KR101560358B1 - Novel mixed metal oxide - Google Patents

Abstract

The present invention relates to a novel mixed metal oxide which can be used for developing products applied to a laser device, a nonlinear optical device, a piezoelectric sensor, wireless communication, a catalyst, a power storage transferring device, a computer device or a quantum interference device or the like based on a laminar framework structure of a mixed metal oxide.

Description

Novel mixed metal oxide < RTI ID = 0.0 >

The present invention relates to novel zeolite yttrium vanadium selenite or tellurite crystallized in a non-centrosymmetric or center symmetric space group.

There is a continuing challenge to explore new non-center-symmetric (NCS) materials due to important features such as second-order nonlinear optical (NLO), piezoelectricity, ferroelectricity and pyroelectric properties. Thus, as building blocks, there has been much effort to find functional NCS materials by combining cations with asymmetric circumstances. In the oxide with extended structure, the macroscopic NCS structure is composed of two cationic families: d ⁰ transition metal cations (V ^{5 +} , Mo ^{6 +} , W ^{6 +} , etc.) and octahedral cations Sb ^{3 +,} Se ^{4 +,} is often found in Te ^{4 +,} etc.). Both cation families tend to exhibit distorted coordination environments due to the second-order Jahn-Teller (SOJT) effect. In the case of d ⁰ transition metal cations in the octahedral coordination environment, the SOJT effect generally occurs when the empty metal d-orbital is mixed with the filled ligand p-orbitals. Octahedral twist is usually observed at the edge (local C ₂ direction), plane (local C ₃ direction) or corner (local C ₄ direction) center. However, in the case of isolated electron pair cations, strong interactions of s- and p-orbital and anion p-orbital of the cation play a crucial role in the formation of isolated electron pairs and subsequent cation distortions. Other important cationic families of NCS chromophores include d ⁰ transition metal cations and borate groups with asymmetric p-orbital systems. At this time it is more important to understand the factors that determine the overall centroid: If the particular circumstances affecting space group symmetry are not reasonably controlled, then the above mentioned local asymmetric units are usually arranged in antiparallel fashion, To form a symmetric (CS) structure. Some important factors that can help determine macroscopic centrality include the size of the metal cations, the hydrogen-bonding effect, and the flexibility of the skeletal structure.

We have investigated Y ^{3 +} -V ^{5 +} -Q ^{4 +} (Q = Se or Te) - oxide systems to synthesize two new stoichiometrically similar quaternary vanadium selenides and tellurite hanba to be looking at the number of four-component system similar stoichiometric vanadium selenite or telru light material, that is, M ₂ O ^{3 +} VQ ₈ (M = Bi, Eu, Gd, Tb, in, and Sc).

As a result of this effort, we have synthesized two new four-component yttrium vanadium selenite or tellurite, YVSe ₂ O ₈ and YVTe ₂ O ₈ through hydrothermal and solid phase synthesis reactions and found that the effect of lone electron pair cation size, Infrared spectra analysis, elemental analysis, thermal analysis, dipole moment calculation, and the like.

Korea Open Patent No. 2012-0101607 (2012.09.14) U.S. Patent No. 4473506 (September 25, 1984)

 Yeong Hun Kim et al., Inorganic Chemistry, vol.52 (19), pp.11450-11456 (2013.09.11)

It is an object of the present invention to provide novel yttrium vanadium selenium or tellurium oxides having a lone pair of cationic linkers and their use.

In order to achieve the above object, the present invention provides a mixed metal oxide represented by the following formula (1) or (2), which represents a Y ^{3 +} -V ^{5 +} -Q ^{4 +} (Q = Se or Te)

[Chemical Formula 1]

YVSe ₂ O ₈

(2)

YVTe ₂ O ₈

The mixed metal oxide may include Y ₂ O ₃ , V ₂ O _5, and SeO ₂ , Or by solid phase synthesis reaction between Y ₂ O ₃ , V ₂ O ₅ and TeO ₂ .

The compound of formula (I) is a compound of formula (I) or (II) is a corner shared VO ₆ The octahedral body and the edge shared by YO ₈ The polyhedral layer is an interlayer linker such as SeO ₃ or TeO ₃ Dimensional skeletal structure connected by a group.

The compound of Formula 1 shows a weight change at 500 to 550 ° C and the compound of Formula 2 shows a weight change at 700 to 750 ° C.

Accordingly, the present invention provides a product in which the mixed metal oxide is applied to any one of a laser device, a nonlinear optical device, a piezoelectric sensor, a wireless communication device, a catalyst, a power storage transport device, a computer device or a quantum interference device.

The present invention provides mixed metal oxides of the new yttrium vanadium selenium / tellurium oxide composition.

The mixed metal oxide may be applied to a laser device, a nonlinear optical device, a piezoelectric sensor, a wireless communication device, a catalyst, a power storage transport device, a computer device, or a quantum interference device based on characteristics of a layered framework structure.

