Substitution of Re7+ into CaMnO3: an efficient free electron generation dopant for tuning of thermoelectric properties.

Highly dense CaMn1-xRexO3 (0 ≤ x ≤ 0.04) samples were prepared by solid-state synthesis. The effect of Re doping was assessed by the characterisation of crystal structure, oxygen content, and electrical and thermal transport properties. The oxidation state of the substituted Re was determined by X-ray absorption near edge spectra to be Re7+, and led to expansion of the lattice and an increase in electron carrier concentration due to the formation of Mn3+. The thermal behaviour of the electrical conductivity and the thermopower over a wide temperature range allowed identification of different conduction mechanisms: (1) below 110 K, 3D variable range hopping, (2) between 110 and 650 K, small polaron transport, and (3) above 650 K, activation of carriers over a mobility edge. Evaluation of the power factor expected for different dopant oxidation states as a function of dopant concentration shows that the doping strategy using a heavy heptavalent ion allows accessibility of the peak power factor at lower dopant concentrations, lowering the amount of non-ionised impurities, and therefore improves the electronic substitution efficiency, the ratio of activated carriers over the nominal doping concentration, compared to previously studied dopants. An increased power factor and a reduced lattice thermal conductivity are obtained with a peak figure of merit ZT = 0.16(3) at 947 K for CaMn0.98Re0.02O3. This is an approximately two-fold increase compared to undoped CaMnO3, and is comparable to the highest values reported for highly dense B-site doped CaMnO3

The effect of Mg location on Co-Mg-Ru/γ-Al2O3 Fischer–Tropsch catalysts

© 2016 The Author(s) Published by the Royal Society. All rights reserved.The effectiveness of Mg as a promoter of Co-Ru/γ-Al2O3 Fischer-Tropsch catalysts depends on how and when the Mg is added. When the Mg is impregnated into the support before the Co and Ru addition, some Mg is incorporated into the support in the form of MgxAl2O3+x if the material is calcined at 550°C or 800°C after the impregnation, while the remainder is present as amorphous MgO/MgCO3 phases. After subsequent Co-Ru impregnation MgxCo3-xO4 is formed which decomposes on reduction, leading to Co(0) particles intimately mixed with Mg, as shown by high-resolution transmission electron microscopy. The process of impregnating Co into an Mg-modified support results in dissolution of the amorphous Mg, and it is this Mg which is then incorporated into MgxCo3-xO4. Acid washing or higher temperature calcination after Mg impregnation can remove most of this amorphous Mg, resulting in lower values of x in MgxCo3-xO4. Catalytic testing of these materials reveals that Mg incorporation into the Co oxide phase is severely detrimental to the site-Time yield, while Mg incorporation into the support may provide some enhancement of activity at high temperature

Effects of Octahedral Tilting on Band Structure and Thermoelectric Power Factor of Titanate Perovskites: A First-Principles Study on SrTiO₃

Doped SrTiO_{3} and other perovskite structured titanates are attracting interest as n-type thermoelectric materials due to their relatively high thermoelectric power factor, low toxicity, and modest cost. Taking SrTiO_{3} as an example, the effects of octahedral tilting on the electronic band structure and thermoelectric power factor of titanate perovskites have been studied from first-principles calculations. By utilizing Glazer’s notation, six representative tilt systems, including three out-of-phase (a^{0}a^{0}c^{–}, a^{0}b^{-}b^{–}, and a^{–}a^{–}a^{–}) and three in-phase tilt systems (a^{0}a^{0}c^{+}, a^{0}b^{+}b^{+}, and a^{+}a^{+}a^{+}), were investigated. It is found that out-of-phase tilting improves the optimum power factor as compared to the cubic aristotype, while in-phase tilting marginally lowers the optimum power factor. The largest increase in power factor (∼100%) is obtained in the one-tilt system a^{0}a^{0}c^{–} at a tilt angle of 15°, which can be achieved with an energy cost of only 44 kJ mol^{–1} per formula unit. These findings agree with the experimental evidence that increased power factors are found in a^{0}a^{0}c^{–} and a^{–}a^{–}a^{–} tilt systems of titanate perovskites. The predicted increase of Seebeck coefficient as a function of tilt angle in the a^{–}a^{–}a^{–} tilt system of SrTiO_{3} is also consistent with the experimental increase of Seebeck coefficient in a^{–}a^{–}a^{–} titanates of La_{0.55}K_{0.45}TiO_{3} and La_{0.5}Na_{0.5}Ti_{0.9}Nb_{0.1}O_{3}. Our simulations provide valuable insights into tuning the thermoelectric power factor of titanate perovskites by controlling octahedral tilting

