Influence of Doping and Nanostructuration on n-Type Bi2(Te0.8Se0.2)3 Alloys Synthesized by Arc Melting

In competitive thermoelectric devices for energy conversion and generation, high-efficiency materials of both n-type and p-type are required. For this, Bi2Te3-based alloys have the best thermoelectric properties in room temperature applications. Partial replacement of tellurium by selenium is expected to introduce new donor states in the band gap, which would alter electrical conductivity and thermopower. We report on the preparation of n-type Bi2(Te1-xSex)3 solid solutions by a straightforward arc-melting technique, yielding nanostructured polycrystalline pellets. X-ray and neutron powder diffraction was used to assess Se inclusion, also indicating that the interactions between quintuple layers constituting this material are weakened upon Se doping, while the covalency of intralayer bonds is augmented. Moreover, scanning electron microscopy shows large surfaces perpendicular to the c crystallographic axis assembled as stacked sheets. Grain boundaries related to this 2D nanostructuration affect the thermal conductivity reducing it below 0.8 Wm−1K−1 at room temperature. Furthermore, Se doping increases the absolute Seebeck coefficient up to −140 μV K−1 at 400 K, which is also beneficial for improved thermoelectric efficiency.This research was funded by the Spanish Ministry of Economy and Competitivity for granting the project MAT2013-41099-R.Peer reviewe

Nanostructured Thermoelectric Chalcogenides

Thermoelectric materials are outstanding to transform temperature differences directly and reversibly into electrical voltage. Exploiting waste heat recovery as a source of power generation could help towards energy sustainability. Recently, the SnSe semiconductor was identified, in single-crystal form, as a mid-temperature thermoelectric material with record high figure of merit, high power factor and surprisingly low thermal conductivity. We describe the preparation of polycrystals of alloys of SnSe obtained by arc-melting; a rapid synthesis that results in strongly nanostructured samples with low thermal conductivity, advantageous for thermoelectricity, approaching the amorphous limit, around 0.3–0.5 W/mK. An initial screening of novel samples Sn1−xMxSe, by alloying with 3d and 4d transition metals such as M = Mn, Y, Ag, Mo, Cd or Au, provides for a means to optimize the power factor. M=Mo, Ag, with excellent values, are described in detail with characterization by x-ray powder diffraction (XRD), scanning electron microscopy (SEM), and electronic and thermal transport measurements. Rietveld analysis of XRD data demonstrates near-perfect stoichiometries of the above-mentioned alloys. SEM analysis shows stacking of nanosized sheets, with large surfaces parallel to layered slabs. An apparatus was developed for the simultaneous measurement of the Seebeck coefficient and electric conductivity at elevated temperatures

Features of the High-Temperature Structural Evolution of GeTe Thermoelectric Probed by Neutron and Synchrotron Powder Diffraction

Among other chalcogenide thermoelectric materials, GeTe and derivative alloys are good candidates for intermediate temperature applications, as a replacement for toxic PbTe. We have prepared pure polycrystalline GeTe by using arc-melting, and investigated its structural evolution by using neutron powder diffraction (NPD) and synchrotron X-ray diffraction (SXRD), as well as its correlation with the thermal variation of the Seebeck coefficient. Besides a significant Ge deficiency (~7% Ge vacancies), the thermal evolution of the unit-cell volume and Ge-Te bond lengths in the rhombohedral phase (space group R3m), below 700 K, show unexpected anomalies involving the abrupt Ge-Te bond lengthening accompanied by increased Te thermal displacements. Above 700 K, the sample is cubic (space group Fm-3m) and shows considerably larger displacement parameters for Ge than for Te, as a consequence of the random distribution of the lone pair lobes of Ge2+. The Seebeck coefficient, reaching 120 μV K−1 at 775 K, shows a shoulder in the 500–570 K region that can be correlated to the structural anomaly, modifying the electron-phonon scattering in this temperature range

Nanostructured State-of-the-Art Thermoelectric Materials Prepared by Straight-Forward Arc-Melting Method

Thermoelectric materials constitute an alternative to harvest sustainable energy from waste heat. Among the most commonly utilized thermoelectric materials, we can mention Bi2Te3 (hole and electron conductivity type), PbTe and recently reported SnSe intermetallic alloys. We review recent results showing that all of them can be readily prepared in nanostructured form by arc-melting synthesis, yielding mechanically robust pellets of highly oriented polycrystals. These materials have been characterized by neutron powder diffraction (NPD), scanning electron microscopy (SEM) and electronic and thermal transport measurements. Analysis of NPD patterns demonstrates near-perfect stoichiometry of above-mentioned alloys and fair amount of anharmonicity of chemical bonds. SEM analysis shows stacking of nanosized sheets, each of them presumably single-crystalline, with large surfaces parallel to layered slabs. This nanostructuration affects notably thermoelectric properties, involving many surface boundaries (interfaces), which are responsible for large phonon scattering factors, yielding low thermal conductivity. Additionally, we describe homemade apparatus developed for the simultaneous measurement of Seebeck coefficient and electric conductivity at elevated temperatures

