A new family of anti-perovskite oxyhydrides with tetrahedral GaO4 polyanions.

New solid compounds A3-xGaO4H1-y (A = Sr, Ba; x ∼0.15, y ∼0.3), which are the first oxyhydrides containing gallium ions, have been synthesized by high-pressure synthesis. Powder X-ray and neutron diffraction experiments revealed that the series adopts an anti-perovskite structure consisting of hydride-anion-centered HA6 octahedra with tetrahedral GaO4 polyanions, wherein the A- and H-sites show partial defect. Formation energy calculations from the raw materials support that stoichiometric Ba3GaO4H is thermodynamically stable with a wide band gap. Annealing the A = Ba powder under flowing Ar and O2 gas suggests topochemical H- desorption and O2-/H- exchange reactions, respectively.

Impact of Na Concentration on the Phase Transition Behavior and H- Conductivities in the Ba-Li-Na-H-O Oxyhydride System.

K2 NiF4 -type Ba-Li oxyhydride (BLHO) transitions to a so-called hydride superionic conductor, exhibiting a high and essentially temperature-independent hydride ion (H- ) conductivity over 0.01 S cm-1 through the disordering of H- vacancies above 300 °C. In this study, a Ba-Li-Na-H-O oxyhydride system synthesized in which lithium is partially substituted with sodium in BLHO and investigated the effects of Na content on the phase transition behavior and the conductivity. Structural refinements and differential scanning calorimetry experiments confirmed a lowering trend in the phase transition temperatures and decreasing enthalpy changes for the transition with increasing Na content. Substitution of not <40% of Li with Na lowered the degree of ordered vacancies at the H- sites at room temperature and improved conductivities by more than two orders of magnitude in the low-temperature region (T < 300 °C) before the phase transition. These findings clearly show that introducing Na into the lattice effectively stabilizes the high-conductive phase of BLHO.

Hydride-ion-conducting K2NiF4-type Ba-Li oxyhydride solid electrolyte.

Hydrogen transport in solids, applied in electrochemical devices such as fuel cells and electrolysis cells, is key to sustainable energy societies. Although using proton (H+) conductors is an attractive choice, practical conductivity at intermediate temperatures (200-400 °C), which would be ideal for most energy and chemical conversion applications, remains a challenge. Alternatively, hydride ions (H-), that is, monovalent anions with high polarizability, can be considered a promising charge carrier that facilitates fast ionic conduction in solids. Here, we report a K2NiF4-type Ba-Li oxyhydride with an appreciable amount of hydrogen vacancies that presents long-range order at room temperature. Increasing the temperature results in the disappearance of the vacancy ordering, triggering a high and essentially temperature-independent H- conductivity of more than 0.01 S cm-1 above 315 °C. Such a remarkable H- conducting nature at intermediate temperatures is anticipated to be important for energy and chemical conversion devices.

Anion ordering enables fast H- conduction at low temperatures.

The introduction of chemical disorder by substitutional chemistry into ionic conductors is the most commonly used strategy to stabilize high-symmetric phases while maintaining ionic conductivity at lower temperatures. In recent years, hydride materials have received much attention owing to their potential for new energy applications, but there remains room for development in ionic conductivity below 300°C. Here, we show that layered anion-ordered Ba2-δH3-2δ X (X = Cl, Br, and I) exhibit a remarkable conductivity, reaching 1 mS cm-1 at 200°C, with low activation barriers allowing H- conduction even at room temperature. In contrast to structurally related BaH2 (i.e., Ba2H4), the layered anion order in Ba2-δH3-2δ X, along with Schottky defects, likely suppresses a structural transition, rather than the traditional chemical disorder, while retaining a highly symmetric hexagonal lattice. This discovery could open a new direction in electrochemical use of hydrogen in synthetic processes and energy devices.

Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides.

