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This study investigates the effect of the exsolution behavior of alumina-rich spinel on the formation and distribution of CA6 (CaAl12O19) in corundum castables bonded with calcium aluminate cement. In this study, alumina-rich spinel is substituted for tabular corundum in the same proportions and grain size. The matrices after curing were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The phase composition and microstructure of the matrices containing alumina-rich spinel were analyzed after firing at 1600 °C. These results showed that the addition of alumina-rich spinel significantly improved the mechanical strength of the castables. This improvement was attributed to the alumina produced by spinel exsolution during firing at 1600 °C, which reacted in situ with CA2 (CaAl4O7) to form CA6. CA6 connects the different particles and forms an interspersed interlocking structure within the spinel. The CA6-MA interspersed interlocking structure replaces part of the CA6-Al2O3 structure and significantly improves the mechanical strength of the castables. [ABSTRACT FROM AUTHOR]

The aim of this work was to verify the possibility of forming Ni-Fe and Co-Fe alloys via topotactic ion exchange exsolution in Fe-infiltrated (La,Sr,Ce)0.9(Ni,Ti)O3-δ or (La,Sr,Ce)0.9(Co,Ti)O3-δ ceramics. For this purpose, samples were synthesized using the Pechini method and then infiltrated with an iron nitrate solution. The reduction process in dry H2 forced the topotactic ion exchange exsolution, leading to the formation of additional round-shape structures on the surfaces of grains. EDS scans and XRD analysis confirmed the formation of bimetallic alloys, which suggests that these materials have great potential for further use as anode materials for Solid Oxide Fuel Cells (SOFCs). [ABSTRACT FROM AUTHOR]

In this review, we have assessed the possibility of metal–perovskite interfacial engineering to enhance the catalytic activity and selectivity in a range of heterogeneous catalytic reactions. We embarked on a literature screening of different perovskite material classes and reactions to show the versatility of the perovskite structures to induce the formation of such hetero-interfaces and the widespread nature of the phenomenon in catalytic research. There is almost no limitation on the chemical composition of the used perovskites and the nature of the catalyzed reaction, be it under reduction or oxidation conditions. We attempted to classify the perovskite materials, discuss the different strategies leading to the hetero-interfaces, and detail the synergistic action of the components of the respective interfaces. We also provide a critical assessment of the large body of data that is available in terms of a knowledge-based approach to the comparison of differently prepared interfaces with varying interfacial extent to gain a deeper understanding of the bi-functional operation of the interfaces and the urgent necessity to study and characterize such interfaces under realistic operation conditions. [ABSTRACT FROM AUTHOR]

Definition: Perovskite-type oxides (ABO3) are a highly versatile class of materials. They are compositionally flexible, as their constituents can be chosen from a wide range of elements across the periodic table with a vast number of possible combinations. This flexibility enables the tuning of the materials' properties by doping the A- and/or B-sites of the base structure, facilitating the application-oriented design of materials. The ability to undergo exsolution under reductive conditions makes perovskite-type oxides particularly well-suited for catalytic applications. Exsolution is a process during which B-site elements migrate to the surface of the material where they form anchored and finely dispersed nanoparticles that are crucially important for obtaining a good catalytic performance, while the perovskite base provides a stable support. Recently, exsolution catalysts have been investigated as possible materials for CO2 utilization reactions like reverse water–gas shift reactions or methane dry reforming. [ABSTRACT FROM AUTHOR]

Given that the attempts to head toward a hydrogen economy are gathering pace, the dry reforming of methane (DRM) to produce hydrogen-rich syngas is a reaction that is worthy of investigation. Nickel-based catalysts have been extensively examined as a cost-effective solution for DRM, though they suffer from fast deactivation caused by coke accumulation. However, a number of published studies report high catalytic performance in terms of both activity and stability for La–Ni-based perovskite-derived catalysts used in DRM in comparison to other corresponding materials. In the work presented herein, a thorough analysis regarding the application of La–Ni-based perovskite catalysts for DRM is carried out. LaNiO3 is known for its anti-coking ability owing to the strong interaction between CO2 and La2O3. A further modification to improve the catalytic performance can be achieved by the partial or complete substitution of A or/and B sites of the perovskite catalysts. The latest developments with respect to this topic are also discussed in this manuscript. Even though the low surface area of perovskite catalysts has always been an obstacle for their commercialization, new supported and porous perovskite materials have recently emerged to address, at least partly, the challenge. Finally, conclusions and future outlooks for developing novel perovskite catalysts that may potentially pioneer new technology are included. [ABSTRACT FROM AUTHOR]

