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Many relevant high-temperature chemical processes require the use of oxide-supported metallic nanocatalysts. The harsh conditions under which these processes operate can trigger catalyst degradation via nanoparticle sintering, carbon depositions or poisoning, among others. This primarily affects metallic nanoparticles created via deposition methods with low metal–support interaction. In this respect, nanoparticle exsolution has emerged as a promising method for fabricating oxide-supported nanocatalysts with high interaction between the metal and the oxide support. This is due to the mechanism involved in nanoparticle exsolution, which is based on the migration of metal cations in the oxide support to its surface, where they nucleate and grow as metallic nanoparticles partially embedded in the oxide. This anchorage confers high robustness against sintering or coking-related problems. For these reasons, exsolution has attracted great interest in the last few years. Multiple works have been devoted to proving the high catalytic stability of exsolved metallic nanoparticles in several applications for high-temperature energy storage and conversion. Additionally, considerable attention has been directed towards understanding the underlying mechanism of metallic nanoparticle exsolution. However, this growing field has not been limited to these types of studies and recent discoveries at the forefront of materials design have opened new research avenues. In this work, we define six new trends in nanoparticle exsolution, taking a tour through the most important advances that have been recently reported. [ABSTRACT FROM AUTHOR]

Proton-conducting barium zirconate ceramics have shown large potential for efficient electrochemical conversion and separation processes at intermediate operation temperatures. The high energy efficiency, robustness, and intermediate-temperature operation (500–650 °C) make proton-conducting cells promising candidates for future energy conversion systems. However, the major disadvantages of these materials are the inevitable high-sintering temperatures (>1500 °C), leading to Ba-evaporation and formation of high-resistance grain boundaries, which dominate the electrochemical performance. Here, we introduce a novel processing route for proton-conducting barium zirconates, which, on the one hand, significantly lowers the maximum processing temperature and, on the other hand, overcomes the dominating influence of grain boundaries on total conductivity. The key step of this novel processing route is the cold sintering of the powder using pure water as a sintering aid to consolidate BaZr0.7Ce0.2Y0.1O3−δ (BZCY) at 350 °C. We show that clean grain boundaries with a high acceptor-dopant concentration are preserved thanks to the recovery of the perovskite phase during thermal treatment at 1300 °C. This compensates the interfacial core charge, resulting in highly conductive grain boundaries, which do not limit the total conductivity. Consequently, dense BZCY electrolytes produced by our novel approach outperform the conductivity of conventionally sintered BZCY irrespective of the significantly lower maximum processing temperature and its nanocrystalline microstructure. Our presented approach opens up new possibilities for grain boundary engineering and might facilitate novel co-sintering pathways for barium zirconate-based components. [ABSTRACT FROM AUTHOR]

This study investigated Lu doping of Ba0.5La0.5CoO3 and its influence on the exsolution of oxide nanoparticles (NPs). As a result of Lu doping, we observed the phase segregation into the main Ba0.4La0.6Co0.85Lu0.15O3 (BLCO–Lu) phase and the secondary Ba0.85La0.15Co0.75Lu0.25O3 (BCO–Lu) phase. We noticed the exsolution of BCO–Lu nanoparticles on the main BLCO–Lu phase. Moreover, the BLCO–Lu phase exsolved in the form of nanoparticles on the adjacent BCO–Lu grains. That shows that the phases are covered with mutually exsolved oxide NPs. In addition, trace amounts of the BaLuCo4O7 phase are detected. We noticed that the exsolved oxides even in the as-prepared sample were fine (average size of 18 nm), and well distributed with a dense population of NPs above 280 per 1 μm2. Furthermore, we showed that the size and shape of the exsolved oxide NPs can be controlled by varying the annealing temperature. For example, at 800 °C the exsolved oxides segregate and form two different shapes; spherical and cuboidal, with an average size of 31 nm and NP population of about 23 NPs per μm2. Meanwhile, with lowering the temperature to 400 °C the oxides form only spherical and quite evenly distributed NPs with the occurrence of 137 NPs per 1 μm2. The obtained results open the possibility of tailoring a novel, more catalytically active material for future applications in electrochemical devices. [ABSTRACT FROM AUTHOR]

This study concerns energetics of formation and the stability in high water partial pressure of BaLnCo2O6−δ, (Ln = La, Pr, Nd, and Gd) (BLnC) and BaGd1−xLaxCo2O6−δ, where x = 0.2, 0.5, and 0.7 (BGLC) double perovskite cobaltites. Those materials are extensively studied due to their potential applications as a positrode in electrochemical devices. Therefore, their stability under such conditions is a key issue. All investigated materials are thermodynamically stable relative to binary oxides and exhibit strongly exothermic enthalpies of formation. Moreover, BaGd0.3La0.7Co2O6−δ and BaGd0.8La0.2Co2O6−δ remain the main perovskite structure up to 3 bars of water vapor at 400 °C. At higher steam pressure, reaching 10 bar at 300 °C, the partial decomposition to constituent oxides and hydroxides was observed. The BGLC compounds exhibit higher negative formation enthalpies in comparison to single-Ln compositions, which does not translate into higher chemical stability under high steam pressures since the BLnC series retained the main perovskite structure at higher temperatures as well as in higher water vapor pressures. [ABSTRACT FROM AUTHOR]

Ba1−xGd1−yLax+yCo2O6−δ (BGLC) compositions with large compositional ranges of Ba, Gd, and La have been characterised with respect to phase compositions, structure, and thermal and chemical expansion. The results show a system with large compositional flexibility, enabling tuning of functional properties and thermal and chemical expansion. We show anisotropic chemical expansion and detailed refinements of emerging phases as La is substituted for Ba and Gd. The dominating phase is the double perovskite structure Pmmm, which is A-site ordered along the c-axes and with O vacancy ordering along the b-axis in the Ln-layer. Phases emerging when substituting La for Ba are orthorhombic Ba-deficient Pbnm and cubic LaCoO3-based R3¯c. When La is almost completely substituted for Gd, the material can be stabilised in Pmmm, or cubic Pm3¯m, depending on thermal and atmospheric history. We list thermal expansion coefficients for x = 0–0.3, y = 0.2. [ABSTRACT FROM AUTHOR]