CN109721624B - Titanium-oxygen cluster compound and synthesis method and application thereof - Google Patents

Abstract

The invention provides a titanium oxide cluster compound, a synthesis method and application thereof, and the molecular formula of the titanium oxide cluster compound is H ₈ {Ti ₄₄ (μ ₂ -O) ₃₆ (μ ₃ -O) ₃₀ (B) _n (A) ₂ (H ₂ O) ₂ } xB'; it utilizes a solvothermal synthesis method, that is, a heating reaction is performed in a solvent, the reaction raw materials are simply mixed, and the titanium oxide can be obtained through a one-step self-assembly reaction Clusters. The method has simple synthesis requirements, low requirements for the purity of the raw materials, easy and low-cost raw materials to obtain, all the raw materials used can be purchased through chemically pure reagents, no further purification is required, and the yield is as high as 90% or more, which is beneficial to large-scale production. The titanium-oxygen cluster compound has efficient and stable photo-splitting water hydrogen production activity, and can be used in water splitting, pollutant degradation, and electronic devices such as solar cells. The method is simple, efficient, and has less pollution in the synthesis process, and meets the requirements of green environmental protection.

Description

Titanium oxide cluster compound and its synthesis method and use

technical field

The invention belongs to the technical field of crystal material preparation, and in particular relates to a titanium oxide cluster compound and a synthesis method and application thereof.

Background technique

Nano-titanium dioxide TiO ₂ is widely used in gas sensing, charge transport, decomposition of toxic organic pollutants, and photocatalysis due to its non-toxic and harmless properties, abundant reserves and excellent physical and chemical properties. As the structure and performance simulating molecules of _TiO2 materials, titanium oxide clusters (also known as _Ti44 clusters, titanium oxide clusters, titanium oxide clusters or titanium oxide fullerenes, etc.) due to their diverse geometric sizes , the atomic structure is clear, the size of the cluster nucleus can be adjusted, the precise modification, and the solubility and reactivity in organic solvents to different degrees have attracted in-depth research by many scientists, and have been applied to physical chemistry, organic-inorganic chemistry, analytical chemistry, biology It is widely used in many interdisciplinary fields such as science, polymer chemistry, medicine, materials science and physics. The reported titanium oxyclusters have poor stability, low cluster nuclei, and poor reproducibility.

To this end, it is necessary to develop high-cluster-nucleated titanium-oxygen clusters that can be comparable to the size of _TiO2 nanoparticles and have high-efficiency and stable photohydrogen production activity from water splitting, especially for electronic devices such as water splitting, pollutant degradation, and solar cells. A new type of titanium oxide cluster material.

SUMMARY OF THE INVENTION

In order to achieve the above purpose, the present invention provides a titanium oxide cluster compound, a synthesis method and application thereof, the titanium oxide cluster compound has efficient and stable photo-splitting water hydrogen production activity, and can be used for splitting water, degrading pollutants and using in electronic devices such as solar cells. The method is simple, efficient, and has less pollution in the synthesis process, and meets the requirements of green environmental protection.

A first aspect of the present invention is to provide a titanium oxide cluster compound, and the molecular formula of the titanium oxide cluster compound is:

H ₈ {Ti ₄₄ (μ ₂ -O) ₃₆ (μ ₃ -O) ₃₀ (B) _n (A) ₂ (H ₂ O) ₂ } xB'

Among them, μ ₂ -O represents a two-connected O atom, and μ ₃ -O represents a three-connected O atom;

A is the same or different and is independently selected from the residues of organic acids of C1-C40;

B is the same or different and independently selected from the residues of organic acids of C1-C30;

B' is the same or different and independently selected from C1-C30 organic acids;

x is the number of B' molecules in the free state, which is an integer between 0 and 10;

When both A's are selected from monoacids, n is 50;

When one A is selected from monobasic acid and one A is selected from polybasic acid, n is 49;

When both A's are selected from polyacids, n is 48.