Solid solutions Nd2−xSrxNiO4±δ (x = 0, 0.5, 1, 1.2, 1.4) with a K2NiF4 structure can be obtained from freeze-dried precursors. The end members of this series can be obtained at T ≥ 1000 °C only, while complex oxides with x = 1; 1.5 are formed at T ≥ 700 °C. Thermal analysis revealed the two stages of Nd2−xSrxNiO4±δ thermal reduction in a 10%H2/Ar gas mixture that was completed at 900 °C. For x < 0.2, the reduction products demonstrated an exsolution-like morphology with Ni nanoparticles allocated at the surface of oxide grains. As-obtained nanocomposites with x = 0 and x > 1 revealed the outstanding catalytic activity and selectivity in the dry reforming of the methane (DRM) reaction at 800 °C with CH4 conversion close to the thermodynamic values. The appearance of two different maxima of the catalytic properties of Ni/(Nd2O3,SrCO3) nanocomposites could be affiliated with the domination of the positive contributions of Nd2O3 and SrCO3, respectively. [ABSTRACT FROM AUTHOR]

A Mn0.2Zr0.8O2−δ mixed oxide catalyst was synthesized via the co-precipitation method and studied in a CO oxidation reaction after different redox pretreatments. The surface and structural properties of the catalyst were studied before and after the pretreatment using XRD, XANES, XPS, and TEM techniques. Operando XRD was used to monitor the changes in the crystal structure under pretreatment and reaction conditions. The catalytic properties were found to depend on the activation procedure: reducing the CO atmosphere at 400–600 °C and the reaction mixture (O2 excess) or oxidative O2 atmosphere at 250–400 °C. A maximum catalytic effect characterized by decreasing T50 from 193 to 171 °C was observed after a reduction at 400 °C and further oxidation in the CO/O2 reaction mixture was observed at 250 °C. Operando XRD showed a reversible reduction-oxidation of Mn cations in the volume of Mn0.2Zr0.8O2−δ solid solution. XPS and TEM detected the segregation of manganese cations on the surface of the mixed oxide. TEM showed that Mn-rich regions have a structure of MnO2. The pretreatment caused the partial decomposition of the Mn0.2Zr0.8O2−δ solid solution and the formation of surface Mn-rich areas that are active in catalytic CO oxidation. In this work it was shown that the introduction of oxidation-reduction pretreatment cycles leads to an increase in catalytic activity due to changes in the origin of active states. [ABSTRACT FROM AUTHOR]

Hydrogen production from biogas over alumina-supported Ce1−xNixO2−x catalysts was studied in a temperature range of 600–850 °C with an initial gas composition of CH4/CO2/H2O of 1/0.8/0.4. To achieve a high and stable hydrogen yield, highly dispersed Ni catalysts were prepared through the exsolution approach. A solid solution of Ce1−xNixO2−x was firstly formed on the surface of Al2O3 and then activated in H2/Ar at 800 °C. The genesis and properties of the Ce1−xNixO2−x/Al2O3 catalysts were established using X-ray fluorescence analysis, thermal analysis, N2 adsorption, ex situ and in situ X-ray diffraction, Raman spectroscopy, electron microscopy, EDX analysis, and temperature-programmed hydrogen reduction. The performance of Ce1−xNixO2−x/Al2O3 catalysts in biogas conversion was tuned by regulation of the dispersion and reducibility of the active component through variation of content (5–20 wt.%) and composition (x = 0.2, 0.5, 0.8) of Ce1−xNixO2−x as well as the mode of its loading (co-impregnation (CI), citrate sol–gel method (SG)). For the 20 wt.% Ce1−xNixO2−x/Al2O3 catalyst, the rate of the coke formation decreased by a factor of 10 as x increased from 0.2 to 0.8. The optimal catalyst composition (20 wt.% Ce0.2Ni0.8O1.8/80 wt.% Al2O3) and preparation mode (citrate sol–gel method) were determined. At 850 °C, the 20 wt.% Ce0.2Ni0.8O1.8/Al2O3-SG catalyst provides 100% hydrogen yield at full CH4 conversion and 85% CO2 utilization. [ABSTRACT FROM AUTHOR]

