KR20120020773A - Novel layered indium selenium oxychloride - Google Patents

Abstract

PURPOSE: Indium selenium oxychloride in a noble layered structure is provided to introduce p-elements such as indium to the structure of selenium oxychloride through a solid phase synthesis reaction. CONSTITUTION: Metal selenium oxychloride contains a layered structure based on an In(3+)-Se(4+)-O-Cl combination. The layered structure is formed by connecting an InO_4Cl_2 octahedron and a SeO_3 octahedron based on an oxygen element. The metal selenium oxychloride contains a structural unit represented by chemical formula 1. A method for manufacturing the metal selenium oxychloride is based on a solid phase synthesis reaction by mixing an indium precursor, a chlorine precursor, and a selenium precursor.

Description

Novel layered indium selenium oxychloride

The present invention relates to a novel layered indium selenium oxide chloride, and more particularly, a twisted InO ₄ Cl ₂ octahedron and an asymmetric SeO ₃ polyhedron are introduced into an oxygen atom by introducing indium into the skeleton of the selenium oxide chloride through a solid phase synthesis reaction. It relates to a novel layered indium selenium oxide chloride having a layered structure, which is separated from each other, halogen affinity and a sulfur-sulfur moiety is separated from each other, crystallized in a tetragonal space group exhibiting excellent physical properties.

Metal oxide chlorides have received great attention not only because of their rich structural chemistry but also because of their excellent physical properties. For example, various amines were able to intercalate between MOCl (Ln = Fe, Ti, V, Ho, Er, Tm, and Yb). Non-symmetrical compound BiSeO ₃ Cl exhibited nonlinear optical (SHG) properties with inherently generated asymmetric lone pairs. On the other hand, (Ca, Na) ₂ CuO ₂ Cl ₂ and (Ca, Na) ₂ CaCu ₂ O ₄ Cl ₂ are known as high temperature superconductor compounds with high T _c , and Te ₄ Nb ₃ O ₁₅ Cl and Bi ₃ Te ₄ O _{It has been shown that 10} Cl ₅ can be used as an anionic template material. Depending on the various coordination geometries of the skeletal elements used, many interesting skeletal structures have been proposed. In general, in mixed metal oxychlorides, the chlorine anion is directly bonded to the halogen-friendly transition metal and becomes part of its backbone, but more phosphate cations tend to bind to oxygen. For this reason, the coupling of halogen-friendly transition metals and phospholipid cations in the mixed metal oxychloride often forms low dimensional structures such as chains or layers. Metal oxide chlorides are usually synthesized through standard solid phase reactions, water (solvent) thermal methods, chemical transport reactions and two-stage pyrohydrolysis processes in air or under vacuum.

In particular, metal selenium oxychlorides such as MSeO ₃ Cl (M = Bi, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) and some transition metals or strontium selenium oxide chlorides Reported. The reported materials exhibit low dimensional structures with very interesting structural and / or physical properties as expected.

However, no example of introducing p-elements such as In ³⁺ into the metal selenium oxychloride has been reported.

An object of the present invention is to provide a metal selenium oxide chloride having a novel structure by introducing a p-element such as indium into the skeleton of selenium oxide chloride through a solid phase synthesis reaction.

Another object of the present invention is to provide a use utilizing the excellent physical properties of the metal selenium oxide chloride.

In order to achieve the above object, the present invention is composed of a combination of In ^{3 +} -Se ^{4 +} -O-Cl, provides a metal selenium oxide chloride having a layered structure.

The present invention also provides a process for preparing the metal selenium oxidized chloride of the present invention comprising the step of performing a solid phase synthesis reaction by mixing an indium precursor, a chlorine precursor and a selenium precursor.

The present invention also provides an article of any one of the intercalation composite, wireless communication, catalyst, power storage and transportation device, computer device, or quantum interference device comprising the metal selenium oxidizing chloride of the present invention.

