CN109721624B - Titanium-oxygen cluster compound and synthesis method and application thereof - Google Patents
Titanium-oxygen cluster compound and synthesis method and application thereof Download PDFInfo
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- CN109721624B CN109721624B CN201810799404.XA CN201810799404A CN109721624B CN 109721624 B CN109721624 B CN 109721624B CN 201810799404 A CN201810799404 A CN 201810799404A CN 109721624 B CN109721624 B CN 109721624B
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Abstract
The invention provides a titanium oxide cluster compound and a synthesis method and application thereof, wherein the molecular formula of the titanium oxide cluster compound is H8{Ti44(μ2‑O)36(μ3‑O)30(B)n(A)2(H2O)2}. xB'; the titanium-oxygen cluster compound is obtained by a solvothermal synthesis method, namely, heating reaction is carried out in a solvent, reaction raw materials are simply mixed, and one-step self-assembly reaction is carried out. The method has the advantages of simple synthesis requirement, low requirement on the purity of raw materials, easy acquisition of the raw materials, low price, no need of further purification due to the purchase of chemically pure reagents for the used raw materials, high yield of more than 90 percent, and contribution to large-scale production. The titanium oxide cluster compound has high-efficiency and stable hydrogen production activity by photolysis of water, and can be used for water splitting and pollutant degradation and electronic devices such as solar cells. The method is simple and efficient, has little pollution of the synthesis process, and meets the requirements of environmental protection.
Description
Technical Field
The invention belongs to the technical field of crystal material preparation, and particularly relates to a titanium oxide cluster compound and a synthesis method and application thereof.
Background
Nano TiO 22The composite material is non-toxic and harmless, has rich reserves and excellent physicochemical properties, and is widely applied to the aspects of gas sensing, charge transmission, toxic organic pollutant decomposition, photocatalysis and the like. As TiO2The structure and performance of the material simulates a molecule, a titanium-oxygen cluster (also known as Ti)44Cluster compound, titanyl cluster or titanyl fullerene, etc.) has attracted the deep research of many scientists due to its diversified geometric dimensions, clear atomic structure, adjustable cluster nucleus size, accurate modification, and different degrees of solubility and reactivity in organic solvents, and has been applied to many interdisciplinary fields of physical chemistry, organic and inorganic chemistry, analytical chemistry, biology, polymer chemistry, medicine, material science, physics, etc., and the application field is very wide. The titanium oxide cluster compounds reported at present have poor stability, low cluster nuclei and poor reproducibility.
For this reason, it is necessary to develop TiO which is comparable to TiO2The titanium oxide cluster material has the advantages of high nanoparticle size, high efficiency and stable activity of hydrolyzing water to produce hydrogen, and can be particularly used as a novel titanium oxide cluster material for electronic devices such as water cracking, pollutant degradation, solar cells and the like.
Disclosure of Invention
In order to achieve the above objects, the present invention provides a titanium oxide cluster, a method for synthesizing the same, and applications thereof, wherein the titanium oxide cluster has high-efficiency and stable photolytic hydrogen production activity, and can be used for water splitting, pollutant degradation, and electronic devices such as solar cells. The method is simple and efficient, has little pollution of the synthesis process, and meets the requirements of environmental protection.
In a first aspect of the present invention, there is provided a titanyl cluster having the formula:
H8{Ti44(μ2-O)36(μ3-O)30(B)n(A)2(H2O)2}·xB’
wherein, mu2O represents a di-bonded O atom,. mu.3-O represents a triple-bonded O atom;
a is the same or different and is independently selected from the residues of organic acids of C1-C40;
b are the same or different and are independently selected from the residues of organic acids of C1-C30;
b', which are identical or different, are independently selected from organic acids from C1 to C30;
x is the number of B' molecules in a free state and is an integer between 0 and 10;
when both A's are selected from monoacids, n is 50;
when one A is selected from monoacids and one A is selected from polyacids, n is 49;
when both a are selected from the group consisting of polyacids, n is 48.