Perovskite oxides can host various anion-vacancy orders, which greatly change their properties, but the order pattern is still difficult to manipulate. Separately, lattice strain between thin film oxides and a substrate induces improved functions and novel states of matter, while little attention has been paid to changes in chemical composition. Here we combine these two aspects to achieve strain-induced creation and switching of anion-vacancy patterns in perovskite films. Epitaxial SrVO3 films are topochemically converted to anion-deficient oxynitrides by ammonia treatment, where the direction or periodicity of defect planes is altered depending on the substrate employed, unlike the known change in crystal orientation. First-principles calculations verified its biaxial strain effect. Like oxide heterostructures, the oxynitride has a superlattice of insulating and metallic blocks. Given the abundance of perovskite families, this study provides new opportunities to design superlattices by chemically modifying simple perovskite oxides with tunable anion-vacancy patterns through epitaxial lattice strain.

Synthesis and H- conductivity of a new oxyhydride Ba2YHO3 with anion-ordered rock-salt layers.

A new layered perovskite oxyhydride Ba2YHO3 was synthesized via high pressure synthesis. Powder X-ray and neutron diffraction experiments revealed that in Ba2YHO3 the ordered H- and O2- anions form [Ba2H2] rock-salt layers wherein H- conduction is allowed. The conductivity reached 0.1 mS cm-1 at 350 °C, which is higher than that of isostructural Ba2ScHO3 with anion-disordered [Ba2HO] layers.

Luminescent ionic liquid formed from a melted rhenium(v) cluster.

Recently, non-crystalline coordination materials have been shown to represent a versatile class of functional materials. However, such materials incorporating metal complex clusters have remained largely unexplored. Herein, we demonstrate that a luminescent tetranuclear ReV cluster melts at 489 K, with the cluster structure being maintained in the corresponding supercooled ionic liquid phase.

Ba2ScHO3: H- Conductive Layered Oxyhydride with H- Site Selectivity.

Hydride (H-) conduction is a new frontier related to hydrogen transport in solids. Here, a new H- conductive oxyhydride Ba2ScHO3 was successfully synthesized using a high-pressure technique. Powder X-ray and neutron diffraction experiments investigated the fact that Ba2ScHO3 adopts a K2NiF4-type structure with H- ions preferentially occupying the apical sites, as supported by theoretical calculations. Electrochemical impedance spectra showed that Ba2ScHO3 exhibited H- conduction and a conductivity of 5.2 × 10-6 S cm-1 at 300 °C. This value is much higher than that of BaScO2H, which has an ideal perovskite structure, suggesting the advantage of layered structures for H- conduction. Tuning site selectivity of H- ions in layered oxyhydrides might be a promising strategy for designing fast H- conductors applicable for novel electrochemical devices.

Chemical Pressure-Induced Anion Order-Disorder Transition in LnHO Enabled by Hydride Size Flexibility.

While cation order-disorder transitions have been achieved in a wide range of materials and provide crucial effects in various physical and chemical properties, anion analogues are scarce. Here we have expanded the number of known lanthanide oxyhydrides, LnHO (Ln = La, Ce, Pr, Nd), to include Ln = Sm, Gd, Tb, Dy, Ho, and Er, which has allowed the observation of an anion order-disorder transition from the anion-ordered fluorite structure ( P4/ nmm) for larger Ln3+ ions (La-Nd) to a disordered arrangement ( Fm3̅ m) for smaller Ln3+ (Sm-Er). Structural analysis reveals that with the increase of Ln3+ radius (application of negative chemical pressure), the oxide anion in the disordered phase becomes too under-bonded, which drives a change to an anion-ordered structure, with smaller OLn4 and larger HLn4 tetrahedra, demonstrating that the size flexibility of hydride anions drives this transition. Such anion ordering control is crucial regarding applications that involve hydride diffusion such as catalysis and electrochemical solid devices.

AgFeOF2: A Fluorine-Rich Perovskite Oxyfluoride.