The present invention has the effect of providing indium selenium oxide chloride having a novel layered structure by introducing indium into the skeleton of selenium oxide chloride.

Figure 1 shows an experimental diagram and a calculation of the powder X-ray diffraction pattern of InSeO ₃ Cl of the present invention.
FIG. 2 is a 50% probability ellipsoids (ORTEP) diagram of InSeO ₃ Cl of the present invention, showing a 6-coordinating twisted octahedral and 3-coordinate polyhedral environment for In ³⁺ and Se ⁴⁺ cations, respectively.
Figure 3 is a co-rod and polyhedral model showing the two-dimensional layered structure of InSeO ₃ Cl of the present invention, the twisted InO ₄ Cl ₂ octahedron and asymmetric SeO ₃ polyhedral is connected to form a layered structure through the oxygen atoms Shown (blue, In; green, Se; red, O; cyan, Cl).
4 shows (a) InO ₄ Cl ₂ octahedral chains sharing an edge surface of the present invention, (b) SeO ₃ groups, and (c) InO ₄ Cl ₂ octahedral chains connected by SeO ₃ groups to form a layered structure Co-rod model, showing that the SeO ₃ group serves as a linker in the chain (blue, In; green, Se; red, O; cyan, Cl).
5 shows the infrared spectral frequency (cm ⁻¹ ) of InSeO ₃ Cl of the present invention.
Figure 6 shows the thermogravimetric analysis of InSeO ₃ Cl of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, the structure of this invention is demonstrated concretely.

The present invention is composed of a combination of In ³⁺ -Se ⁴⁺ -O-Cl, and relates to a metal selenium oxide chloride having a layered structure.

The metal selenium oxide chloride of the present invention is a novel indium selenium oxide chloride having an In ³⁺ -Se ⁴⁺ -O-Cl combination by introducing In ³⁺ into the selenium oxide chloride skeleton through a solid phase synthesis reaction.

The metal selenium oxide chloride of the present invention exhibits a low dimensional structure, that is, a two-dimensional layered structure, wherein the layered structure is characterized in that InO ₄ Cl ₂ octahedron and SeO ₃ polyhedron are connected by oxygen atoms.

The introduction of p-elements, such as In ³⁺ , into the backbone of the oxidized chloride can create a relatively large octahedral environment. In addition, stable octahedral binding of Se ⁴⁺ and In ³⁺ cations, including local asymmetric coordination geometry due to stereoactive lone pairs, can lead to interesting structural features.

"Solid phase synthesis reaction" as used herein means a conventional standard solid phase synthesis reaction in which solid compounds are mixed without solvent and heated to high temperatures to synthesize them. The solid phase synthesis reaction is similar to the starting material and the manufacturing process, but when the structure of the synthesized solid compound is different, it can be applied in various fields by deriving completely different characteristics.

Metal selenium oxide chloride of the present invention may preferably include a structural unit represented by the following formula (1):

[Formula 1]

InSeO ₃ Cl

Structural features of the metal selenium oxide chloride of the present invention will be described in more detail with reference to FIGS. 2 to 4 as follows.

The metal selenium oxychloride of the present invention consists of a twisted InO ₄ Cl ₂ octahedron and an asymmetric SeO ₃ polyhedron and is connected to each other via an oxygen atom.

A single In ³⁺ cation is linked to four oxygen and two chlorine atoms. In-O and In-Cl bond distances are 2.109 (8) -2.178 (8) Å and 2.531 (3) 각각, respectively. O-In-O, O-In-Cl and Cl-In-Cl bond angles are 87.4 (3) -179.6 (3) °, 79.8 (2) -170.1 (2) ° and 91.30 (11) °, respectively.

A single Se ⁴⁺ cation is coordinated by three oxygen atoms. Se ⁴⁺ cations are in a very asymmetric coordination environment due to unpaired electron pairs. Se—O bond lengths range from 1.678 (8) to 1.766 (8) μs. O-Se-O bond angles are 97.2 (4) to 107.7 (4) °.

