Transformation of the Defective Layered Structure into the Three-Dimensional Perovskite Structure under High Pressure

Byeon, Song‐Ho; Kim, Hyunhwa; Yoon, Jong-Jin; Dong, Yongkwan; Hu, Yun; Inaguma, Yoshiyuki; Itoh, Makoto

doi:10.1021/cm9801892

Cited by 7 publications

(8 citation statements)

References 18 publications

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“…There are, however, several important examples of structural transformations in perovskites that do not necessarily fit into the above categories. For example, there are high-pressure techniques that convert layered perovskites into three-dimensional phases without requiring any interlayer condensation reactions. , Low-temperature oxygen intercalation and deintercalation reactions − as well as fluorine insertion reactions − can be used to synthesize interesting phases that are inaccessible by other routes. Finally, there are multistep intercalation reactions of layered superconductors that probe the nature of superconductivity as well as open the door to new organic/inorganic hybrid superconductors. − …”

Section: Other Structural Transformations Of Perovskitesmentioning

confidence: 99%

“…Byeon and co-workers transformed a layered perovskite directly into a nondefective three-dimensional perovskite using a high-pressure technique rather than a condensation reaction . While this approach does not require reducible cations in the layered precursor, it instead requires anion vacancies in the perovskite block.…”

Section: Other Structural Transformations Of Perovskitesmentioning

confidence: 99%

“…The large Rb + cation favors the formation of a layered structure, and the incorporation of M 2+ cations into the B-sites of the layered phase creates anion vacancies in the perovskite lattice to maintain charge balance . Because RbLaSrNb 2 M II O 9 has both the ABO 3 stoichiometry and anion vacancies, Byeon and co-workers recently discovered that it is possible under high pressure to form the stable three-dimensional perovskite phases of the same stoichiometry . Interestingly, some of the RbLaSrNb 2 M II O 9 (M II = Mg, Cu, Zn) phases remain cubic, while others have a tetragonal distortion, depending on the choice of the M 2+ cation .…”

Section: Other Structural Transformations Of Perovskitesmentioning

confidence: 99%

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Perovskites by Design: A Toolbox of Solid-State Reactions

2002

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In recent years, many soft-chemical reactions of layered perovskites have been reported, and they can be classified into sets of similar reactions. Simple ion-exchange and intercalation reactions replace or modify the interlayer cations of layered perovskites, and more complex metathesis reactions replace interlayer cations with cationic structural units. Topochemical condensation reactions that involve dehydration and reduction provide access to a variety of metastable structural features in three-dimensional perovskites, and similar reactions can be used to convert among higher order layered perovskite homologues. Other techniques, such as high pressure and anion intercalation/deintercalation, also yield interesting metastable phases. When combined, the individual reactions complement each other, and a powerful toolbox of solid-state reactions emerges. By using layered perovskites as templates, it is possible to retrosynthetically design new product perovskites that retain the structural features of the precursor layered phases. The toolbox of reactions was used to synthesize a new Ruddlesden-Popper phase, Na 2 Sr 2 Nb 2 MnO 10 , and to demonstrate the first example of a complete cycle of reactions of layered perovskites. In addition, topochemical dehydration and reduction were combined to synthesize the new A-site defective cubic perovskite Ca 0.67 -Eu 1.33 La 0.67 Ti 3 O 9 . It should be possible to extend the toolbox to include more complex systems using layer-by-layer assembly of perovskite thin films, which provide access to "made to order" stacking sequences.

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Section: Other Structural Transformations Of Perovskitesmentioning

confidence: 99%

Section: Other Structural Transformations Of Perovskitesmentioning

confidence: 99%

Section: Other Structural Transformations Of Perovskitesmentioning

confidence: 99%

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Perovskites by Design: A Toolbox of Solid-State Reactions

2002

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“…Among the perovskite family of transition-metal oxides, topochemical reactions have been used to make novel cation-deficient metastable phases such as La 2/3 TiO 3 , Nd 2 Ti 3 O 9 , SrTa 2- x Nb x O 6 , and Ca 4 Nb 6 O 19 . Currently, the only routes available to transform layered perovskites into metastable three-dimensional phases involve either a dehydration mechanism, , which inevitably leaves a cation deficiency on the A site, or high-pressure techniques, which require low coordination numbers or anion deficiency in the lamellar precursor.…”

Section: Introductionmentioning

confidence: 99%

Topochemical Synthesis of Three-Dimensional Perovskites from Lamellar Precursors

Schaak

Mallouk

2000

J. Am. Chem. Soc.

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A topochemical route to nondefect, three-dimensional perovskites from lamellar Dion-Jacobson and Ruddlesden-Popper precursors was demonstrated. The method involves reduction of one of the ions (in this case Eu 3+ ) in the precursor phase and concomitant loss of oxygen. CsEu 2 Ti 2 NbO 10 , a three-layer Dion-Jacobson compound, was ion-exchanged to AEu 2 Ti 2 NbO 10 (A ) Na, Li) and reduced in hydrogen to form the SrTiO 3 -type perovskites AEu 2 Ti 2 NbO 9 . Similarly, K 2 Eu 2 Ti 3 O 10 , a three-layer Ruddlesden-Popper compound, underwent divalent ion exchange to form the Dion-Jacobson compounds A II Eu 2 Ti 3 O 10 (A II ) Ca, Sr) and M II Eu 2 Ti 3 O 10 (M II ) Ni, Cu, Zn), which were reduced in hydrogen to perovskite-type A II Eu 2 Ti 3 O 9 and M II -Eu 2 Ti 3 O 9 , respectively. The A II and Eu 2+ ions of A II Eu 2 Ti 3 O 9 remain ordered, while A-site disordering occurs in the other perovskites. In all cases, the anisotropic texture of the layered precursors is retained in the product perovskite phase.

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“…They revert to a cubic pyrochlore structure upon heating above 1000 K. The structure of the two materials is pseudo monoclinic (β > 90 • , with a = c), and they are thought to be antiferroelectric, similar to other perovskites of the series (RE 3+ = Lu-Dy). Another series of complex niobate perovskites, RbLaSrNb 2 MO 9 (M = Cu, Mg, Zn) [34], have also been prepared by high-pressure treatment of hexagonal layered structures, although no cation ordering is apparent.…”

Section: Vanadium Groupmentioning

confidence: 99%