Spinodal decomposition is an important mechanism of exsolution. However, spinodal decomposition has not been observed in natural sulfide intergrowths. We utilized focused ion beam (FIB) and transmission electron microscopy (TEM) techniques to confirm spinodal decomposition in natural sulfide intergrowths (chalcopyrite and bornite). According to FIB and TEM analyses, spinodal decomposition occurred as small and curving alternating dark and bright fluctuations in natural bornite–chalcopyrite intergrowths. Due to the low temperature that drove the exsolution mechanism, fluctuations ~10 nm wide and 20–200 nm long contained non-stoichiometric and tetragonal bornite and chalcopyrite. The corresponding electron diffraction of spinodal decomposition displayed a satellite spot in the [−210] direction for bornite, and the (200)* and (224)* of chalcopyrite paralleled the (24−2)* and (242)* of bornite, respectively. These observations all agreed with spinodal decomposition, two coexisting phases formed with a crystallographic orientation relationship, which indicated the first observation of spinodal decomposition in natural sulfide intergrowths. These findings confirmed that spinodal decomposition is a mechanism for natural crystal growth. As spinodal decomposition is larger in extent and faster than nucleation and growth, other Cu ore deposits may also form via this mechanism. [ABSTRACT FROM AUTHOR]

Hydrogen production through the bi-reforming of methane over exsolution-derived Ni catalysts has been studied. Nickel-based catalysts were prepared through the activation of (CeM)1−xNixOy (M = Al, La, Mg) solid solutions in a reducing gaseous medium. Their performance and resistance to coking under the reaction conditions were controlled by regulating their textural, structural, morphological, and redox properties through adjustments to the composition of the oxide matrix (M/Ce = 0–4; x = 0.2–0.8; y = 1.0–2.0). The role of the M-dopant type in the genesis and properties of the catalysts was established. The efficiency of the catalysts in the bi-reforming of methane increased in the following series of M: M-free < La < Al < Mg, correlating with the structural behavior of the nickel active component and the anti-coking properties of the support matrix. The preferred M-type and M/Ce ratio determined the best performance of (CeM)1−xNixOy catalysts. At 800 °C the optimum Ce0.6Mg0.2Ni0.2O1.6 catalyst provided a stable H2 yield of 90% at a high level of CO2 and CH4 conversions (>85%). [ABSTRACT FROM AUTHOR]

Six different perovskite-type oxides were investigated with respect to their ability for methanol synthesis via H2 and CO2: Fe-, Mn-, and Ti-based perovskites were prepared with and without Cu doping. For assessment, the catalysts were subjected to preliminary tests at atmospheric pressure to evaluate their ability to activate CO2. Additional catalytic tests with the doped versions of each catalyst type were carried out in a pressured reactor at 21 bar. After the measurements, the catalysts were characterized with X-ray diffraction (XRD) and scanning electron microscopy (SEM). All catalysts were able to produce methanol in the pressure tests. CO2 conversions between 14% and 23% were reached at 400 °C, with the highest methanol selectivity at the lower temperature of 250 °C. The combination of XRD and SEM revealed that the Fe-based and Ti-based perovskites were stable under reaction conditions and that catalytically highly active and stable nanoparticles had formed. The minor formation of CaCO3, which is a deactivating phase, was observed for one catalyst. These nanoparticles showed resistance to coking and sintering. However, the yield and selectivity for methanol need to be improved via the further tailoring of the perovskite composition. [ABSTRACT FROM AUTHOR]