Figure 1 shows calculated and experimental values of the powder X-ray diffraction pattern for the mixed metal oxides of the present invention, YVSe ₂ O ₈ (A) and YVTe ₂ O ₈ (B).
FIG. 2 is a diagram showing a ball-and-stick representation of the mixed metal oxide, YVSe ₂ O ₈ skeleton of the present invention, a layer (a) composed of VO ₆ octahedrons with a corner, a layer made of YO ₈ polyhedrons (b) and YVSe ₂ O ₈ (blue, V; green, Se; yellow, Y; red, O).
Figure 3 is a view of a mixed metal oxide, the skeleton of the YVTe ₂ O ₈ of the present invention-and-stick represented road, floor corner is made of a shared VO ₆ octahedral (a), a layer made of YO ₈ polyhedron an edge is shared (b), and YVTe ₂ O ₈ (blue, V; green, Se; yellow, Y; red, O).
4 shows an infrared spectrum of the mixed metal oxide, YVSe ₂ O ₈ (A) and YVTe ₂ O ₈ (B) of the present invention.
5 shows the UV-Vis spectra of the mixed metal oxides YVSe ₂ O ₈ and YVTe ₂ O ₈ of the present invention.
FIG. 6 shows a thermogravimetric analysis (TGA) (A) of a mixed metal oxide, YVSe ₂ O ₈ , and a powder XRD pattern (B) of a YVSe ₂ O ₈ calcined product of the present invention.
7 shows a thermogravimetric analysis (TGA) (A) of a mixed metal oxide, YVTe ₂ O ₈ , and a powder XRD pattern (B) of a calcined product of YVSe ₂ O ₈ of the present invention.
Figure 8 shows the approximate type 1 phase matching curve of the mixed metal oxide, YVSe ₂ O ₆ , of the present invention.
9 is a ball-and-stick model (blue, V; green, Se; yellow; Y; red, O) showing the arrangement of the asymmetric polyhedra of the mixed metal oxide, YVSe ₂ O ₆ , of the present invention.

Hereinafter, the configuration of the present invention will be described in detail.

The present invention relates to a mixed metal oxide represented by the following formula (1) or (2): Y ^{3 +} -V ^{5 +} -Q ^{4 +} (Q = Se or Te)

[Chemical Formula 1]

YVSe ₂ O ₈

(2)

YVTe ₂ O ₈

Y to crystallize the mixed metal oxide of the present invention in a non-centrosymmetric or centrosymmetric space group ^{3 + -V 5 + -Q 4 +} (Q = Se , or Te) - representing a compound oxide composition, the corner of the shared VO ₆ The octahedral body and the edge shared by YO ₈ The polyhedral layer is an interlayer linker such as SeO ₃ or TeO ₃ Dimensional skeletal structure connected by a group. YVSe ₂ O ₈ of the first embodiment is Y ₂ O ₃ , V ₂ O ₅ and SeO ₂ YVTe ₂ O ₈ of the second embodiment is obtained by a solid phase synthesis reaction between Y ₂ O ₃ , V ₂ O ₅ and TeO _{2 as} green block type and light yellow block type crystal phase, respectively .

More specifically, the YVSe ₂ O ₈ of the first embodiment is Y ₂ O ₃ , V ₂ O ₅ , SeO ₂ And water is maintained at a temperature of 200 to 240 ° C for 3 to 5 days to effect hydrothermal reaction. The reaction product is cooled to room temperature at a rate of 0.05 to 5 ° C / minute to obtain crystals to obtain green crystals.

YVTe ₂ O ₈ of the second embodiment is obtained by heating a mixture of Y ₂ O ₃ , V ₂ O ₅ and TeO ₂ under vacuum at a temperature of 600 to 700 ° C. for 24 to 72 hours to carry out a solid phase synthesis reaction, And cooling to room temperature at a rate of 0.01 to 5 캜 / min to obtain bright yellow crystals, respectively.

Fig. 1 shows a powder X-ray diffraction pattern for a single crystal of a mixed metal oxide according to the present invention. The calculated values for the YVSe ₂ O ₈ and YVTe ₂ O ₈ single crystals of the first embodiment and the second embodiment, As shown in the IR spectrum of FIG. 4, the YO frequencies are observed in the 406-487 cm ^-1 region, and the bands appearing around 507-555 and 821-862 cm ^-1 are in the OVO and VO frequencies, respectively And the peaks appearing at about 663-779 and 603-759 cm ^-1 , respectively, are due to the Se-O and Te-O frequencies, and thus the mixed metal oxide synthesis of the present invention can be confirmed.

In addition, a definite crystal structure can be presented from the single crystal for the mixed metal oxide of the present invention.