The warped InO ₄ Cl ₂ octahedron and the asymmetric SeO ₃ polyhedron are connected via oxygen atoms to form a two-dimensional layered structure. More specifically, warped InO ₄ Cl ₂ octahedrons share their edge surfaces through Cl (1) and O (3) to form infinity chains along the [010] direction (see FIG. 4 (a)). These chains are linked by three coordinating asymmetric SeO ₃ polyhedra through O (1), O (2), and O (3). Thus, the SeO ₃ group is InO ₄ Cl ₂ which shares an edge surface with lone pairs of electrons on Se ⁴⁺ oriented in approximately [101], [-10-1], [-101], and [10-1] directions. Connect the chains That is, SeO ₃ groups provide inter-chain linkers to form a layered structure of InSeO ₃ Cl. However, the overall polarity of the lone pair associated with Se ⁴⁺ disappears when the directions of the individual local lone pairs are summed together, and InSeO ₃ Cl is {[In ³⁺ O _2/2 O _2/3 Cl _{2 / 2} ] ^{4 / 3-} [Se ⁴⁺ O _2/2 O _1/3 ] _4/3 ⁺ } ⁰ can be expressed as a neutral layer.

In addition, the lone pair cation, Se ⁴⁺ , contains only an oxygen ligand and all chlorine atoms are coordinated with In ³⁺ . Thus, lone pairs of electrons completely separate the halogen affinity element, In ³⁺ and the sulfur element, Se ⁴⁺ . Thus, the layered structure of InSeO ₃ Cl seems to be due to the separation of halogen affinity and hydrophilic substructure.

The binding value is 3.098 and 3.979 for In ³⁺ and Se ⁴⁺ , respectively.

In addition, the metal selenium oxide chloride of the present invention can be crystallized in a tetragonal space group Pbca (No. 61) to obtain a colorless plate crystal form.

The crystal data of the metal selenium oxychloride of the present invention is as follows:

Is crystallized in orthorhombic space group Pbca (No. 61), a = 7.0580 (14) Å, b = 7.0390 (14) Å, c = 16.206 (3) Å, V = 805.1 (3) Å 3, and Z = 8

In addition, the metal selenium oxide chloride of the present invention may be decomposed at 480 ° C. or higher as a result of thermogravimetric analysis.

In infrared spectral analysis, the metal selenium oxychloride of the present invention exhibits Se-O frequency at approximately 422 and 762-865 cm ⁻¹ and In-O stretch at 637 cm ⁻¹ .

In addition, the metal selenium oxide chloride of the present invention includes a ^sequestered electron pair cation, Se ⁴⁺ in an asymmetric coordination environment, and the twist direction and size in the polyhedron of the cation can be quantified by measuring dipole moments. The dipole moment of the SeO ₃ polyhedron of the compound of the present invention by measuring the dipole moment is approximately 7.43 Debyes.

The present invention also relates to a process for preparing the metal selenium oxidized chloride of the present invention comprising the step of performing a solid phase synthesis reaction by mixing an indium precursor, a chlorine precursor and a selenium precursor.

The metal selenium oxide chloride of the present invention can be prepared in the form of colorless plate crystals through solid phase synthesis reaction of indium precursor, chlorine precursor and selenium precursor.

As the indium precursor, In ₂ O ₃ , InCl ₃ , or the like may be used alone or in combination of two or more.

As the chlorine precursor, InCl ₃ , SeCl ₄ , or the like may be used alone or in combination of two or more.

The selenium precursor may be used alone or two or more kinds SeO ₂ , SeCl ₄ and the like.

The indium precursor, the chlorine precursor and the selenium precursor are mixed in a stoichiometric content to reduce the generation of impurities. More specifically, 1 mmol of In ₂ O ₃ , 1 mmol of InCl ₃ and 3 mmol of SeO ₂ may be mixed. have.

