RESUMEN
In practical scenarios, viologen-derivatives face an accelerated degradation in the unavoidable presence of traces of oxygen in large-scale redox flow batteries. Herein, we confirm the primary degradation mechanism and propose a straightforward, cheap, and fast method to evaluate the stability of viologen-derivatives toward this degradation. Considering that the cleavage of the N-substituent is the main proposed pathway for viologen degradation, a new viologen-derivative, bearing an alkylsulfonate chain with a secondary carbon center joined to the N atom, is synthesized to illustrate how molecular engineering can be used to improve stability.
RESUMEN
Lithography-based ceramics manufacturing (LCM) processes enable the sophisticated 3 dimensional (3D) shaping of ceramics by additive manufacturing (AM). The build-up occurs, like many other AM processes, layer by layer, and is initiated by light. The built-in digital mirror device (DMD) enables the specific exposure of desired pixels for every layer, giving as a consequence a first estimation of the printing resolution in the x and y axes. In this work, a commercial zirconia slurry and the CeraFab 7500, both from Lithoz GmbH (Vienna, Austria), were used to investigate the potential of reaching this resolution. The results showed that the precision of a part is strongly dependent on the applied exposure energy. Higher exposure energies resulted in oversized dimensions of a part, whereas too low energy was not able to guarantee the formation of a stable part. Furthermore, the investigation of the layer thickness showed that the applied exposure energy (mJ/cm2) was acting in a volume, and the impact is visible in x, y, and z dimensions. The lowest applied exposure energy was 83 mJ/cm2 and showed the most accurate results for a layer thickness of 25 µm. With this energy, holes and gaps smaller than 500 µm could be printed; however, the measurements differed significantly from the dimensions defined in the design. Holes and gaps larger than 500 µm showed deviations smaller than 50 µm from the design and could be printed reliably. The thinnest printable gaps were between 100 and 200 µm. Concerning the wall thickness, the experiments were conducted to a height of 1 cm. Taking into account the stability and deformation of the walls as well, the best results after sintering were achieved with thicknesses of 200-300 µm.
RESUMEN
Perovskite oxides have been at the forefront among catalysts for the oxygen evolution reaction (OER) in alkaline media offering a higher degree of freedom in cation arrangement. Several highly OER active Co-based perovskites have been known to show extraordinary activities and stabilities when the B-site is partially occupied by Fe. At the current stage, the role of Fe in enhancing the OER activity and stability is still unclear. In order to elucidate the roles of Co and Fe in the OER mechanism of cubic perovskites, two prospective perovskite oxides, La0.2Sr0.8Co1- xFe xO3-δ and Ba0.5Sr0.5Co1- xFe xO3-δ with x = 0 and 0.2, were prepared by flame spray synthesis as nanoparticles. This study highlights the importance of Fe in order to achieve high OER activity and stability by drawing relations between their physicochemical and electrochemical properties. Ex situ and operando X-ray absorption spectroscopy (XAS) was used to study the local electronic and geometric structure under oxygen evolving conditions. In parallel, density function theory computational studies were conducted to provide theoretical insights into our findings. Our findings show that the incorporation of Fe into Co-based perovskite oxides alters intrinsic properties rendering efficient OER activity and prolonged stability.
RESUMEN
TiO(2) and TiO(2)/Er(3+) nanoparticulate sols were obtained by the colloidal sol-gel route. Thanks to the combination of three optical techniques (laser diffraction, LD, dynamic light scattering, DLS, and multiple light scattering, MLS), the peptization time was quantified, demonstrating that erbium(III) ions retard the process. The isoelectric point of TiO(2) shifts up to higher pH's when Er(3+) ions are present, which suggests that they are adsorbed onto the surface of the TiO(2) nanoparticles. Moreover, the viscosity of the sols increases when the erbium(III) amount increases. The xerogels obtained from each sol were characterized by XRD and HRTEM, obtaining in all cases anatase as the major phase, although traces of brookite were also present. In the EPD experiments, the addition of ethanol was necessary to reduce the water hydrolysis and facilitate the drying process. As a result, transparent thin films were obtained at short times and low current densities and opal films for larger current densities and deposition times; in addition, the thickness, measured by ellipsometry, increased gradually, but the refractive index did not change significantly (1.9-2). The topography profile of the films and the particle size were obtained by atomic force microscopy (AFM), giving similar values to those measured by DLS, indicating that the addition of ethanol helps to maintain stabilization without further agglomeration or sedimentation.