Effects of A-site Cations in Quadruple Perovskite Ruthenates on Oxygen Evolution Catalysis in Acidic Aqueous Solutions.

The quadruple perovskite ruthenate CaCu3 Ru4 O12 is more active and stable than the benchmark catalyst RuO2 in the oxygen evolution reaction (OER) in acidic aqueous solutions, where many oxide-based catalysts are dissolved. Studies on the crystal structures of quadruple perovskite ruthenates are rare, and the origin of OER activity or stability from a structural aspect has not been clarified in detail. This presents the need to study the effects of cations at the A site of quadruple perovskite ruthenates ACu3 Ru4 O12 (A = Ca, Sr, La, Nd, and Ce) on the OER catalytic activity and stability in acidic aqueous solutions. CaCu3 Ru4 O12 has the highest activity and stability among all quadruple perovskite samples. The type of cation at the A site changes the average Cu and Ru valence states, and the plot of OER activity versus the average Cu valence number shows a volcano-type relationship. In addition, stability increases with a decrease in Ru-O bond length. This research provides a good design principle for OER catalysts with high activity and stability in severely acidic aqueous solutions.

V-V Dimerization and Magnetic State of Cobalt Ions in Ilmenite-Type CoVO3.

The nature of chemical bonds determines the electronic and magnetic properties of compounds. A metal-metal bonding (V-V dimer) and its effect on the magnetism of ilmenite-type CoVO3 were studied. Polycrystalline CoVO3 samples were synthesized using a high-pressure synthesis method. Crystal structure refinement revealed that V-V dimers exist at temperatures below 550 K in the vanadium layers. Co2+ in CoVO3 exhibits an S = 3/2 state, whereas a Jeff = 1/2 state was reported in ilmenite-type CoTiO3. The existence of V-V dimers reduces the structural symmetry (from R3 to P1), which can change the magnetic ground state.

Electrochemical deposition of amorphous cobalt oxides for oxygen evolution catalysis.

The oxygen evolution reaction (OER) is crucial in water splitting for hydrogen production. However, its high over-potential and sluggish kinetics cause an additional energy loss and hinder its practical application. The cobalt spinel oxide Co3O4 exhibits a high catalytic activity for the OER in alkaline solutions. However, the activity requires further enhancement to meet the industrial demand for hydrogen production. This paper presents an electrochemical deposition method to obtain cobalt oxides with a controllable crystallinity on carbon paper (CP). Usually, cobalt oxides grown on CP have a Co3O4 spinel oxide structure. The self-supported Co3O4/CP exhibited a considerable catalytic activity for the OER. When a VS2 layer grown on the CP beforehand by a hydrothermal method was used as substrate, the deposited cobalt oxides were in an amorphous state, denoted as CoO x /VS2/CP, which exhibited a higher OER activity and better stability than those of Co3O4/CP. The enhancement in the catalytic activity was attributed to the mixture formation of different types of cobalt species, including Co3O4, CoO, Co(OH)2, and metallic Co, because of the reduction by VS2. We also clarify the significance of the crystallinity of cobalt oxides in the improvement in the OER activity. This process can also be applied to the direct formation of other types of self-supported oxide electrodes for OER catalysis.

Highly active postspinel-structured catalysts for oxygen evolution reaction.

The rational design principle of highly active catalysts for the oxygen evolution reaction (OER) is desired because of its versatility for energy-conversion applications. Postspinel-structured oxides, CaB 2O4 (B = Cr3+, Mn3+, and Fe3+), have exhibited higher OER activities than nominally isoelectronic conventional counterparts of perovskite oxides LaBO3 and spinel oxides ZnB 2O4. Electrochemical impedance spectroscopy reveals that the higher OER activities for CaB 2O4 series are attributed to the lower charge-transfer resistances. A density-functional-theory calculation proposes a novel mechanism associated with lattice oxygen pairing with adsorbed oxygen, demonstrating the lowest theoretical OER overpotential than other mechanisms examined in this study. This finding proposes a structure-driven design of electrocatalysts associated with a novel OER mechanism.

Cation Dimerization in a 3d1 Honeycomb Lattice System.

