Co2MnO4/Ce0.8Tb0.2O2-δ Dual-Phase Membrane Material with High CO2 Stability and Enhanced Oxygen Transport for Oxycombustion Processes.

Oxygen transport membranes (OTMs) are a promising oxygen production technology with high energy efficiency due to the potential for thermal integration. However, conventional perovskite materials of OTMs are unstable in CO2 atmospheres, which limits their applicability in oxycombustion processes. On the other hand, some dual-phase membranes are stable in CO2 and SO2 without permanent degradation. However, oxygen permeation is still insufficient; therefore, intensive research focuses on boosting oxygen permeation. Here, we present a novel dual-phase membrane composed of an ion-conducting fluorite phase (Ce0.8Tb0.2O2-δ, CTO) and an electronic-conducting spinel phase (Co2MnO4, CMO). CMO spinel exhibits high electronic conductivity (60 S·cm-1 at 800 °C) compared to other spinels used in dual-phase membranes, i.e., 230 times higher than that of NiFe2O4 (NFO). This higher conductivity ameliorates gas-solid surface exchange and bulk diffusion mechanisms. By activating the bulk membrane with a CMO/CTO porous catalytic layer, it was possible to achieve an oxygen flux of 0.25 mL·min-1·cm-2 for the 40CMO/60CTO (%vol), 680 µm-thick membrane at 850 °C even under CO2-rich environments. This dual-phase membrane shows excellent potential as an oxygen transport membrane or oxygen electrode under high CO2 and oxycombustion operation.

Microwave-Driven Exsolution of Ni Nanoparticles in A-Site Deficient Perovskites.

Exsolution has emerged as a promising method for generating metallic nanoparticles, whose robustness and stability outperform those of more conventional deposition methods, such as impregnation. In general, exsolution involves the migration of transition metal cations, typically perovskites, under reducing conditions, leading to the nucleation of well-anchored metallic nanoparticles on the oxide surface with particular properties. There is growing interest in exploring alternative methods for exsolution that do not rely on high-temperature reduction via hydrogen. For example, utilizing electrochemical potentials or plasma technologies has shown promising results in terms of faster exsolution, leading to better dispersion of nanoparticles under milder conditions. To avoid limitations in scaling up exhibited by electrochemical cells and plasma-generation devices, we proposed a method based on pulsed microwave (MW) radiation to drive the exsolution of metallic nanoparticles. Here, we demonstrate the H2-free MW-driven exsolution of Ni nanoparticles from lanthanum strontium titanates, characterizing the mechanism that provides control over nanoparticle size and dispersion and enhanced catalytic activity and stability for CO2 hydrogenation. The presented method will enable the production of metallic nanoparticles with a high potential for scalability, requiring short exposure times and low temperatures.

Determining the Role of Fe-Doping on Promoting the Thermochemical Energy Storage Performance of (Mn1- x Fex )3 O4 Spinels.

Mn oxides are promising materials for thermochemical heat store, but slow reoxidation of Mn3 O4 to Mn2 O3 limits efficiency. In contrast, (Mn1- x Fex )3 O4 oxides show an enhanced transformation rate, but fundamental understanding of the role played by Fe cations is lacking. Here, nanoscale characterization of Fe-doped Mn oxides is performed to elucidate how Fe incorporation influences solid-state transformations. X-ray diffraction reveals the presence of two distinct spinel phases, cubic jacobsite and tetragonal hausmannite for samples with more than 10% of Fe. Chemical mapping exposes wide variation of Fe content between grains, but an even distribution within crystallites. Due to the similarities of spinels structures, high-resolution scanning transmission electron microscopy cannot discriminate unambiguously between them, but Fe-enriched crystallites likely correspond to jacobsite. In situ X-ray absorption spectroscopy confirms that increasing Fe content up to 20% boosts the reoxidation rate, leading to the transformation of Mn2+  in the spinel phase to Mn3+ in bixbyite. Extended X-ray absorption fine structure shows that FeO length is larger than MnO, but both electron energy loss spectroscopy and X-ray absorption near edge structure indicate that iron is always present as Fe3+  in octahedral sites. These structural modifications may facilitate ionic diffusion during bixbyite formation.

Toward Controlling Filament Size and Location for Resistive Switches via Nanoparticle Exsolution at Oxide Interfaces.

Memristive devices are among the most prominent candidates for future computer memory storage and neuromorphic computing. Though promising, the major hurdle for their industrial fabrication is their device-to-device and cycle-to-cycle variability. These occur due to the random nature of nanoionic conductive filaments, whose rupture and formation govern device operation. Changes in filament location, shape, and chemical composition cause cycle-to-cycle variability. This challenge is tackled by spatially confining conductive filaments with Ni nanoparticles. Ni nanoparticles are integrated on the bottom La0.2 Sr0.7 Ti0.9 Ni0.1 O3- δ electrode by an exsolution method, in which, at high temperatures under reducing conditions, Ni cations migrate to the perovskite surface, generating metallic nanoparticles. This fabrication method offers fine control over particle size and density and ensures strong particle anchorage in the bottom electrode, preventing movement and agglomeration. In devices based on amorphous SrTiO3 , it is demonstrated that as the exsolved Ni nanoparticle diameter increases up to ≈50 nm, the ratio between the ON and OFF resistance states increases from single units to 180 and the variability of the low resistance state reaches values below 5%. Exsolution is applied for the first time to engineer solid-solid interfaces extending its realm of application to electronic devices.

Oxygen Exchange in Dual-Phase La0.65Sr0.35MnO3-CeO2 Composites for Solar Thermochemical Fuel Production.