We synthesized a silver iron oxyfluoride AgFeOF2 by using a high-pressure reaction. Synchrotron X-ray and neutron diffraction, X-ray absorption, and 57Fe Mössbauer spectroscopy indicate that AgFeOF2 crystallizes in the ideal perovskite structure with iron in a trivalent state, although electron microscopy revealed weak super-reflections. A possible partial ordering in the FeO2F4 octahedron is inferred from Mössbauer spectroscopy. The synthesis of the fluorine-rich sample offers an opportunity to study a composition-property relation in AFeIIIO3- nF n ( n = 0, 1, and 2). AgFeOF2 exhibits a G-type antiferromagnetic ordering below TN ≈ 480 K, which is much lower than the n = 0 and 1 cases, suggesting a weaker superexchange interaction between Fe moments via F 2p orbitals (vs O 2p orbitals).

Promoted Hydride/Oxide Exchange in SrTiO3 by Introduction of Anion Vacancy via Aliovalent Cation Substitution.

We investigated topochemical anion exchange reactions for a ScIII-substituted SrTiIVO3 perovskite, Sr(Ti1-yScy)O3-y/2□y/2 (y ≤ 0.1), using CaH2. It was found that the initial introduction of a small amount of anion vacancies (y/2) is crucial to enhance the anion (H-/O2-) exchangeability. For example, hydride reduction of Sr(Ti0.95Sc0.05)O2.975 yielded the oxyhydride SrTi0.95Sc0.05O2.56H0.41 in which the hydride concentration is increased by 33% with respect to pristine SrTiO3 (leading to SrTiO2.76H0.24). This observation highlights the importance of anion vacancies to improve anion (H-/O2-) diffusion, which is a well-known strategy for improving oxide anion conductivity, and suggests that such a vacancy-assisted reaction could be applied to other anion exchange reactions (e.g., F-/O2- and N3-/O2-) to extend the solubility range.

Hypervalent Bismuthides La3MBi5 (M = Ti, Zr, Hf) and Related Antimonides: Absence of Superconductivity.

We successfully synthesized the ternary bismuthides La3MBi5 (M = Ti, Zr, Hf). These compounds crystallize in the hexagonal Hf5Sn3Cu-anti type structure (space group: P63/mcm) consisting of face-sharing MBi6 octahedral chains and hypervalent Bi linear chains, both separated by La atoms. Magnetic susceptibility and electrical resistivity measurements revealed that all of the compounds, including the solid solution La3Ti(Bi1-xSbx)5, exhibit a Pauli paramagnetic behavior without any trace of superconductivity down to 1.85 K, as opposed to a recently reported 4 K superconductivity in La3TiSb5. The absence of superconductivity is supported by first-principles band calculations of La3TiBi5 and La3TiSb5 that demonstrate similar electronic structures with three-dimensional Fermi surfaces.

ZnTaO2N: Stabilized High-Temperature LiNbO3-type Structure.

By using a high-pressure reaction, we prepared a new oxynitride ZnTaO2N that crystallizes in a centrosymmetric (R3̅c) high-temperature LiNbO3-type structure (HTLN-type). The stabilization of the HTLN-type structure down to low temperatures (at least 20 K) makes it possible to investigate not only the stability of this phase, but also the phase transition to a noncentrosymmetric (R3c) LiNbO3-type structure (LN-type) which is yet to be clarified. Synchrotron and neutron diffraction studies in combination with transmission electron microscopy show that Zn is located at a disordered 12c site instead of 6a, implying an order-disorder mechanism of the phase transition. It is found that the closed d-shell of Zn2+, as well as the high-valent Ta5+ ion, is responsible for the stabilization of the HTLN-type structure, affording a novel quasitriangular ZnO2N coordination. Interestingly, only 3% Zn substitution for MnTaO2N induces a phase transition from LN- to HTLN-type structure, implying the proximity in energy between the two structural types, which is supported by the first-principles calculations.

High-Pressure Synthesis of Manganese Oxyhydride with Partial Anion Order.