According to the invention, said A, which are identical or different, are independently from each other residues of organic acids from C1 to C30; for example residues of organic acids selected from C1-C20; residues of organic acids selected from C1-C10; residues of organic acids also selected from C1-C6, for example;
according to the invention, said a, which are identical or different, are selected, independently of one another, from HOC (═ O) -, CH3C(＝O)O-、CH3CH2C(＝O)O-、CH3CH2CH2C(＝O)O-、-O(O＝)CCH2C(＝O)O-、-O(O＝C)CH2CH2C (═ O) O-or-O (O ═ CCH2CH2CH2C (═ O) O-; preferably, it is HOC (═ O) -or — O (O ═ C) CH2CH2CH2C(＝O)O-。
According to the invention, said B, which are identical or different, are chosen, independently of one another, from residues of organic acids from C1 to C20; for example residues of organic acids selected from C1-C10; residues of organic acids selected from C1-C6;
according to the invention, said B, which are identical or different, are chosen, independently of one another, from HOC (═ O) -, CH3C(＝O)O-、CH3CH2C(＝O)O-、CH3CH2CH2C(＝O)O-、CH3CH(CH3)C(＝O)O-、(CH3)3CC(＝O)O-、CH3(CH2)4C(＝O)O-、CH3(CH2)6C(＝O)O-、-O(O＝C)CH2CH2CH2CH2CH2C(＝O)O-、-O(O＝C)CH2C(＝O)O-、-O(O＝C)CH2CH2C(＝O)O-、-O(O＝)CCH2CH2CH2C (═ O) O-; preferably CH3C(＝O)O-。
According to the invention, said B', equal or different, are chosen independently of one another from organic acids from C1 to C20; for example, an organic acid selected from C1-C10; an organic acid selected from C1-C6;
according to the invention, said B' are identical or different and are chosen, independently of one another, from HCOOH, CH3COOH、CH3CH2COOH、CH3CH2CH2COOH、CH3CH(CH3)COOH、(CH3)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 titanium oxygen cluster compound has a molecular formula of
H8{Ti44(μ2-O)36(μ3-O)30(B)50(A)2(H2O)2}·4B’；
Wherein a is selected from HOC (═ O) -; b is selected from CH3CH2C (═ O) O-; b' is selected from CH3CH2C(＝O)OH。
According to an embodiment of the present invention, the titanium oxygen cluster compound has a molecular formula of
H8{Ti44(μ2-O)36(μ3-O)30(B)48(A)2(H2O)2}·6B’；
Wherein A is selected from-O (O ═ C) CH2CH2CH2C (═ O) O-; b is selected from CH3CH2C (═ O) O-; b' is selected from CH3CH2C(＝O)OH。
According to the invention, the organic acid is a mono-or polybasic acid; the polybasic acid is dibasic acid or tribasic or more acid.
In the present invention, the residue refers to a residue obtained by removing all the hydrogens from the carboxyl groups with an organic acid, and for example, the residue of formic acid is HOC (═ O) -, and the residue of acetic acid is CH3C (═ O) O-, with the residue of propionic acid being CH3CH2C (═ O) O-, the residue of glutaric acid is-O (O ═ C) CH2CH2CH2C(＝O)O-。
Specifically, the molecular formula of the titanium oxygen cluster compound is C164H288O180Ti44Marked as titanium-oxygen cluster compound a, Mr is 7247.53; the crystal system of the crystalline substance of the titanium-oxygen cluster compound a is a triclinic crystal system, and the space group is
Cell parameter a is
b is
c is
α is 74.63 degrees, β is 84.42 degrees, gamma is 76.43 degrees, and V is
The crystalline form of the titanyl cluster a has an X-ray powder diffraction pattern substantially as shown in figure 2.
The crystal parameters of the crystalline substance of the titanium-oxygen cluster compound a are shown in the following table 1:
TABLE 1
Specifically, the molecular formula of the titanium oxygen cluster compound is C172H300O184Ti44Is marked as titanium-oxygen cluster b, and Mr is 7418.26; the titanium oxygen cluster compound b is a pure-phase colorless strip-shaped crystalline substance; the crystal system of the crystalline substance of the titanium-oxygen cluster compound b is a triclinic crystal system, and the space group is
Cell parameter a is
b is
c is
α at 74.3 °, β at 81.9 °, γ at 75.6 °, and V at
The crystalline form of the titanyl cluster b has an X-ray powder diffraction pattern substantially as shown in figure 6.
