and 700 °C transforms 6R-CaSi2 quantitatively into 3R-CaSi2. In the 3R polymorph (space group R-3m (no. 166), a=3.8284(1), c=15.8966(4), Z=3) puckered hexagon layers are stacked in an ABC fashion. The volume per formula unit is about 3% larger compared to 6R-CaSi2. First principles density functional calculations reveal that 6R and 3R-CaSi2 are energetically degenerate at zero Kelvin. With increasing temperature 6R-CaSi2 stabilizes over 3R because of its higher entropy. This suggests that 3R-CaSi2 should revert to 6R at elevated temperatures, which however is not observed up to 800 °C. 3R-CaSi2 may be stabilized by small amounts of incorporated hydrogen and/or defects.