Water electrolysis can use renewable electricity to produce green hydrogen, a portable fuel and sustainable chemical precursor. Improving electrolyzer efficiency hinges on the activity of the oxygen evolution reaction (OER) catalyst. Earth-abundant, ABO3-type perovskite oxides offer great compositional, structural, and electronic tunability, with previous studies showing compositional substitution can increase the OER activity drastically. However, the relationship between the tailored bulk composition and that of the surface, where OER occurs, remains unclear. Here, we study the effects of electrochemical cycling on the OER activity of La 0.5 Sr 0.5 Ni 1-x Fe x O 3-δ (x = 0-0.5) epitaxial films grown by oxide molecular beam epitaxy as a model Sr-containing perovskite oxide. Electrochemical testing and surface-sensitive spectroscopic analyses show Ni segregation, which is affected by electrochemical history, along with surface amorphization, coupled with changes in OER activity. Our findings highlight the importance of surface composition and electrochemical cycling conditions in understanding OER performance on mixed metal oxide catalysts, suggesting common motifs of the active surface with high surface area systems.
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Strain‐Induced Orbital Contributions to Oxygen Electrocatalysis in Transition‐Metal Perovskites
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 La0.5Sr0.5CoO3and La0.8Sr0.2Co0.2Fe0.8O3thin 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 the
- PAR ID:
- 10448382
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Energy Materials
- Volume:
- 11
- Issue:
- 46
- ISSN:
- 1614-6832
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Spin-orbit coupling (SOC), the interaction between the electron spin and the orbital angular momentum, can unlock rich phenomena at interfaces, in particular interconverting spin and charge currents. Conventional heavy metals have been extensively explored due to their strong SOC of conduction electrons. However, spin-orbit effects in classes of materials such as epitaxial 5 d -electron transition-metal complex oxides, which also host strong SOC, remain largely unreported. In addition to strong SOC, these complex oxides can also provide the additional tuning knob of epitaxy to control the electronic structure and the engineering of spin-to-charge conversion by crystalline symmetry. Here, we demonstrate room-temperature generation of spin-orbit torque on a ferromagnet with extremely high efficiency via the spin-Hall effect in epitaxial metastable perovskite SrIrO 3 . We first predict a large intrinsic spin-Hall conductivity in orthorhombic bulk SrIrO 3 arising from the Berry curvature in the electronic band structure. By manipulating the intricate interplay between SOC and crystalline symmetry, we control the spin-Hall torque ratio by engineering the tilt of the corner-sharing oxygen octahedra in perovskite SrIrO 3 through epitaxial strain. This allows the presence of an anisotropic spin-Hall effect due to a characteristic structural anisotropy in SrIrO 3 with orthorhombic symmetry. Our experimental findings demonstrate the heteroepitaxial symmetry design approach to engineer spin-orbit effects. We therefore anticipate that these epitaxial 5 d transition-metal oxide thin films can be an ideal building block for low-power spintronics.more » « less
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Abstract Ultrafast time‐domain thermoreflectance (TDTR) is utilized to extract the through‐plane thermal conductivity (
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