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New Compounds In3Ti2AO10, In6Ti6BO22, and Their Solid Solutions (A: Al, Cr, Mn, Fe, or Ga; B: Mg, Mn, Co, Ni, Cu, or Zn): Synthesis and Crystal Structures

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Abstract

New compounds, In3Ti2AO10 (A: Al, Cr, Mn, Fe, or Ga) and In6Ti6BO22 (B: Mg, Mn, Co, Ni, Cu, or Zn) were synthesized at and above 1000°C in air through solid-state reactions among the constituent cation oxide powders. They are isostructural with the monoclinic and/or orthorhombic In3Ti2FeO10 having a pyrochlore-related crystal structure with a commensurate or incommensurate modulated structure. The high-temperature phase is orthorhombic, and the low-temperature phase is monoclinic. The lattice constants of In3Ti2AO10 are as follows: In3Ti2AlO10 (1200°C): a(Å)=5.833(2), b(Å)=3.371(2), and c(Å)=12.060(6); In3Ti2AlO10 (1100°C): a(Å)=5.8368(7), b(Å)=3.3721(4), c(Å)=6.3402(8), and β(°)=107.87(1); In3Ti2CrO10 (1200°C): a(Å)=5.9246(8), b(Å)=3.3562(5), c(Å)=6.3546(9), and β(°)=108.10(1); In3Ti2GaO10 (1200°C): a(Å)=5.861(2), b(Å)=3.385(1), and c(Å)=12.094(4); In3Ti2GaO10 (1000°C): a(Å)=5.8742(9), b(Å)=3.3828(5), c(Å)=6.353(1), and β(°)=107.87(1). In3Ti2AlO10 and In3Ti2GaO10 are polymorphic. The lattice constants of In6Ti6BO22 are as follows: In6Ti6MgO22 (1200°C): a(Å)=5.9236(7), b(Å)=3.3862(4), c(Å)=6.3609(7), and β(°)=108.15(1); In6Ti6MnO22 (1200°C): a(Å)=5.9361(9), b(Å)=3.4031(5), c(Å)=6.3435(10), and β(°)=108.26(1); In6Ti6CoO22 (1200°C): a(Å)=5.9243(5), b(Å)=3.3841(3), c(Å)=6.3495(6), and β(°)=108.18(1); In6Ti6NiO22 (1200°C): a(Å)=5.9191(6), b(Å)=3.3729(3), c(Å)=6.3568(6), and β(°)=108.13(1); In6Ti6CuO22 (1000°C): a(Å)=5.916(2), b(Å)=3.379(1), and c(Å)=12.029(4); In6Ti6ZnO22 (1200°C): a(Å)=5.9223(6), b(Å)=3.3830(3), c(Å)=6.3576(6), and β(°)=108.16(1). In6Ti6BO22 (B: Mg, Mn, Co, Ni, or Zn) are monoclinic and In6Ti6CuO22 is orthorhombic. Solid solutions were synthesized in between In3Ti2AO10 (A: Al, Cr, Mn, Fe, or Ga) and In6Ti6BO22 (B: Mg, Mn, Co, Ni, Cu or Zn), and their lattice constants were determined. Temperature in the parenthesis means synthesis temperature, and all the lattice constants were measured at room temperature. The relationship between the unit cells of In3Ti2AO10, In6Ti6BO22, their solid solutions, and the constituent cation elements of A and B are discussed in terms of their tendency for site preference.

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Cited by (16)

  • Phase relations in the pseudo ternary system In<inf>2</inf>O<inf>3</inf>-TiO<inf>2</inf>-BO (B: Zn, Co and Ni) at 1200 °C in air

    2018, Journal of Solid State Chemistry
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    The fact that In1+x(Ti1/2Zn1/2)1−xO3(ZnO) takes the layered structure and both In(Ti1/2Mg1/2)O3(MgO) and In(Ti1/2B1/2)O3(BO) (B: Mg and Ni) take the spinel one is consistent to the aforementioned experimental properties (i)–(iv). Both In3Ti2AO10 (A: Fe, Ga, Al and Cr) and In6Ti6BO22 (B: Mg, Co, Ni, Cu, Zn and Ca) having the monoclinic In(Fe1/4Ti3/4)O27/8-type of structure have been reported so far [22]. As mentioned before, both Fe(III) and Ti(IV) in the monoclinic structure of the In(Fe1/4Ti3/4)O27/8 occupy CN = 5–6 in its crystal structure because of the composite crystal.

  • Photocatalytic H<inf>2</inf> evolution over a new visible-light-driven photocatalyst In<inf>12</inf>NiCr<inf>2</inf>Ti<inf>10</inf>O<inf>42</inf>

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    The lattice constants calculated by the least square method are as follows: a = 5.932(2) Å, b = 10.098(1) Å, c = 6.358(2) Å and β = 108.12(2)°. These results are consistent with those reported by Brown et al. [22], who ever reported that all the compounds In6Ti6AO22, In3Ti2BO10 and their solid solutions In12AB2Ti10O42 (A: divalent cations Mg, Ni, Zn, etc.; B: trivalent cations Al, Cr, Fe, Ga, etc.) have the same crystal structure. Referring to the structure of the monoclinic In6Ti6AO22[23,24] and InB1 − xTixO3 + x/2 (A = Mg, Zn; B = Fe, Cr; x = 2/3) [25,26] as reported by Michiue and Kimizuka et al., the pyrochlore-related layered structure of In12NiCr2Ti10O42 with a pseudorhombohedral symmetry is depicted in Fig. 2.

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