In order to clarify the role of R2O3 in the metal-oxide catalysts derived from complex oxide precursors, a series of R1.5Ca0.5NiO4 (R = Nd, Sm, Eu) complex oxides was obtained. A significant systematic increase in the orthorhombic distortion of the R1.5Ca0.5NiO4 structure (K2NiF4 type, Cmce) from Nd to Eu correlates with a corresponding decrease in their ionic radii. A reduction of R1.5Ca0.5NiO4 in the Ar/H2 gas mixture at 800 °C causes a formation of dense agglomerates of CaO and R2O3 coated with spherical 25–30 nm particles of Ni metal. The size of metal particles and oxide agglomerates is similar in all Ni/(R2O3,CaO) composites in the study. Their morphology is rather similar to the products of redox exsolution obtained by the partial reduction of complex oxides. All obtained composites demonstrated a significant catalytic activity in the dry reforming (DRM) and partial oxidation (POM) of methane at 700–800 °C. A systematic decrease in the DRM catalytic activity of composites from Nd to Eu could be attributed to the basicity reduction of R2O3 components of the composite catalysts. The maximum CH4 conversion in POM reaction was observed for Ni/(Sm2O3,CaO), while the maximum selectivity was demonstrated by Nd2O3-based composite. The possible reasons for the observed difference are discussed. [ABSTRACT FROM AUTHOR]

To design metal nanoparticles (NPs) on a perovskite surface, the exsolution method has been extensively used for efficient catalytic reactions. However, there are still the challenges of finding a combination and optimization for the NPs' control. Thus, we report in situ control of the exsolved Ni NPs from perovskite to apply as a catalyst for dry reforming of methane (DRM). The La0.8Ce0.1Ti0.6Ni0.4O3 (LCTN) is designed by Ce doping to incorporate high amounts of Ni in the perovskite lattice and also facilitate the exsolution phenomenon. By control of the eluted Ni NPs through exsolution, the morphological properties of exsolved Ni NPs are observed to have a size range of 10~49 nm, while the reduction temperatures are changed. At the same time, the chemical structure of the eluted Ni NPs is also changed by an increased reduction temperature to a highly metallic Ni phase with an increased oxygen vacancy at the perovskite oxide surface. The optimized composite nanomaterial displays outstanding catalytic performance of 85.5% CH4 conversion to produce H2 with a value of 15.5 × 1011 mol/s·gcat at 60.2% CO conversion, which shows the importance of the control of the exsolution mechanism for catalytic applications. [ABSTRACT FROM AUTHOR]

The catalyst exsolved from nickel-doped perovskite oxide, La0.9Ni0.05Fe0.95O3, has been proven to be effective for gas-phase reactions. To obtain the optimum amount of exsolved nanoparticles from the parent perovskite oxide, control of the reduction treatment condition is vital. Here, the effect of reduction time on the exsolved nanoparticle distribution, and thus the catalytic activity of the high-temperature water gas shift reaction (WGSR), was investigated. Upon conducting a wide range of characterizations, we assumed that the exsolution process might be a two-step process. Firstly, the surface oxygen is extracted. Secondly, due to the unstable perovskite structure, the Ni ions in the bulk La0.9Ni0.05Fe0.95O3 continuously diffuse toward the surface and, as the reduction progresses, more nuclei are generated to form a greater number of nanoparticles. This assumption is proven by the fact that, with an increase in the exsolution treatment time, the population of exsolution nanoparticles increases. Moreover, as the reduction time increases, the high-temperature WGSR activity also increases. The temperature-programmed measurements suggest that the exsolved nanoparticles are the active reaction sites. We believe that this study is helpful for understanding exsolution behavior during reduction treatment and, thus, developing a perovskite exsolution catalyst for the WGSR. [ABSTRACT FROM AUTHOR]

The Kunene Intrusive Complex (KIC), in NW Namibia and SW Angola, is one of the largest Proterozoic anorthosite massif-type exposures in the world. A geochemical, mineralogical and petrological study of four Fe-Ti(-V) oxide bodies located in the understudied Angolan part of the KIC has been performed. The massive Fe-Ti(-V) oxide bodies, locally apatite-rich (nelsonites), are lenticular or dike-like. They consist mostly of titaniferous magnetite, ilmenite and minor aluminous spinel, apatite, olivine and graphite. Titaniferous magnetite displays a wide variety of subsolvus features, including aluminous spinel-magnetite-ulvöspinel exsolutions and ilmenite (Trellis) exsolutions. This work estimated the composition of the titaniferous magnetite prior to the exsolution, in order to calculate the temperature and oxygen fugacity of the different lithologies of each ore body. The thermo-oxybarometry results obtained range from 600 °C to 820 °C and fO2 from 10-24.7 to 10-14.7. These values do not correspond to magmatic crystallization in equilibrium, but to a later re-equilibration. In addition, the mineralogical and geochemical results indicate that the studied ore bodies contain economic reserves of Ti, V, and possibly of P and REE. [ABSTRACT FROM AUTHOR]

