Effect of the rare earth in the perovskite-type mixed oxides AMnO3 (A=Y, La, Pr, Sm, Dy) as catalysts in methanol oxidation

The effect of the rare earth in the perovskite-type mixed oxides AMnO₃ (A=Y, La, Pr, Sm, Dy) on catalytic properties in methanol oxidation was investigated in this work. The perovskites were prepared by reactive grinding in order to enhance the specific surface area in comparison with other classical synthesis procedures. These catalysts were characterized by N₂ adsorption, X-ray diffraction, H₂ temperature-programmed reduction (TPR-H₂), O₂-, CH₃OH- and CO₂-temperature-programmed desorption (TPD). The activity of the five catalysts under study in the methanol oxidation reaction was evaluated. The behaviour of the α-O₂ from the surface of the perovskite was strongly related to the nature of the A-site cation and particularly to its electronegativity but also to its density. Concerning the β-O₂ from the bulk, the rare earth only induces an indirect effect notably due to structural modifications. As suggested in a previous study, the activity in methanol oxidation was directly linked with the surface oxygen density. Under an excess of α-oxygen, the reaction intermediate was found to be a monodentate carbonate that decomposes into CO₂. The stability of monodentate carbonates was also found to be related to the electronegativity of the rare earth during both CH₃OH- and CO₂-temperature-programmed desorption. However, as soon as a lack of α-oxygen was observed in the structure, the dominant reaction intermediate was a bidentate carbonate that induces a consumption of anion vacancies in spite of the production of CO₂. Nevertheless, the accumulation of these carbonates leads to a decrease in the oxidation rate since their desorption requires high temperatures.     

Oxygen production using La0.6Sr0.4Co0.2Fe0.8O3−α (LSCF) perovskite hollow fibre membrane modules

A phase-inversion/sintering technique has been employed in the production of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−α (LSCF) hollow fibre membranes, a bundle of which has then been placed in a high-temperature furnace for production of high purity oxygen from air at temperatures between 980 °C and 1060 °C. By applying a vacuum in the hollow fibre lumens, a product stream containing oxygen purity of 97.15% has been obtained. The downstream vacuum degree higher than 99 kPa shows negligible effect on the oxygen production rate. Studies on long-term operation suggest that the LSCF hollow fibre membranes are less stable for the oxygen production due to the segregation of the constituent membrane elements and the formation of new phases on the outer membrane surfaces. The effect of the operating cycle on the retrogression of membrane performance is much larger than that of duration used in a single cycle.     

The enhancement of oxygen flux on Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) hollow fibers using silver surface modification

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) hollow fibers were fabricated using a phase inversion/sintering method. As oxygen permeation of BSCF hollow fibers is controlled by the rate surface exchange kinetics, catalytic Ag particles were coated on both inner and outer surfaces using chemical deposition method, as verified by SEM and EDX. The Ag coated BSCF membranes showed up to 100% increase in oxygen permeation at 700 °C, and improvements lower than 10% were measured at 950 °C as compared with unmodified membranes. It was found that Ag catalyst surface loading was non-homogenous and concentrated on the perovskite grain boundaries. As a result, lighter Ag surface loading delivered improved oxygen flux while oxygen flux reached a maximum even though in the presence of excess catalyst loading. The catalytic activity of Ag was beneficial in enhancing surface reaction kinetics up to 850 °C attributed to the spillover effect. Above this temperature, the increase in oxygen permeation rate was marginally diminished due to the reduction of the spillover effect.     

Preparation and characterization of KTa0.9Fe0.1O3– δ perovskite electrodes

The effect of the partial substitution of tantalum by iron on the structural and electrical properties of the KTaO₃ perovskite-type oxide powders has been studied. The powders were prepared by the standard ceramic method, and the respective structural characterization performed by X-ray powder diffraction. From the synthesized oxide samples, iron-coated electrodes were fabricated and tested as the anode for the oxygen evolution reaction in alkaline medium. An estimation of the electrode's capacity has been calculated from the charging currents and the corresponding roughness factor evaluated. The electrocatalytic activity/stability of the oxide electrodes in alkaline solutions has been analysed through the kinetic parameters. Electronic Publication     

Raman study of orbital mediated multiphonons in RMnO3 (R = Pr,Sm,Eu,Tb,Y)

We have studied RMnO₃ manganites (R = Pr, Sm, Eu, Tb, Y) Raman excitations in the 200–2800 cm^-1 range as a function of temperature. Combinations of phonon energies are observed up to the fourth order, indicating the presence of electron-phonon coupling. In comparison to Γ-point phonon combinations, double phonon excitations appear to be blue shifted in large size rare earth ion compounds. The phonon combination intensities decrease rapidly with their increasing order, confirming other studies which conclude that the electron-phonon coupling is not as strong as supposed in the localized limit. Moreover, different intensity order dependences are observed between the phonon combination and the so-called Jahn-Teller mode. These effects are better described in the orbiton-phonon coupling scheme.     