Self-assembled dynamic perovskite composite cathodes for intermediate temperature solid oxide fuel cells

Electrode materials for intermediate temperature (500–700 ∘C) solid oxide fuel cells require electrical and mechanical stability to maintain performance during the cell lifetime. This has proven difficult to achieve for many candidate cathode materials and their derivatives with good transport and electrocatalytic properties because of reactivity towards cell components, and the fuels and oxidants. Here we present Ba0.5Sr0.5(Co0.7Fe0.3)0.6875W0.3125O3−δ (BSCFW), a self-assembled composite prepared through simple solid state synthesis, consisting of B-site cation ordered double perovskite and disordered single perovskite oxide phases, as a candidate cathode material. These phases interact by dynamic compositional change at the operating temperature, promoting both chemical stability through the increased amount of W in the catalytically active single perovskite provided from the W-reservoir double perovskite, and microstructural stability through reduced sintering of the supported catalytically active phase. This interactive catalyst-support system enabled stable high electrochemical activity through the synergic integration of the distinct properties of the two phases

Vibrational properties of hexagonal LiBC: Infrared and Raman spectroscopy

The paper presents infrared reflectivity and micro-Raman scattering spectra of LiBC powder pellets. The experiment allowed assignment of frequencies of all infrared and Raman active zone center modes. Results are compared with available ab-initio calculations; prediction of large Born effective charges on the nodes of B-C graphene sheets is confirmed.Comment: 4 pages, 5 figures (change: Fig 2 replaced

Band structure engineering of carbon nitride hybrid photocatalysts for CO2 reduction in aqueous solutions

Through the co-polymerisation of dicyandiamide and barbituric acid precursors, a series of visible light active carbon nitride photocatalysts has been prepared and characterized, and their photocatalytic activity has been evaluated. Structural and electronic characterisation has enabled variations in observed activity towards water splitting and CO2 reduction to be understood, both in the presence and absence of the iron porphyrin co-catalyst Feiii tetra(4-carboxylphenyl)porphyrin (FeTCPP). A combination of the most active carbon nitride catalyst using 5 wt% barbituric acid and FeTCPP provides a hybrid system where the alignment of band structure with appropriate reduction potentials and enhanced carrier lifetimes is capable of CO2 reduction in an aqueous solution with >60% selectivity for CO production. This study is one of only a few that achieves selective CO2 reduction using a hybrid molecular catalyst-carbon nitride photocatalyst in aqueous solution

Upper critical field reaches 90 tesla near the Mott transition in fulleride superconductors

分子からなる超伝導体が従来超伝導線材を凌駕する臨界磁場90テスラを達成 -分子性固体における超伝導材料開発の新たな指針-. 京都大学プレスリリース. 2017-02-20

Highly Absorbing Lead-Free Semiconductor Cu₂AgBiI₆ for Photovoltaic Applications from the Quaternary CuI-AgI-BiI₃ Phase Space

Since the emergence of lead halide perovskites for photovoltaic research, there has been mounting effort in the search for alternative compounds with improved or complementary physical, chemical, or optoelectronic properties. Here, we report the discovery of Cu_{2}AgBiI_{6}: a stable, inorganic, lead-free wide-band-gap semiconductor, well suited for use in lead-free tandem photovoltaics. We measure a very high absorption coefficient of 1.0 × 10^{5} cm^{–1} near the absorption onset, several times that of CH_{3}NH_{3}PbI_{3}. Solution-processed Cu2AgBiI6 thin films show a direct band gap of 2.06(1) eV, an exciton binding energy of 25 meV, a substantial charge-carrier mobility (1.7 cm^{2} V^{–1} s^{–1}), a long photoluminescence lifetime (33 ns), and a relatively small Stokes shift between absorption and emission. Crucially, we solve the structure of the first quaternary compound in the phase space among CuI, AgI and BiI_{3}. The structure includes both tetrahedral and octahedral species which are open to compositional tuning and chemical substitution to further enhance properties. Since the proposed double-perovskite Cs2AgBiI6 thin films have not been synthesized to date, Cu_{2}AgBiI_{6} is a valuable example of a stable Ag^{+}/Bi^{3+} octahedral motif in a close-packed iodide sublattice that is accessed via the enhanced chemical diversity of the quaternary phase space