The Kovdor phoscorite-carbonatite ore-pipe rocks form a natural series, where apatite and magnetite first gradually increase due to the presence of earlier crystallizing forsterite in the pipe marginal zone and then decrease as a result of carbonate development in the axial zone. In all lithologies, magnetite grains contain (oxy)exsolution inclusions of comparatively earlier ilmenite group minerals and/or later spinel, and their relationship reflects the concentric zonation of the pipe. The temperature and oxygen fugacity of titanomagnetite oxy-exsolution decreases in the natural rock sequence from about 500 °C to about 300 °C and from NNO + 1 to NNO - 3 (NNO is Ni-NiO oxygen fugacity buffer), with a secondary positive maximum for vein calcite carbonatite. Exsolution spinel forms spherical grains, octahedral crystals, six-beam and eight-beam skeletal crystals co-oriented with host magnetite. The ilmenite group minerals occur as lamellae oriented along {111} and {100} planes of oxy-exsolved magnetite. The kinetics of inclusion growth depends mainly on the diffusivity of cations in magnetite: their comparatively low diffusivities in phoscorite and carbonatites of the ore-pipe internal part cause size-independent growth of exsolution inclusions; while higher diffusivities of cations in surrounding rocks, marginal forsterite-rich phoscorite and vein calcite carbonatite result in size-dependent growth of inclusions. [ABSTRACT FROM AUTHOR]

Perovskite-type oxides are highly flexible materials that show properties that are beneficial for application in reverse water-gas shift processes (rWGS). Due to their stable nature, the ability to incorporate catalytically active dopants in their lattice structure, and the corresponding feature of nanoparticle exsolution, they are promising candidates for a materials design approach. On an industrial level, the rWGS has proven to be an excellent choice for the efficient utilisation of CO2 as an abundant and renewable carbon source, reflected by the current research on novel and improved catalyst materials. In the current study, a correlation between rWGS reaction environments (CO2 to H2 ratios and temperature), surface morphology, and catalytic activity of three perovskite catalysts (Nd0.6Ca0.4Fe0.9Co0.1O3-δ, Nd0.6Ca0.4Fe0.97Co0.03O3-δ, and Nd0.6Ca0.4Fe0.97Ni0.03O3-δ) is investigated, combining catalytic measurements with SEM and NAP-XPS. The materials were found to react dynamically to the conditions showing both activation due to in situ nanoparticle exsolution and deactivation via CaCO3 formation. This phenomenon could be influenced by choice of material and conditions: less reductive conditions (larger CO2 to H2 or lower temperature) lead to smaller exsolved particles and reduced carbonate formation. However, the B-site doping was also important; only with 10% Co-doping, a predominant activation could be achieved. [ABSTRACT FROM AUTHOR]

Exsolution is emerging as a promising route for the creation of nanoparticles that remain anchored to the oxide support, imparting remarkable stability in high temperature chemical processes such as dry reforming of methane. This process takes place at temperatures around 850 °C, which causes sintering-related issues in catalysts prepared using conventional impregnation methods, which could be overcome by using exsolution functionalized oxides. In this work, FeNi3 alloy nanoparticles exsolved from Sr2FexNi1-xMoO6-δ double-layered perovskites were evaluated as a dry reforming catalyst, paying special attention to structure–activity relationships. Our results indicate that increasing the Ni content favors the nanoparticle dispersion, eventually leading to increased CO2 and CH4 conversions. The exsolved nanoparticles presented remarkable nanoparticle size (ca. 30 nm) stability after the 10 h treatment, although the formation of some phase segregations over the course of the reaction caused a minor decrease in the nanoparticle population. Overall, the results presented here serve as materials processing guidelines that could find further potential use in the design of more efficient (electro)catalysts in other fuel production or energy conversion technologies. [ABSTRACT FROM AUTHOR]