Figures 2 and 3 show a ball-and-stick model of a skeleton in a single crystal of a mixed metal oxide of the present invention,

YVSe ₂ O ₈ of the first embodiment is a quadrature component Y ^{3 +} -V ^{5 which} is crystallized in the orthotropic polar non-center symmetric space group A bm2 (No. 39) and contains YO ₈ , VO ₆ and SeO ₃ polyhedra -Se ^{+ + 4} - oxide, the original V ^{5 +} cations is at the very distorted octahedral coordination environment and six oxygen atoms, due to SOJT variation, two independent Se ^{4 +} cations are present in the asymmetric unit, two Se ^{4 +} cations exhibit an asymmetric coordination environment including stereoselectively active lone pairs. The twisted VO ₆ octahedrons share their corners through O (2) and O (3) along the [001] and [010] directions, respectively, so that layers of corner-shared VO ₆ octahedrons are obtained in the bc-plane . In this layer, a 4-membered ring (4MRs) is observed. The twisted YO ₈ rectangular half-prisms share their edges through O (4) and O (5) along the [010] direction through O (6) along the [001] direction so that edges on the bc- YO ₈ polyhedra and other layers of their 4 MRs. Finally, the SeO ₃ group and the Se (2) O ₃ group act as connectors in the interlayer and in the layer, respectively, of these VO ₆ and YO ₈ polyhedrons. This completes the YVSe ₂ O ₈ of the three-dimensional framework structure. Thus, the structure of YVSe ₂ O ₈ is a neutral framework _{structure, {[YO 8/3]} -2.333 [VO 6/2] -1.000 [Se (1) O 2/2 O 1/3] +1.333 [Se (2 ) O _3/3 ] ^+2.000 } ⁰ .

The YVTe ₂ O ₈ of the second embodiment crystallizes in the monoclinic central symmetric space group C 2 / m (No. 12), and has a three-dimensional structure including twisted YO ₈ polyhedron, VO ₆ octahedron and asymmetric TeO ₃ group component ^{Y 3 + -V 5 + -Te 4} + - of an oxide, within the asymmetric unit unique V ^{5 +} cations are present in the distorted octahedral coordination environment, with six oxygen atoms, the four original Te ⁴⁺ cations 1.846 (5) in the asymmetric triangular pyramid configuration environment with three oxygen atoms originating from the Te-O bond and the lone electron pair in the range exceeding -1.912 (4) Å. There are two proprietary Y ^{3 +} cations surrounded by eight oxygen atoms in a twisted, quasi-prismatic environment. The twisted VO ₆ octahedrons share their vertices through O (10) along the [100] direction and through O (9) and O (11) along the [010] direction, To form the layers of the VO ₆ octahedron. In YVTe ₂ O ₈ , short and long VO bonds along the [100] direction alternate between layers. However, in the NCS polarity YVSe ₂ O ₈ , both short VO bonds are collected toward the [001] direction, but both long VO bonds are directed toward the [00-1] direction. O (2) and O (3) [or O (5)] along the [010] direction through the O (1) through and O (8)] it is obtained by sharing the edges of the twisted YO ₈ group. TeO ₃ groups act as an interlayer and interlaminar linker to complete the three-dimensional framework structure of YVTe ₂ O ₈ . The isolated electron pair on Te ^{4 +} indicates approximately one of the four directions [001], [00-1], [-100], and [100]. Thus, the structure of YVTe ₂ O ₈ is a neutral framework structure, {[Y (1) O 8/3] -2.333 [Y (2) O 8/3] -2.333 2 [VO 6/2] -1.000 [Te ( ^{_{1) O 3/3] +2.000 [Te}} (2) O 2/2 O 1/3] +1.333 [Te (3) O 2/2 O 1/3] +1.333 [Te (4) O 3/3 ] ^+2.000 } ⁰ .

Hereinafter, physical properties and characteristics of the mixed metal oxide of the present invention will be described with reference to the drawings.

6 and 7 show the result of thermogravimetric analysis of the mixed metal oxide of the present invention. From the results of the TGA diagram, YVSe ₂ O ₈ shows a change in weight at 500 to 550 ° C. and SeO ₂ finally decomposes into YVO ₄ . YVTe ₂ O ₈ showed a weight change at 700 to 750 ° C and finally decomposed into YVO ₄ and Y ₂ Te ₆ O ₁₅ .

Table 3 shows the results of measuring the local dipole moments of the mixed metal oxides of the present invention. By measuring the local dipole moments, it is possible to quantify the direction and size of twist in the SeO ₃ and TeO ₄ polyhedrons, in the oxide, VO _6, SeO _3, and if the polyhedron TeO _{3 2} O of from about YVSe each dipole moment _8, 8.70D, 7.83D, 9.42D and, YVTe in _{2 O 8, 10.42D, 10.61D,} 9.69D (D = Debyes).

Mixed metal oxide, YVSe ₂ O ₈ and YVTe ₂ O ₈ of the present invention because it contains the VO ₆ octahedron with a deformation out of the C ₄ center centrality is both different in variant off-center for the VO ₆ octahedral (D _d) As a result, the D _d values of VO ₆ octahedra in YVSe ₂ O ₈ and YVTe ₂ O ₈ were 0.69 and 0.72, respectively. The value is less than the average degree of octahedral body variations of the V ^{5 +} (1.10). Although stoichiometrically similar, YVSe ₂ O ₈ crystallizes in the NCS space group and YVTe ₂ O ₈ crystallizes in CS. YVTe ₂ O ₈ requires more space around the YO ₈ polyhedron, because the average radius for Te ^{4 +} and the cation-isolated electron pair distance are much larger than for Se ^{4 +} . That is, if larger TeO ₃ polyhedra are arranged in the same direction in a confined space, unfavorable lone pair-lone pair interaction may be expected. Thus, the TeO ₃ linker is arranged in the opposite direction to become the CS space group. However, smaller and more robust SeO ₃ groups can remain in a limited space without any repulsion, stabilizing the NCS structure.

