Effects of Doping Ni on the Microstructures and Thermoelectric Properties of Co-Excessive NbCoSn Half-Heusler Compounds.

The half-Heusler (HH) compound NbCoSn with 18 valence electrons is a promising thermoelectric (TE) material due to its appropriate electrical properties as well as its suitable thermal and chemical stability. Nowadays, doping/substitution and tailoring of microstructures are common experimental approaches to enhance the TE performance of HH compounds. However, detailed theoretical insights into the effects of doping on the microstructures and TE properties are still missing. In this work, the microstructure of NbCoSn was tailored through precipitating the full-Heusler phases in the matrix by changing the nominal ratio of Co and Ni on the Co sites, focusing on the resulting TE properties. Further, first-principles calculations were employed to understand the relationship between the microstructure and the TE properties from the thermodynamic point of view. Detailed analysis of the electronic structure reveals that the presence of excess Co/Ni contributes to the increasing carrier concentration. Through an increase in the electrical conductivity and a reduction in the thermal conductivity, the TE performance is improved. Therefore, the present work offers a new pathway and insights to enhance the TE properties by modifying the microstructure of HH compounds via tailoring the chemical compositions.

Holistic View on Materials Development: Water Electrolysis as a Case Study.

In view of rising ecological awareness, materials development is primarily aimed at improving the performance and efficiency of innovative and more elaborate materials. However, a materials performance figure of merit should include essential aspects of materials: environmental impact, economic constraints, technical feasibility, etc. Thus, we promote the inclusion of sustainability criteria already during the materials design process. With such a holistic design approach, new products may be more likely to meet the circular economy requirements than when traditional development strategies are pursued. Using catalysts for water electrolysis as an example, we present a modelling method based on experimental data to holistically evaluate processes.

Tailoring the structure and thermoelectric properties of BaTiO3via Eu2+ substitution.

A series of Ba1-xEuxTiO3-δ (0.1 ≤ x ≤ 0.9) phases with ∼40 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 Å (equal to ∼5 unit cells) deviations from the cubic structure model (Pm3[combining macron]m) were detected by evaluation of the pair distribution function (PDF). These deviations cannot be explained by a simple symmetry breaking model like in EuTiO3-δ. The best fit was achieved in the space group Amm2 allowing for a movement of Ti and Ba/Eu along 〈110〉 of the parent unit cell as observed for BaTiO3. Density functional calculations delivered an insight into the electronic structure of Ba1-xEuxTiO3-δ. 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-europium 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 < T < 1123 K) the conduction mechanism of Ba1-xEuxTiO3-δ (0.1 ≤ x ≤ 0.9) is a polaron hopping when 0 < x ≤ 0.6 and is a thermally activated process when 0.6 < x < 1. Besides, the thermal conductivity increases with increasing Eu2+ concentration. Due to a remarkable improvement of the power factor, Ba0.1Eu0.9TiO3-δ showed a ZT value of 0.24 at 1123 K.

Low-temperature-processed efficient semi-transparent planar perovskite solar cells for bifacial and tandem applications.

Semi-transparent perovskite solar cells are highly attractive for a wide range of applications, such as bifacial and tandem solar cells; however, the power conversion efficiency of semi-transparent devices still lags behind due to missing suitable transparent rear electrode or deposition process. Here we report a low-temperature process for efficient semi-transparent planar perovskite solar cells. A hybrid thermal evaporation-spin coating technique is developed to allow the introduction of PCBM in regular device configuration, which facilitates the growth of high-quality absorber, resulting in hysteresis-free devices. We employ high-mobility hydrogenated indium oxide as transparent rear electrode by room-temperature radio-frequency magnetron sputtering, yielding a semi-transparent solar cell with steady-state efficiency of 14.2% along with 72% average transmittance in the near-infrared region. With such semi-transparent devices, we show a substantial power enhancement when operating as bifacial solar cell, and in combination with low-bandgap copper indium gallium diselenide we further demonstrate 20.5% efficiency in four-terminal tandem configuration.

The electrodeposition of FeCrNi stainless steel: microstructural changes induced by anode reactions.

The FeCrNi alloy, whose composition is close to that of stainless steel 304, was prepared by electrodeposition and characterized. Nanocrystalline FeCrNi (nc-FeCrNi) was obtained by employing a double-compartment cell where the anode is separated from the cathode compartment, while amorphous FeCrNi (a-FeCrNi) was deposited in a conventional single electrochemical cell. The carbon content of nc-FeCrNi was found to be significantly lower than that of a-FeCrNi, suggesting that carbon inclusion is responsible for the change in the microstructure. The major source of carbon is associated with the reaction compounds at the anode electrode, presumably decomposed glycine. Crystal structure analysis by XRD and TEM revealed that the as-deposited nc-FeCrNi deposits consist of α-Fe which transforms to γ-Fe upon thermal annealing. Nanoindentation tests showed that nc-FeCrNi exhibits higher hardness than a-FeCrNi, which is consistent with the inverse Hall-Petch behavior.

Revealing the dynamic structure of complex solid catalysts using modulated excitation X-ray diffraction.