The crystal parameters of the crystalline substance of the titanium-oxygen cluster b are shown in Table 2:
TABLE 2
According to the invention, the titanium-oxygen cluster compound is a pure-phase colorless strip-shaped crystalline substance.
According to the invention, the titanyl cluster compound is an organic-inorganic hybrid compound.
According to the invention, the crystalline substance of the titanium-oxygen cluster has a cluster core size of 2.8 +/-0.2 nm.
According to the present invention, the crystalline substance of the titanyl cluster compound has a symmetrical structure.
In a second aspect of the present invention, there is provided a method for preparing the above-mentioned titanyl cluster compound, comprising the steps of: mixing titanium salt, organic acid A and organic acid B, and carrying out solvothermal reaction to obtain the titanium-oxygen cluster compound.
According to the invention, the method comprises in particular the following steps:
1) mixing the titanium salt, the organic acid A and the organic acid B, and carrying out solvothermal reaction to obtain a mixture;
2) separating the mixture obtained after the reaction in the step 1), wherein the solid phase is the titanium oxide cluster.
According to the invention, the titanium salt is a compound formed by removing hydrogen on an alcoholic hydroxyl group of titanium ions and alcohol.
According to the invention, the titanium salt is one or more of titanium ethoxide, titanium tert-butoxide, titanium isobutoxide, titanium n-butoxide, titanium n-propoxide and titanium isopropoxide, preferably titanium isopropoxide.
According to the invention, the organic acid A is chosen from acids or mixtures of acids containing from 1 to 40 carbon atoms (for example from 1 to 30 carbon atoms, from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms).
Preferably, the organic acid A is selected from one or two of formic acid, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid or glutaric acid; preferably formic acid and/or glutaric acid.
According to the invention, the organic acid B is chosen from acids or mixtures of acids containing from 1 to 30 carbon atoms (for example from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 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, octanoic acid, adipic acid, oxalic acid, malonic acid, succinic acid or a mixture of any two or more thereof.
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, for example propionic acid or a mixture of propionic acid and acetic acid or propionic acid and butyric acid.
According to the invention, the organic acid A and the organic acid B are identical or different; illustratively, when the organic acid a is selected from formic acid, the organic acid B may be selected from formic acid alone, or from a mixture of formic acid and other organic acids, or from other organic acids other than formic acid.
According to the 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), in particular 1 (0.2-0.5).
According to the 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), in particular 1 (0.03-0.3).
According to the invention, the temperature of the solvothermal reaction is 40-160 ℃; preferably 60 to 100 deg.C, for example 70 to 90 deg.C, such as 80 deg.C. If the reaction temperature is too low, the reaction time is long and the crystal size is small.
According to the invention, the solvothermal reaction time is 24-240 hours; preferably 48 to 150 hours, such as 72 hours and 120 hours.
As a preferred embodiment of the present invention, the reaction may be carried out at 80 ℃ for 72 hours or 96 hours, or at 100 ℃ for 48 hours or 72 hours.
According to the invention, step 1) comprises in particular: mixing the titanium salt, the organic acid A and the organic acid B, stirring, placing in a glass bottle or a polytetrafluoroethylene pressure container, reacting at constant temperature, and cooling to room temperature.
According to the invention, in step 2), the solid phase obtained by separation is washed;
preferably, the separated solid phase is washed with water, acid or alcohol and dried at room temperature.
According to the invention, the yield of the titanium-oxygen cluster compound can reach more than 90%.
According to the invention, sodium hydroxide, potassium chloride, water or hydrogen peroxide can also be added to the mixed system of the titanium salt, the organic acid A and the organic acid B.
The addition of sodium hydroxide, potassium chloride, water or hydrogen peroxide as a co-reactant substance promotes the reaction, and the amount thereof is not particularly limited, and may be selected conventionally by those skilled in the art, for example, from 0.05 to 5 wt% of the objective product.