High temperature water-gas shift (HT-WGS) is an industrially highly relevant reaction. Moreover, climate change and the resulting necessary search for sustainable energy sources are making WGS and reverse-WGS catalytic key reactions for synthetic fuel production. Hence, extensive research has been done to develop improved or novel catalysts. An extremely promising material class for novel highly active HT-WGS catalysts with superior thermal stability are perovskite-type oxides. With their large compositional flexibility, they enable new options for rational catalyst design. Particularly, both cation sites (A and B in ABO3) can be doped with promoters or catalytically active elements. Additionally, B-site dopants are able to migrate to the surface under reducing conditions (a process called exsolution), forming catalytically active nanoparticles and creating an interface that can strongly boost catalytic performance. In this study, we varied A-site composition and B-site doping (Ni, Co), thus comparing six novel perovskites and testing them for their HT-WGS activity: La0.9Ca0.1FeO3-δ, La0.6Ca0.4FeO3-δ, Nd0.9Ca0.1FeO3-δ, Nd0.6Ca0.4FeO3-δ, Nd0.6Ca0.4Fe0.9Ni0.1O3-δ and Nd0.6Ca0.4Fe0.9Co0.1O3-δ. Cobalt and Nickel doping resulted in the highest activity observed in our study, highlighting that doped perovskites are promising novel HT-WGS catalysts. The effect of the compositional variations is discussed considering the kinetics of the two partial reactions of WGS-CO oxidation and water splitting. [ABSTRACT FROM AUTHOR]

Exsolution of surface and bulk nanoparticles in perovskites has been recently employed in chemical looping methane partial oxidation because of the emergent materials' properties such as oxygen capacity, redox stability, durability, coke resistance and enhanced activity. Here we attempt to further lower the temperature of methane conversion by complementing exsolution with infiltration. We prepare an endo/exo-particle system using exsolution and infiltrate it with minimal amount of Rh (0.1 wt%) in order to functionalize the surface and induce low temperature activity. We achieve a temperature decrease by almost 220 °C and an increase of the activity up to 40%. We also show that the initial microstructure of the perovskite plays a key role in controlling nanoparticle anchorage and carbon deposition. Our results demonstrate that microstructure tuning and surface functionalization are important aspects to consider when designing materials for redox cycling applications. [ABSTRACT FROM AUTHOR]

In heterogeneous catalysis, surfaces decorated with uniformly dispersed, catalytically-active (nano)particles are a key requirement for excellent performance. Beside standard catalyst preparation routines—with limitations in controlling catalyst surface structure (i.e., particle size distribution or dispersion)—we present here a novel time efficient route to precisely tailor catalyst surface morphology and composition of perovskites. Perovskite-type oxides of nominal composition ABO3 with transition metal cations on the B-site can exsolve the B-site transition metal upon controlled reduction. In this exsolution process, the transition metal emerges from the oxide lattice and migrates to the surface where it forms catalytically active nanoparticles. Doping the B-site with reducible and catalytically highly active elements, offers the opportunity of tailoring properties of exsolution catalysts. Here, we present the synthesis of two novel perovskite catalysts Nd0.6Ca0.4FeO3-δ and Nd0.6Ca0.4Fe0.9Co0.1O3-δ with characterisation by (in situ) XRD, SEM/TEM and XPS, supported by theory (DFT+U). Fe nanoparticle formation was observed for Nd0.6Ca0.4FeO3-δ. In comparison, B site cobalt doping leads, already at lower reduction temperatures, to formation of finely dispersed Co nanoparticles on the surface. These novel perovskite-type catalysts are highly promising for applications in chemical energy conversion. First measurements revealed that exsolved Co nanoparticles significantly improve the catalytic activity for CO2 activation via reverse water gas shift reaction. [ABSTRACT FROM AUTHOR]

