Perovskite‐like Mn<sub>2</sub>O<sub>3</sub>: A Path to New Manganites

Ovsyannikov, Sergey V.; Abakumov, Artem M.; Tsirlin, Alexander A.; Schnelle, Walter; Egoavil, Ricardo; Verbeeck, Jo; Tendeloo, Gustaaf Van; Glazyrin, Konstantin; Hanfland, Michael; Dubrovinsky, Leonid

doi:10.1002/ange.201208553

Cited by 19 publications

(17 citation statements)

References 56 publications

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“…9A). Surprisingly, it is identical (both the frequency of all lines as well as their relative intensities) to the spectrum of the recently discovered perovskite-like z-Mn 2 O 3 (narrow bandgap semiconductor), which is thermodynamically stable at very high pressures of about 20 GPa and temperatures of about 1200 C. 45,49 As we observe only subtle changes in the EXAFS spectrum of the Oxide 2 heated to 300 C, we conclude that only a minor fraction (up to 20%) of the MnO 2 is converted to z-Mn 2 O 3 but this fraction dominates the Raman spectrum (the spectrum of the amorphous material has broad features with a low amplitude visible as a background). To illustrate the compatibility of the z-Mn 2 O 3 structure with our EXAFS results, we repeated the EXAFS simulations including the shortest Mn-Mn distance of 3.04Å observed in the z-Mn 2 O 3 structure, and found that this distance is compatible with the experimental spectra ( Fig.…”

Section: Optical Spectroscopic Techniquessupporting

confidence: 54%

Origin of the heat-induced improvement of catalytic activity and stability of MnO_x electrocatalysts for water oxidation

et al. 2019

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Section: Optical Spectroscopic Techniquessupporting

confidence: 54%

Origin of the heat-induced improvement of catalytic activity and stability of MnO_x electrocatalysts for water oxidation

et al. 2019

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“…[39,40] So far, the transition to perovskite and PPv structural types having eight-coordinated metal atoms in bicapped trigonal prisms has been reported only for Mn 2 O 3 . [41] In our experiments, the orthorhombic Fe 2 O 3 (Rh 2 O 3 -II-type) phase was not observed during compression up to 73 GPa at ambient temperature; a transformation to the monoclinic (P2 1 /n) phase was detected at 54 GPa instead. The transition to the Rh 2 O 3 -II-type phase [8] is accompanied with an abrupt volume decrease, but it is relatively small (∼1.3%) to be attributed to the HS-to-LS transition suggested previously.…”

Section: Phase Transformation Of M-fe 2 O 3 Into Ppv-fe 2 O 3 Upon Lamentioning

confidence: 46%

Novel high pressure monoclinic Fe₂O₃ polymorph revealed by single-crystal synchrotron X-ray diffraction studies

Bykova

Bykov

Prakapenka

et al. 2013

High Pressure Research

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A novel high pressure polymorph of iron sesquioxide, m-Fe 2 O 3 , has been identified by means of singlecrystal synchrotron X-ray diffraction (XRD). Upon compression of a single crystal of hematite, α-Fe 2 O 3 , in a diamond anvil cell, the transition occurs at pressure of about 54 GPa and results in ∼10% volume reduction. The crystal structure of the new phase was solved by the direct method (monoclinic space group P2 1 /n, a = 4.588(3), b = 4.945(2), c = 6.679(7) Å and β = 91.31(9) • ) and refined to R 1 ∼11%. It belongs to the cryolite double-perovskite structure type and consists of corner-linked FeO 6 octahedra and FeO 6 trigonal prisms filling the free space between the octahedra. Upon compression up to ∼71 GPa at ambient temperature no further phase transitions were observed. Laser heating to ∼ 2100 ± 100 K promotes a transition to the Cmcm CaIrO 3 -type (post-perovskite (PPv)) phase. The PPv-Fe 2 O 3 crystal structure was refined by means of single-crystal XRD at ∼65 GPa. On decompression the PPv-Fe 2 O 3 phase fully transforms back to hematite at pressures between ∼25 and 15 GPa.

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“…We synthesized the Fe 5 O 6 samples under moderate HP‐HT conditions using a multi‐anvil press at Bayerisches Geoinstitut (BGI; see experimental procedures in the Supporting Information) and selected a set of high‐quality single crystals for the present investigation (Figure a), including a temperature‐dependent single‐crystal X‐ray diffraction at the European synchrotron radiation facility . The Fe 5 O 6 samples adopted the orthorhombic Cmcm structure (No.…”

Section: Figurementioning

confidence: 99%

A Room‐Temperature Verwey‐type Transition in Iron Oxide, Fe₅O₆

et al. 2020

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Functional oxides whose physicochemical properties may be reversibly changed at standard conditions are potential candidates for the use in next‐generation nanoelectronic devices. To date, vanadium dioxide (VO2) is the only known simple transition‐metal oxide that demonstrates a near‐room‐temperature metal–insulator transition that may be used in such appliances. In this work, we synthesized and investigated the crystals of a novel mixed‐valent iron oxide with an unconventional Fe5O6 stoichiometry. Near 275 K, Fe5O6 undergoes a Verwey‐type charge‐ordering transition that is concurrent with a dimerization in the iron chains and a following formation of new Fe−Fe chemical bonds. This unique feature highlights Fe5O6 as a promising candidate for the use in innovative applications. We established that the minimal Fe−Fe distance in the octahedral chains is a key parameter that determines the type and temperature of charge ordering. This model provides new insights into charge‐ordering phenomena in transition‐metal oxides in general.

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Perovskite‐like Mn₂O₃: A Path to New Manganites

Cited by 19 publications

References 56 publications

Origin of the heat-induced improvement of catalytic activity and stability of MnO_x electrocatalysts for water oxidation

Origin of the heat-induced improvement of catalytic activity and stability of MnO_x electrocatalysts for water oxidation

Novel high pressure monoclinic Fe₂O₃ polymorph revealed by single-crystal synchrotron X-ray diffraction studies

A Room‐Temperature Verwey‐type Transition in Iron Oxide, Fe₅O₆

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Perovskite‐like Mn2O3: A Path to New Manganites

Cited by 19 publications

References 56 publications

Origin of the heat-induced improvement of catalytic activity and stability of MnOx electrocatalysts for water oxidation

Origin of the heat-induced improvement of catalytic activity and stability of MnOx electrocatalysts for water oxidation

Novel high pressure monoclinic Fe2O3 polymorph revealed by single-crystal synchrotron X-ray diffraction studies

A Room‐Temperature Verwey‐type Transition in Iron Oxide, Fe5O6

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Perovskite‐like Mn₂O₃: A Path to New Manganites

Origin of the heat-induced improvement of catalytic activity and stability of MnO_x electrocatalysts for water oxidation

Origin of the heat-induced improvement of catalytic activity and stability of MnO_x electrocatalysts for water oxidation

Novel high pressure monoclinic Fe₂O₃ polymorph revealed by single-crystal synchrotron X-ray diffraction studies

A Room‐Temperature Verwey‐type Transition in Iron Oxide, Fe₅O₆