According to the present invention, the titanium oxide cluster compound of the above first aspect is produced by the method of the above second aspect.
A third aspect of the present invention is to provide a use of the above titanium oxide cluster compound, which can be used for water splitting, pollutant degradation, or electronic devices (e.g., solar cells).
Advantageous effects
The invention provides a novel material, namely an organic-inorganic hybrid titanium oxide cluster which is of a symmetrical structure, the size of a cluster core is about 2.8 +/-0.2 nm, and the titanium oxide cluster has high-efficiency and stable water photolysis hydrogen production activity and can be used in the fields of water splitting, pollutant degradation or electronic devices and the like.
The invention also provides a brand new method for preparing the titanium-oxygen cluster compound, which utilizes a solvothermal synthesis method, namely, the titanium-oxygen cluster compound can be obtained by heating reaction in a solvent, simply mixing reaction raw materials and carrying out one-step self-assembly reaction. The method has the advantages of simple synthesis requirement, low requirement on the purity of raw materials, easy acquisition of the raw materials, low price, no need of further purification due to the purchase of chemically pure reagents for the used raw materials, high yield of more than 90 percent, and contribution to large-scale production. In addition, the post-treatment of the method is simple and feasible, and pure-phase crystalline products can be obtained only by simple water washing, acid washing or alcohol washing separation and room-temperature air drying. Moreover, the method has less pollution and meets the requirement of green environmental protection.
Drawings
FIG. 1 is a schematic representation of the crystal structure of the crystalline product prepared in example 1;
FIG. 2 is an X-ray powder diffraction pattern of the crystalline product prepared in example 1, each line from bottom to top representing a simulated powder diffraction pattern, respectively, of a crystal placed in air for the first day, the second day, and the third day; wherein the theoretical value is an X-ray powder diffraction pattern obtained according to crystal structure simulation; the experimental value is an X-ray powder diffraction pattern obtained by testing on an X-ray powder diffractometer;
FIG. 3 is an infrared spectrum of a crystalline product prepared in example 1;
FIG. 4 is a product photograph of the crystalline product prepared in example 1;
FIG. 5 is a schematic representation of the crystal structure of the crystalline product prepared in example 2;
FIG. 6 is an X-ray powder diffraction pattern of the crystalline product prepared in example 2, each line from bottom to top representing a simulated powder diffraction pattern, respectively, of a crystal placed in air for the first day, the second day, and the third day; wherein the theoretical value is an X-ray powder diffraction pattern obtained according to crystal structure simulation; the experimental value is an X-ray powder diffraction pattern obtained by testing on an X-ray powder diffractometer;
FIG. 7 is an infrared spectrum of a crystalline product prepared in example 2;
fig. 8 is a product photograph of the crystalline product prepared in example 2.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
Unless otherwise indicated, reagents for use in the invention are commercially available.
The single crystal structure analysis of the present invention uses a supernova single crystal diffractometer in japan.
X-ray powder diffraction pattern the radiation source used was Cu-K α radiation.
Example 1
Placing titanium isopropoxide (3.3mmol), formic acid (26.5mmol) and propionic acid (73.6mmol) in a 20ml glass bottle, uniformly mixing at room temperature, keeping the temperature in an oven at 80 ℃ for 3 days, taking out, naturally cooling to room temperature, separating out a solid phase, and washing with propionic acid to obtain a colorless strip crystalline target product. The crystal product can be obtained by adding a small amount of sodium hydroxide, potassium chloride and the like into the reaction system or adding a small amount of water and hydrogen peroxide into the reaction system.
It can be seen from FIG. 1 that this compound has 44 titanium atoms, and the remaining ligands, with the exception of the two formic acid and the two water-based 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;
from FIG. 3, it can be seen that the oscillation characteristic peak of the Ti-O cluster nucleus of the compound is 1000-500cm-1Vibration characteristic peak of organic ligand 3500-1000cm-1；
It can be seen from FIG. 4 that the compound is a colorless bar.
