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Title: Oxygen-storage behavior and local structure in Ti-substituted YMnO 3

Abstract

Hexagonal manganates RMnO3 (R=Y, Ho, Dy) have been recently shown to exhibit oxygen-storage capacities promising for three-way catalysts, air-separation, and related technologies. Here, we demonstrate that Ti substitution for Mn can be used to chemically tune the oxygen-breathing properties of these materials towards practical applications. Specifically, Y(Mn1-xTix)O3 solid solutions exhibit facile oxygen absorption/desorption via reversible Ti3+↔Ti4+ and Mn3+↔Mn4+ reactions already in ambient air at ≈400 °C and ≈250 °C, respectively. On cooling, the oxidation of both cations is accompanied by oxygen uptake yielding a formula YMn3+1-x-yMn4+yTi4+xO3+δ. The presence of Ti promotes the oxidation of Mn3+ to Mn4+, which is almost negligible for YMnO3 in air, thereby increasing the uptake of oxygen beyond that required for a given Ti4+ concentration. The reversibility of the redox reactions is limited by sluggish kinetics; however, the oxidation process continues, if slowly, even at room temperature. The extra oxygen atoms are accommodated by the large interstices within a triangular lattice formed by the [MnO5] trigonal bipyramids. According to bond distances from Rietveld refinements using the neutron diffraction data, the YMnO3 structure features under-bonded Mn and even more severely under-bonded oxygen atoms that form the trigonal bases of the [MnO5] bipyramids. The tensile bond strain aroundmore » the 5-fold coordinated Mn site and the strong preference of Ti4+(and Mn4+) for higher coordination numbers likely provide driving forces for the oxidation reaction. Reverse Monte Carlo refinements of the local atomic displacements using neutron total scattering revealed how the excess oxygen atoms are accommodated in the structure by correlated local displacements of the host atoms. Large displacements of the under-bonded host oxygen atoms play a key part in this lattice-relaxation process, facilitating reversible exchange of significant amounts of oxygen with atmosphere.« less