According to the present invention, the A is the same or different, and is independently selected from the residues of organic acids of C1-C30; for example, the residues of organic acids selected from C1-C20; residues; also for example, residues of organic acids selected from C1-C6;

According to the present invention, said A is the same or different and independently selected from HOC(=O)-, _CH3C (=O)O-, _CH3CH2C ( ₌ O) _O- , _{CH3CH2CH 2} C(=O)O-, -O(O=)CCH ₂ C(=O)O-, -O(O=C)CH ₂ CH ₂ C(=O)O- or -O(O=) CCH2CH2CH2C(=O) _O- ; preferably HOC(=O)- or _-O (O=C _{) CH2CH2CH2C (} =O) _O- .

According to the present invention, said B is the same or different and independently selected from the residues of organic acids of C1-C20; for example, the residues of organic acids selected from C1-C10; the residues of organic acids selected from C1-C6 ;

According to the present invention, said B is the same or different and independently selected from HOC(=O)-, _CH3C (=O)O-, _CH3CH2C ( ₌ O) _O- , _{CH3CH2CH 2} C(=O)O-, CH ₃ CH(CH ₃ )C(=O)O-, (CH ₃ ) ₃ CC(=O)O-, CH ₃ (CH ₂ ) ₄ C(=O)O -, CH ₃ (CH ₂ ) ₆ C(=O)O-, -O(O=C)CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ C(=O)O-, -O(O=C)CH ₂ C(=O)O-, -O(O=C)CH ₂ CH ₂ C(=O)O-, -O(O=)CCH ₂ CH ₂ CH ₂ C(=O)O-; preferably _CH3C (=O)O-.

According to the present invention, the B' is the same or different, and is independently selected from C1-C20 organic acids; for example, selected from C1-C10 organic acids; selected from C1-C6 organic acids;

According to the present invention, the B' are the same or different, and are independently selected from HCOOH, CH ₃ COOH, CH ₃ CH ₂ COOH, CH ₃ CH ₂ CH ₂ COOH, CH ₃ CH(CH ₃ )COOH, (CH ₃ ) _3CCOOH , _CH3 ( _CH2 ) _4COOH , _CH3 ( _{CH2 ) 6OOH} , HO(O=C _{) CH2CH2CH2CH2CH2COOH} , HO ₍ O=C _{) CH2COOH} , HO (O=C _{) CH2CH2COOH} , HO(O=C _{) CH2CH2CH2COOH ;} preferably _CH3COOH .

According to an embodiment of the present invention, the molecular formula of the titanium oxide cluster is:

H ₈ {Ti ₄₄ (μ ₂ -O) ₃₆ (μ ₃ -O) ₃₀ (B) ₅₀ (A) ₂ (H ₂ O) ₂ }·4B';

Wherein, A is selected from HOC(=O)-; B is selected from CH ₃ CH ₂ C(=O)O-; B' is selected from CH ₃ CH ₂ C(=O)OH.

According to an embodiment of the present invention, the molecular formula of the titanium oxide cluster is:

H ₈ {Ti ₄₄ (μ ₂ -O) ₃₆ (μ ₃ -O) ₃₀ (B) ₄₈ (A) ₂ (H ₂ O) ₂ }·6B';

Wherein, A is selected from -O(O=C)CH ₂ CH ₂ CH ₂ C(=O)O-; B is selected from CH ₃ CH ₂ C(=O)O-; B' is selected from CH ₃ CH ₂ C (=O)OH.

According to the present invention, the organic acid is a monobasic acid or a polybasic acid; the polybasic acid is a dibasic acid or a tribasic acid or more.

In the present invention, the residue refers to the group remaining after the organic acid removes all the hydrogens on the carboxyl group, for example, the residue of formic acid is HOC(=O)-, and the residue of acetic acid is CH ₃ C(=O) O-, the residue of propionic acid is CH3CH2C(=O) _O- , and the residue of glutaric acid is -O(O=C _{) CH2CH2CH2C (} =O) _O- .