Example 2
Placing titanium isopropoxide (3.3mmol), glutaric acid (1.5mmol) and propionic acid (73.6mmol) in a 20ml glass bottle, uniformly mixing at room temperature, keeping the temperature in an oven at 80 ℃ for 3 days, taking out, naturally cooling to room temperature, separating out a solid phase, and washing with propionic acid to obtain a colorless strip crystalline target product. The crystal product can be obtained by adding a small amount of sodium hydroxide, potassium chloride and the like into the reaction system or adding a small amount of water, hydrogen peroxide and the like.
It can be seen from FIG. 5 that this compound has 44 titanium atoms, the remaining ligands, with the exception of the two glutaric acid and two water-based ligands, being all propionic acid ligands;
it can be seen from figure 6 that this compound is stable in air for at least three days;
from FIG. 7, it can be seen that the oscillation characteristic peak of the Ti-O cluster nucleus of the compound is 1000-500cm-1Organic preparation ofVibration characteristic peak of ligand 3500-1000cm-1；
From FIG. 8, it can be seen that this compound is a colorless bar.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (38)
1. A titanyl cluster compound characterized by the molecular formula:
H8{Ti44(μ2-O)36(μ3-O)30(B)n(A)2(H2O)2}·xB’
wherein, mu2O represents a di-bonded O atom,. mu.3-O represents a triple-bonded O atom;
a is the same or different and is independently selected from the residues of C1-C10 organic monocarboxylic or dicarboxylic acids;
b are the same or different and are independently selected from the residues of C1-C10 organic monocarboxylic or dicarboxylic acids; and A and B are different;
b' are the same or different and are independently selected from C1-C10 organic monocarboxylic acids or organic dicarboxylic acids;
x is the number of B' molecules in a free state and is an integer between 0 and 10;
when both A's 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. A titanium cluster compound according to claim 1, wherein a, which are the same or different, are independently selected from residues of organic monocarboxylic or dicarboxylic acids of C1-C6.
3. A titanium oxygen cluster compound according to claim 2, wherein a is the same or different and is selected from the group consisting of HOC (= O) -, CH, independently of each other3C(=O)O-、CH3CH2C(=O)O-、CH3CH2CH2C(=O)O-、-O(O=)CCH2C(=O)O-、-O(O=C)CH2CH2C (= O) O-or-O (O =) CCH2CH2CH2C(=O)O-。
4. A titanium oxygen cluster compound according to claim 3, characterized in that said a are the same or different and are selected from HOC (= O) -or-O (O = C) CH independently of each other2CH2CH2C(=O)O-。
5. A titanium oxide cluster according to claim 1, wherein B is the same or different and is independently selected from the group consisting of residues of organic monocarboxylic or dicarboxylic acids of C1-C6.
6. A titanium oxygen cluster compound according to claim 5, wherein the B's are the same or different and are independently selected from the group consisting of HOC (= O) -, CH3C(=O)O-、CH3CH2C(=O)O-、CH3CH2CH2C(=O)O-、CH3CH(CH3)C(=O)O-、(CH3)3CC(=O)O-、CH3(CH2)4C(=O)O-、CH3(CH2)6C(=O)O-、-O(O=C)CH2CH2CH2CH2CH2C(=O)O-、-O(O=C)CH2C(=O)O-、-O(O=C)CH2CH2C(=O)O-、-O(O=)CCH2CH2CH2C(=O)O-。
7. The titanium oxygen cluster compound according to claim 6, wherein B is selected from CH3C(=O)O-。
8. A titanium oxide cluster according to claim 1, wherein B' is the same or different and is independently selected from organic monocarboxylic acids or organic dicarboxylic acids selected from C1-C6.