Enhanced stability in CH3NH3PbI3 hybrid perovskite from mechano-chemical synthesis: structural, microstructural and optoelectronic characterization

Among the hybrid organic–inorganic perovskites MAPbX3 (MA: methyl-ammonium CH3–NH3+, X = halogen), the triiodide specimen (MAPbI3) is still the material of choice for solar energy applications. Although it is able to absorb light above its 1.6 eV bandgap, its poor stability in humid air atmosphere has been a major drawback for its use in solar cells. However, we discovered that this perovskite can be prepared by ball milling in a straightforward way, yielding specimens with a superior stability. This fact allowed us to take atomic-resolution STEM images for the first time, with sufficient quality to unveil microscopic aspects of this material. We demonstrated full Iodine content, which might be related to the enhanced stability, in a more compact PbI6 framework with reduced unit-cell volume. A structural investigation from neutron powder diffraction (NPD) data of an undeuterated specimen was essential to determine the configuration of the organic MA unit in the 100–298 K temperature range. A phase transition is identified, from the tetragonal structure observed at RT (space group I4/mcm) to an orthorhombic (space group Pnma) phase where the methyl-ammonium organic units are fully localized. Our NPD data reveal that the MA changes are gradual and start before reaching the phase transition. Optoelectronic measurements yield a photocurrent peak at an illumination wavelength of 820 nm, which is redshifted by 30 nm with respect to previously reported measurements on MAPbI3 perovskites synthesized by crystallization from organic solvents.Fil: Lopez, Carlos Alberto. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Área Química General e Inorgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Abia, Carmen. Instituto de Ciencia de Materiales de Madrid; España. Institut Laue Langevin; FranciaFil: Rodrigues, Joao E.. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Serrano Sánchez, Federico. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Nemes, Norbert M.. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Martínez, José L.. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Fernandez Díaz, María T.. Institut Laue Langevin; FranciaFil: Biškup, Neven. Universidad Complutense de Madrid; EspañaFil: Alvarez Galván, Consuelo. Consejo Superior de Investigaciones Científicas; EspañaFil: Carrascoso, Felix. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Castellanos Gomez, Andres. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Alonso, José A.. Instituto de Ciencia de Materiales de Madrid; Españ

Impact of antibiotic therapy on systemic cytokine expression in pneumococcal pneumonia

The aim of this study was to compare the evolution of systemic cytokine levels over time in patients with pneumococal pneumonia treated either with β-lactam monotherapy or with combination therapy (β-lactam plus fluoroquinolone). Prospective observational study of hospitalized non-immunocompromised adults with PP. Concentrations of IL-6, IL-8, IL-10, and TNF-α were determined on days 0, 1, 2, 3, 5, and 7. Patients on β-lactam monotherapy were compared with those receiving combination therapy. Fifty-two patients were enrolled in the study. Concentrations of IL-6, IL-8, and IL-10 decreased rapidly in the first days after admission, in accordance with the mean time to defervescence. High levels of IL-6 were found in patients with the worst outcomes, measured by the need for intensive care unit admission and mortality. No major differences in demographic or clinical characteristics or severity of disease were found between patients treated with β-lactam monotherapy and those treated with combination therapy. IL-6 levels fell more rapidly in patients with combination therapy in the first 48 h (p = 0.016). Our data suggest that systemic expression of IL-6 production in patients with PP correlates with prognosis. Initial combination antibiotic therapy produces a faster decrease in this cytokine in the first 48 h

Reduced thermal conductivity in Nnnostructured AgSbTe_(2) thermoelectric material, obtained by Arc-Melting

AgSbTe_(2) intermetallic compound is a promising thermoelectric material. It has also been described as necessary to obtain LAST and TAGS alloys, some of the best performing thermoelectrics of the last decades. Due to the random location of Ag and Sb atoms in the crystal structure, the electronic structure is highly influenced by the atomic ordering of these atoms and makes the accurate determination of the Ag/Sb occupancy of paramount importance. We report on the synthesis of polycrystalline AgSbTe_(2) by arc-melting, yielding nanostructured dense pellets. SEM images show a conspicuous layered nanostructuration, with a layer thickness of 25-30 nm. Neutron powder diffraction data show that AgSbTe_(2) crystalizes in the cubic Pm-3m space group, with a slight deficiency of Te, probably due to volatilization during the arc-melting process. The transport properties show some anomalies at similar to 600 K, which can be related to the onset temperature for atomic ordering. The average thermoelectric figure of merit remains around similar to 0.6 from similar to 550 up to similar to 680 K

