JPS606891B2 - Compound having hexagonal layered structure represented by TmGaCuO↓4 and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound TmGaCu04 having a hexagonal layered structure and a method for producing the same.

Conventionally, a compound having a hexagonal layered structure represented by YFe204 was synthesized by the present applicant, and its existence is already known.

In this compound, as shown in Y30Fe20Fe3042-, divalent and trivalent ions of iron are surrounded by oxygen ions at the 5-position, and yttrium (Y) is
It is a compound that has six-coordinated oxygen ions around it, and is magnetic. The present invention provides the above-mentioned Y30Fe
20Fe30042 - Tm3 instead of Y30 in the compound
Ten, C instead of Fe2 ten, G instead of Fe3 ten
The object of the present invention is to provide a novel compound that replaces a30 and a method for producing the same.

In the compound represented by TmGaCu04 of the present invention, thulium is Tm30 ion, gallium is Ga3
10. Copper exists as Cze+ and can be expressed as Tm3+Ga30Cu2+042-.

This crystal has a hexagonal layered structure as shown in FIG. The largest circle indicates oxygen, the middle circle indicates thulium, and the smallest black circle indicates gallium and copper. Gallium and copper are randomly distributed. The divalent ions of copper and the trivalent ions of gallium are surrounded by five-coordinated oxygen ions. Crystallographically, they occupy the same position. Moreover, Tm has six-coordinated oxygen around it. Oxygen, an anion, has a delicate structure. s, t and u indicate positions within the unit cell. Planar index (hkl) and interplanar spacing (d(A)) of this crystal [do indicates actual measurement, dc indicates calculated value.

], relative reflection intensity for X-rays, 1 (%) are as shown in Table 1. TmGa○u04 The first table space group is Rmim, its crystal habit is plate-like, and its lattice constant is as follows.

ao=3.4726 ±0.0004 (
A) Co=25.160 ±0.006
(A) This compound is useful as a semiconductor material and a catalyst.

This compound can be produced by the following method.

Thulium metal (Tm) is also known as thulium oxide (Tm2).
03) Moshi is a compound that decomposes into thulium oxide (Tm203) when heated, and metal gallium,
Alternatively, gallium oxide (Ga203) or a compound that decomposes into gallium oxide (Ga203) when heated, and metallic copper or oxidized steel (Cu○), or a compound that decomposes when heated to produce oxidized steel (Cuo). ytterbium, gallium, and copper in an atomic ratio of 1:1:1, and
It can be produced by heating in the air, in an oxidizing atmosphere, or in a reducing atmosphere to the extent that gallium and copper are not reduced from their trivalent ion state and divalent ion state, respectively, at a temperature of 100 yen or more.

Commercially available starting materials used in the present invention may be used as they are, but in order to rapidly advance the chemical reaction between the starting materials, the smaller the particle size, the better.
It is preferable that it is below m. Furthermore, when used as an electrical material, contamination with impurities is avoided, so the higher the purity of the starting raw materials, the better.

This raw material is thoroughly mixed as is or with alcohol or acetone. The mixing ratio of these is 1:1:1 as an atomic ratio of thulium, gallium, and copper.
This is the percentage of

If this ratio is exceeded, the target compound cannot be obtained. This mixture was mixed in air, or in an oxidizing atmosphere or in a reducing atmosphere such that gallium and copper could not be reduced from their trivalent and divalent ionic states.
Heat at a temperature of 00:00 or higher. The heating time is one day or more. There are no restrictions on the rate of temperature increase during heating. After the reaction is completed, the temperature may be raised to 0° C. or the solution may be rapidly drawn out into the atmosphere. The obtained TmGaCu04 compound exhibited black color and was found to have a crystal structure by powder X-ray diffraction. The crystal structure was found to be the same as that of YFe204 already obtained by the applicant. The weights of the starting mixed sample and the reaction product were precisely weighed, and the stoichiometry of the resulting sample was determined. Examples Thulium oxide (Tm203) powder with a purity of 99.9% or more, gallium oxide (Ga203) with a purity of 99.9% or more
Powder and reagent-grade oxidized steel (Cu○) powder were weighed at a molar ratio of 1:1:2, and ethyl alcohol was added in a mortar and mixed thoroughly to form a fine powder with an average particle size of several meters. A powder was obtained.

The mixture was filled in a platinum rubbo and placed in a box-shaped siliconite furnace set at 1020 qo 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 Tm○aCu04, and it was confirmed by powder X-ray diffraction that it was crystallographically the same type as the previously reported YFe204. The weight of the sample was precisely weighed before and after heating, and the stoichiometry of the resulting sample was determined. Table 1 shows the crystallographic properties of the samples obtained.

[Brief explanation of the drawing]

The drawing is a diagram of a TmGaCu04 crystal of the present invention. The largest circle indicates oxygen, the middle circle indicates thulium, and the smallest black circle indicates gallium and copper. Figure 1

Claims (1)

[Claims] 1 A compound having a hexagonal layered structure represented by TmGaCuO_4. 2 Thulium metal (Tm) or thulium oxide (Tm
_2O_3) or a compound that decomposes into thulium oxide (Tm_2O_3) when heated, and metallic gallium (Ga) or gallium oxide (Ga_2O_3).
) or gallium oxide (Ga
_2O_3) and copper (Cu) or copper oxide (CuO), or a compound that decomposes to produce copper oxide (CuO) when heated, with the ratio of ytterbium, gallium, and copper being atomic. Mix at a ratio of 1:1:1 and place in the air at a temperature of 700°C or higher in an oxidizing atmosphere or in a reducing atmosphere to the extent that gallium and copper are not reduced from the trivalent ion state and divalent ion state, respectively. TmGaCuO_ characterized by heating under
A method for producing a compound having a hexagonal layered structure represented by No. 4.