The electrolysis of water is of global importance to store renewable energy and the methodical design of next-generation oxygen evolution catalysts requires a greater understanding of the structural and electronic contributions that give rise to increased activities. Herein, we report a series of Ruddlesden–Popper La0.5Sr1.5Ni1−xFexO4±δ oxides that promote charge transfer via cross-gap hybridization to enhance electrocatalytic water splitting. Using selective substitution of lanthanum with strontium and nickel with iron to tune the extent to which transition metal and oxygen valence bands hybridize, we demonstrate remarkable catalytic activity of 10 mA cm−2 at a 360 mV overpotential and mass activity of 1930 mA mg−1ox at 1.63 V via a mechanism that utilizes lattice oxygen. This work demonstrates that Ruddlesden–Popper materials can be utilized as active catalysts for oxygen evolution through rational design of structural and electronic configurations that are unattainable in many other crystalline metal oxide phases.
International audienceThe electrochemical properties of the O3-type NaxMn1/3Fe2/3O2 (x = 0.77) phase used as positive electrode material in Na batteries were investigated in the 1.5–3.8 V, 1.5–4.0 V and 1.5–4.3 V ranges. We show that cycling the Na cells in a wider voltage range do not induce a significant gain on long term cycling as the discharge capacities reached for the three experiments are identical after the 14th cycle. The structural changes the material undergoes from 1.5 V (fully intercalated state) to 4.3 V were investigated by operando in situ X-ray powder diffraction (XRPD) and were further characterized by ex situ synchrotron XRPD. We show that the low amount of Mn3+ ions (≈33% of total Mn+ ions) is enough to induce a cooperative Jahn–Teller effect for all MO6 octahedra in the fully intercalated state. Upon deintercalation the material exhibits several structural transitions: O′3 → O3 → P3. Furthermore, several residual phases are observed during the experiment. In particular, a small part of the O3 type is not transformed to P3 but is always involved in the electrochemical process. To explain this behaviour the hypothesis of an inhomogeneity, which is not detected by XRD, is suggested. All phases converge into a poorly crystallized phase for x ≈ 0.15. The short interslab distance of the resulting phase strongly suggests an octahedral environment for the Na+ ions. X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy were used to confirm the activity of the Mn4+/Mn3+ and Fe4+/Fe3+ redox couples in the low and high voltage regions, respectively. 57Fe Mössbauer spectroscopy also showed an increase of the disorder into the material upon deintercalation
BaFe2(PO4)2 was recently prepared by hydrothermal synthesis and identified as the first two-dimensional (2D) Ising ferromagnetic oxide, in which honeycomb layers made up of edge-sharing FeO6 octahedra containing high-spin Fe(2+) ions (S = 2) are isolated by PO4 groups and Ba(2+) cations. BaFe2(PO4)2 has a trigonal R-3 structure at room temperature but adopts a triclinic P-1 structure below 140 K due to the Jahn-Teller (JT) instability arising from the (t2g)(4)(eg)(2) configuration. The triclinic crystal structure was refined to find significantly distorted Fe(2+)O6 octahedra in the honeycomb layers while the distortion amplitude QJT was estimated to 0.019 Å. The JT stabilization energy is estimated to be ∼7 meV per formula unit by DFT calculations. Below ∼70 K, very close to the ferromagnetic transition temperature Tc = 65.5 K, the structure of BaFe2(PO4)2 returns to a trigonal R-3 structure in the presence of significant ferromagnetic domains. This rare re-entrant structural transition is accompanied by a discontinuous change in the quadrupolar splitting of Fe(2+), as determined by Mössbauer spectroscopy. EPR measurements show the presence of magnetic domains well above Tc , as expected for a ferromagnetic 2D Ising system, and support that the magnetism of BaFe2(PO4)2 is uniaxial (g⊥ = 0).
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