JPH0437009B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention is a novel compound with the general formula InABMnO ₅
(A is Fe, Ga or Cr, B is Mg, Co, Ni
The present invention relates to a compound having a cubic spinel structure represented by (or Zn) and a method for producing the same. This new compound is useful as an anionic conductor, semiconductor material, and catalytic material. Prior Art Conventional compounds having a cubic spinel structure include (1) compounds with a stoichiometric composition represented by the general formula IABM ₂₂₄ (A represents a divalent cation and B represents a trivalent cation); 2) γ-Fe ₂ O ₃ , Ti ₃ CO ₂ O ₈ ,
Compounds with cation defects represented by Ti ₄ CO ₄ O ₁₂ are known. These compounds had a ratio of cations to anions of 3:4, 2:3 or 5:8. Purpose of the Invention The present invention provides a cubic system having anion defects (oxygen ion defects) in a ratio of 4 to 5, which is different from the ratio of the number of cations to the number of anions in conventional compounds having a cubic spinel structure. An object of the present invention is to provide a compound having a crystalline spinel structure. Structure of the Invention The novel compound of the present invention has the general formula InABMnO ₅ (A
is Fe, Ga, or Cr, and B is Mg, Co, Ni, or Zn), and has a cubic spinel structure with a ratio of cations to anions of 4:5. be. This ratio of the number of cations to the number of anions is significantly different from the conventionally known stoichiometric composition of 3:4, or the composition of the cation-deficient spinel structure of 2:3. It is a compound. The values of the lattice constants (a (Å)) of these compounds are shown in Table A below.

[Table] The fact that these compounds have anion defects means that
Assuming an anion defect state, it is concluded that the density obtained from the above-mentioned lattice constant and the actual value measured by the Archimedes method are in good agreement (see Table A). Planar index (hkl) and interplanar spacing (d
(Å)), do (Å) is the measured value, dc (Å) is the calculated value), and relative reflection intensity for X-rays (I (%))
Tables 1 to 12 (numbers 1 to 1 of the above chemical composition)
12). All of these compounds are oxygen ion conductors,
It is useful as a semiconductor material and a catalyst material. In the case of a compound containing Fe, in addition to the above, it can also be used as a magnetic material.

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[Table] These compounds can be produced by the following method. General formula InABMnO ₅ (A is Fe, Ga or Cr,
B represents Mg, Co, Ni or Zn) The metals or metal oxides of In, A, B, Mn, or compounds that are decomposed into metal oxides by heating, are ,B,Mn
In, A and A are mixed in an atomic ratio of 1:1:1:1, and this mixture is heated at a temperature of 1200°C or higher to form In,A.
It can be produced by heating under an atmosphere in which B and Mn each maintain a trivalent ion state, and B and Mn each maintain a divalent ion state. Commercially available starting materials used in the present invention may be used as they are, but in order to allow the chemical reaction between the starting materials to proceed quickly, the smaller the particle size, the better, and it is particularly desirable that the particle size is 10 μm or less. Furthermore, when using the material as an anion conductor, a semiconductor material, a catalyst material, etc., the purity of the starting material is preferably as high as possible since contamination with impurities is avoided. Examples of compounds that are decomposed into metal oxides by heating include hydroxides, carbonates, and nitrates of the respective metals. These raw materials may be thoroughly mixed as is or with alcohol or acetone. The mixing ratio of the raw materials is In, A, B, and Mn (A and B are the same as above) in an atomic ratio of 1:1:1:1. If this ratio is exceeded, the target compound cannot be obtained in a single phase. In this mixture, In and A are each in a 33-valent ion state,
