Structural, magnetic, and oxygen storage properties of hexagonal Dy1−xYxMnO3+δ

Abughayada, C.; Da̧browski, B.; Avdeev, Maxim; Koleśnik, S.; Remsen, S.; Chmaissem, O.

doi:10.1016/j.jssc.2014.05.017

Cited by 32 publications

(51 citation statements)

References 23 publications

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“…25 Alternative to materials using the oxygen partial pressure swing process, the hexagonal-type manganites LnMnO 3+d (Ln = smaller lanthanides, e.g. Dy, Ho, Er and Y) were found to operate in the much more promising temperature swing process in pure oxygen or air, as recently documented by Remsen et al 7 and Abughayada et al 8,26 The advantage of such compounds stems from a low and narrow temperature range at which the oxygen exchanges occur, and most importantly, there is no need to use special gas mixtures for the reduction process. However, the kinetics of the redox processes reported to date have been relatively slow, and the achievable OSC has been somewhat lower than that for the layer-ordered perovskites.…”

Section: Introductionmentioning

confidence: 92%

“…The LnMnO 3AEd manganites are known to exhibit the perovskiteor hexagonal-type crystal structure depending on the size of the lanthanide and, to some degree, on the oxygen content during the synthesis. 26,27 For larger lanthanides (La-Dy), the distorted perovskite structure is observed when synthesized in air. For smaller ones (Ho-Lu, In and Sc), the hexagonal structure (Hex0, d = 0) is formed with layers of 8-fold coordinated Ln 3+ cations and layers of the corner-shared MnO 5 trigonal-bipyramids.…”

Section: Introductionmentioning

confidence: 99%

“…For smaller ones (Ho-Lu, In and Sc), the hexagonal structure (Hex0, d = 0) is formed with layers of 8-fold coordinated Ln 3+ cations and layers of the corner-shared MnO 5 trigonal-bipyramids. 8,26 This five-fold coordination of Mn 3+ causes splitting of the 3d 4 electronic orbitals into three sets: empty a 0 (d z 2) and filled up e 0 (d x 2 Ày 2, d xy ) and e 00 (d xz , d yz ) with high spin states e 02 and e 002 . As a result of orbital filling, the elongation of basal Mn-O bonds and the compression of the apical Mn-O bond are observed.…”

Section: Introductionmentioning

confidence: 99%

“…7 Until the recent reports by Remsen et al regarding DyMnO 3+d and substituted Dy 1Àx Y x MnO 3+d , 7,31 not much was known about the oxygen hyperstoichiometry in hexagonal manganites. The subsequent paper focused on the structural, magnetic and oxygen storage-related properties of the Dy 1Àx Y x MnO 3+d series, 26 in which the superstructure R3c (tripled along the c-axis, Hex1) of Dy 0.7 Y 0.3 MnO 3.29 was reported. Furthermore, similar behavior was also observed for the hexagonal HoMnO 3+d , ErMnO 3+d , and YMnO 3+d , obtained by high oxygen pressure annealing (Hex2, d E 0.41) for which OSC, as well as the temperatures of oxidation and reduction, were reported depending on the ionic radius of R 3+ .…”

Section: Introductionmentioning

confidence: 99%

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Oxygen storage properties of hexagonal HoMnO_3+δ

Świerczek

Klimkowicz

Nishihara

et al. 2017

Phys. Chem. Chem. Phys.

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Structural and oxygen content changes of hexagonal HoMnO manganite at the stability boundary in the perovskite phase have been studied by X-ray diffraction and thermogravimetry using in situ oxidation and reduction processes at elevated temperatures in oxygen and air. The oxygen storage properties during structural transformation between stoichiometric Hex0 and oxygen-loaded Hex1 phases, transition temperatures and kinetics of the oxygen incorporation and release are reported for materials prepared by the solid-state synthesis and high-impact mechanical milling. Long-term annealing experiments have shown that the Hex0 (δ = 0) → Hex1 (δ ≈ 0.28) phase transition is limited by the surface reaction and nucleation of the new phase for HoMnO 15MM. The temperatures of Hex0 ↔ Hex1 transitions have been established at 290 °C and 250 °C upon heating and cooling, respectively, at a rate of 0.1° min, also indicating that the temperature hysteresis of the transition could possibly be as small as 10 °C in the equilibrium. Ball-milling of HoMnO has only a small effect on improving the speed of the reduction/oxidation processes in oxygen, but importantly, allowed for considerable oxygen incorporation in air at a temperature range of 220-255 °C after prolonged heating. The Mn 2p XAS results of the Mn valence in oxygen loaded samples support the oxygen content determined by the TG method. The magnetic susceptibility data of the effective Mn valence gave inconclusive results due to dominating magnetism of the Ho ions. Comparison of HoMnO with previously studied DyMnO indicates that a tiny increase in the ionic size of lanthanide has a huge effect on the redox properties of hexagonal manganites and that practical properties could be significantly improved by synthesizing the larger average size (Y,Ln)MnO manganites.

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Section: Introductionmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Oxygen storage properties of hexagonal HoMnO_3+δ

Świerczek

Klimkowicz

Nishihara

et al. 2017

Phys. Chem. Chem. Phys.

