Spinel-type InGaMgO4 with a = 8.56615(3) Å was prepared by treating layered YbFe2O4-type InGaMgO4 at 6 GPa and 1473 K. DFT calculation and Rietveld analysis of synchrotron X-ray powder diffraction data revealed the inverse spinel structure with In3+:Ga3+/Mg2+ = 0.726:0.274 in the tetrahedral site and 0.137:0.863 in the octahedral site. InGaMgO4 spinel is an insulator with an experimental band gap of 2.80 eV, and the attempt at hole doping by post-annealing in a reducing atmosphere to introduce an oxygen defect was unsuccessful. This is the first report of the bulk synthesis of AB2O4 compounds with both YbFe2O4 and spinel polymorphs.
Mixed-anion compounds have recently attracted attention as solid-state materials that exhibit properties unattainable with those of their single-anion counterparts. However, the use of mixed-anion compounds to control the morphology and engineer the crystal facets of electrocatalysts has been limited because their synthesis method is still immature. This study explored the electrocatalytic properties of a Pb–Fe oxyfluoride, Pb3Fe2O5F2, with a layered perovskite structure for oxygen evolution reaction (OER) and compared its properties in detail with those of a bulk-type cubic three-dimensional (3D) perovskite, PbFeO2F. A Pb3Fe2O5F2 electrode prepared with carbon nanotubes and a graphite sheet as a conductive support and a substrate, respectively, demonstrated better OER performance than a PbFeO2F electrode. The role of specific crystal facets of Pb3Fe2O5F2 in enhancing the OER activity was elucidated through electrochemical analysis. Density functional theory calculations indicated that the Pb3Fe2O5F2 (060) facet with Fe sites exhibited a lower theoretical overpotential for the OER, which was attributed to a moderately strong interaction between the active sites and the reaction intermediates; this interaction was reinforced by the strong electron-withdrawing behavior of fluoride ions. This finding offers new insights for developing efficient electrocatalysts based on oxyfluorides, leveraging the high electronegativity of fluorine to optimize the electronic states at active sites for the OER, without relying on precious metals.
Mixed anion compounds such as oxynitrides and oxychalcogenides are recognized as potential candidates of visible-light-driven photocatalysts since, as compared with oxygen 2p orbitals, p orbitals of less electronegative anion (e.g., N3–, S2–) can form a valence band that has more negative potential. In this regard, oxyfluorides appear unsuitable because of the higher electronegativity of fluorine. Here we show an exceptional case, an anion-ordered pyrochlore oxyfluoride Pb2Ti2O5.4F1.2 that has a small band gap (ca. 2.4 eV). With suitable modification of Pb2Ti2O5.4F1.2 by promoters such as platinum nanoparticles and a binuclear ruthenium(II) complex, Pb2Ti2O5.4F1.2 worked as a stable photocatalyst for visible-light-driven H2 evolution and CO2 reduction. Density functional theory calculations have revealed that the unprecedented visible-light-response of Pb2Ti2O5.4F1.2 arises from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb–O bond in the pyrochlore lattice due to the fluorine substitution.
The unusual property of negative thermal expansion is of fundamental interest and may be used to fabricate composites with zero or other controlled thermal expansion values. Here we report that colossal negative thermal expansion (defined as linear expansion <−10−4 K−1 over a temperature range ~100 K) is accessible in perovskite oxides showing charge-transfer transitions. BiNiO3 shows a 2.6% volume reduction under pressure due to a Bi/Ni charge transfer that is shifted to ambient pressure through lanthanum substitution for Bi. Changing proportions of coexisting low- and high-temperature phases leads to smooth volume shrinkage on heating. The crystallographic linear expansion coefficient for Bi0.95La0.05NiO3 is −137×10−6 K−1 and a value of −82×10−6 K−1 is observed between 320 and 380 K from a dilatometric measurement on a ceramic pellet. Colossal negative thermal expansion materials operating at ambient conditions may also be accessible through metal-insulator transitions driven by other phenomena such as ferroelectric orders. Negative thermal expansion—contraction upon heating—is an unusual process that may be exploited to produce materials with zero or other controlled thermal expansion values. Azumaet al. observe negative thermal expansion in BiNiO3which is a result of Bi/Ni charge-transfer transitions.
In a polar material, a laser pulse can trigger nonlinear optical phenomena, such as second-harmonic generation (SHG). The authors investigate the variation of SHG in BiCoO${}_{3}$ upon irradiation with femtosecond terahertz pulses. Applying a THz pulse, they observe enhancement of SHG by more than 50% at room temperature, the response being so fast that it simply follows the THz pulse. This huge, ultrafast enhancement, explained in terms of a photon dressed state, could be used to control nonlinear optical properties at the femtosecond timescale.
Magnetic and electrical properties of InFe2O4 were investigated. InFe2O4 belongs to the RFe2O4 family where R is trivalent cation (R= In, Yb, Lu, Er, or Y). In the rhombohedral crystal structure of this compound, the double layers of FeO5 bipyramids make two-dimensional triangular lattices and are separated by RO6 octahedra. Since the numbers of Fe2+ and Fe3+ ions are equal in the triangular lattice, the coexistence of charge and magnetic frustrations is expected. We succeeded in preparing high-quality InFe2O4 samples by a solid state reaction from In2O3, Fe and Fe2O3 in a vacuum sealed tube. A small amount of Fe3O4 was magnetically separated. The dielectric constant, magnetic susceptibility, high-field magetization, Mössbauer spectroscopy, and the specific heat data suggested that charge and ferrimagnetic ordering took place simultaneously at 240K in this compound.
An entry from the Inorganic Crystal Structure Database, the world’s repository for inorganic crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the joint CCDC and FIZ Karlsruhe Access Structures service and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Improved activity of visible-light H2 evolution was reported using NaCl–CsCl-treated Pb2Ti2O5.4F1.2 photocatalyst, along with the underlying mechanism of activation.