The mixing may be to mix the solid powder in the mortar under dry argon atmosphere, but is not particularly limited thereto.

Solid phase synthesis reaction of the mixture

First heating the mixture of indium precursor, chlorine precursor and selenium oxide under vacuum at a temperature of 200 to 250 ° C. for 3 to 5 hours, and then second heating at a temperature of 450 to 550 ° C. for 20 to 30 hours; And

It is preferable to include the step of cooling the mixture heated in the step to room temperature at a rate of 0.1 to 1 ℃ / min.

The invention also relates to the product of any one of the intercalation composites, radiocommunications, catalysts, power storage and transport devices, computer devices, or quantum interference devices comprising the metal selenium oxychloride of the invention.

Since the metal selenium oxide chloride of the present invention has a layered structural feature composed of an asymmetric cation, the intercalation reaction is possible. It can be used for wireless communication, power storage and transportation device, computer device, quantum interference device, etc., and it can be used as heterogeneous acid catalyst that can easily convert various organic materials such as acetalization reaction of aldehyde. Can be.

Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention, but the scope of the present invention is not limited by the following Examples.

Example 1 Synthesis of Indium Selenium Oxide Chloride

In ₂ O ₃ (99.9%, Alfa Aesar), InCl ₃ (Aldrich, 98%), SeO ₂ (Aldrich, 98%) used to synthesize indium selenium oxide chloride was used as purchased. InSeO ₃ Cl was synthesized according to standard solid phase reaction method. Under the atmosphere of dry argon, using a mortar and pestle, the stoichiometric content of In ₂ O ₃ (0.278 g, 1.00 mmol), InCl ₃ (0.221 g, 1.00 mmol), and SeO ₂ (0.333 g, 3.00 mmol) Was mixed thoroughly. The reaction mixture was placed in a fused silica tube and then evacuated. The tube sealed with fire under vacuum was gradually heated to 250 ° C. for 5 hours and then to 500 ° C. for 24 hours. The tube was then cooled to room temperature at a rate of 1 ° C./min. The final product was obtained in the form of colorless plate crystals.

Powder X-ray diffraction patterns for the final product were collected on a SCINTAG XDS2000 diffractometer using Cu Ka radiation at 35 kV and 30 mA at room temperature. A fine powder sample of InSeO ₃ Cl was placed on a glass sample holder and scanned in a 2θ range 5-70 ° with a step size of 0.02 ° and a step time of 1 second. The powder X-ray diffraction pattern for the synthetic material was consistent with the pattern calculated from the single crystal data (FIG. 1).

Experimental Example 1 Structure Analysis

The crystal structure of InSeO ₃ Cl was measured according to standard crystallographic measurement methods. Colorless plate crystals having a width of 0.02 × 0.12 × 0.20 mm were used for the structure measurement. The data were obtained from Bruker SMART APEX CCD X-ray diffractometer at 200K using graphite monochromated Mo Kα radiation at Korea Research Institute of Basic Science. Half of the data was collected using the narrow-frame method at a scan width of 0.30 ° in omega and an exposure time of 5 seconds per frame. At the end of the data collection, the first 50 frames were measured again to monitor the device and crystal stability. The maximum collection applied to the intensity was less than 1%. The SAINT program was used to integrate the data and the collected intensities for Lorentz, polarization, air adsorption and absorbance by variables in the path length through the detector faceplate. The neighboring absorbance for half of the data was collected using the SADABS program. The data were interpreted and purified using SHELXS-97 and SHELXL-97A, respectively. All atoms were purified to anisotropic displacement parameters and converged for I > 2 ( I ). All calculations were performed using the WinGX-98 crystallographic software package.

The selected bond distances and angles along with crystallographic data, atomic coordination and displacement constants, and bond value calculations for InSeO ₃ Cl are shown in Tables 1-3.

