Reversible control of the electronic density of states at the Fermi level of Ca3Co4O9+δ misfit-layered oxide single crystals through O+/H+ plasma exposure

Misfit-layered Ca3Co4O9 crystals were grown and characterized via XRD, SEM, and photo-emission spectroscopy (PES). The evolution of the intensity at the Fermi level (E F) with varying oxygen content was studied by PES. Oxygen species were successfully introduced and removed through O+ and H+ microwave-plasma (2.45GHz, 2-5mbar) treatments, respectively. A 5min O+ plasma exposure was observed to result into a drastic enhancement in the E F intensity, demonstrating the influence of oxygen content to the charge carrier population in layered cobalt-oxide material

Emergence of a Dynamic Super-Structural Order Integrating Antiferroelectric and Antiferrodistortive Competing Instabilities in EuTiO3

Microscopic structural instabilities of EuTiO3 single crystal were investigated by synchrotron x-ray diffraction. Antiferrodistortive (AFD) oxygen octahedral rotational order was observed alongside Ti derived antiferroelectric (AFE) distortions. The competition between the two instabilities is reconciled through a cooperatively modulated structure allowing both to coexist. The electric and magnetic field effect on the modulated AFD order shows that the origin of large magnetoelectric coupling is based upon the dynamic equilibrium between the AFD - antiferromagnetic interactions versus the electric polarization - ferromagnetic interactions

Anomalous transport properties of the halfmetallic ferromagnets Co2TiSi, Co2TiGe, and Co2TiSn

In this work the theoretical and experimental investigations of Co2TiZ (Z = Si, Ge, or Sn) compounds are reported. Half-metallic ferromagnetism is predicted for all three compounds with only two bands crossing the Fermi energy in the majority channel. The magnetic moments fulfill the Slater-Pauling rule and the Curie temperatures are well above room temperature. All compounds show a metallic like resistivity for low temperatures up to their Curie temperature, above the resistivity changes to semiconducting like behavior. A large negative magnetoresistance of 55% is observed for Co2TiSn at room temperature in an applied magnetic field of 4T which is comparable to the large negative magnetoresistances of the manganites. The Seebeck coefficients are negative for all three compounds and reach their maximum values at their respective Curie temperatures and stay almost constant up to 950 K. The highest value achieved is -52muV/K m for Co2TiSn which is large for a metal. The combination of half-metallicity and the constant large Seebeck coefficient over a wide temperature range makes these compounds interesting materials for thermoelectric applications and further spincaloric investigations.Comment: 4 pages 4 figure

Lab Scale Fixed-Bed Reactor for Operando X-Ray Absorption Spectroscopy for Structure Activity Studies of Supported Metal Oxide Catalysts

Lab scale fixed-bed reactor is applied for operando transmission X-ray absorption spectroscopy (XAS) for structure-activity studies of supported metal oxide catalysts under real reaction conditions. This setup includes many properties of an optimal fixed-bed reactor for operando transmission XAS studies. For instance, it is usable in a wide range of temperature (up to 1,000°C), pressure and space velocity. Besides, this operando setup can be used for transmission XAS measurements in a wide edge energy range. The potential of this reactor for operando transmission XAS is demonstrated by, as examples, the three-way catalytic performance of Pd/Al2O3/CeZrO2 and Rh/Al2O

Synthesis and Characterization of New Ceramic Thermoelectrics Implemented in a Thermoelectric Oxide Module

Novel thermoelectric oxides were developed, produced, and characterized to demonstrate their promising thermoelectric conversion potential in a thermoelectric converter. Four-leg thermoelectric oxide modules were fabricated by combining p- and n-type oxide thermoelements made of pressed polycrystalline GdCo0.95Ni0.05O3 and CaMn0.98Nb0.02O3, respectively. In these modules, the p- and n-type thermoelements were connected electrically in series and thermally in parallel. The materials were joined by electrical contacts consisting of a Ag/CuO composite material. Fairly good thermal contacts were ensured by pressing the thermoelements between alumina substrates. Cross-sections of the alumina/Ag-CuO mixture/thermoelement interface were investigated by scanning electron microscopy. The temperature distribution across the module was monitored using K-type thermocouples and a micro-infrared (IR) camera. The open-circuit voltage and the load voltages of the module were measured up to a temperature difference of ΔT=500K while keeping the temperature of the cold side at 300K. The output power and internal resistance were calculated. The characteristics of the module evaluated from electrical measurements were compared with respective values of the p- and n-type leg materials. An output power of 0.04W at ΔT=500K led to a power density of ~0.125W/cm3, where the volume of thermoelectric material was determined by a cross-section of 4mm×4mm and a leg length of 5m