As described above, the mixed metal oxide of the present invention exhibits a non-center-symmetric structure having a polarity in a specific direction when viewed from a structural point of view. Due to such a structural feature, the mixed metal oxide emits light with a frequency corresponding to twice the irradiated light, Can be amplified. The following characteristics are called nonlinear optical properties and can be used in wireless communication, various laser devices, nonlinear optical devices, piezoelectric sensors, computer devices, quantum interference devices, etc., and various organic substances such as acetalization reaction of aldehyde A heterogeneous acid catalyst which can be converted, and the like.

Therefore, the present invention is useful for the development of a product using the mixed metal oxide of the present invention, such as a laser device, a nonlinear optical device, a piezoelectric sensor, a wireless communication, a catalyst, a power storage transportation device, a computer device or a quantum interference device.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

≪ Example 1 > Synthesis of mixed metal oxide

Purchase of Y ₂ O ₃ (Alfa Aesar, 99.9%), V ₂ O ₅ (Junsei, 99%), SeO ₂ (Aldrich, 99.8%) and TeO ₂ (Alfa Aesar, 98% As shown in Fig.

The single crystals of YVSe ₂ O ₈ were grown by hydrothermal synthesis. , Y ₂ O ₃ of 0.113 g (5.00 × 10 ^-4 mol), V ₂ O ₅ of 0.091 g (5.00 × 10 ^-4 mol), 0.222 g (2.00 × 10 ^-3 mol) of SeO ₂ , The ionized water was placed in a 23 mL-Teflon cup and placed in a stainless steel autoclave. The reactor was tightly sealed, heated to 230 占 폚 for 4 days, and cooled to room temperature at a rate of 6 占 폚 / h. After cooling, the autoclave was opened and the product was collected by filtration and washed with distilled water. Y (SeO ₃₎ of light green crystals of YVSe ₂ O ₈ and the colorless crystals (HSeO ₃₎ · a single product containing the 2H ₂ O - determination was confirmed by X- ray diffraction.

YVTe ₂ O ₈ crystals were obtained by standard solid phase reaction. 0.113 g (5.0 x 10 ^-4 mol) of Y ₂ O ₃ , 0.091 g (5.0 x 10 ^-4 mol) of V ₂ O ₅ And ^{0.638 g (4.0 × 10 -3 mol} ) of the fully after grinding using an agate pestle and causing the TeO _2, was compressed into pellets. The pellet was transferred to a fused silica tube. The tube was vacuum treated for 20 minutes and sealed with a flame. The sealed silica tube was heated to 650 占 폚 for 48 hours, cooled to 500 占 폚 at a rate of 3 占 폚 / h, and cooled again to room temperature. Yellow crystals of YVTe ₂ O ₈ were grown from the reaction to have an amorphous phase.

Pure polycrystalline samples of YVSe ₂ O ₈ and YVTe ₂ O ₈ were synthesized through a similar solid phase reaction. The stoichiometric amounts of Y ₂ O ₃ , V ₂ O ₅ and SeO ₂ (or TeO ₂ ) were mixed thoroughly and compressed into pellets. The pellets were placed in a quartz tube, vacuum treated and sealed. For a while performing the intermediate tube 3 times replay dry for YVSe ₂ O ₈ to 450 ℃, YVTe ₂ O ₈ was heated for 48 h to 550 ℃.

Experimental Example 1 Powder X-ray diffraction pattern analysis

Powder X-ray diffraction was used to determine the phase purity for the synthesized compound. Powder XRD data were collected on a Bruker D8-Advance diffractometer using Cu Kα radiation at 40 kV and 40 mA at 2-70 at room temperature, 5-70 °.

FIG. 1 compares the calculated XRD patterns of the polycrystalline synthesized in Example 1 with the calculated values, and the experimental powder XRD pattern for the synthesized material is in agreement with the data calculated in the single-crystal model. Powder X-ray diffraction data for the bulk sample obtained above show that each synthesized material is pure and substantially matches the pattern calculated in the single-crystal data.

<Experimental Example 2> Structural analysis

The structures of the compounds synthesized in Example 1 were analyzed and purified according to standard crystallographic methods. For single crystal data were analyzed using the green block YVTe ₂ O ₈ in YVSe- ₂ O _8, and a bright yellow block ^{(0.021 × 0.025 × 0.041 mm 3} ) of ^{(0.017 × 0.020 × 0.032 mm 3} ).