9. The titanium oxide cluster according to claim 8, wherein B' is the same or different and is independently selected from HCOOH, CH3COOH、CH3CH2COOH、CH3CH2CH2COOH、CH3CH(CH3)COOH、(CH3)3CCOOH、CH3(CH2)4COOH、CH3(CH2)6OOH、HO(O=C)CH2CH2CH2CH2CH2COOH、HO(O=C)CH2COOH、HO(O=C)CH2CH2COOH、HO(O=C)CH2CH2CH2COOH。
10. The titanium oxygen cluster compound of claim 9, wherein B' is selected from CH3COOH。
11. A titanium oxy cluster according to claim 1, characterized in that the titanium oxy cluster has the molecular formula H8{Ti44(μ2-O)36(μ3-O)30(B)50(A)2(H2O)2}·4B’；
Wherein, A is selected from HOC (= O) -; b is selected from CH3CH2C (= O) O-; b' is selected from CH3CH2C(=O)OH。
12. A titanium oxy cluster according to claim 1, characterized in that the titanium oxy cluster has the formula
H8{Ti44(μ2-O)36(μ3-O)30(B)48(A)2(H2O)2}·6B’；
Wherein A is selected from-O (O = C) CH2CH2CH2C (= O) O-; b is selected from CH3CH2C (= O) O-; b' is selected from CH3CH2C(=O)OH。
13. A titanium oxy cluster according to claim 1, characterized in that the titanium oxy cluster has the molecular formula C164H288O180Ti44Marked as titanium-oxygen cluster compound a, Mr is 7247.53; the crystal system of the crystalline substance of the titanium-oxygen cluster compound a is a triclinic crystal system, and the space group isP 
Cell parameteraIs a mixture of 15.59 Å (weight percent),bis a mixture of at least one of the compounds of 18.01 Å,cis a mixture of at least 25.90 Å,αis 74.63o，βIs 84.42o，γIs 76.43oAnd V is 6816 Å3。
14. A titanium oxo cluster according to claim 13, wherein the crystal parameters of the crystalline substance of titanium oxo cluster a are as shown in table 1:
TABLE 1
15. A titanium oxy cluster according to claim 1, characterized in that the titanium oxy cluster has the molecular formula C172H300O184Ti44Is marked as titanium-oxygen cluster b, and Mr is 7418.26; the titanium oxygen cluster compound b is a pure-phase colorless strip-shaped crystalline substance; the crystal system of the crystalline substance of the titanium-oxygen cluster compound b is a triclinic crystal system, and the space group isP 
Cell parameteraIs a mixture of at least 15.5 Å,bis a mixture of at least 18.6 Å,cis a mixture of at least 25.9 Å,αis 74.3o，βIs 81.9o，γIs 75.6oAnd V is 6922 Å3。
16. A titanium oxo cluster according to claim 15, wherein the crystal parameters of the crystalline substance of titanium oxo cluster b are as shown in table 2:
TABLE 2
17. A titanium oxy cluster according to any one of claims 1 to 16, characterized in that it is a pure phase colorless ribbon crystal.
18. A titanium oxy cluster according to any one of claims 1 to 16, characterized in that it is an organic-inorganic hybrid compound.
19. A titanium oxy cluster according to any one of claims 1 to 16, characterized in that the crystalline substance of the titanium oxy cluster has a cluster core size of 2.8 ± 0.2 nm.
20. A titanium oxy cluster according to any one of claims 1 to 16, characterized in that the crystalline substance of the titanium oxy cluster has a symmetrical structure.
21. A method for producing the titanium oxygen cluster compound of any one of claims 1 to 20, the method comprising the steps of: mixing titanium salt, C1-C10 organic monocarboxylic acid or organic dicarboxylic acid A and C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B, and carrying out solvothermal reaction to obtain the titanium-oxygen cluster compound; wherein the titanium salt is a compound formed by removing hydrogen on an alcoholic hydroxyl group by titanium ions and alcohol.
22. The method according to claim 21, wherein the method comprises in particular the steps of:
1) mixing the titanium salt, organic monocarboxylic acid or organic dicarboxylic acid A of C1-C10 and organic monocarboxylic acid or organic dicarboxylic acid B of C1-C10, and carrying out solvothermal reaction to obtain a mixture;
2) separating the mixture obtained after the reaction in the step 1), wherein the solid phase is the titanium oxide cluster.
23. The method according to claim 21 or 22, wherein the titanium salt is one or more selected from the group consisting of titanium ethoxide, titanium tert-butoxide, titanium isobutoxide, titanium n-butoxide, titanium n-propoxide, and titanium isopropoxide.