晶胞参数a为

b为

c为

α为74.63°，β为84.42°，γ为76.43°，V为

Specifically, the molecular formula of the titanium oxide cluster compound is C ₁₆₄ H ₂₈₈ O ₁₈₀ Ti ₄₄ , denoted as titanium oxide cluster compound a, and Mr is 7247.53; the crystal system of the crystalline substance of the titanium oxide cluster compound a is a triclinic crystal system, and the space group is

The unit cell parameter a is

b is

c is

α is 74.63°, β is 84.42°, γ is 76.43°, and V is

The crystalline substance of the titanium oxide cluster compound a has an X-ray powder diffraction pattern substantially as shown in FIG. 2 .

The crystal parameters of the crystalline state of the titanium oxide cluster compound a are shown in Table 1:

Table 1

晶胞参数a为

b为

c为

α为74.3°，β为81.9°，γ为75.6°，V为

Specifically, the molecular formula of the titanium oxide cluster compound is C ₁₇₂ H ₃₀₀ O ₁₈₄ Ti ₄₄ , denoted as titanium oxide cluster compound b, and Mr is 7418.26; the titanium oxide cluster compound b is a colorless strip of pure phase State crystalline substance; the crystal system of the crystalline substance of the titanium oxide cluster compound b is triclinic, and the space group is

The unit cell parameter a is

b is

c is

α is 74.3°, β is 81.9°, γ is 75.6°, and V is

The crystalline substance of the titanium oxycluster compound b has an X-ray powder diffraction pattern substantially as shown in FIG. 6 .

The crystal parameters of the crystalline state of the titanium oxide cluster compound b are shown in Table 2:

Table 2

According to the present invention, the titanium oxide cluster compound is a colorless strip-like crystal of pure phase.

According to the present invention, the titanium oxide cluster compound is an organic-inorganic hybrid compound.

According to the present invention, the size of the cluster nucleus of the crystalline substance of the titanium oxide cluster compound is 2.8±0.2 nm.

According to the present invention, the crystalline substance of the titanium oxide cluster compound has a symmetrical structure.

The second aspect of the present invention is to provide a method for preparing the above-mentioned titanium oxide cluster, the method comprising the steps of: mixing a titanium salt, an organic acid A and an organic acid B, and performing a solvothermal reaction to obtain the titanium Oxygen complex.

According to the present invention, the method specifically comprises the following steps:

1) mixing the titanium salt, organic acid A and organic acid B, and carrying out a solvothermal reaction to obtain a mixture;

2) Separating the mixture obtained after the reaction in step 1), wherein the solid phase is a titanium oxide cluster compound.

According to the present invention, the titanium salt is a compound formed by removing the hydrogen on the hydroxyl group of the alcohol from the titanium ion and the alcohol.

According to the present invention, the titanium salt is one or more combinations of titanium ethoxide, titanium tert-butoxide, titanium isobutoxide, titanium n-butoxide, titanium n-propoxide and titanium isopropoxide, preferably isopropanol titanium.

According to the present invention, the organic acid A is selected from acids containing 1-40 carbon atoms (eg 1-30 carbon atoms, 1-20 carbon atoms, 1-10 carbon atoms, 1-6 carbon atoms) or acid mixture.

Preferably, the organic acid A is selected from one or both of formic acid, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid or glutaric acid, etc.; preferably formic acid and/or glutaric acid.

According to the present invention, the organic acid B is selected from acids or mixtures of acids containing 1-30 carbon atoms (eg 1-20 carbon atoms, 1-10 carbon atoms, 1-6 carbon atoms).

Preferably, the organic acid B is selected from formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, n-hexanoic acid, caprylic acid, adipic acid, oxalic acid, malonic acid, succinic acid or wherein A mixture of any two or more.