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1409579
Report Number(s):
BNL-114631-2017-JA¿¿¿
Journal ID: ISSN 0022-4596
DOE Contract Number:
SC0012704
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 246; Journal Issue: C
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Levin, I., Krayzman, V., Vanderah, T. A., Tomczyk, M., Wu, H., Tucker, M. G., Playford, H. Y., Woicik, J. C., Dennis, C. L., and Vilarinho, P. M.. Oxygen-storage behavior and local structure in Ti-substituted YMnO 3. United States: N. p., 2017. Web. doi:10.1016/j.jssc.2016.10.029.
Levin, I., Krayzman, V., Vanderah, T. A., Tomczyk, M., Wu, H., Tucker, M. G., Playford, H. Y., Woicik, J. C., Dennis, C. L., & Vilarinho, P. M.. Oxygen-storage behavior and local structure in Ti-substituted YMnO 3. United States. doi:10.1016/j.jssc.2016.10.029.
Levin, I., Krayzman, V., Vanderah, T. A., Tomczyk, M., Wu, H., Tucker, M. G., Playford, H. Y., Woicik, J. C., Dennis, C. L., and Vilarinho, P. M.. Wed . "Oxygen-storage behavior and local structure in Ti-substituted YMnO 3". United States. doi:10.1016/j.jssc.2016.10.029.
@article{osti_1409579,
title = {Oxygen-storage behavior and local structure in Ti-substituted YMnO 3},
author = {Levin, I. and Krayzman, V. and Vanderah, T. A. and Tomczyk, M. and Wu, H. and Tucker, M. G. and Playford, H. Y. and Woicik, J. C. and Dennis, C. L. and Vilarinho, P. M.},
abstractNote = {Hexagonal manganates RMnO3 (R=Y, Ho, Dy) have been recently shown to exhibit oxygen-storage capacities promising for three-way catalysts, air-separation, and related technologies. Here, we demonstrate that Ti substitution for Mn can be used to chemically tune the oxygen-breathing properties of these materials towards practical applications. Specifically, Y(Mn1-xTix)O3 solid solutions exhibit facile oxygen absorption/desorption via reversible Ti3+↔Ti4+ and Mn3+↔Mn4+ reactions already in ambient air at ≈400 °C and ≈250 °C, respectively. On cooling, the oxidation of both cations is accompanied by oxygen uptake yielding a formula YMn3+1-x-yMn4+yTi4+xO3+δ. The presence of Ti promotes the oxidation of Mn3+ to Mn4+, which is almost negligible for YMnO3 in air, thereby increasing the uptake of oxygen beyond that required for a given Ti4+ concentration. The reversibility of the redox reactions is limited by sluggish kinetics; however, the oxidation process continues, if slowly, even at room temperature. The extra oxygen atoms are accommodated by the large interstices within a triangular lattice formed by the [MnO5] trigonal bipyramids. According to bond distances from Rietveld refinements using the neutron diffraction data, the YMnO3 structure features under-bonded Mn and even more severely under-bonded oxygen atoms that form the trigonal bases of the [MnO5] bipyramids. The tensile bond strain around the 5-fold coordinated Mn site and the strong preference of Ti4+(and Mn4+) for higher coordination numbers likely provide driving forces for the oxidation reaction. Reverse Monte Carlo refinements of the local atomic displacements using neutron total scattering revealed how the excess oxygen atoms are accommodated in the structure by correlated local displacements of the host atoms. Large displacements of the under-bonded host oxygen atoms play a key part in this lattice-relaxation process, facilitating reversible exchange of significant amounts of oxygen with atmosphere.},
doi = {10.1016/j.jssc.2016.10.029},
journal = {Journal of Solid State Chemistry},
number = C,
volume = 246,
place = {United States},
year = {Wed Feb 01 00:00:00 EST 2017},
month = {Wed Feb 01 00:00:00 EST 2017}
}
  • Hexagonal manganates RMnO{sub 3} (R=Y, Ho, Dy) have been recently shown to exhibit oxygen-storage capacities promising for three-way catalysts, air-separation, and related technologies. Here, we demonstrate that Ti substitution for Mn can be used to chemically tune the oxygen-breathing properties of these materials towards practical applications. Specifically, Y(Mn{sub 1−x}Ti{sub x})O{sub 3} solid solutions exhibit facile oxygen absorption/desorption via reversible Ti{sup 3+}↔Ti{sup 4+} and Mn{sup 3+}↔Mn{sup 4+} reactions already in ambient air at ≈400 °C and ≈250 °C, respectively. On cooling, the oxidation of both cations is accompanied by oxygen uptake yielding a formula YMn{sup 3+}{sub 1−x-y}Mn{sup 4+}{sub y}Ti{sup 4+}{sub x}O{submore » 3+δ}. The presence of Ti promotes the oxidation of Mn{sup 3+} to Mn{sup 4+}, which is almost negligible for YMnO{sub 3} in air, thereby increasing the uptake of oxygen beyond that required for a given Ti{sup 4+} concentration. The reversibility of the redox reactions is limited by sluggish kinetics; however, the oxidation process continues, if slowly, even at room temperature. The extra oxygen atoms are accommodated by the large interstices within a triangular lattice formed by the [MnO{sub 5}] trigonal bipyramids. According to bond distances from Rietveld refinements using the neutron diffraction data, the YMnO{sub 3} structure features under-bonded Mn and even more severely under-bonded oxygen atoms that form the trigonal bases of the [MnO{sub 5}] bipyramids. The tensile bond strain around the 5-fold coordinated Mn site and the strong preference of Ti{sup 4+}(and Mn{sup 4+}) for higher coordination numbers likely provide driving forces for the oxidation reaction. Reverse Monte Carlo refinements of the local atomic displacements using neutron total scattering revealed how the excess oxygen atoms are accommodated in the structure by correlated local displacements of the host atoms. Large displacements of the under-bonded host oxygen atoms play a key part in this lattice-relaxation process, facilitating reversible exchange of significant amounts of oxygen with atmosphere. - Graphical abstract: Concurrent redox reactions involving Ti and Mn yield facile absorption/desorption of excess oxygen. - Highlights: • Concurrent redox reactions involving Ti and Mn yield oxygen absorption/desorption. • Excess oxygen is accommodated as interstitials via correlated atomic shifts. • Oxygen breathing is facilitated by the under-bonding of host Mn and O atoms.« less
  • Cited by 1
  • Here, the widely spread oxygen vacancies (V O) in multiferroic materials can strongly affect their physical properties. However, their exact influence has rarely been identified in hexagonal manganites. Here, with the combined use of transmission electron microscopy (TEM) and first-principles calculations, we have systematically studied the electronic and crystal structure modifications induced by V O located at the same Mn atomic plane (in-plane V O). Our TEM experiments reveal that the easily formed in-plane V O not only influence the electronic structure of YMnO 3 but alter the in-plane Wyckoff positions of Mn ions, which may subsequently affect the intraplanemore » and interplane exchange interaction of Mn ions. The ferroelectricity is also impaired due to the introduction of V O. Further calculations confirm these electronic and structural changes and modifications. Our results indicate that the electronic and crystal structure of YMnO 3 can be manipulated by the creation of V O.« less
  • New substituted copper titanates with the CaCu/sub 3/Ti/sub 4/O/sub 12/ perovskite-like structure were synthesized and characterized. Their formula is Li absolute value of Cu/sub 3-x/Li/sub x/ absolute value of Ti/sub 3-x/M/sub 1 + x//sup V/ O/sub 12/. There is a homogeneity range for M/sup V/ = Nb, 0.12 less than or equal to x less than or equal to 0.33, and a unique composition for M/sup V/ = Ta, x = 0.33. The unit cell is cubic: a approx. 2a/sub p/ (parameter of the ideal cubic cell) approx. 7.40 A. The CaCu/sub 3/Ti/sub 4/O/sub 12/-type structure was confirmed from anmore » X-ray powder structural determination. Lithium occupies both square planar sites where it replaces copper and icosahedral sites, with a probable delocalization. Crystal chemistry of the AC/sub 3/B/sub 4/O/sub 12/ structure is considered, taking into account the evolution of anion packing and the distortion of polyhedra. A diagrammatic representation is proposed so that precise information on the regularity of the C/sub 3/B/sub 4/O/sub 12/ network can be obtained.« less
  • We synthesized hexagonal YMnO{sub 3} doped with Ti ions and investigated the crystal structure by means of transmission electron microscopy. Superlattice reflection spots with a modulation wave vector q=(1/3)c{sup *} appeared for the Ti-doped YMnO{sub 3}. We found that Ti-doped YMnO{sub 3} intrinsically consists of the hexagonal phase and the rhombohedral phase derived from formation of a superstructure with the 3d{sub 001} period along the c axis. The hexagonal-to-rhombohedral phase transition results from a change of the stacking manner in Mn(Ti) trimers in Mn(Ti)O layers.