All data were collected on a Bruker SMART BREEZE diffractometer equipped with a 1K CCD area detector using graphite monochromated Mo Kα radiation at room temperature. Data were collected using a narrow-frame method with a scan width of 0.30 ° in Omega and an exposure time of 10 s / frame. The first 50 frames were measured again at the end of data collection to monitor equipment and crystal stability. The maximum correction applied to the strength was <1%. The SAINT program was used to integrate data with corrected intensities for Lorentz factor, polarization, air absorption and adsorption due to variables in the path length through the detector faceplate. Semi-empirical absorption correction was performed using the SADABS program. The structure was solved using SHELXS-97 and the data were refined using SHELXL-97. The orthorhombic matrix observed in YVTe ₂ O ₈ is Laue class 2 / m suggesting a pseudo-merohedral twinning of the crystal to mmm . In fact, when we refined the structure in the orthotropic space group, Cmca , all constituent atoms were disordered and unreasonable coordination environments occurred. However, the structure of YVTe ₂ O ₈ was successfully purified in monoclinic space group, C 2 / m . All calculations were performed using the WinGX-98 crystallographic software package. Crystal data and selected binding distances of the synthesized compounds are shown in Tables 1 and 2, respectively.

Crystallographic data of YVSe ₂ O ₈ and YVTe ₂ O ₈ expression YVSe ₂ O ₈ YVTe ₂ O ₈ fw 425.77 523.05 Space group A bm2 (No. 39) C 2 / m (No. 12) a (A) 10.4036 (4) 7.9396 (10) b (A) 7.5904 (3) 7.5625 (10) c (A) 7.8341 (3) 21.282 (2) β (°) 90 90.010 (10) V (Å ³ ) 618.64 (4) 1277.85 (3) Z 4 8 T (K) 298.0 (2) 298.0 (2) l (A) 0.71073 0.71073 r _calcd (g cm ^-3 ) 4.571 5.438 m (mm ^-1 ) 22.617 19.458 Flack parameter -0.06 (3) N / A R ( F ) ^a 0.0463 0.0288 R _w ( F _o ² ) ^b 0.1126 0.0682 ^a R (F) = S || F _o | - | F _c || / S | F _o |. ^b R _w ( F _o ² ) = [S w ( F _o ² - F _c ² ) ² / S w ( F _o ² ) ² ] ^1/2

YVSe ₂ O ₈ and YVTe ₂ O ₈ Selected bond distance (A) YVSe ₂ O ₈ YVTe ₂ O ₈ V (1) -O (1) x 2 1.923 (9) V (1) -O (4) 1.911 (4) V (1) -O (2) 1.616 (4) V (1) -O (6) 1.909 (4) V (1) -O (2) 2.301 (14) V (1) -O (9) 1.950 (2) V (1) -O (3) x 2 1.972 (4) V (1) -O (10) 1.628 (4) Se (1) -O (1) x 2 1.722 (8) V (1) -O (10) 2.342 (4) Se (1) -O (4) 1.690 (12) V (1) -O (11) 1.953 (2) Se (2) -O (5) 1.724 (12) Te (1) -O (1) x 2 1.879 (4) Se (2) -O (6) x 2 1.703 (8) Te (1) -O (2) 1.893 (5) Y (1) -O (4) x 2 2.360 (7) Te (2) -O (3) 1.858 (5) Y (1) -O (5) x 2 2.365 (7) Te (2) -O (4) x 2 1.906 (4) Y (1) -O (6) x 2 2.326 (9) Te (3) -O (5) 1.846 (5) Y (1) -O (6) x 2 2.369 (9) Te (3) -O (6) x 2 1.912 (4) Te (4) -O (7) x 2 1.878 (4) Te (4) -O (8) 1.891 (5) Y (1) -O (1) x 2 2.331 (4) Y (1) -O (1) x 2 2.439 (4) Y (1) -O (2) x 2 2.393 (3) Y (1) -O (3) x 2 2.304 (3) Y (2) -O (5) x 2 2.312 (3) Y (2) -O (7) x 2 2.336 (4) Y (2) -O (7) x 2 2.436 (4) Y (2) -O (8) x 2 2.391 (3)

2 and 3 show a ball-and-stick model diagram of the crystal structure of YVSe ₂ O ₈ and YVTe ₂ O ₈ of the present invention,