As an example, the organic acid B may be selected from acetic acid, propionic acid, butyric acid or a mixture of two or more thereof, such as propionic acid or a mixture of propionic acid and acetic acid or propionic acid and butyric acid.

According to the present invention, the organic acid A and the organic acid B are the same or different; exemplarily, when the organic acid A is selected from formic acid, the organic acid B can be selected from formic acid alone, or can also be selected from formic acid and other organic acids The mixture of acids can also be selected from other organic acids than formic acid.

According to the present invention, the molar ratio of the titanium salt to the organic acid A is 1:(0.01-1), for example, 1:(0.1-0.8), specifically 1:(0.2-0.5).

According to the present invention, the molar ratio of the titanium salt to the organic acid B is 1:(0.01-1), for example, 1:(0.02-0.5), specifically 1:(0.03-0.3).

According to the present invention, the temperature of the solvothermal reaction is 40-160°C; preferably 60-100°C, such as 70-90°C, such as 80°C. If the reaction temperature is too low, the reaction time will be longer and the crystal size will be smaller.

According to the present invention, the time of the solvothermal reaction is 24-240 hours; preferably, it is 48-150 hours, such as 72 hours, 120 hours.

As a preferred embodiment of the present invention, the reaction can be carried out at 80°C for 72 hours or 96 hours, or at 100°C for 48 hours or 72 hours.

According to the present invention, step 1) specifically includes: after mixing the titanium salt, organic acid A and organic acid B, stirring, placing in a glass bottle or a polytetrafluoroethylene pressure vessel, reacting at a constant temperature, and then cooling to room temperature.

According to the present invention, in step 2), the solid phase obtained by separation is cleaned;

Preferably, the separated solid phase is washed with water, acid or alcohol, and dried at room temperature.

According to the present invention, the yield of the titanium-oxygen cluster compound can reach more than 90%.

According to the present invention, sodium hydroxide, potassium chloride, water or hydrogen peroxide can also be added to the mixed system of titanium salt, organic acid A and organic acid B.

The addition of the sodium hydroxide, potassium chloride, water or hydrogen peroxide as a kind of auxiliary reaction material, promotes the carrying out of the reaction, its consumption is not particularly limited, the routine selection of those skilled in the art can be, for example, the target product 0.05-5wt% can be used.

According to the present invention, the titanium oxide cluster compound of the above-mentioned first aspect is prepared by the method of the above-mentioned second aspect.

The third aspect of the present invention is to provide the use of the above-mentioned titanium-oxygen cluster compound, which can be used for splitting water, degrading pollutants or electronic devices (such as solar cells).

beneficial effect

The present invention provides a new class of materials, namely organic-inorganic hybrid titanium oxide clusters, which have a symmetrical structure and a cluster core size of about 2.8±0.2 nm. The titanium oxide clusters have efficient and stable optical properties Hydrogen production activity from water splitting can be used in the fields of splitting water, pollutant degradation or electronic devices.

The present invention also provides a brand-new method for preparing titanium oxide clusters, which utilizes a solvothermal synthesis method, that is, a heating reaction is carried out in a solvent, the reaction raw materials are simply mixed, and a single-step self-assembly reaction can be used to obtain the obtained compound. The titanium oxide cluster compound. The method has simple synthesis requirements, low requirements on the purity of raw materials, easy and low-cost raw materials to obtain, all raw materials used can be purchased by chemically pure reagents, no further purification is required, and the yield is as high as 90% or more, which is conducive to large-scale production. In addition, the post-treatment of the method is simple and feasible, and the pure-phase crystalline product can be obtained only by simple water washing, acid washing or alcohol washing separation, and drying at room temperature. Furthermore, the method has less pollution and meets the requirements of green environmental protection.

