CN109721624A - Titanyl cluster compound and its synthetic method and purposes - Google Patents
Titanyl cluster compound and its synthetic method and purposes Download PDFInfo
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- CN109721624A CN109721624A CN201810799404.XA CN201810799404A CN109721624A CN 109721624 A CN109721624 A CN 109721624A CN 201810799404 A CN201810799404 A CN 201810799404A CN 109721624 A CN109721624 A CN 109721624A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of titanyl cluster compound and its synthetic method and purposes, and the molecular formula of the titanyl cluster compound is H8{Ti44(μ2‑O)36(μ3‑O)30(B)n(A)2(H2O)2}·xB'；It utilizes solvent-thermal process method, as carries out heating reaction in a solvent, reaction raw materials are simply mixed, by a step self-assembling reaction, can be obtained the titanyl cluster compound.The synthesis of this method requires simple, and low to the purity requirement of raw material, raw material is easy and cheap, raw materials used not need further to purify, and yield is up to 90% or more, conducive to being mass produced by buying chemically pure reagent.The titanyl cluster compound has efficient, stable photodissociation aquatic products hydrogen activity, can be used for splitting water, contaminant degradation and in the electronic devices such as solar battery.The method is simple, the pollution of efficient and synthesis technology is few, meets environment protection requirement.
Description
Technical field
The invention belongs to crystalline material preparation technical fields, and in particular to a kind of titanyl cluster compound and its synthetic method and use
On the way.
Background technique
Nano-titanium dioxide TiO2Since its is nontoxic, rich reserves and excellent in physical and chemical performance, gas sensing,
Charge transmission, decomposition toxic organic pollutant and photocatalysis etc. are widely used.As TiO2The structure and performance of material
Model molecule, titanyl cluster compound (alternatively referred to as Ti44Cluster compound, titanyl cluster, titanyl cluster or titanyl fullerene etc.) since it is more
The geometric dimension of sample, atomic structure is apparent, cluster core size adjustable, precisely modifies, different degrees of molten in organic solvent
Xie Xingyu reactivity, has attracted the further investigation of many scientists, and have application to physical chemistry, organic-inorganic chemistry,
Many interdisciplinary fields such as analytical chemistry, biology, polymer chemistry, medicine and pharmacology, material science and physics, application field
Widely.Titanyl cluster compound stability reported at present is poor, and cluster core is low, and reproducibility is bad.
For this reason, it is necessary to develop the TiO that can match in excellence or beauty2Nanoparticle size, while having efficient, stable photodissociation aquatic products hydrogen living
The high cluster core titanyl cluster compound of property, can be especially useful for the novel of the electronic devices such as splitting water, contaminant degradation, solar battery
Titanyl cluster compound material.
Summary of the invention
To achieve the goals above, the present invention provides a kind of titanyl cluster compound and its synthetic method and application, the titanyl
Cluster compound has efficient, stable photodissociation aquatic products hydrogen activity, can be used for splitting water, contaminant degradation and for solar battery
In equal electronic devices.The method is simple, the pollution of efficient and synthesis technology is few, meets environment protection requirement.
The first aspect of the present invention is to provide a kind of titanyl cluster compound, the molecular formula of the titanyl cluster compound are as follows:
H8{Ti44(μ2-O)36(μ3-O)30(B)n(A)2(H2O)2}·xB’
Wherein, μ2- O represents the O atom of two connections, μ3- O represents the O atom of three connections；
A is identical or different, is independently from each other the residue of the organic acid of C1-C40；
B is identical or different, is independently from each other the residue of the organic acid of C1-C30；
B ' is identical or different, is independently from each other the organic acid of C1-C30；
X is the quantity of the B ' molecule of free state, the integer between 0-10；
When two A are selected from monoacid, n 50；
When an A is selected from monoacid, and an A is selected from polyacid, n 49；
When two A are selected from polyacid, n 48.
According to the present invention, the A is identical or different, is independently from each other the residue of the organic acid of C1-C30；Such as it selects
From the residue of the organic acid of C1-C20；Such as residue of the organic acid selected from C1-C10 again；Also for example selected from the organic acid of C1-C6
Residue；
According to the present invention, the A is identical or different, is independently from each other 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 HOC (=O)-or-O (O=C) CH2CH2CH2C (=O) O-.
According to the present invention, the B is identical or different, is independently from each other the residue of the organic acid of C1-C20；Such as it selects
From the residue of the organic acid of C1-C10；The residue of organic acid selected from C1-C6；
According to the present invention, the B is identical or different, is independently from each other 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 present invention, the B ' is identical or different, is independently from each other the organic acid of C1-C20；Such as selected from C1-
The organic acid of C10；Organic acid selected from C1-C6；
According to the present invention, the B ' is identical or different, is independently from each other 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；It is preferred that
For CH3COOH。
According to an embodiment of the invention, the molecular formula of the titanyl cluster compound is
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 invention, the molecular formula of the titanyl cluster compound is
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 present invention, the organic acid is monoacid or polyacid；The polyacid is binary acid or ternary or more
Acid.