In one-dimensional systems with partially filled valence bands, simultaneous changes occur in the electronic states and crystal structures. This is known as the Peierls transition. The Peierls transition (cation dimerization) in VO2, which has a quasi-one-dimensional structure, is well-known, and its mechanism has been extensively discussed. Honeycomb lattices exhibit the Peierls instability owing to their low dimensionality. However, cation dimerization is rare in the 3d1 honeycomb lattice system. Here, we perform an in-depth examination of the V-V dimerization (formation of V-V direct bond) in ilmenite-type MgVO3, which is a 3d1 honeycomb lattice system. A ladderlike pattern was observed in the V-V dimers through synchrotron X-ray experiments at temperatures below 500 K. This dimerization was accompanied by a magnetic-to-nonmagnetic transition. Moreover, a valence bond liquid phase may exist at 500-600 K. Our results reveal the behavior of the valence electrons in the 3d1 honeycomb lattice system.

High-Pressure Synthesis and Magnetic States of Magnetoplumbite Cobaltates CaCo12O19 and BaCo12O19.

Novel cobalt oxides, CaCo12O19 and BaCo12O19, have been synthesized under high-pressure and high-temperature conditions of 7 GPa and 1373 K, respectively. Rietveld refinement using synchrotron X-ray diffraction data indicates that the CaCo12O19 and BaCo12O19 crystallize in a magnetoplumbite structure with a hexagonal space group of P63/mmc (No. 194) as well as SrCo12O19. The magnetic study demonstrates that itinerant and localized 3d electrons coexist in all ACo12O19 (A = Ca, Sr, Ba) and the magnetic ground state transforms from antiferromagnetic (A = Ca) to ferrimagnetic (A = Sr) to antiferromagnetic (A = Ba), which is in stark contrast to the systematic change in the magnetoplumbite-related cobalt oxides of ACo6O11 from antiferromagnet (A = Ca) to ferrimagnet (A = Sr) to ferromagnet (A = Ba). The nonmonotonic magnetic evolution with isoelectronic A-site substitution in ACo12O19 is probably attributed to changes in the interactions between two magnetic sublattices of localized 3d electrons at trigonal-bipyramidal and tetrahedral sites for ACo12O19. This finding proposes the complex magnetic properties in the layered cobalt oxides with multiple magnetic sublattices in the coexistence system of itinerant and localized electrons.

Metamagnetic Behavior in a Quadruple Perovskite Oxide.

A cubic quadruple perovskite oxide CeMn3Cr4O12 has been synthesized under high-pressure and high-temperature conditions of 8 GPa and 1273 K. The X-ray absorption spectroscopy reveals that the Ce ions are in a trivalent state, as represented by the ionic model of Ce3+Mn3+3Cr3+4O12. The magnetic study demonstrates three independent antiferromagnetic transitions attributed to Ce (∼10 K), Mn (46 K), and Cr (133 K) ions. Furthermore, a magnetic field-induced antiferromagnetic-to-ferromagnetic (metamagnetic) transition of Ce3+ 4f moments is observed at low temperatures below 20 K, exhibiting a rare example of metamagnetism in the Ce3+-oxides. This finding represents that the 3d-electron magnetic sublattices play a role in the metamagnetism of 4f-electron magnetic moments, demonstrating a new aspect of the 3d-4f complex electron systems.

A Sequential Electron Doping for Quadruple Perovskite Oxides ACu3Co4O12 (A = Ca, Y, Ce).

A novel quadruple perovskite oxide CeCu3Co4O12 has been synthesized in high-pressure and high-temperature conditions of 12 GPa and 1273 K. Rietveld refinement of the synchrotron X-ray powder diffraction pattern reveals that this oxide crystallizes in a cubic quadruple perovskite structure with the 1:3-type ordering of Ce and Cu ions at the A-site. X-ray absorption spectroscopy analysis demonstrates the valence-state transitions in the ACu3Co4O12 series (A = Ca, Y, Ce) from Ca2+Cu3+3Co3.25+4O12 to Y3+Cu3+3Co3+4O12 to Ce4+Cu2.67+3Co3+4O12, where the electrons are doped in the order from B-site (Co3.25+ → Co3+) to A'-site (Cu3+ → Cu2.67+). This electron-doping sequence is in stark contrast to the typical B-site electron doping for simple ABO3-type perovskite and quadruple perovskites CaCu3B4O12 (B = V, Cr, Mn), further differing from the monotonical A'-site electron doping for Na1-xLaxMn3Ti4O12 and A'- and B-site electron doping for AMn3V4O12 (A = Na, Ca, La). The differences in the electron-doping sequences are interpreted by rigid-band models, proposing a wide variety of electronic states for the complex transition-metal oxides containing the multiple valence-variable ions.

ϵ-FeOOH: A Novel Negative Electrode Material for Li- and Na-Ion Batteries.