Description of drawings

1 is a schematic diagram of the crystal structure of the crystalline product prepared in Example 1;

Figure 2 is the X-ray powder diffraction pattern of the crystalline product prepared in Example 1, from bottom to top each line represents the simulated powder diffraction pattern, the crystals were placed in the air for the first day, the second day, and the third day The powder diffraction pattern of ; wherein, the theoretical value is the X-ray powder diffraction pattern obtained by simulating the crystal structure; the experimental value is the X-ray powder diffraction pattern obtained by testing on an X-ray powder diffractometer;

Fig. 3 is the infrared spectrogram of the crystalline product prepared in embodiment 1;

Figure 4 is a product photo of the crystalline product prepared in Example 1;

5 is a schematic diagram of the crystal structure of the crystalline product prepared in Example 2;

Figure 6 is the X-ray powder diffraction pattern of the crystalline product prepared in Example 2, each line from bottom to top represents the simulated powder diffraction pattern, the crystals were placed in the air for the first day, the second day, and the third day The powder diffraction pattern of ; wherein, the theoretical value is the X-ray powder diffraction pattern obtained by simulating the crystal structure; the experimental value is the X-ray powder diffraction pattern obtained by testing on an X-ray powder diffractometer;

Fig. 7 is the infrared spectrogram of the crystalline product prepared in embodiment 2;

FIG. 8 is a product photograph of the crystalline product prepared in Example 2. FIG.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the protection scope of the present invention. In addition, it should be understood that after reading the content disclosed in the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the protection scope defined by the present invention.

Unless otherwise stated, the reagents used in the present invention are all commercially available.

The single crystal structure analysis of the present invention uses a supernova single crystal diffractometer from Rigaku Japan.

The radiation source used in the X-ray powder diffraction pattern was Cu-Kα radiation.

Example 1

Titanium isopropoxide (3.3mmol), formic acid (26.5mmol), and propionic acid (73.6mmol) were placed in a 20ml glass bottle, mixed well at room temperature, kept in an oven at 80°C for 3 days, taken out, cooled to room temperature naturally, and separated The solid phase was removed and rinsed with propionic acid to obtain the target product in the form of colorless strips. This crystal product can be obtained by adding a small amount of sodium hydroxide, potassium chloride, etc., or adding a small amount of water and hydrogen peroxide to the reaction system.

It can be seen from Figure 1 that this compound has 44 titanium atoms. Except for two formic acid and two water-based ligands, the rest of the ligands are all propionic acid ligands;

It can be seen from Figure 2 that this compound is stable in air for at least three days;

It can be seen from Fig. 3 that the vibration characteristic peak of the Ti-O cluster core of this compound is 1000-500cm ^-1 , and the vibration characteristic peak of the organic ligand is 3500-1000cm ^-1 ;

It can be seen from Figure 4 that this compound is in the form of a colorless bar.

Example 2

Titanium isopropoxide (3.3mmol), glutaric acid (1.5mmol), and propionic acid (73.6mmol) were placed in a 20ml glass bottle, mixed evenly at room temperature, kept at 80°C oven for 3 days, taken out, and cooled to room temperature naturally , separate the solid phase and rinse with propionic acid to obtain the target product in colorless strip state. This crystal product can be obtained by adding a small amount of sodium hydroxide, potassium chloride, etc., or adding a small amount of water and hydrogen peroxide to the reaction system.

It can be seen from Figure 5 that this compound has 44 titanium atoms. Except for two glutaric acid and two water-based ligands, the rest of the ligands are all propionic acid ligands;

It can be seen from Figure 6 that this compound is stable in air for at least three days;

It can be seen from Fig. 7 that the vibration characteristic peak of the Ti-O cluster core of this compound is 1000-500 cm ^-1 , and the vibration characteristic peak of the organic ligand is 3500-1000 cm ^-1 ;

It can be seen from Figure 8 that this compound is in the form of a colorless bar.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (38)