YVSe ₂ O ₈ crystallized in Abm 2 (No. 39), an orthotropic polar noncentral symmetric space group. The structural backbone of YVSe ₂ O ₈ consists of YO ₈ , VO ₆ and SeO ₃ polyhedra. The unique V ^{5 +} cations are in a highly twisted octahedral coordination environment with six oxygen atoms due to SOJT deformation: V ^{5 +} cations are distorted towards the corners of the octahedral (local C ₄ [001] orientation) 1.616 (14) Å], four intermediate lengths [1.923 (9) to 1.972 (4) Å], and one long-length [2.301 (14) Å] VO coupling distance. Two unique Se ^{4 +} cations are present in the asymmetric unit, and two Se ^{4 +} cations contain the stereospecific lone pair of electrons to represent the asymmetric coordination environment. The Se-O bonding distance is 1.690 (12) to 1.724 (12) A. The Y ^{3 +} cations are connected by eight oxygen atoms in a twisted rectangular antiprismatic coordination environment with a YO bond length of 2.326 (9) to 2.369 (9) Å. As shown in FIG. 2, the warped VO ₆ octahedrons share their corners through O (2) and O (3) along the [001] and [010] directions, respectively. Thus, layers of VO ₆ octahedra sharing corners are obtained at bc - plane. In this layer, a 4-membered ring (4MRs) is observed. The twisted YO ₈ rectangular half-prisms share their edges through O (4) and O (5) along the [010] direction through O (6) along the [001] direction so that edges on the bc- YO ₈ polyhedra and other layers of their 4 MRs (see Figure 2b). Finally, the SeO ₃ group connects these VO ₆ and YO ₈ polyhedra. The Se (1) O ₃ group serves as an interlayer linker, while the Se (2) O ₃ group serves as an in-layer connector (FIG. This completes the YVSe ₂ O ₈ of the three-dimensional framework structure. Thus, the structure of YVSe ₂ O ₈ is a neutral framework _{structure, {[YO 8/3]} -2.333 [VO 6/2] -1.000 [Se (1) O 2/2 O 1/3] +1.333 [Se (2 ) O _3/3 ] ^+2.000 } ⁰ . ^{3 +} Y, ^{+ 5} V, and the total valence calculation results for Se ^{4 +,} showed a value of each of 3.18, 4.62, and 3.89 to 3.91.

Another new quaternary component YVTe ₂ O ₈ crystallized in monoclinic center symmetric space group C 2 / m (No. 12). YVTe ₂ O ₈ is a three-dimensional four-component Y ^{3 +} -V ^{5 +} -Te ^{4 +} -oxide containing twisted YO ₈ polyhedra, VO ₆ octahedral, and asymmetric TeO ₃ groups. Within the asymmetric unit, the unique V ^{5 +} cations are present in a twisted octahedral coordination environment with six oxygen atoms. Similar to YVSe ₂ O ₈ , proprietary V ^{5 +} cations are distorted along the local C ₄ direction, one with shorter length [1.628 (4) Å] and four with intermediate length [1.909 (4) -1.953 (2) Å], and one has a VO junction length of long length [2.342 (4) Å]. In addition, the four proprietary Te ^{4 +} cations are in an asymmetric triangular pyramid coordination environment with three oxygen atoms originating from Te-O bonds and isolated electron pairs ranging from 1.846 (5) -1.912 (4) Å. There are two unique Y ^{3 +} cations surrounded by eight oxygen atoms in a twisted rectangular half-prismatic environment with an YO bond length in the range of 2.304 (3) to 2.439 (4) Å. The twisted VO ₆ octahedrons share their vertices through O (10) along the [100] direction and through O (9) and O (11) along the [010] direction, To form layers of the VO ₆ octahedron (see FIG. 3A). Note that short and long VO bonds along the [100] direction in YVTe ₂ O ₈ alternate between layers (FIG. 3A). However, in the NCS polarity YVSe ₂ O ₈ , both short VO bonds are collected toward the [001] direction, but both long VO bonds are directed toward the [00-1] direction (FIG. 2). Also, similar to that of YVSe ₂ O ₈ , different kinds of layers are formed along O (1) [or O (7)] along the [100] (Fig. 3B) by sharing the edges of the YO ₈ group twisted via the O (3) [or O (5) and O (8)]. The TeO ₃ groups act as intra- and interlayer linkers to complete the three-dimensional framework structure of YVTe ₂ O ₈ (Figure 3c). It can be easily noticed that the isolated electron pair on Te ^{4 + indicates} approximately one of the four directions [001], [00-1], [-100], and [100] (FIG. Overall, disappears along with the lone pair of electrons polarized incidental Te ^{4 +.} Thus, the structure of YVTe ₂ O ₈ is a neutral framework structure, {[Y (1) O 8/3] -2.333 [Y (2) O 8/3] -2.333 2 [VO 6/2] -1.000 [Te ( ^{_{1) O 3/3] +2.000 [Te}} (2) O 2/2 O 1/3] +1.333 [Te (3) O 2/2 O 1/3] +1.333 [Te (4) O 3/3 ] it can be described as ^{+2.000 0}.} Y ^{3 +} , V ^{5 +} , and Te ^{4 +} , respectively, the values of the values were in the range of 3.09-3.12, 4.68, and 3.80-3.88, respectively.

<Experimental Example 3> Infrared spectrum analysis

Infrared spectra were recorded on a Varian 1000 FT-IR spectrometer with samples embedded in KBr matrix at 400-4000 cm ^-1 range.

As shown in FIG. 4, YO, VO, Se-O, and Te-O frequencies were observed in the infrared spectra of YVSe ₂ O ₈ and YVTe ₂ O ₈ . The YO frequency is ca. Was observed at 406-487 cm ^-1 . The bands observed around 507-555 and 821-862 cm ^-1 correspond to the OVO and VO frequencies, respectively. Peaks appearing at about 663-779 and 603-759 cm ^-1 appear to be due to Se-O and Te-O frequencies, respectively.