In the present invention, the residue refers to that organic acid removes remaining group after the hydrogen on whole carboxyls, such as formic acid
Residue be HOC (=O)-, the residue of acetic acid is CH3C (=O) O-, the residue of propionic acid are CH3CH2C (=O) O-, glutaric acid
Residue is-O (O=C) CH2CH2CH2C (=O) O-.
Specifically, the molecular formula of the titanyl cluster compound is C164H288O180Ti44, being denoted as titanyl cluster compound a, Mr is
7247.53；The crystallographic system of the crystalline state object of the titanyl cluster compound a is anorthic system, and space group isCell parameter a isB isC isα is 74.63 °, and β is 84.42 °, and γ is 76.43 °, and V is
The crystalline state object of the titanyl cluster compound a have basically as in Figure 2 shown in X-ray powder diffraction figure.
The crystal parameter of the crystalline state object of the titanyl cluster compound a is as shown in table 1:
Table 1
Specifically, the molecular formula of the titanyl cluster compound is C172H300O184Ti44, being denoted as titanyl cluster compound b, Mr is
7418.26；The titanyl cluster compound b is pure phase without color strip-shaped crystalline state object；The crystallographic system of the crystalline state object of the titanyl cluster compound b is
Anorthic system, space group areCell parameter a isB isC isα is 74.3 °, and β is
81.9 °, γ is 75.6 °, and V is
The crystalline state object of the titanyl cluster compound b has X-ray powder diffraction figure substantially as shown in FIG. 6.
The crystal parameter of the crystalline state object of the titanyl cluster compound b is as shown in table 2:
Table 2
According to the present invention, the titanyl cluster compound is pure phase without color strip-shaped crystalline state object.
According to the present invention, the titanyl cluster compound is hybrid inorganic-organic compound.
According to the present invention, the cluster core of the crystalline state object of the titanyl cluster compound is having a size of 2.8 ± 0.2nm.
According to the present invention, the crystalline state object of the titanyl cluster compound has symmetrical structure.
The second aspect of the present invention is to provide a kind of method for preparing above-mentioned titanyl cluster compound, and the method includes following steps
It is rapid: titanium salt, organic acid A and organic acid B being mixed, carry out solvent thermal reaction to get the titanyl cluster compound is arrived.
According to the present invention, the method specifically includes the following steps:
1) titanium salt, organic acid A and organic acid B are mixed, carries out solvent thermal reaction, obtains mixture；
2) mixture obtained after step 1) reaction is separated, solid phase therein is titanyl cluster compound.
According to the present invention, the titanium salt is that titanium ion and alcohol slough the compound formed after the hydrogen on alcoholic extract hydroxyl group.
According to the present invention, the titanium salt is titanium ethanolate, tert-butyl alcohol titanium, titanium isobutoxide, n-butyl titanium, normal propyl alcohol titanium and isopropyl
One of alcohol titanium or multiple combinations, preferably isopropyl titanate.
According to the present invention, the organic acid A is selected from containing 1-40 carbon atom (such as 1-30 carbon atom, 1-20 carbon original
Son, 1-10 carbon atom, 1-6 carbon atom) acid or acid mixture.
Preferably, the organic acid A is in formic acid, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid or glutaric acid etc.
It is one or two kinds of；Preferably formic acid and/or glutaric acid.
According to the present invention, the organic acid B is selected from containing 1-30 carbon atom (such as 1-20 carbon atom, 1-10 carbon original
Son, 1-6 carbon atom) acid or sour mixture.
Preferably, the organic acid B be selected from formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, n-caproic acid, octanoic acid,
Adipic acid, ethanedioic acid, malonic acid, succinic acid or in which two or more any mixture.
As example, the organic acid B can be selected from acetic acid, propionic acid, butyric acid or in which the mixture of two or more,
Such as the mixture of propionic acid or propionic acid and acetic acid or propionic acid and butyric acid.
According to the present invention, the organic acid A and organic acid B are identical or different；Illustratively, the organic acid A is selected from first
When sour, the organic acid B can be independently chosen from formic acid, can also be selected from the mixture of formic acid and other organic acids, can also select
From other organic acids in addition to formic acid.
According to the present invention, the molar ratio of the titanium salt and the organic acid A are 1:(0.01-1), for example, 1:(0.1-
0.8), specific such as 1:(0.2-0.5).