Unravelling the effects of calcium substitution in BaGd2CoO5 Haldane gap 1D material and its thermoelectric performance

Ecobenign and high-temperature-stable oxides are considered a promising alternative to traditional Bi2Te3-, Bi2Se3-, and PbTe-based thermoelectric materials. The quest for high-performing thermoelectric oxides is still open and, among other challenges, includes the screening of various materials systems for potentially promising electrical and thermal transport properties. In this work, a new family of acceptor-substituted Haldane gap 1D BaGd2CoO5 dense ceramic materials was characterized in this respect. The substitution of this material with calcium results in a general improvement of the electrical performance, contributed by an interplay between the charge carrier concentration and their mobility. Nevertheless, a relatively low electrical conductivity was measured, reaching ∼5 S/cm at 1175 K, resulting in a maximum power factor of ∼25 μW/(K × m2) at 1173 K for BaGd1.80Ca0.20CoO5. On the other hand, the unique anisotropic 1D structure of the prepared materials promotes efficient phonon scattering, leading to low thermal conductivities, rarely observed in oxide electroceramics. While the BaGd2–xCaxCoO5 materials show attractive Seebeck coefficient values in the range 210–440 μV/K, the resulting dimensionless figure of merit is still relatively low, reaching ∼0.02 at 1173 K. The substituted BaGd2–xCaxCoO5 ceramics show comparable thermoelectric performance in both inert and air atmospheres. These features highlight the potential relevance of this structure type for thermoelectric applications, with future emphasis placed on methods to improve conductivity.publishe

Tailoring the structure and thermoelectric properties of BaTiO3via Eu2+ substitution

A series of Ba1_xEuxTiO3_d (0.1 < x < 0.9) phases with B40 nm particle size were synthesized via a Pechini method followed by annealing and sintering under a reducing atmosphere. The effects of Eu2+ substitution on the BaTiO3 crystal structure and the thermoelectric transport properties were systematically investigated. According to synchrotron X-ray diffraction data only cubic perovskite structures were observed. On the local scale below about 20 \uc5 (equal to B5 unit cells) deviations from the cubic structure model (Pm%3m) were detected by evaluation of the pair distribution function (PDF). These deviations cannot be explained by a simple symmetry breaking model like in EuTiO3_d. The best fit was achieved in the space group Amm2 allowing for a movement of Ti and Ba/Eu along h110i of the parent unit cell as observed for BaTiO3. Density functional calculations delivered an insight into the electronic structure of Ba1_xEuxTiO3_d. From the obtained density of states a significant reduction of the band gap by the presence of filled Eu2+ 4f states at the top of the valence band was observed. The physical property measurements revealed that barium\u2013europium titanates exhibit n-type semiconducting behavior and at high temperature the electrical conductivity strongly depended on the Eu2+ content. Activation energies calculated from the electrical conductivity and Seebeck coefficient data indicate that at high temperatures (800 K o T o 1123 K) the conduction mechanism of Ba1_xEuxTiO3_d (0.1 r x r 0.9) is a polaron hopping when 0 o x r 0.6 and is a thermally activated process when 0.6 o x o 1. Besides, the thermal conduc tivity increases with increasing Eu2+ concentration. Due to a remarkable improvement of the power factor, Ba0.1Eu0.9TiO3_d showed a ZT value of 0.24 at 1123 K

Multi-scale Designed CoxMn3–xO4 Spinels : Smart Pre-Catalysts towards High-Efficiency Pyrolysis-Catalysis Recycling of Waste Plastics

Acknowledgements M. W. and A. W. highly acknowledge the funding by the German Federal Ministry of Education and Research (BMBF) within the NexPlas project (project number: 03SF0618B). Y. S. Z is grateful for financial supports provided by the Royal Society of Chemistry Enablement Grant (E21-5819318767) and Royal Society of Chemistry Mobility Grant (M19-2899).Peer reviewedPostprin