The demand for eco-friendly materials for secondary batteries has stimulated the exploration of a wide variety of Fe oxides, but their potential as electrode materials remains unknown. In this contribution, ϵ-FeOOH was synthesized using a high-pressure/high-temperature method and examined for the first time in nonaqueous Li and Na cells. Under a pressure of 8 GPa, α-FeOOH transformed into ϵ-FeOOH at 400 °C and then decomposed into α-Fe2O3 and H2O above 500 °C. Here, FeO6 octahedra form [2 × 1] tunnels in α-FeOOH or [1 × 1] tunnels in ϵ-FeOOH. The ϵ-FeOOH/Li cell exhibited a rechargeable capacity (Q recha) of ∼700 mA h·g-1 at 0.02-3.0 V, whereas the ϵ-FeOOH/Na cell indicated a Q recha of less than 30 mA h·g-1 at 0.02-2.7 V. The discharge and charge profiles of ϵ-FeOOH and α-FeOOH were similar, but the rate capability of ϵ-FeOOH was superior to that of α-FeOOH.

A robust thermal-energy-storage property associated with electronic phase transitions for quadruple perovskite oxides.

The quadruple perovskite oxides RCu3Fe4O12 (R: rare-earth metals) exhibit large latent-heat capacities (25 J g-1 at maximum) with variable transition temperatures between 254 and 368 K, whereas their transition entropies are almost completely retained. This finding proposes an effective way to design robust thermal-energy-storage materials with various operating temperatures.

ZIF-Derived Co9-xNixS8 Nanoparticles Immobilized on N-Doped Carbons as Efficient Catalysts for High-Performance Zinc-Air Batteries.

Bimetallic sulfides have been attracting considerable attention because of their high catalytic activities for oxygen reduction reaction (ORR) and oxygen evolution reaction; thus, they are considered efficient catalysts for important energy conversion devices such as fuel cells and metal-air batteries. Here, the catalytic activity of a novel catalyst composed of Co9-xNixS8 nanoparticles immobilized on N-doped carbons (Co9-xNixS8/NC) is reported. The catalyst is synthesized using a Ni-adsorbed Co-Zn zeolitic imidazolate framework (ZIF) precursor (NiCoZn-ZIF). Because of the porous structure of ZIF and the high intrinsic activity of the bimetallic sulfide nanoparticles, the Co9-xNixS8/NC catalyst exhibits high half-wave potential 0.86 V versus reversible hydrogen electrode for ORR and outstanding bifunctional catalytic performance. When Co9-xNixS8/NC is applied as a cathode catalyst in zinc-air batteries, considerably higher power density of about 75 mW cm-2 and discharge voltage are achieved compared to those of batteries with commercial Pt/C and other ZIF-derived catalysts. The zinc-air battery with the Co9-xNixS8/NC catalyst shows a high cyclability more than 170 cycles for 60 h with almost negligible decline at 10 mA cm-2. Our work provides a new insight into the design of bimetallic sulfide composites with high catalytic activities.

High-pressure synthesis of ε-FeOOH from ß-FeOOH and its application to the water oxidation catalyst.

Research on materials under extreme conditions such as high pressures provides new insights into the evolution and dynamics of the earth and space sciences, but recently, this research has focused on applications as functional materials. In this contribution, we examined high-pressure/high-temperature phases of ß-FeO1-x (OH)1+x Cl x with x = 0.12 (ß-FeOOH) and their catalytic activities of water oxidation, i.e., oxygen evolution reaction (OER). Under pressures above 6 GPa and temperatures of 100-700 °C, ß-FeOOH transformed into ε-FeOOH, as in the case of α-FeOOH. However, the established pressure-temperature phase diagram of ß-FeOOH differs from that of α-FeOOH, probably owing to its open framework structure and partial occupation of Cl- ions. The OER activities of ε-FeOOH strongly depended on the FeOOH sources, synthesis conditions, and composite electrodes. Nevertheless, one of the ε-FeOOH samples exhibited a low OER overpotential compared with α-FeOOH and its parent ß-FeOOH, which are widely used as OER catalysts. Hence, ε-FeOOH is a potential candidate as a next-generation earth-abundant OER catalyst.

Structure, Magnetism, and Electrochemistry of LiMg1-xZnxVO4 Spinels with 0 ≤ x ≤ 1.