Compositionally engineered a La1-xBaxCoO3-δ-(1-a) BaZr0.9Y0.1O2.95 (a = 0.6, 0.7, 0.8 and x = 0.5, 0.6, 0.7) (LBZ) nanocomposite cathodes were prepared by oxidation driven in situ exsolution of a single-phase material deposited on a BaZr0.9Y0.1O2.95 electrolyte. The processing procedure of the cathode was optimized by reducing the number of thermal treatments as the single-phase precursor was deposited directly on the electrolyte. The exsolution and firing of the cathodes occurred in one step. The electrochemical performance of symmetrical cells with the compositionally engineered cathodes was investigated by impedance spectroscopy in controlled atmospheres. The optimized materials processing gave web-like nanostructured cathodes with superior electrochemical performance for all compositions. The area specific resistances obtained were all below 12 Ω·cm2 at 400 °C and below 0.59 Ω·cm2 at 600 °C in 3% moist synthetic air. The resistances of the nominal 0.6 La0.5Ba0.5CoO3-δ-0.4 BaZr0.9Y0.1O2.95 and 0.8 La0.5Ba0.5CoO3-δ-0.2 BaZr0.9Y0.1O2.95 composite cathodes were among the lowest reported for protonic ceramic fuel cells cathodes in symmetrical cell configuration with ASR equal to 4.04 and 4.84 Ω·cm2 at 400 °C, and 0.21 and 0.27 Ω·cm2 at 600 °C, respectively. [ABSTRACT FROM AUTHOR]

The titanomagnetite of the Lac Doré Complex, an Archean layered intrusion that is located in the Abitibi greenstone belt in Québec (Canada), contains a wide variety of exsolution textures, which are the remnants of a complex cooling history. In the present study, we reconstitute the decomposition stages of the original solid solution in order to explain the formation of ilmenite, Al-spinel (hercynite and gahnite), and corundum exsolutions in magnetite. This was conducted through a detailed mineralogical and textural examination and in situ determination of mineral chemistry. Our investigation reveals two discrete types of ilmenite exsolutions, which are ascribed, respectively, to the oxidation of ulvöspinel at temperatures above and below the magnetite-ulvöspinel solvus. Exsolutions of Al-spinel result from either a decrease in the solubility of the (FeZn)Al2O4 components upon cooling, or local excesses of Al and Zn due to the removal of ulvöspinel during the early oxidation. The origin of corundum is ascribed to the oxidation of pre-existing hercynite exsolutions. The trace element composition of the titanomagnetite indicates stratigraphic reversals in Cr, Mg, Co, Ti, and Si and important changes in redox conditions. We interpret this as a direct consequence of a major event of magma chamber replenishment, which strongly influenced the distribution of exsolutions. [ABSTRACT FROM AUTHOR]

A novel exsolution process was used to fabricate complex all-oxide nanocomposite cathodes for Protonic Ceramic Fuel Cells (PCFCs). The nanocomposite cathodes with La0.5Ba0.5Co1/3Mn1/3Fe1/3O3−δ-BaZr1−zYzO3−δ nominal composition were prepared from a single-phase precursor via an oxidation-driven exsolution mechanism. The exsolution process results in a highly nanostructured and intimately interconnected percolating network of the two final phases, one proton conducting (BaZr1−zYzO3−δ) and one mixed oxygen ion and electron conducting (La0.5Ba0.5Co1/3Mn1/3Fe1/3O3−δ), yielding excellent cathode performance. The cathode powder is synthesized as a single-phase cubic precursor by a modified Pechini route followed by annealing at 700 °C in N2. The precursor phase is exsolved into two cubic perovskite phases by further heat treatment in air. The phase composition and chemical composition of the two phases were confirmed by Rietveld refinement. The electrical conductivity of the composites was measured and the electrochemical performance was determined by impedance spectroscopy of symmetrical cells using BaZr0.9Y0.1O2.95 as electrolyte. Our results establish the potential of this exsolution method where a large number of different cations can be used to design composite cathodes. The La0.5Ba0.5Co1/3Mn1/3Fe1/3O3−δ-BaZr0.9Y0.1O2.95 composite cathode shows the best performance of 0.44 Ω·cm2 at 600 °C in 3% moist synthetic air. [ABSTRACT FROM AUTHOR]