According to the present invention, the molar ratio of the titanium salt and the organic acid B are 1:(0.01-1), for example, 1:(0.02-
0.5), specific such as 1:(0.03-0.3).
According to the present invention, the temperature of the solvent thermal reaction is 40~160 DEG C；Preferably 60~100 DEG C, such as 70~90
DEG C, such as 80 DEG C.If reaction temperature is too low, it will lead to that the reaction time is longer, and crystalline size is smaller.
According to the present invention, the time of the solvent thermal reaction is 24~240 hours；Preferably 48~150 hours, such as 72 is small
When, 120 hours.
It as a preferred embodiment of the present invention, can be reacted at 80 DEG C 72 hours or 96 hours, or 100
It is reacted 48 hours or 72 hours at DEG C.
According to the present invention, step 1) specifically includes: after the titanium salt, organic acid A and organic acid B are mixed, stirring, places
In vial or polytetrafluoroethylene (PTFE) pressure vessel, isothermal reaction is then cooled to room temperature.
According to the present invention, in step 2), isolated solid phase is cleaned；
Preferably, the solid phase after separation is cleaned using water, acid or alcohol, room temperature is dried.
According to the present invention, the yield of the titanyl cluster compound is up to 90% or more.
According to the invention, it is further possible to which sodium hydroxide, chlorination are added into the mixed system of titanium salt, organic acid A and organic acid B
Potassium, water or hydrogen peroxide.
The addition of the sodium hydroxide, potassium chloride, water or hydrogen peroxide helps reactive material as one kind, promote reaction into
Row, there is no particular limitation for dosage, the conventional selection of those skilled in the art, for example, the 0.05- of target product
5wt%.
According to the present invention, the titanyl cluster compound of above-mentioned first aspect is prepared by the method for above-mentioned second aspect
's.
The third aspect of the present invention is to provide a kind of purposes of above-mentioned titanyl cluster compound, can be used for splitting water, degradation dirt
It contaminates in object or electronic device (such as solar battery).
Beneficial effect
The present invention provides a kind of novel materials, i.e. hybrid inorganic-organic titanyl cluster compound, are symmetrical structure, cluster
Core size is about 2.8 ± 0.2nm, and the titanyl cluster compound has efficient, stable photodissociation aquatic products hydrogen activity, can be used for cracking
The fields such as water, contaminant degradation or electronic device.
The present invention also provides a kind of completely new methods for preparing titanyl cluster compound, utilize solvent-thermal process method, as
Heating reaction is carried out in a solvent, reaction raw materials are simply mixed, and by a step self-assembling reaction, can be obtained the titanyl cluster
Close object.The synthesis of this method requires simple, and low to the purity requirement of raw material, raw material is easy and cheap, raw materials used
It can not need further to purify, and yield is up to 90% or more, be conducive to large-scale production by buying chemically pure reagent.
In addition, the post-processing of this method is simple and easy, it is only necessary to by simply washing, pickling or alcohol wash separation, room temperature, which is dried, to be obtained
To the crystalline products of pure phase.Further more, this method pollution is few, meet environment protection requirement.
Detailed description of the invention
Fig. 1 is the crystal structure schematic diagram of the crystalline products prepared in embodiment 1；
Fig. 2 is the X-ray powder diffraction figure of the crystalline products prepared in embodiment 1, and every line respectively represents from bottom to top
The powder diagram of simulation, crystal are put in air first day, and second day, the powder diagram in third day；Wherein, theoretical value is
The X-ray powder diffraction figure simulated according to crystal structure；Experiment value is the X tested on x-ray powder diffraction instrument
Ray powder diffraction pattern；
Fig. 3 is the infrared spectrogram of the crystalline products prepared in embodiment 1；
Fig. 4 is the product photo of the crystalline products prepared in embodiment 1；
Fig. 5 is the crystal structure schematic diagram of the crystalline products prepared in embodiment 2；
Fig. 6 is the X-ray powder diffraction figure of the crystalline products prepared in embodiment 2, and every line respectively represents from bottom to top
The powder diagram of simulation, crystal are put in air first day, and second day, the powder diagram in third day；Wherein, theoretical value is
The X-ray powder diffraction figure simulated according to crystal structure；Experiment value is the X tested on x-ray powder diffraction instrument
Ray powder diffraction pattern；
Fig. 7 is the infrared spectrogram of the crystalline products prepared in embodiment 2；
Fig. 8 is the product photo of the crystalline products prepared in embodiment 2.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Unless otherwise indicated, reagent used in the present invention is commercially available.
Mono-crystalline structures parsing of the invention uses the supernova single crystal diffractometer of Rigaku.
The radiographic source that X-ray powder diffraction figure uses is Cu-K alpha ray.