EXPERIMENTAL EXAMPLE 4 UV-Vis Diffuse Reflectance Spectroscopy (Diffuse Reflectance Spectroscopy)

The UV-visible diffuse reflectance data were collected on a Varian Cary 500 scan UV-vis-NIR spectrophotometer at a room temperature in the Korean photovoltaic source in excess of the 200-2500 nm spectral range. The reflectance spectra were converted to absorbance using the Kubelka-Munk function:

[Equation 1]

Here, K represents absorption, S represents scattering, and R represents reflection.

On a (K / S) -to- E plot, extrapolating the straight line portion of the rising curve to zero yields an absorption start at 2.7 and 2.2 eV for YVSe ₂ O ₈ and YVTe ₂ O ₈ , respectively. The bandgap for the compound synthesized in Example 1 will be due to the degree of V (3d) orbital associated with the conduction band as well as the twist from the SeO ₃ or TeO ₃ polyhedron. The onset of absorption values for the synthesized compounds is consistent with previous studies of vanadium selenite and tellurite. The ( K / S ) -to- E plot for YVSe ₂ O ₈ and YVTe ₂ O ₈ is shown in FIG.

&Lt; Experimental Example 5 >

A thermogravimetric (TGA) analysis was used to investigate the thermal behavior of the compounds of Example 1 above. Thermogravimetric analysis was performed on a Setaram LABSYS TG-DTA / DSC thermogravimetric analyzer. The polycrystalline sample was placed in an aluminum crucible and heated from room temperature to 1000 캜 at a rate of 10 캜 / min under argon.

As shown in FIGS. 6 and 7, YVSe ₂ O ₈ was thermally stable up to 500 ° C. Above this temperature, this material decomposes to YVO ₄ due to the sublimation of SeO ₂ , as confirmed by powder XRD. In the case of YVTe ₂ O ₈ , TGA analysis showed no weight loss up to 1000 ° C. However, as a result of powder XRD measurement for YVTe ₂ O ₈ at different temperatures, it was decomposed to YVO ₄ and Y ₂ Te ₆ O ₁₅ at 750 ° C. The endothermic peak at the same temperature in the heat curve of differential thermal analysis (DTA) for YVTe ₂ O ₈ was consistent with the XRD data by temperature. The TG-DTA plot and XRD pattern for the calcined product are shown in Figures 6B and 7B.

Experimental Example 6 SEM / EDAX analysis

SEM / EDAX (Scanning Electron Microscope / Energy-Dispersive Analysis by X-ray (SEM / EDAX)) analysis was performed using Hitachi S-3400N / Horiba Energy EX-250 instruments.

EDAX results for YVSe ₂ O ₈ and _{YVTe 2 O 8, Y: V} : Se ratio of (or Te) are respectively 1.1: 1.0: 2.1 and 0.8: 1.0: 2.0 as shown.

<Experimental Example 7> Measurement of powder second-harmonic generation (SHG) characteristics

Since YVSe ₂ O ₈ crystallizes in the non-center-symmetric space group, Abm 2, SHG measurements on polycrystalline samples are performed with a Q-switched Nd: YAG laser (DAWA).

Powder SHG measurements using 1064 nm radiation showed that YVSe ₂ O ₈ possesses an SHG efficiency similar to that of NH ₄ H ₂ PO ₄ (ADP). Since the powder SHG efficiency is strongly dependent on the particle size, polycrystalline samples were further ground and sieved with a sieve (Newark Wire Cloth Co.) to obtain a range of particle sizes (20-45, 45-63, 63-75, 75- 90, 90-125, 125-150, 150-200, 200-250, > 250 [mu] m). Powder samples ranging in particle size ranging from 45 to 63 mu m were used to compare SHG strength. All samples with different particle sizes were placed in separate capillary tubes. No experiment used an index matching fluid. The SHG beam, ie the 532 nm line, was obtained from reflection and detected by a Hamamatsu photomultiplier tube. A 532 nm narrow-pass interference filter was attached to the tube to detect only the SHG line. To monitor the SHG signal, a digital oscilloscope (Tektronix TDS1032) was used. A detailed description of the method and equipment is given in Og Kangmin et al . ( Chem . Soc . Rev. 2006, 35, pp . 710).

As shown in FIG. 8, YVSe ₂ O ₈ appears to be nonphase-matchable and can be classified as a class C SHG material according to the definition of Kurtz and Perry. If compounds of the SHG efficiency and type of phase I - if it is more than the ability to match the substrate, can be evaluated in a bulk SHG efficiency, <d _{eff> exp.} Thus, <d _eff> of _exp YVSe ₂ O ₈ was calculated to be approximately 1.7 pm V ^-1.