1. a titanium oxide cluster compound, is characterized in that, the molecular formula of described titanium oxide cluster compound is: H ₈ {Ti ₄₄ (μ ₂ -O) ₃₆ (μ ₃ -O) ₃₀ (B) _n (A) ₂ (H ₂ O) ₂ } xB' Among them, μ ₂ -O represents a two-connected O atom, and μ ₃ -O represents a three-connected O atom; A is the same or different, independently selected from the residues of C1-C10 organic monocarboxylic acids or organic dicarboxylic acids; B is the same or different and independently selected from the residues of C1-C10 organic monocarboxylic acids or organic dicarboxylic acids; and A and B are not the same; B' is the same or different and independently selected from C1-C10 organic monocarboxylic acids or organic dicarboxylic acids; x is the number of B' molecules in the free state, which is an integer between 0 and 10; When both A are selected from organic monocarboxylic acids, n is 50; When one A is selected from organic monocarboxylic acids and one A is selected from organic dicarboxylic acids, n is 49; When both A's are selected from organic dicarboxylic acids, n is 48. 2 . The titanium oxide cluster compound according to claim 1 , wherein the A is the same or different, and is independently selected from the residues of C1-C6 organic monocarboxylic acids or organic dicarboxylic acids. 3 . 3. The titanium oxide cluster compound according to claim 2, wherein the A is the same or different, and is independently selected from HOC(=O)-, _CH3C (=O)O-, _CH3 CH ₂ C(=O)O-, CH ₃ CH ₂ CH ₂ C(=O)O-, -O(O=)CCH ₂ C(=O)O-, -O(O=C)CH ₂ CH ₂ C(=O)O- or -O(O=)CCH ₂ CH ₂ CH ₂ C(=O)O-. 4. The titanium oxide cluster compound according to claim 3, wherein the A is the same or different and independently selected from HOC(=O)- or -O(O=C)CH ₂ CH ₂ CH ₂ C(=O)O-. 5 . The titanium oxide cluster compound according to claim 1 , wherein the B are the same or different, and are independently selected from the residues of C1-C6 organic monocarboxylic acids or organic dicarboxylic acids. 6 . 6 . The titanium oxide cluster compound according to claim 5 , wherein the B are the same or different, and are independently selected from HOC(=O)-, CH ₃ C(=O)O-, CH ₃ . 7 . CH ₂ C(=O)O-, CH ₃ CH ₂ CH ₂ C(=O)O-, CH ₃ CH(CH ₃ )C(=O)O-, (CH ₃ ) ₃ CC(=O)O -, CH ₃ (CH ₂ ) ₄ C(=O)O-, CH ₃ (CH ₂ ) ₆ C(=O)O-, -O(O=C)CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ C (=O)O-, -O(O=C)CH ₂ C(=O)O-, -O(O=C)CH ₂ CH ₂ C(=O)O-, -O(O=)CCH _{2CH2CH2C (} =O) _O- . 7 . The titanium oxide cluster compound according to claim 6 , wherein the B is selected from CH ₃ C(=O)O-. 8 . 8. The titanium oxide cluster compound according to claim 1, wherein the B' are the same or different, and are independently selected from organic monocarboxylic acids or organic dicarboxylic acids selected from C1-C6. 9 . The titanium oxide cluster compound according to claim 8 , wherein the B′ are the same or different, and are independently selected from HCOOH, CH ₃ COOH, CH ₃ CH ₂ COOH, CH ₃ CH ₂ CH ₂ COOH, CH3CH( _CH3 ) _COOH , ( _CH3 ) _3CCOOH , _CH3 ( _CH2 ) _4COOH , _CH3 ( _{CH2 ) 6OOH} , HO ₍ O=C _{) CH2CH2CH2CH2 CH2COOH} , HO(O=C) _CH2COOH , HO(O=C _{) CH2CH2COOH} , HO ₍ O=C _{) CH2CH2CH2COOH} . 10 . The titanium oxide cluster compound according to claim 9 , wherein the B′ is selected from CH ₃ COOH. 11 . 11. The titanium oxide cluster compound according to claim 1, wherein the molecular formula of the titanium oxide cluster compound is H ₈ {Ti ₄₄ (μ ₂ -O) ₃₆ (μ ₃ -O) ₃₀ (B ) ₅₀ (A) ₂ (H ₂ O) ₂ } 4B'; Wherein, A is selected from HOC(=O)-; B is selected from CH ₃ CH ₂ C(=O)O-; B' is selected from CH ₃ CH ₂ C(=O)OH. 12. The titanium oxide cluster compound according to claim 1, wherein the molecular formula of the titanium oxide cluster compound is: H ₈ {Ti ₄₄ (μ ₂ -O) ₃₆ (μ ₃ -O) ₃₀ (B) ₄₈ (A) ₂ (H ₂ O) ₂ }·6B'; Wherein, A is selected from -O(O=C)CH ₂ CH ₂ CH ₂ C(=O)O-; B is selected from CH ₃ CH ₂ C(=O)O-; B' is selected from CH ₃ CH ₂ C (=O)OH. 13. The titanium oxide cluster compound according to claim 1, wherein the molecular formula of the titanium oxide cluster compound is C ₁₆₄ H ₂₈₈ O ₁₈₀ Ti ₄₄ , denoted as titanium oxide cluster compound a, and Mr is 7247.53 ; The crystal system of the crystalline substance of the titanium oxide cluster compound a is a triclinic crystal system, and the space group is P