The high-pressure synthesis of a manganese oxyhydride LaSrMnO3.3 H0.7 is reported. Neutron and X-ray Rietveld analyses showed that this compound adopts the K2 NiF4 structure with hydride ions positioned exclusively at the equatorial site. This result makes a striking contrast to topochemical reductions of LaSrMnO4 that result in only oxygen-deficient phases down to LaSrMnO3.5 . This suggests that high H2 pressure plays a key role in stabilizing the oxyhydride phase, offering an opportunity to synthesize other transition-metal oxyhydrides. Magnetic susceptibility revealed a spin-glass transition at 24 K that is due to competing ferromagnetic (Mn(2+) -Mn(3+) ) and antiferromagnetic (Mn(2+) -Mn(2) , Mn(3+) -Mn(3+) ) interactions.

Topochemical Nitridation with Anion Vacancy-Assisted N(3-)/O(2-) Exchange.

We present how the introduction of anion vacancies in oxyhydrides enables a route to access new oxynitrides, by conducting ammonolysis of perovskite oxyhydride EuTiO3-xHx (x ∼ 0.18). At 400 °C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EuTi(3.82+)O2.82H0.18, leading to the N(3-)/H(-)-exchanged product EuTi(4+)O2.82N0.12□0.06. When the ammonolysis temperature was increased up to 800 °C, we observed a further nitridation involving N(3-)/O(2-) exchange, yielding a fully oxidized Eu(3+)Ti(4+)O2N with the GdFeO3-type distortion (Pnma) as a metastable phase, instead of pyrochlore structure. Interestingly, the same reactions using the oxide EuTiO3 proceeded through a 1:1 exchange of N(3-) with O(2-) only above 600 °C and resulted in incomplete nitridation to EuTiO2.25N0.75, indicating that anion vacancies created during the initial nitridation process of EuTiO2.82H0.18 play a crucial role in promoting anion (N(3-)/O(2-)) exchange at high temperatures. Hence, by using (hydride-induced) anion-deficient precursors, we should be able to expand the accessible anion composition of perovskite oxynitrides.

A labile hydride strategy for the synthesis of heavily nitridized BaTiO3.

Oxynitrides have been explored extensively in the past decade because of their interesting properties, such as visible-light absorption, photocatalytic activity and high dielectric permittivity. Their synthesis typically requires high-temperature NH3 treatment (800-1,300 °C) of precursors, such as oxides, but the highly reducing conditions and the low mobility of N(3-) species in the lattice place significant constraints on the composition and structure-and hence the properties-of the resulting oxynitrides. Here we show a topochemical route that enables the preparation of an oxynitride at low temperatures (<500 °C), using a perovskite oxyhydride as a host. The lability of H(-) in BaTiO3-xHx (x ≤ 0.6) allows H(-)/N(3-) exchange to occur, and yields a room-temperature ferroelectric BaTiO3-xN2x/3. This anion exchange is accompanied by a metal-to-insulator crossover via mixed O-H-N intermediates. These findings suggest that this 'labile hydride' strategy can be used to explore various oxynitrides, and perhaps other mixed anionic compounds.

Oxyhydrides of (Ca,Sr,Ba)TiO3 perovskite solid solutions.

The oxyhydride solid solutions (Ca,Sr)TiO(3-x)H(x) and (Sr,Ba)TiO(3-x)H(x) have been prepared by reducing the corresponding ATiO(3) oxides with calcium hydride. Under the reaction conditions examined, a hydride content of x = 0.1-0.3 was obtained for all compositions. Compared to our previous result with BaTiO(3-x)H(x), the larger particle size in this study (20-30 µm vs 170 nm) resulted in a somewhat lower hydride amount despite prolonged reaction times. We examined changes in cell volume, octahedral tilt angle, and site occupancy of different anion sites after conversion to oxyhydrides; it appears that these oxyhydrides fit the geometrical descriptions typical for regular ABO(3) perovskites quite well. The hydrogen release temperature, previously shown to be indicative of the hydride exchange temperature, however, does not scale linearly with the A-site composition, indicating a potential effect of chemical randomness.