Increasing the capacity and kinetics of oxygen exchange in solid oxides is important to improve the performance of numerous energy-related materials, especially those for the solar-to-fuel technology. Dual-phase metal oxide composites of La0.65Sr0.35MnO3-x%CeO2, with x = 0, 5, 10, 20, 50, and 100, have been experimentally investigated for oxygen exchange and CO2 splitting via thermochemical redox reactions. The prepared metal oxide powders were tested in a temperature range from 1000 to 1400 °C under isothermal and two-step cycling conditions relevant for solar thermochemical fuel production. We reveal synergetic oxygen exchange of the dual-phase composite La0.65Sr0.35MnO3-CeO2 compared to its individual components. The enhanced oxygen exchange in the composite has a beneficial effect on the rate of oxygen release and the total CO produced by CO2 splitting, while it has an adverse effect on the maximum rate of CO evolution. Ex situ Raman and XRD analyses are used to shed light on the relative oxygen content during thermochemical cycling. Based on the relative oxygen content in both phases, we discuss possible mechanisms that can explain the observed behavior. Overall, the presented findings highlight the beneficial effects of dual-phase composites in enhancing the oxygen exchange capacity of redox materials for renewable fuel production.

Solar Energy on Demand: A Review on High Temperature Thermochemical Heat Storage Systems and Materials.

Among renewable energies, wind and solar are inherently intermittent and therefore both require efficient energy storage systems to facilitate a round-the-clock electricity production at a global scale. In this context, concentrated solar power (CSP) stands out among other sustainable technologies because it offers the interesting possibility of storing energy collected from the sun as heat by sensible, latent, or thermochemical means. Accordingly, continuous electricity generation in the power block is possible even during off-sun periods, providing CSP plants with a remarkable dispatchability. Sensible heat storage has been already incorporated to commercial CSP plants. However, because of its potentially higher energy storage density, thermochemical heat storage (TCS) systems emerge as an attractive alternative for the design of next-generation power plants, which are expected to operate at higher temperatures. Through these systems, thermal energy is used to drive endothermic chemical reactions, which can subsequently release the stored energy when needed through a reversible exothermic step. This review analyzes the status of this prominent energy storage technology, its major challenges, and future perspectives, covering in detail the numerous strategies proposed for the improvement of materials and thermochemical reactors. Thermodynamic calculations allow selecting high energy density systems, but experimental findings indicate that sufficiently rapid kinetics and long-term stability trough continuous cycles of chemical transformation are also necessary for practical implementation. In addition, selecting easy-to-handle materials with reduced cost and limited toxicity is crucial for large-scale deployment of this technology. In this work, the possible utilization of materials as diverse as metal hydrides, hydroxides, or carbonates for thermochemical storage is discussed. Furthermore, special attention is paid to the development of redox metal oxides, such as Co3O4/CoO, Mn2O3/Mn3O4, and perovskites of different compositions, as an auspicious new class of TCS materials due to the advantage of working with atmospheric air as reactant, avoiding the need of gas storage tanks. Current knowledge about the structural, morphological, and chemical modifications of these solids, either caused during redox transformations or induced wittingly as a way to improve their properties, is revised in detail. In addition, the design of new reactor concepts proposed for the most efficient use of TCS in concentrated solar facilities is also critically considered. Finally, strategies for the harmonic integration of these units in functioning solar power plants as well as the economic aspects are also briefly assessed.

Improving the Thermochemical Energy Storage Performance of the Mn2 O3 /Mn3 O4 Redox Couple by the Incorporation of Iron.

Redox cycles of manganese oxides (Mn2 O3 /Mn3 O4 ) are a promising alternative for thermochemical heat storage systems coupled to concentrated solar power plants as manganese oxides are abundant and inexpensive materials. Although their cyclability for such a purpose has been proved, sintering processes, related to the high-temperature conditions at which charge-discharge cycles are performed, generally cause a cycle-to-cycle decrease in the oxidation rate of Mn3 O4 . To guarantee proper operation, both reactions should present stable reaction rates. In this study, it has been demonstrated that the incorporation of Fe, which is also an abundant material, into the manganese oxides improves the redox performance of this system by increasing the heat storage density, narrowing the redox thermal hysteresis, and, above all, stabilizing and enhancing the oxidation rate over long-term operation, which counteracts the negative effects caused by sintering, although its presence is not avoided.

Anidulafungin in treatment of experimental invasive infection by Candida parapsilosis: in vitro activity, (1-->3)-beta-D-glucan and mannan serum levels, histopathological findings, and in vivo efficacy.

We have evaluated the in vitro activity of anidulafungin (AFG) against 31 strains of Candida parapsilosis sensu stricto by using broth microdilution, disk diffusion, and minimal fungicidal concentration (MFC) determination procedures. The two first methods showed a high level of activity of the drug, while MFCs were 1 to 5 dilutions higher than their corresponding MICs. To assess if MICs were predictive of in vivo outcomes, six strains representing different AFG MICs (0.12 to 2 µg/ml) were tested in a murine model of disseminated infection treated with different doses of the drug (1, 5, or 10 mg/kg of body weight). AFG was able to prolong the survival of mice infected with all the strains tested but was able to reduce the tissue burden of those mice infected only with the strains that showed the lowest MIC (0.12 µg/ml).

In vitro interactions of micafungin with amphotericin B against clinical isolates of Candida spp.

The in vitro activity of amphotericin B in combination with micafungin was evaluated against 115 isolates representing seven species of Candida. Overall, the percentages of synergistic interactions were 50% and 20% when the MIC-2 (lowest drug concentration to cause a prominent reduction in growth) and MIC-0 (lowest drug concentration to cause 100% growth inhibition) end point criteria, respectively, were used. Antagonism was not observed. Some of the interactions were confirmed by time-kill assays.