, the unit cell parameters a is 15.59 Å, b is 18.01 Å, c is 25.90 Å, α is 74.63 ^o , β is ^{84.42 o} , γ is 76.43 ^o , and V is 6816 Å. 14. The titanium oxide cluster compound according to claim 13, wherein the crystal parameters of the crystalline state of the titanium oxide cluster compound a are as shown in Table 1: Table 1

15. The titanium oxide cluster compound according to claim 1, wherein the molecular formula of the titanium oxide cluster compound is C ₁₇₂ H ₃₀₀ O ₁₈₄ Ti ₄₄ , denoted as titanium oxide cluster compound b, and Mr is 7418.26 ; The titanium oxide cluster compound b is a pure phase colorless stripe crystal; the crystal system of the titanium oxide cluster compound b is a triclinic crystal system, and the space group is P

, the unit cell parameters a is 15.5 Å, b is 18.6 Å, c is 25.9 Å, α is 74.3 ^Å , β is 81.9 ^Å , γ is 75.6 ^Å , and V is 6922 ^Å . 16. The titanium oxide cluster compound according to claim 15, wherein the crystal parameters of the crystalline state of the titanium oxide cluster compound b are as shown in Table 2: Table 2

17 . The titanium oxide cluster compound according to any one of claims 1 to 16 , wherein the titanium oxide cluster compound is a pure-phase colorless strip-like crystalline substance. 18 . 18. The titanium oxide cluster compound according to any one of claims 1-16, wherein the titanium oxide cluster compound is an organic-inorganic hybrid compound. 19 . The titanium oxide cluster compound according to any one of claims 1 to 16 , wherein the size of the cluster nucleus of the crystalline substance of the titanium oxide cluster compound is 2.8±0.2 nm. 20 . 20. The titanium oxy cluster compound according to any one of claims 1-16, characterized in that the crystalline substance of the titanium oxy cluster compound has a symmetrical structure. 21. A method for preparing the titanium oxide cluster compound described in any one of claims 1-20, the method comprising the steps of: mixing titanium salt, C1-C10 organic monocarboxylic acid or organic dicarboxylic acid A Mixing with organic monocarboxylic acid or organic dicarboxylic acid B of C1-C10, and carrying out solvothermal reaction, the titanium oxide cluster compound is obtained; wherein the titanium salt is titanium ion and alcohol to remove the hydrogen on the alcohol hydroxyl group compound formed later. 22. The method according to claim 21, wherein the method specifically comprises the following steps: 1) Mixing the titanium salt, C1-C10 organic monocarboxylic acid or organic dicarboxylic acid A and C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B, and performing a solvothermal reaction to obtain a mixture; 2) The mixture obtained after the reaction in step 1) is separated, and the solid phase therein is the titanium oxide cluster compound. 23. The preparation method according to claim 21 or 22, wherein the titanium salt is titanium ethoxide, titanium tert-butoxide, titanium isobutoxide, titanium n-butoxide, titanium n-propoxide and titanium isopropoxide One or more combinations of . 