24. The method of claim 21 or 22, wherein the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid a is selected from organic monocarboxylic acids or organic dicarboxylic acids having 1-10 carbon atoms, or a mixture thereof.
25. The method as claimed in claim 24, wherein the C1-C10 organic monocarboxylic or dicarboxylic acid A is selected from the group consisting of organic monocarboxylic or dicarboxylic acids having 1-6 carbon atoms and mixtures thereof.
26. The preparation method of claim 25, wherein the organic monocarboxylic acid or organic dicarboxylic acid A having a carbon number of from 1 to 10 is one or two selected from formic acid, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid and glutaric acid.
27. The method of claim 26, wherein the C1-C10 organic monocarboxylic or dicarboxylic acid a is selected from formic acid and/or glutaric acid.
28. The method of claim 21 or 22, wherein the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B is selected from organic monocarboxylic acids or organic dicarboxylic acids having 1-10 carbon atoms or a mixture thereof.
29. The method as claimed in claim 28, wherein the C1-C10 organic monocarboxylic acid or organic dicarboxylic acid B is selected from organic monocarboxylic acids or organic dicarboxylic acids having 1-6 carbon atoms or a mixture thereof.
30. The method of 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, pivalic acid, n-hexanoic acid, octanoic acid, adipic acid, oxalic acid, malonic acid, succinic acid, or a mixture of any two or more thereof.
31. The method for preparing the titanium dioxide film according to claim 21 or 22, wherein the molar ratio of the titanium salt to the organic monocarboxylic acid or the organic dicarboxylic acid A of C1-C10 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. The method as claimed in claim 31, wherein the molar ratio of the titanium salt to the organic monocarboxylic acid or organic dicarboxylic acid A having C1-C10 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. The method as claimed in claim 32, wherein the molar ratio of the titanium salt to the organic monocarboxylic acid or organic dicarboxylic acid A of C1-C10 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 ℃; the solvothermal reaction time is 24-240 hours.
35. The preparation method of claim 34, wherein the temperature of the solvothermal reaction is 60-100 ℃; the solvothermal reaction time is 48-150 hours.
36. The method of claim 21 or 22, wherein sodium hydroxide, potassium chloride, water or hydrogen peroxide is added to the titanium salt, the organic monocarboxylic acid or organic dicarboxylic acid a of C1-C10 and the organic monocarboxylic acid or organic dicarboxylic acid B of C1-C10.
37. A titanium oxygen cluster selected from the titanium oxygen clusters defined in any one of claims 1 to 20 and produced by the method defined in any one of claims 21 to 36.
38. Use of the titanium oxygen cluster compound of any one of claims 1 to 20, 37 in cracking water, degrading pollutants or in electronic devices.
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| CN111573773B (en) * | 2020-05-27 | 2022-09-06 | 齐鲁工业大学 | Application of titanium-based coordination polymer in photocatalytic degradation of dye wastewater |
| CN111786024B (en) * | 2020-06-22 | 2021-12-17 | 厦门大学 | Titanium oxygen cluster based solid polymer electrolyte and preparation method and application thereof |
| CN111804344B (en) * | 2020-07-15 | 2022-12-23 | 江苏师范大学 | Calixarene-based titanium oxide cluster compound, preparation method thereof and application thereof in dye photodegradation |
| CN111790451B (en) * | 2020-08-04 | 2023-01-20 | 江苏师范大学 | Dissimilar metal titanium-oxygen cluster crystalline material, preparation method thereof and application thereof in dye photodegradation |
| CN111943976B (en) * | 2020-08-07 | 2022-08-23 | 江苏师范大学 | Crystalline material of hexanuclear titanium-oxygen cluster compound, preparation method thereof and application thereof in photodegradation of rhodamine B |
| CN112029212B (en) * | 2020-08-10 | 2022-11-01 | 厦门大学 | Gel polymer electrolyte containing ligand-modified cluster and preparation method thereof |
| CN111939936A (en) * | 2020-08-24 | 2020-11-17 | 安徽建筑大学 | In2S3/TiO2Preparation method and application of photocatalyst |
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