&Lt; Experimental Example 8 >

The macroscopic NCS of YVSe ₂ O ₈ can be analyzed according to the arrangement of local asymmetric polyhedra. Moreover, the observed SHG response and its origin can be explained by measuring the net direction of polarity. Since Y ^{3 +} is not a secondary yarn-Teller modified cation, the effect on the SHG efficiency resulting from the deformation of YO ₈ polyhedra may be negligible. The dorsal VO ₆ octahedron consisting of d ⁰ cations, V ^{5 +} , is arranged in one direction: the long and short VO bonds are alternating along the shared chain, and the net moment is observed towards the [00-1] direction 9). Finally, net dipole moments can be expected in an array of asymmetric SeO ₃ polyhedra containing lone electron pairs. As mentioned above, there are two unique Se ^{4 +} cations in the asymmetric unit. In the case of Se (1) ⁴⁺ , the isolated electron pair is oriented substantially parallel to the [00-1] direction and the moment occurs in the [001] direction (FIG. However, the isolated electron pair on the Se (2) O ₃ ⁴⁺ is oriented in the [100] and [-100] directions so that the polarity almost disappears. Thus, the net moment generated in the SeO ₃ ^{4 +} polyhedron is expected in the [001] direction (FIG. 9). The present inventors have found that the moments generated in the VO ₆ octahedron and the SeO ₃ polyhedron exist in opposite directions. Local dipole moments for V ^{5 +} and Se ^{4 +} were calculated using the method described previously to determine the net direction as well as the net moment observed in YVSe ₂ O ₈ (Galy, J. et al . J. Solid State Chem . 1975, 13, pp. 142; Maggard, PA et al . J. Solid State Chem . 2003, 175, pp. 25; Izumi, HK et al . Inorg . Chem . 2005, 44, pp. 884).

As a result, the local dipole moments for VO ₆ , Se (1) O ₃ , and Se (2) O ₃ polyhedra in YVSe ₂ O ₈ were about 8.70, 7.83, and 9.42 D (Debyes), respectively. Taking the overall moment results in a small net moment along the [00-1] direction, which is consistent with the SHG measurement described above (similar to that of ADP). Also, SHG light (532 nm) may be neglected due to the color of YVSe ₂ O ₈ . For comparison, the local dipole moments for the central symmetric YVTe ₂ O ₈ to VO ₆ octahedra and the two proprietary TeO ₃ octahedra, Te (1) O ₃ and Te (2) O ₃ , were calculated and found to be YVSe ₂ O ₈ And those of recently reported mixed metal oxides. The calculated local dipole moments for the VO ₆ , SeO ₃ and TeO ₃ groups are shown in Table 3.

Calculating the dipole moments of VO ₆ , SeO ₃ , and TeO ₃ polyhedra (D = Debyes) compound Bell Dipole moment (D) YVSe ₂ O ₈ V (1) O ₆ 8.70 Se (1) O ₃ 7.83 Se (2) O ₃ 9.42 YVTe ₂ O ₈ V (1) O ₆ 10.42 Te (1) O ₃ 10.61 Te (2) O ₃ 9.69

Although it is different, even if the central include VO ₆ octahedron with YVSe ₂ O ₈ and YVTe ₂ O _8, both (out-of-center) deformation out of the C ₄ center. Thus, it is necessary to quantify the off-center strain (D _d ) with respect to the VO ₆ octahedron. The D _d values for VO ₆ octahedra in YVSe ₂ O ₈ and YVTe ₂ O ₈ were calculated according to the method described in the literature (Halasyamani, PS, Chem . Mater . 2004, 16, pp. 3586) . The value is less than the average degree of octahedral body variations of the V ^{5 +} (1.10). Although stoichiometrically similar, YVSe ₂ O ₈ crystallizes in the NCS space group and YVTe ₂ O ₈ crystallizes in CS. YVTe ₂ O ₈ requires more space around the YO ₈ polyhedron, because the average radius for Te ^{4 +} and the cation-isolated electron pair distance are much larger than for Se ^{4 +} . That is, if larger TeO ₃ polyhedra are arranged in the same direction in a confined space, unfavorable lone pair-lone pair interaction may be expected. Thus, the TeO ₃ linker is arranged in the opposite direction to become the CS space group (FIG. 3C). However, smaller and more robust SeO ₃ groups can remain in a limited space without any repulsion, stabilizing the NCS structure.

Claims (6)

Y ^{3 +} -V ^{5 +} -Q ^{4 +} (Q = Se or Te) - mixed metal oxide represented by the following chemical formula 1 or 2:
[Chemical Formula 1]
YVSe ₂ O ₈
(2)
YVTe ₂ O ₈
The method according to claim 1,
The mixed metal oxides include Y ₂ O ₃ , V ₂ O _5, and SeO ₂ , Or obtained by a solid phase synthesis reaction between Y ₂ O ₃ , V ₂ O ₅ and TeO ₂ .
The method according to claim 1,
The compounds of formulas 1 or 2 has a corner shared VO ₆ The octahedral body and the edge shared by YO ₈ The polyhedral layer is an interlayer linker SeO ₃ Or TeO ₃ A mixed metal oxide showing a three-dimensional framework structure connected by groups.
The method according to claim 1,
The compound of formula (1) exhibits a weight change at 500-550 占 폚.
The method according to claim 1,
The compound of formula (2) exhibits a weight change at 700 to 750 占 폚.
A product in which the mixed metal oxide according to claim 1 is applied to any one of a laser device, a nonlinear optical device, a piezoelectric sensor, a wireless communication, a catalyst, a power storage transportation device, a computer device or a quantum interference device.

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