Heat to 1200° C. or higher in an atmosphere where B and Mn each maintain a divalent ion state. The heating time is several hours or more. After heating, it may be rapidly cooled to 0°C or rapidly drawn out into the atmosphere. Example 1 Synthesis of InFeMgMnO ₅ Indium oxide (In ₂ O ₃ ) powder with a purity of 99.99% or more, iron oxide (Fe ₂ O ₂ ) powder with a purity of 99.99% or more, magnesium oxide (MgO) powder with a purity of 99.9% or more, and purity More than 99.9% manganese oxide (MnO)
The powders were weighed in a molar ratio of 1:1:2:2, and ethanol was added to these powders in an agate mortar and mixed for about 30 minutes to obtain a fine powder mixture with an average particle size of several μm. This mixture was sealed in a platinum tube and 1450
After being placed in a tubular siliconite furnace set at .degree. C. and heated for 4 days, the sample was taken out of the furnace and rapidly cooled to room temperature. The obtained sample had a single phase of InFeMgMnO ₅ . The planar index (hkl), interplanar spacing (do (Å)), and relative reflection intensity (I (%)) for X-rays were measured using powder X-ray diffraction method, and the results are shown in Table-
It was as shown in 1. The lattice constant as a cubic system was a=8.603±0.001 (Å). The above lattice constants and the surface index (hkl) in Table-1
The calculated interplanar spacing (dc (Å)) showed extremely good agreement with the actually measured interplanar spacing (do (Å)). Example 2 Synthesis of InFeCoMnO ₅ A sample was obtained in the same manner as in Example 1 except that cobalt oxide (CoO) was used in place of the magnesium oxide powder in Example 1. This sample is InFeCoMnO ₅
It was of a single phase. The planar index (hkl), interplanar spacing (do (Å)), and relative reflection intensity (I (%)) for X-rays were measured using powder X-ray diffraction, and the results are shown in Table 2. Ta. The lattice constant as a cubic system was a=8.625±0.001 (Å). The above lattice constants and the surface index (hkl) in Table 2
The calculated interplanar spacing (dc (Å)) showed extremely good agreement with the actually measured interplanar spacing (do (Å)). Example 3 Synthesis of InFeNiMnO ₅ Another example 1 using nickel oxide (NiO) powder instead of magnesium oxide powder in Example 1
A sample was obtained in the same manner. This sample is
It was of a single phase _{of InFeNiMnO5} . The surface index (hkl), interplanar spacing (do (Å)), and relative reflection intensity for X-rays (I
(%)) The results were as shown in Table 3. The lattice constant as a cubic system was a=8.604±0.001 (Å). The above lattice constants and the surface index (hkl) in Table 3
The calculated interplanar spacing (dc (Å)) showed extremely good agreement with the actually measured interplanar spacing (do (Å)). Example 4 Synthesis of InFeZnMnO ₅ A sample was obtained in the same manner as in Example 1, except that zinc oxide (ZnO) powder was used in place of the magnesium oxide powder in Example 1. This sample was of a single phase of _InFeZnMnO5 . The planar index (hkl), interplanar spacing (do (Å)), and
The results of measuring the relative reflection intensity (I (%)) with respect to the line were as shown in Table 4. The lattice constant as a cubic system was a=8.661±0.001. The above lattice constants and the surface index (hkl) in Table 4
The calculated interplanar spacing (dc (Å)) showed extremely good agreement with the actually measured interplanar spacing (do (Å)). Example 5 Synthesis of InGaMgMnO ₅ Indium oxide (In ₂ O ₃ ) powder with a purity of 99.99% or more, gallium oxide (Ga ₂ O ₃ ) with a purity of 99.99% or more
Magnesium oxide (MgO) powder with a purity of 99.9% or more and manganese oxide (MgO) powder with a purity of 99.9% or more are weighed in a molar ratio of 1:1:2:2, and these powders are placed in an agate mortar. Add ethanol and mix for about 30 minutes until the average particle size is several μm.