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“…8 15 On the other hand the synthesis conditions could also be designed to destabilize the perovskite phase of, for example, DyMnO 3 in favor of the hexagonal P6 3 cm, which exhibits exceptional oxygen absorption/desorption properties at unusually low temperatures. 7,16 The similarity of the observed perovskite and layered hexagonal R3c phases of RMnO 3 to the RMO 3 compounds with the fixed oxidation state M 3+ = In, Ga, Al motivated us to study and compare these systems by focusing on R = Pr.…”

Section: Introductionmentioning

confidence: 99%

High temperature neutron diffraction studies of PrInO₃and the measures of perovskite structure distortion

2015

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The crystal structure of PrInO(3) was investigated in the temperature range 303-1123 K by high-resolution neutron-powder diffraction. The PrInO(3) adopts a highly distorted variant of the perovskite structure with the orthorhombic Pnma space group in the whole temperature range investigated. The bond length and bond-angle analysis revealed a very slow tendency to decrease structural distortion with increasing temperature. Comparison of different parameters quantifying perovskite structure distortion calculated for PrInO(3) and the similar PrAlO(3) and PrGaO(3) shows the advantage of using the tolerance factor t12 calculated for the 12-fold coordinated Pr by geometrical averaging of the individual interatomic distances. An additional advantage of the tolerance factor method results from the possibility of extending it to predict the average structural distortion and the geometrical stability of the perovskites at various temperatures once the accurate dependence of t(x,T,d) on the composition, temperature and oxygen content is found. By comparing PrInO(3) with several AMO(3) perovskites containing ions in the fixed oxidation state on the A and M crystal sites it was found that structural distortion and the tolerance factor t12 for PrInO(3) are consistent with the empirical thermal expansion coefficient based on the bond strength calculation [R. M. Hazen, and C. T. Prewitt, Am. Mineral., 1977, 62(3-4), 309]. In contrast to perovskites AMO(3-d) containing mixed-valent M ions, which allow for a wide range of changes of the tolerance factor t(12)(T,d) as a function of oxygen content, perovskites AMO(3) with M ions in the fixed oxidation state show much less flexibility. This flexibility is further reduced for the A(3+)M(3+)O(3) perovskites like PrInO(3) for which even a large change of the synthesis temperature has a minor effect on controlling the resulting t(12)(T) and the structural phase in comparison with A(2+)M(4+)O3 perovskites. The only parameter left for A(3+)M(3+)O(3) materials allowing formation of various perovskites and hexagonal phases is the total pressure, which may significantly change t(12)(T,P).

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A Fast, Low‐Temperature Synthesis Method for Hexagonal YMnO₃: Kinetics, Purity, Size and Shape as Studied by In Situ X‐ray Diffraction

Marshall

Blichfeld

Skjærvø

et al. 2020

Chemistry A European J

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The reaction mechanisms, phase development and kinetics of the hydrothermal synthesis of hexagonal‐YMnO 3 from Y 2 O 3 and Mn 2 O 3 using in situ X‐ray diffraction are reported under different reaction conditions with temperatures ranging from 300 to 350 °C, and using 1, 5 and 10 m KOH, and 5 m NaOH mineraliser. Reactions initiated with Y 2 O 3 hydrating to Y(OH) 3 , which then dehydrated to YO(OH). Higher temperatures and KOH concentrations led to faster, more complete dehydrations. However, 1 m KOH led to YO(OH) forming concurrently with Y(OH) 3 before Y(OH) 3 fully dehydrated but yielded a very low phase purity of hexagonal‐YMnO 3 . Using NaOH mineraliser, no YO(OH) was observed. Dehydration also initiated at a higher temperature in the absence of Mn 2 O 3 . The evolution of Rietveld refined scale factors was used to determine kinetic information and approximate activation energies for the reaction. The described hydrothermal synthesis offers a fast, low‐temperature method for producing anisometric h‐YMnO 3 particles.

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Structural, magnetic, and oxygen storage properties of hexagonal Dy1−xYxMnO3+δ

Cited by 32 publications

References 23 publications

Oxygen storage properties of hexagonal HoMnO_3+δ

Oxygen storage properties of hexagonal HoMnO_3+δ

High temperature neutron diffraction studies of PrInO₃and the measures of perovskite structure distortion

A Fast, Low‐Temperature Synthesis Method for Hexagonal YMnO₃: Kinetics, Purity, Size and Shape as Studied by In Situ X‐ray Diffraction

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Structural, magnetic, and oxygen storage properties of hexagonal Dy1−xYxMnO3+δ

Cited by 32 publications

References 23 publications

Oxygen storage properties of hexagonal HoMnO3+δ

Oxygen storage properties of hexagonal HoMnO3+δ

High temperature neutron diffraction studies of PrInO3and the measures of perovskite structure distortion

A Fast, Low‐Temperature Synthesis Method for Hexagonal YMnO3: Kinetics, Purity, Size and Shape as Studied by In Situ X‐ray Diffraction

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Oxygen storage properties of hexagonal HoMnO_3+δ

Oxygen storage properties of hexagonal HoMnO_3+δ

High temperature neutron diffraction studies of PrInO₃and the measures of perovskite structure distortion

A Fast, Low‐Temperature Synthesis Method for Hexagonal YMnO₃: Kinetics, Purity, Size and Shape as Studied by In Situ X‐ray Diffraction