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1. High stability SrTi _1−x Fe _x O _3−δ electrodes for oxygen reduction and oxygen evolution reactions

   https://doi.org/10.1039/c9ta07548h  

   Zhang, Shan-Lin; Cox, Dalton; Yang, Hao; Park, Beom-Kyeong; Li, Cheng-Xin; Li, Chang-Jiu; Barnett, Scott A. (September 2019, Journal of Materials Chemistry A)

   Sr(Ti 1−x Fe x )O 3−δ (STF) has recently been explored as an oxygen electrode for solid oxide electrochemical cells (SOCs). Model thin film electrode studies show oxygen surface exchange rates that generally improve with increasing Fe content when x < 0.5, and are comparable to the best Co-containing perovskite electrode materials. Recent results on porous electrodes with the specific composition Sr(Ti 0.3 Fe 0.7 )O 3−δ show excellent electrode performance and stability, but other compositions have not been tested. Here we report results for porous electrodes with a range of compositions from x = 0.5 to 0.9. The polarization resistance decreases with increasing Fe content up to x = 0.7, but increases for further increases in x . This results from the interaction of two effects – the oxygen solid state diffusion coefficient increases with increasing x , but the electrode surface area and surface oxygen exchange rate decrease due to increased sinterability and Sr surface segregation for the Fe-rich compositions. Symmetric cells showed no degradation during 1000 h life tests at 700 °C even at a current density of 1.5 A cm −2 , showing that all the STF electrode compositions worked stably in both fuel cell mode and electrolysis modes. The excellent stability may be explained by X-ray Photoelectron Spectroscopy (XPS) results showing that the amount of surface segregated Sr did not change during the long-term testing, and by relatively low polarization resistances that help avoid electrode delamination. 

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2. Chemical Stability of BaMg _0.33 Nb _0.67-X Fe _x O _3-δ in High Temperature Methane Conversion Environments

   https://doi.org/10.1149/11106.0587ecst  

   Denoyer, Luke H; Benavidez, Angelica; Brearley, Adrian; Ramaiyan, Kannan; Garzon, Fernando H. (May 2023, ECS Transactions)

   Doped perovskite metal oxide catalysts of the form A(B_xM_1-x)O_3-δhave been instrumental in the development of solid oxide electrolyzers/fuel cells. In addition, this material class has also been demonstrated to be effective as a heterogeneous catalyst. Co-doped barium niobate perovskites have shown remarkable stability in highly acidic CO₂sensing measurements/environments (1). However, the reason for their chemical stability is not well understood. Doping with transition metal cations for B site cations often leads to exsolution under reducing conditions. Many perovskites used for the oxidative coupling of methane (OCM) or the electrochemical oxidative coupling of methane (E-OCM) either lack long term stability, or catalytic activity within these highly reducing methane environments. The Mg and Fe co-doped barium niobate BaMg_0.33Nb_0.67-xFe_xO_3-δshown activity in E-OCM reactors over long periods (2) (>100 hrs) with no iron metal exsolution observed by diffraction or STEM EDX measurements. In contrast, iron decorated BaMg_0.33Nb_0.67O₃showed little C2 conversion activity. 

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3. Phase Stabilized MOCVD Growth of β‐Ga ₂ O ₃ Using SiO _x on c‐Plane Sapphire and AlN/Sapphire Template

   https://doi.org/10.1002/pssa.202300036  

   Jewel, Mohi Uddin; Hasan, Samiul; Crittenden, Scott R.; Avrutin, Vitaliy; Özgür, Ümit; Morkoç, Hadis; Ahmad, Iftikhar (April 2023, physica status solidi (a))

   The growth of monoclinic phase‐pure gallium oxide (β‐Ga₂O₃) layers by metal–organic chemical vapor deposition on c‐plane sapphire and aluminum nitride (AlN) templates using silicon‐oxygen bonding (SiO_x) as a phase stabilizer is reported. The β‐Ga₂O₃layers are grown using triethylgallium, oxygen, and silane for gallium, oxygen, and silicon precursors, respectively, at 700 °C, with and without silane flow in the process. The samples grown on sapphire with SiO_xphase stabilization show a notable change from samples without phase stabilization in the roughness and resistivity, from 16.2 to 4.2 nm and from 85.82 to 135.64 Ω cm, respectively. X‐ray diffraction reveals a pure‐monoclinic phase, and Raman spatial mapping exhibits higher tensile strain in the films in the presence of SiO_x. The β‐Ga₂O₃layers grown on an AlN template, using the same processes as for sapphire, show an excellent epitaxial relationship between β‐Ga₂O₃and AlN and have a significant change in β‐Ga₂O₃surface morphology. 

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4. Strain‐Induced Orbital Contributions to Oxygen Electrocatalysis in Transition‐Metal Perovskites

   https://doi.org/10.1002/aenm.202102175  

   Fernandez, Abel; Caretta, Lucas; Das, Sujit; Klewe, Christoph; Lou, Djamila; Parsonnet, Eric; Gao, Ran; Luo, Aileen; Shafer, Padraic; Martin, Lane_W (October 2021, Advanced Energy Materials)

   Abstract Epitaxial strain has been shown to produce dramatic changes to the orbital structure in transition metal perovskite oxides and, in turn, the rate of oxygen electrocatalysis therein. Here, epitaxial strain is used to investigate the relationship between surface electronic structure and oxygen electrocatalysis in prototypical fuel cell cathode systems. Combining high‐temperature electrical‐conductivity‐relaxation studies and synchrotron‐based X‐ray absorption spectroscopy studies of La_0.5Sr_0.5CoO₃and La_0.8Sr_0.2Co_0.2Fe_0.8O₃thin films under varying degrees of epitaxial strain reveals a strong correlation between orbital structure and catalysis rates. In both systems, films under biaxial tensile strain simultaneously exhibit the fastest reaction kinetics and lowest electron occupation in thed_z²orbitals. These results are discussed in the context of broader chemical trends and electronic descriptors are proposed for oxygen electrocatalysis in transition metal perovskite oxides. 

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5. Intrinsic exchange bias from interfacial reconstruction in an epitaxial Ni _x Co _y Fe _{3− x −y} O ₄ (111)/ $\alpha$ -Al ₂ O ₃ (0001) thin film family

   https://doi.org/10.1088/1361-648X/ad789d  

   Yang, Detian; Liu, Yaohua; Xu, Xiaoshan (September 2024, Journal of Physics: Condensed Matter)

   Abstract Intrinsic exchange bias is known as the unidirectional exchange anisotropy that emerges in a nominally single-component ferro-(ferri-)magnetic system. In this work, with magnetic and structural characterizations, we demonstrate that intrinsic exchange bias is a general phenomenon in (Ni, Co, Fe)-based spinel oxide films deposited on $\alpha$-Al₂O₃(0001) substrates, due to the emergence of a rock-salt interfacial layer consisting of antiferromagnetic CoO from interfacial reconstruction. We show that in Ni_xCo_yFe_3−x−yO₄(111)/ $\alpha$-Al₂O₃(0001) films, intrinsic exchange bias and interfacial reconstruction have consistent dependences on Co concentrationy, while the Ni and Fe concentration appears to be less important. This work establishes a family of intrinsic exchange bias materials with great tunability by stoichiometry and highlights the strategy of interface engineering in controlling material functionalities. 

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