Negative electrode materials with lower operating voltages are urgently required to increase the energy density of lithium-ion batteries. In this study, LiMgVO4 with a Na2CrO4-type structure, LiZnVO4 with a phenacite structure, and their mixture were treated under a high pressure of 12 GPa and a high temperature of 1273 K, and their electrochemical reactivities were examined in a nonaqueous lithium cell. Synchrotron X-ray diffraction (XRD) measurements and Raman spectroscopy revealed that the LiMg1-xZnxVO4 samples with 0 ≤ x ≤ 1 are in a single phase of the inverse spinel structure that forms a solid solution compound over the whole x range. All of the samples were brown or light black due to the presence of a small amount of V4+ ions with S = 1/2 and oxygen deficiencies. Since the majority of the vanadium ions are located at the route of the Li+ ion conduction pathway, no rechargeable capacity (Qrecha) would be expected. Nevertheless, all LiMg1-xZnxVO4 samples exhibited a Qrecha value of more than 200 mAh g-1 with an operating voltage of ∼0.8 V. This operating voltage is ∼1.6 V lower than that of LiV2O4 with a normal spinel structure. Furthermore, the x = 0.5 sample demonstrated an extremely stable cycle performance over 1 month. Ex situ XRD measurements clarified that the reversible electrochemical reaction can be attributed to the movement of vanadium ions from the tetrahedral 8a to octahedral 16c sites during the initial discharge reaction. Details regarding the crystal structure, magnetism, and electrochemistry of LiMg1-xZnxVO4 are presented.

Structural and Electrochemical Analyses on the Transformation of CaFe2O4-Type LiMn2O4 from Spinel-Type LiMn2O4.

Lithium manganese oxides have received much attention as positive electrode materials for lithium-ion batteries. In this study, a post-spinel material, CaFe2O4-type LiMn2O4 (CF-LMO), was synthesized at high pressures above 6 GPa, and its crystal structure and electrochemical properties were examined. CF-LMO exhibits a one-dimensional (1D) conduction pathway for Li ions, which is predicted to be superior to the three-dimensional conduction pathway for these ions. The stoichiometric LiMn2O4 spinel (SP-LMO) was decomposed into three phases of Li2MnO3, MnO2, and Mn2O3 at 600 °C and then started to transform into the CF-LMO structure above 800 °C. The rechargeable capacity (Q recha) of the sample synthesized at 1000 °C was limited to ∼40 mA h·g-1 in the voltage range between 1.5 and 5.3 V because of the presence of a small amount of Li2MnO3 phase in the sample (=9.1 wt %). In addition, the Li-rich spinels, Li[Li x Mn2-x ]O4 with x = 0.1, 0.2, and 0.333, were also employed for the synthesis of CF-LMO. The sample prepared from x = 0.2 exhibited a Q recha value exceeding 120 mA h·g-1 with a stable cycling performance, despite the presence of large amounts of the phases Li2MnO3, MnO2, and Mn2O3. Details of the structural transformation from SP-LMO to CF-LMO and the effect of Mn ions on the 1D conduction pathway are discussed.

Synthesis of Rhombohedral LiCo0.64Mn0.36O2 Using a High-Pressure Method.

Lithium transition metal (M) oxides with a rhombohedral structure, r-LiMO2, have attracted a great deal of attention as a positive electrode material for lithium-ion batteries. Despite intensive studies thus far, Mn-rich r-LiMO2 compounds have remained unattainable, due to a cooperative Jahn-Teller distortion of Mn3+ ions in the MnO6 octahedra. We employed a high-pressure method for synthesizing r-LiCo xMn1- xO2 ( r-LCMO) with x = 0.5 and examined its electrochemical properties in a nonaqueous lithium cell. The high-pressure method successfully suppressed the Jahn-Teller distortion of Mn3+ ions, and the r-LCMO phase was observed in a wide temperature-pressure region when using a LiOH·H2O precursor. The rechargeable capacity of the sample synthesized at 600 °C and 12 GPa reached 126 mAh g-1, although the r-LCMO phase was contaminated with electrochemically inactive rock-salt LCMO and hexagonal LCMO phases. Compositional and structural analyses clarified that the actual Co/Mn ratio of the r-LCMO phase was 64/36, which deviated slightly from the initial composition (50/50). The high-pressure method was found to be effective for synthesizing Mn-rich r-LiMO2 compounds, although their electrochemical properties should be improved.

Complementary evaluation of structure stability of perovskite oxides using bond-valence and density-functional-theory calculations.

Estimation of structure stability is an essential issue in materials design and synthesis. Global instability index (GII) based on bond-valence method is applied as a simple indication, while density functional theory calculation is adopted for accurate evaluation of formation energy. We compare the GII and total energy of typical ABO3-type perovskite oxides and rationalize their relationship, proposing that the criteria for empirically unstable structures (GII > 0.2 valence unit) correspond to the difference in total energy of 50-200 meV per formula unit.

High-pressure synthesis and electrochemical properties of tetragonal LiMnO2.