Similar to the structure of the InTeO InSeO ₃ Cl Cl ₃ of the monoclinic system has a one, it is a little more space group symmetry of the material. That is, it crystallizes into a tetragonal space group Pbca (No. 61).

The structure consists of a twisted InO ₄ Cl ₂ octahedron and SeO ₃ polyhedron and is connected to each other via an oxygen atom (FIG. 2).

A single In ³⁺ cation is linked to four oxygen and two chlorine atoms. In-O and In-Cl bond distances were 2.109 (8) -2.178 (8) Å and 2.531 (3) 각각, respectively. O-In-O, O-In-Cl and Cl-In-Cl bond angles were 87.4 (3) -179.6 (3) °, 79.8 (2) -170.1 (2) ° and 91.30 (11) °, respectively.

A single Se ⁴⁺ cation is coordinated by three oxygen atoms. Se ⁴⁺ cations are in a very asymmetric coordination environment due to unpaired electron pairs. Se—O bond lengths range from 1.678 (8) to 1.766 (8) μs. O-Se-O bond angles were 97.2 (4) to 107.7 (4) °.

As shown in FIG. 3, the warped InO ₄ Cl ₂ octahedron and the asymmetric SeO ₃ polyhedron are connected via oxygen atoms to form a two-dimensional layered structure.

Looking more closely at the layered structure, interesting structural features of InSeO ₃ Cl can be found. Twisted InO ₄ Cl ₂ octahedrons share their edge surfaces through Cl (1) and O (3) to form infinity chains along the [010] direction (see FIG. 4 (a)). These chains are linked by three coordinating asymmetric SeO ₃ polyhedra through O (1), O (2), and O (3). Thus, the SeO ₃ group is InO ₄ Cl ₂ which shares an edge surface with lone pairs of electrons on Se ⁴⁺ oriented in approximately [101], [-10-1], [-101], and [10-1] directions. The chains are connecting. In other words, SeO ₃ groups provide inter-chain linkers to form a layered structure of InSeO ₃ Cl. However, the overall polarity of the lone pair associated with Se ⁴⁺ disappears when the directions of the individual local lone pairs are summed together, and InSeO ₃ Cl is {[In ³⁺ O _2/2 O _2/3 Cl _{2 / 2} ] ^{4 / 3-} [Se ⁴⁺ O _2/2 O _1/3 ] _4/3 ⁺ } ⁰ can be expressed as a neutral layer.

Interestingly, the lone pair cation Se ⁴⁺ contains only an oxygen ligand and all chlorine atoms are coordinated with In ³⁺ . Thus, the lone pairs completely separate the halogen affinity element, In ³⁺ and the sulfur element, Se ⁴⁺ . Thus, the layered structure of InSeO ₃ Cl seems to be due to the separation of halogen affinity and hydrophilic substructure. And, the layered structure of InSeO ₃ Cl is probably due to the separation of halogen affinity and sulfurous substructures.

The result of the calculation of the bond was 3.098 and 3.979 for In ³⁺ and Se ⁴⁺ , respectively.

Experimental Example 2 Infrared Spectrum Analysis

Infrared spectra were recorded on a Varian 1000 FT-IR spectrometer in the 400-4000 cm ^-1 range using samples compressed directly between two KBr pellets.

Infrared spectra of the compounds of the present invention showed Se-O frequencies at approximately 422 and 762-865 cm ⁻¹ . The frequency at 637 cm ⁻¹ may correspond to In-O stretching (FIG. 5).

Experimental Example 3 Thermogravimetric Analysis

Thermogravimetric analysis was performed on a Setaram LABSYS TG-DTA / DSC Thermogravimetric Analyzer. A polycrystalline sample of InSeO ₃ Cl was placed in an alumina crucible and heated from room temperature to 1000 ° C. at a rate of 10 ° C. per minute while providing argon.