X-ray diffraction (XRD) is typically silent towards information on low loadings of precious metals on solid catalysts because of their finely dispersed nature. When combined with a concentration modulation approach, time-resolved high-energy XRD is able to provide the detailed redox dynamics of palladium nanoparticles with a diameter of 2 nm in 2 wt % Pd/CZ (CZ = ceria-zirconia), which is a difficult sample for extended X-ray absorption fine structure (EXAFS) measurements because of the cerium component. The temporal evolution of the Pd(111) and Ce(111) reflections together with surface information from synchronous diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements reveals that Ce maintains Pd oxidized in the CO pulse, whereas reduction is detected at the beginning of the O2 pulse. Oxygen is likely transferred from Pd to Ce(3+) before the onset of Pd re-oxidation. In this context, adsorbed carbonates appear to be the rate-limiting species for re-oxidation.

Synchrotron high energy X-ray methods coupled to phase sensitive analysis to characterize aging of solid catalysts with enhanced sensitivity.

X-ray absorption spectroscopy and X-ray diffraction are suitable probes of the chemical state of a catalyst under working conditions but are limited to bulk information. Here we show in two case studies related to hydrothermal aging and chemical modification of model automotive catalysts that enhanced detailed information of structural changes can be obtained when the two methods are combined with a concentration modulated excitation (cME) approach and phase sensitive detection (PSD). The catalysts are subject to a modulation experiment consisting of the periodic variation of the gas feed composition to the catalyst and the time-resolved data are additionally treated by PSD. In the case of a 2 wt% Rh/Al2O3 catalyst, a very small fraction (ca. 2%) of Rh remaining exposed at the alumina surface after hydrothermal aging at 1273 K can be detected by PSD. This Rh is sensitive to the red-ox oscillations of the experiment and is likely responsible for the observed catalytic activity and selectivity during NO reduction by CO. In the case of a 1.6 wt% Pd/Al2O3-Ce(1-x)Zr(x)O2 catalyst, preliminary results of cME-XRD demonstrate that access to the kinetics of the whole material at work can be obtained. Both the red-ox processes involving the oxygen storage support and the Pd component can be followed with great precision. PSD enables the differentiation between Pd deposited on Al2O3 or on Ce(1-x)Zr(x)O2. Modification of the catalyst by phosphorous clearly induces loss of the structural dynamics required for oxygen storage capacity that is provided by the Ce(4+)/Ce(3+) pair. The two case studies demonstrate that detailed kinetics of subtle changes can be uncovered by the combination of in situ X-ray absorption and high energy diffraction methods with PSD.

Synthesis, characterization, electronic and gas-sensing properties towards H2 and CO of transparent, large-area, low-layer graphene.

Low-layered, transparent graphene is accessible by a chemical vapor deposition (CVD) technique on a Ni-catalyst layer, which is deposited on a <100> silicon substrate. The number of graphene layers on the substrate is controlled by the grain boundaries in the Ni-catalyst layer and can be studied by micro Raman analysis. Electrical studies showed a sheet resistance (R(sheet)) of approximately 1435 Ω per □, a contact resistance (R(c)) of about 127 Ω, and a specific contact resistance (R(sc)) of approximately 2.8×10(-4) â€…Ω cm(2) for the CVD graphene samples. Transistor output characteristics for the graphene sample demonstrated linear current/voltage behavior. A current versus voltage (I(ds)-V(ds)) plot clearly indicates a p-conducting characteristic of the synthesized graphene. Gas-sensor measurements revealed a high sensor activity of the low-layer graphene material towards H(2) and CO. At 300 °C, a sensor response of approximately 29 towards low H(2) concentrations (1 vol %) was observed, which is by a factor of four higher than recently reported.

LaTiO2N/In2O3 photoanodes with improved performance for solar water splitting.

LaTiO(2)N photoanodes for solar water splitting were prepared by electrophoretic deposition and demonstrated the best photocurrents ever reported for this material. Further important enhancement of the performance was obtained by the use of a sputtered In(2)O(3) overlayer.

Surfactant-free hydrothermal synthesis of highly tetragonal barium titanate nanowires: a structural investigation.

Barium titanate nanowires synthesized with a surfactant-free hydrothermal method have been characterized by various techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), synchrotron X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The TEM and SEM analyses show the uniform cylindrical nanowires. The Rietveld refinement with synchrotron X-ray powder diffraction showed that the lattice parameters of cubic and tetragonal phases were a (= b = c) = 4.0134 A and a (= b) = 3.9998 A, c = 4.0303 A, respectively. The final weighted R-factor, R(wp), was 6.75% and the goodness of fit indicator was 1.30. The mass fraction of tetragonal and cubic phases based on the refined scale factor for the two phases were 98.4% and 1.6%, respectively, which clearly show the nanowires are tetragonal. The XPS analysis has shown that as-obtained BaTiO3 nanowires were phase pure. The Raman spectra confirm the tetragonal phase of the BaTiO3 nanowires. The dielectric constant measurement shows the shift in the transition temperature (Tc = 105 degrees C) compared to the bulk transition temperature (Tc = 132 degrees C). The dielectric constant at Tc was 174 measured at 1 kHz frequency.