A fine powder mixture was obtained. This mixture was sealed in a platinum tube, placed in a tubular siliconite furnace set at 1450°C, and heated for 4 days, after which the sample was taken out of the furnace and rapidly cooled to room temperature. The obtained sample is InGaMgMnO ₅
It was of a single phase. The planar index (hkl), interplanar spacing (do (Å)), and relative reflection intensity (I (%)) for X-rays were measured using the powder X-ray diffraction method, and the results are shown in Table 5. Ta. As a cubic system, the lattice constant was a=8.562±0.001 (Å). The above lattice constants and the surface index (hkl) in Table-5
The calculated interplanar spacing (dc (Å)) showed extremely good agreement with the actually measured interplanar spacing (do (Å)). Examples 6 to 8 (6) Synthesis of InGaCoMnO ₅ (7) Synthesis of InGaNiMnO ₅ (8) Synthesis of InGaZnMnO ₅ Instead of magnesium oxide powder in Example 5, cobalt oxide (6), nickel oxide (7), zinc oxide
Samples were obtained in the same manner as in Example 5 using the powder of (8). Each sample obtained was
It had a single phase of InGaCoMnO ₅ , InGaNiMnO ₅ , and InGaZnMnO ₅ . The planar index (hkl), interplanar spacing (do (Å)), and relative reflection intensity (I (%)) for X-rays were measured using the powder X-ray diffraction method, and the results are shown in Table 6 and Table 2, respectively. 7. It was as shown in Table-8. The lattice constants for the cubic system are a=8.597±0.001 (Å) ……(6) a=8.558±0.001 (Å) ……(7) a=8.591±0.001 (Å) ……(8) Above The interplanar spacing (dc (Å)) calculated from the lattice constant and the planar index (hkl) in each table showed extremely good agreement with the actually measured interplanar spacing (do (Å)). Example 9 Synthesis of InGrMgMnO ₅ Indium oxide (In ₂ O ₃ ) powder with a purity of 99.99% or more, chromium oxide (Cr ₂ O ₃ ) powder with a purity of 99.99% or more, magnesium oxide (MgO) with a purity of 99.9% or more
and manganese oxide (MnO) powder with a purity of 99.9% were weighed in a molar ratio of 1:1:2:2, and these powders were mixed with ethanol in an agate mortar for 30 minutes.
The mixture was mixed for a minute to obtain a fine powder mixture with an average particle size of several μm. This mixture was sealed in a platinum tube, placed in a tubular siliconite furnace set at 1450°C, and heated for 4 days, after which the sample was taken out of the furnace and rapidly cooled to room temperature.
The obtained sample was of a single phase of _InCrMgMnO5 . The planar index (hkl), interplanar spacing (do (Å)), and relative reflection intensity (I (%)) for X-rays were measured using the powder X-ray diffraction method, and the results are shown in Table 9. Ta. The lattice constant as a cubic system was a=8.561±0.001 (Å). The interplanar spacing (dc (Å)) calculated from the above lattice constant and the planar index (hkl) shown in Table 9 was in excellent agreement with the actually measured interplanar spacing (do (Å)). Examples 10 to 12 (10) Synthesis of InCrCoMnO ₅ (11) Synthesis of InCrMiMnO ₅ (12) Synthesis of InCrZnMnO ₅ Cobalt oxide (10), nickel oxide (11), zinc oxide ( Samples were obtained in the same manner as in Example 9 using the powder of 12). Each sample obtained was
It had a single phase of InCrCoMnO ₅ , InCrNiMnO ₅ , and InCrZnMnO ₅ . Table 10 and Table 11 show the results of measuring the planar index (hkl), interplanar spacing (do (Å)), and relative reflection intensity (I (%)) for X-rays using powder X-ray diffraction method. , as shown in Table-12. The lattice constants for the cubic system are a=8.586±0.001 (Å) ……(10) a=8.570±0.001 (Å) ……(11) a=8.602±0.001 (Å) ……(12) Ta. The interplanar spacing (dc (Å)) calculated from the above lattice constant and the planar index (hkl) in each table showed extremely good agreement with the actually measured interplanar spacing (do (Å)). Effects of the Invention The present invention has provided a compound having a novel cubic spinel structure having an anion defect and useful as an anion conductor, a semiconductor material, a catalyst material, and a magnetic material.

Claims (1)

[Claims] 1 General formula InABMnO ₅ (A is Fe, Ga or Cr
, B represents Mg, Co, Ni, or Zn) and has a cubic spinel structure. 2 General formula InABMnO ₅ (A is Fe, Ga or Cr
, B represents Mg, Co, Ni or Zn).
In, A,
B and Mn are mixed in an atomic ratio of 1:1:1:1, and this mixture is heated to a temperature of 1200°C or higher, so that In and A are each in a trivalent ion state, and B and Mn are each in a divalent state. The general formula InABMnO ₅ (A, B
each represents the same thing as above).