Correlation of band electronic structure with efficiency in perovskite solar cells with vanadium (Ⅳ) oxide thin film buffers

Perovskite solar cells have been studied extensively in the area of perovskite solar cells because they have a comparatively free hysteresis. Through fabrication of a perovskite solar cell based on a vanadium oxide buffer, this study clarified the mechanism of electron and hole transport in the laminated layer upon irradiation with light. The power conversion efficiency (PCE) of the Vanadium (Ⅳ) oxide (VO₂) sputtering process device was approximately 13% and with the spin-coating process was 8.5%. To investigate the physicochemical origin of such PCE differences depending on the process type, comprehensive band alignment and band structure analyses of the actual cell stacks were performed using X-ray photoelectron spectroscopy depth measurements. Accordingly, it was found that the inconsistent valence band offset between the perovskite absorption layer and V₂O₅ layer as a function of the VO₂ process type caused a difference in the hole transport, resulting in the difference in the efficiency.     

Metal grid technologies for flexible transparent conductors in large-area optoelectronics

Mechanically flexible optoelectronic devices such as flexible displays, touch-screens, wearable electronics and solar cells are attracting significant commercial interest. In these devices, a transparent conductor is an essential element that delivers or collects the electrical current to the active material while it allows light to enter or exit from the device. The transparent conductor is composed of a transparent conductive film and a metallic grid providing electrical conduction over the large area. In this article, we review the established processes used by the industry as well as emerging solution-based methods for processing metal grids. Furthermore, we review the issues and potentials of these emerging processes facing for large-area deployment. In the final section, we evaluate three applications of flexible transparent conductors in: perovskite-based solar cells, organic light emitting diodes and electrochromic windows.     

Room temperature magnetocaloric effect of La-deficient bulk perovskite manganite La0.7MnO3−δ

Room temperature magnetocaloric effect in La-deficient bulk perovskite manganite La_0.7MnO_3−δ prepared by conventional solid-state reaction has been reported. The maximum value of the magnetic entropy change (about−1.32 J/kg K) and the refrigerant capacity (approximately close to 37 J/kg) had been obtained at 290 K corresponding to a magnetic field variation of 1 T for La_0.7MnO_3−δ. It is the strong Jahn-Teller coupling that changes Mn-O bond length and Mn-O-Mn bond angles and then the canted spin arrangement and induces the strong double-exchange coupling to a comparatively high magnetic transition temperature. This Curie temperature near room temperature with easy fabrication and higher chemical stability makes La_0.7MnO_3−δ a potential candidate as a working substance in magnetic refrigeration technology.     

烧结温度、La掺杂对Bi_(1-x)La_xMnO_3结构及磁性能的影响

用溶胶-凝胶(so-lgel)法制备了多铁Bi1-xLaxMnO3(BLMO,0.1≤x≤0.4)系列样品.样品的结构表征(X-射线衍射,扫描电子显微镜)及差热-热重(TG-DTA)分析测量显示,形成稳定的BLMO钙钛矿相的烧结温度位于900~950℃.La掺杂对BLMO样品(950℃烧结)的结构和磁性能的影响也被仔细研究.结果显示,随着La掺杂减少,样品中BLMO钙钛矿相减弱,铁磁转变温度(TC)由53K降至41K,而饱和磁化强度经历了先降低再升高的变化.这可归因于La含量较少的样品中Bi空位浓度的增加诱导了Mn-O-Mn键角的减小和局域Mn4+离子的增多,使得Mn3+和Mn4+离子的铁磁超交换增强和Mn3+离子的dz2轨道有序受到局域破坏.     

固相反应法制备的Gd0.7Sr0.3MnO3粉末的磁学特性

利用固相反应法制备了用Sr部分替换GdMnO3中Gd的锰基钙钛矿氧化物Gd0.7Sr0.3MnO3.X射线衍射表明其晶体结构为正交晶系,空间群为Pnma.通过测量样品在零场冷却和加场冷却下的磁化强度及磁化率随温度的变化曲线,得出样品显示亚铁磁特性,Mn和Gd两个子晶格相互反平行.根据居里-外斯定律得知其居里温度为61 ...