Tetragonal structured LiMnO2 (t-LiMnO2) samples were synthesized under pressures above 8 GPa and investigated as a positive electrode material for lithium-ion batteries. Rietveld analyses based on X-ray diffraction measurements indicated that t-LiMnO2 belongs to a γ-LiFeO2-type crystal structure with the I41/amd space group. The charge capacity during the initial cycle was 37 mA h g-1 at 25 °C, but improved to 185 mA h g-1 at 40 °C with an average voltage of 4.56 V vs. Li+/Li. This demonstrated the superiority of t-LiMnO2 over other lithium manganese oxides in terms of energy density. The X-ray diffraction measurements and Raman spectroscopy of cycled t-LiMnO2 indicated an irreversible transformation from the γ-LiFeO2-type structure into a Li x Mn2O4 spinel structure by the displacement of 25% of the Mn ions to vacant octahedral sites through adjacent octahedral sites.

Novel catalytic properties of quadruple perovskites.

Quadruple perovskite oxides AA'3B4O12 demonstrate a rich variety of structural and electronic properties. A large number of constituent elements for A/A'/B-site cations can be introduced using the ultra-high-pressure synthesis method. Development of novel functional materials consisting of earth-abundant elements plays a crucial role in current materials science. In this paper, functional properties, especially oxygen reaction catalysis, for quadruple perovskite oxides CaCu3Fe4O12 and AMn7O12 (A = Ca, La) composed of earth-abundant elements are reviewed.

Perovskite-Type InCoO3 with Low-Spin Co3+: Effect of In-O Covalency on Structural Stabilization in Comparison with Rare-Earth Series.

Perovskite rare-earth cobaltites ACoO3 (A = Sc, Y, La-Lu) have been of enduring interest for decades due to their unusual structural and physical properties associated with the spin-state transitions of low-spin Co3+ ions. Herein, we have synthesized a non-rare-earth perovskite cobaltite, InCoO3, at 15 GPa and 1400 °C and investigated its crystal structure and magnetic ground state. Under the same high-pressure and high-temperature conditions, we also prepared a perovskite-type ScCoO3 with an improved cation stoichiometry in comparison to that in a previous study, where synthesis at 6 GPa and 1297 °C yielded a perovskite cobaltite with cation mixing on the A-site, (Sc0.95Co0.05)CoO3. The two perovskite phases have nearly stoichiometric cation compositions, crystallizing in the orthorhombic Pnma space group. In the present investigation, comprehensive studies on newly developed and well-known Pnma ACoO3 perovskites (A = In, Sc, Y, Pr-Lu) show that InCoO3 does not fulfill the general evolution of crystal metrics with A-site cation size, indicating that InCoO3 and rare-earth counterparts have different chemistry for stabilizing the Pnma structures. Detailed structural analyses combined with first-principles calculations reveal that the origin of the anomaly for InCoO3 is ascribed to the A-site cation displacements that accompany octahedral tilts; despite the highly tilted CoO6 network, the In-O covalency makes In3+ ions reluctant to move from their ideal cubic-symmetry position, leading to less orthorhombic distortion than would be expected from electrostatic/ionic size mismatch effects. Magnetic studies demonstrate that InCoO3 and ScCoO3 are diamagnetic with a low-spin state of Co3+ below 300 K, in contrast to the case of (Sc0.95Co0.05)CoO3, where the high-spin Co3+ ions on the A-site generate a large paramagnetic moment. The present work extends the accessible composition range of the low-spin orthocobaltite series and thus should help to establish a more comprehensive understanding of the structure-property relation.

Covalency Competition in the Quadruple Perovskite CdCu3Fe4O12.

Cadmium ions (Cd2+) are similar to calcium ions (Ca2+) in size, whereas the Cd2+ ions tend to form covalent bonds with the neighboring anions because of the high electronegativity. The covalent Cd-O bonds affect other metal-oxygen bonds, inducing drastic changes in crystal structures and electronic states. Herein, we demonstrate high-pressure synthesis, crystal structure, and properties of a new quadruple perovskite CdCu3Fe4O12. This compound exhibits an electronic phase transition accompanying a charge disproportionation of Fe ions without charge ordering below ∼200 K, unlike charge-disproportionation transition with rock-salt-type charge ordering for CaCu3Fe4O12. First-principle calculations and Mössbauer spectroscopy display that covalent Cd-O bonds effectively suppress the Fe-O bond covalency, resulting in an electronic state different from that of CaCu3Fe4O12. This finding proposes covalency competition among constituent metal ions dominating electronic states of complex metal oxides.