Thermal expansion and rattling behavior of Gd-filled Co_(4)Sb_(12) skutterudite determined by high-resolution synchrotron x-ray diffraction

In this work, Gd-filled skutterudite Gd_(x)Co_(4)Sb_(12) was prepared using one step method under high pressure in a piston-cylinder-based press at 3.5 GPa and moderate temperature of 800 degrees C. A detailed structural characterization was performed using synchrotron X-ray diffraction (SXRD), revealing a filling fraction of x = 0.033(2) and an average bond length of 3.3499(3) angstrom. The lattice thermal expansion accessed via temperature-dependent SXRD led to a precise determination of a Debye temperature of 322(3) K, from the fitting of the unit-cell volume expansion using the second order Gruneisen approximation. This parameter, when evaluated through the mean square displacements of Co and Sb, displayed a value of 265(2) K, meaning that the application of the harmonic Debye theory underestimates the Debye temperature in skutterudites. Regarding the Gd atom, its intrinsic disorder value was similar to 5x and similar to 25x higher than those of the Co and Sb, respectively, denoting that Gd has a strong rattling behavior with an Einstein temperature of theta(E) = 67(2) K. As a result, an ultra-low thermal conductivity of 0.89 W/m center dot K at 773 K was obtained, leading to a thermoelectric efficiency zT of 0.5 at 673 K

Evidence of hydrogen content and monovalent Ni oxidation state in non-superconducting bulk anchored infinite-layer nickelates

Since superconductivity was first reported in nickelate thin films, many studies have been published about this family of materials, and different hypotheses have been proposed for explaining the mechanisms and structural dependence. Here, we report the synthesis of anchored infinite-layer LaNi0.9Al0.1O2.1 and its hole-doped derivatives by topotactic reduction from La1−xSrxNi0.9Al0.1O3 rhombohedral perovskites. LaNiO2 derivatives constitute a new family of high-temperature superconductors, with the same structure as high-Tc cuprates but based on nickel, only showing superconductivity in thin films for now. We describe a strategy to stabilize LaNiO2 derivatives in bulk: the presence of Al at the octahedral sites helps to stabilize/anchor the infinite-layer structure. The reasons for the bulk being non-superconductors are hotly debated in the literature. An important question is whether there is some hydrogen incorporated into the structure during the reduction process from LaNiO3 to LaNiO2, predicted theoretically but not reported experimentally. Our neutron powder diffraction data show that, indeed, hydrogen occupies the centers of the Ni–O squares, and spectroscopic evidence from EELS and XAS suggests that Ni is reduced to the Ni+ oxidation state, consistent with the crystallochemical data. © 2023 The AuthorsJ.E.F.S.R. thanks Dr. Carlos Pecharroman and the Service of IR spectroscopy and ellipsometry of the ‘‘Instituto de Ciencia de Materiales de Madrid-CSIC’’ for FTIR measurements. The authors wish to express their gratitude to the ILL and the European Synchrotron Radiation Facility (ESRF) for making all facilities available for neutron and synchrotron diffraction experiments (ESRF proposal HC-4990 in ID22 and in-house beamtime in BM23). Electron microscopy observations were carried out at the Centro Nacional de Microscopia Electronica (CNME-UCM). We are thankful for funding from the Spanish Ministry of Science and Innovation (MCIN/AEI/10.13039/501100011033) with grant nos. PID2021-122477OB-I00, TED2021-129254B-C21, and TED2021-129254B-C22. J.G. thanks MCIN for granting the contract PRE2018-083398. F.S.-S. is thankful for the grant RYC2021- 033518-I, funded by NextGenerationEU and MICIN.Supplemental information can be found online at https://doi.org/10.1016/j.xcrp. 2023.101724.Peer reviewe

Structural evolution from neutron powder diffraction of nanostructured snte obtained by arc melting

Among chalcogenide thermoelectric materials, SnTe is an excellent candidate for intermediate temperature applications, in replacement of toxic PbTe. We have prepared pure polycrystalline SnTe by arc melting, and investigated the structural evolution by temperature-dependent neutron powder diffraction (NPD) from room temperature up to 973 K. In this temperature range, the sample is cubic (space group Fm-3m) and shows considerably larger displacement parameters for Te than for Sn. The structural analysis allowed the determination of the Debye model parameters and provided information on the Sn-Te chemical bonds. SEM images show a conspicuous nanostructuration in layers below 30 nm thick, which contributes to the reduction of the thermal conductivity down to 2.5 W/m center dot K at 800 K. The SPS treatment seems to reduce the number of Sn vacancies, thus diminishing the carrier density and increasing the Seebeck coefficient, which reaches 60 mu V K^(-1) at 700 K, as well as the weighted mobility, almost doubled compared with that of the as-grown sample