Thermogravimetric analysis was used to investigate the thermal behavior of InSeO ₃ Cl. The compounds of the present invention were not stable at high temperatures. One-stage decomposition that volatilized above 480 ° C. occurred (FIG. 6).

Experimental Example 4 Analysis of Energy Dispersion by Scanning Electron Microscope / X-ray (SEM / EDAX)

SEM / EDAX analysis was performed using Hitachi S-3400N / Horiba Energy EX-250 instruments.

EDAX to InSeO ₃ Cl indicated that the In / Se / O / Cl ratio was 1: 1: 3: 1.

Experimental Example 5 Dipole Moment Calculation

Although InSeO ₃ Cl is crystallized in a centrally symmetric space group, the material contains a lone electron pair cation, Se ⁴⁺ , in an asymmetric coordination environment. The main purpose of investigating materials containing asymmetric lone electron pair cations is to better understand the coordination environment. For example, the direction and magnitude of distortion in the polyhedron of Se ⁴⁺ lone electron pair cations can be quantified by measuring their local dipole moments. A systematic approach by calculating the valence has been introduced to calculate the direction and magnitude of the local dipole moment.

In the case of a polyhedron containing an isolated electron pair, the isolated electron pair was provided with -2 valence, and the distance of the local Se ⁴⁺ -isolated electron pair was evaluated to be 1.22 Å based on a previous study by Galy et al.

Using this method the dipole moment of the SeO ₃ polyhedron in InSeO ₃ Cl can be calculated to be approximately 7.43 Debyes (D).

For comparison, the dipole moments of SeO ₃ polyhedra at different mixed metal selenium oxides (or halogen oxides) were calculated.

As shown in Table 4, 52 examples of SeO ₃ polyhedra were tested and the dipole moments ranged from 6.17 to 9.70 D with an average value of 7.82 ± 0.96 D.

Claims (11)

Metal selenium oxide chloride consisting of In ³⁺ -Se ⁴⁺ -O-Cl combination and having a layered structure.
The method of claim 1,
The layered structure is a metal selenium oxide chloride formed by connecting InO ₄ Cl ₂ octahedron and SeO ₃ polyhedron by oxygen atoms.
The method of claim 1,
Metal selenium oxide chloride comprising a structural unit represented by the formula (1):
[Formula 1]
InSeO ₃ Cl
The method of claim 1,
Metal selenium oxide chloride crystallized in a tetragonal space group Pbca (No. 61).
A method for producing the metal selenium oxidized chloride of claim 1, comprising performing a solid phase synthesis reaction by mixing an indium precursor, a chlorine precursor, and a selenium precursor.
The method of claim 5,
Indium precursor is a method of producing a metal selenium oxide chloride comprising at least one selected from the group consisting of In ₂ O ₃ and InCl ₃ .
The method of claim 5,
Chlorine precursor is a method of producing a metal selenium oxide chloride comprising at least one selected from the group consisting of InCl ₃ and SeCl ₄ .
The method of claim 5,
Selenium precursor is a method of producing a metal selenium oxide chloride comprising at least one selected from the group consisting of SeO ₂ and SeCl ₄ .
The method of claim 5,
Indium precursor, chlorine precursor and selenium precursor are mixed in a stoichiometric content.
The method of claim 5, wherein the solid phase synthesis reaction
First heating the mixture of indium precursor, chlorine precursor and selenium precursor under vacuum at a temperature of 200 to 250 ° C. for 3 to 5 hours, and then second heating at a temperature of 450 to 550 ° C. for 20 to 30 hours; And
Method for producing a metal selenium oxide chloride comprising the step of cooling the mixture heated in the step to room temperature at a rate of 0.1 to 1 ℃ / min.
A product of any one of the intercalation composites, radiocommunications, catalysts, power storage and transportation devices, computer devices, or quantum interference devices comprising the metal selenium oxide chloride of claim 1.

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