24. The preparation method according to claim 21 or 22, wherein the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid A is selected from organic monocarboxylic acids containing 1-10 carbon atoms or Organic dicarboxylic acids or mixtures of both. 25. preparation method according to claim 24 is characterized in that, the organic monocarboxylic acid or organic dicarboxylic acid A of described C1-C10 is selected from organic monocarboxylic acid or organic dicarboxylic acid containing 1-6 carbon atoms carboxylic acid or a mixture of the two. 26. preparation method according to claim 25 is characterized in that, the organic monocarboxylic acid of described C1-C10 or organic dicarboxylic acid A is selected from formic acid, acetic acid, propionic acid, butyric acid, malonic acid, butyric acid One or both of diacid or glutaric acid. 27. The preparation method according to claim 26, wherein the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid A is selected from formic acid and/or glutaric acid. 28. The preparation method according to claim 21 or 22, wherein the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B is selected from organic monocarboxylic acids containing 1-10 carbon atoms or Organic dicarboxylic acids or mixtures of both. 29. The preparation method according to claim 28, wherein the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B is selected from organic monocarboxylic acids or organic dicarboxylic acids containing 1-6 carbon atoms carboxylic acid or a mixture of the two. 30. The preparation method according to claim 29, wherein the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B is selected from formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, special Valeric acid, n-hexanoic acid, octanoic acid, adipic acid, oxalic acid, malonic acid, succinic acid, or a mixture of any two or more thereof. 31. preparation method according to claim 21 or 22 is characterized in that, the mol ratio of described titanium salt and described C1-C10 organic monocarboxylic acid or organic dicarboxylic acid A is 1:(0.01-1 ); the molar ratio of the titanium salt to the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B is 1:(0.01-1). 32. preparation method according to claim 31, is characterized in that, the mol ratio of described titanium salt and described C1-C10 organic monocarboxylic acid or organic dicarboxylic acid A is 1:(0.1-0.8); The molar ratio of the titanium salt to the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B is 1:(0.02-0.5). 33. preparation method according to claim 32, is characterized in that, the mol ratio of described titanium salt and described C1-C10 organic monocarboxylic acid or organic dicarboxylic acid A is 1:(0.2-0.5); The molar ratio of the titanium salt to the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B is 1:(0.03-0.3). 34. The preparation method according to claim 21 or 22, wherein the temperature of the solvothermal reaction is 40 to 160°C; the time of the solvothermal reaction is 24 to 240 hours. 35. The preparation method according to claim 34, wherein the temperature of the solvothermal reaction is 60-100°C; the time of the solvothermal reaction is 48-150 hours. 36. preparation method according to claim 21 or 22 is characterized in that, to titanium salt, organic monocarboxylic acid of C1-C10 or organic dicarboxylic acid A and organic monocarboxylic acid or organic dicarboxylic acid of C1-C10 Sodium hydroxide, potassium chloride, water or hydrogen peroxide are added to the mixed system of carboxylic acid B. 37. A titanium oxide cluster compound selected from the titanium oxide cluster compound according to any one of claims 1-20 and prepared by the method according to any one of claims 21-36. 38. Use of the titanium-oxygen cluster compound according to any one of claims 1-20 and 37 for splitting water, degrading pollutants or electronic devices.

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