Embodiment 1
Isopropyl titanate (3.3mmol), formic acid (26.5mmol), propionic acid (73.6mmol) are placed in 20ml vial, room temperature
Lower to be uniformly mixed, the constant temperature 3 days in 80 DEG C of baking ovens takes out, and cooled to room temperature is isolated solid phase and rinsed again with propionic acid, i.e.,
It obtains without color strip-shaped crystalline state target product.A small amount of sodium hydroxide, potassium chloride etc. are added in reaction system, or a small amount of water and mistake is added
Such crystalline product can be obtained in hydrogen oxide.
As can be seen from Figure 1 this compound has 44 titanium atoms, in addition to two formic acid and two it is water base with external,
Remaining ligand is entirely propionic acid ligand；
As can be seen from Figure 2 this compound can at least be stablized three days in air；
As can be seen from Figure 3 the vibration performance peak of this compound Ti-O cluster core is in 1000-500cm-1, organic with ligand
Vibration performance peak 3500-1000cm-1；
As can be seen from Figure 4 this compound is no color strip-shaped.
Embodiment 2
Isopropyl titanate (3.3mmol), glutaric acid (1.5mmol), propionic acid (73.6mmol) are placed in 20ml vial, room temperature
Lower to be uniformly mixed, the constant temperature 3 days in 80 DEG C of baking ovens takes out, and cooled to room temperature is isolated solid phase and rinsed again with propionic acid, i.e.,
It obtains without color strip-shaped crystalline state target product.A small amount of sodium hydroxide, potassium chloride etc. are added in reaction system, or a small amount of water and mistake is added
Such crystalline product can be obtained in hydrogen oxide etc..
As can be seen from Figure 5 this compound has 44 titanium atoms, in addition to two glutaric acids and two it is water base with external,
Remaining ligand is entirely propionic acid ligand；
As can be seen from Figure 6 this compound can at least be stablized three days in air；
As can be seen from Figure 7 the vibration performance peak of this compound Ti-O cluster core is in 1000-500cm-1, organic with ligand
Vibration performance peak 3500-1000cm-1；
As can be seen from Figure 8 this compound is no color strip-shaped.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of titanyl cluster compound, which is characterized in that the molecular formula of the titanyl cluster compound are as follows:
H8{Ti44(μ2-O)36(μ3-O)30(B)n(A)2(H2O)2}·xB’
Wherein, μ2- O represents the O atom of two connections, μ3- O represents the O atom of three connections；
A is identical or different, is independently from each other the residue of the organic acid of C1-C40；
B is identical or different, is independently from each other the residue of the organic acid of C1-C30；
B ' is identical or different, is independently from each other the organic acid of C1-C30；
X is the quantity of the B molecule of free state, the integer between 0-10；
When two A are selected from monoacid, n 50；
When an A is selected from monoacid, and an A is selected from polyacid, n 49；
When two A are selected from polyacid, n 48.
2. titanyl cluster compound according to claim 1, which is characterized in that the A is identical or different, is independently from each other
The residue of the organic acid of C1-C30；Such as the residue of the organic acid selected from C1-C20；Such as organic acid selected from C1-C10 again
Residue；The also such as residue of the organic acid selected from C1-C6；
Preferably, the A is identical or different, is independently from each other 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 HOC (=O)-or-O (O=C) CH2CH2CH2C (=O) O-.
Preferably, the B is identical or different, is independently from each other the residue of the organic acid of C1-C20；Such as selected from C1-C10
Organic acid residue；The residue of organic acid selected from C1-C6；
Preferably, the B is identical or different, is independently from each other 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-；
Preferably, the B ' is identical or different, is independently from each other the organic acid of C1-C20；Such as selected from the organic of C1-C10
Acid；Organic acid selected from C1-C6；
Preferably, the B ' is identical or different, is independently from each other 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；It is preferred that
For CH3COOH。
3. titanyl cluster compound according to claim 1 or 2, which is characterized in that the molecular formula of the titanyl cluster compound is 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.
Preferably, the molecular formula of the titanyl cluster compound is
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。
4. titanyl cluster compound according to claim 1-3, which is characterized in that the molecular formula of the titanyl cluster compound
For C164H288O180Ti44, it is denoted as titanyl cluster compound a, Mr 7247.53；The crystallographic system of the crystalline state object of the titanyl cluster compound a is three
Oblique system, space group areCell parameter a isB is C isα is 74.63 °, and β is
84.42 °, γ is 76.43 °, and V is
The crystal parameter of the crystalline state object of the titanyl cluster compound a is as shown in table 1:
Table 1
5. titanyl cluster compound according to claim 1-3, which is characterized in that the molecular formula of the titanyl cluster compound
For C172H300O184Ti44, it is denoted as titanyl cluster compound b, Mr 7418.26；The titanyl cluster compound b is pure phase without color strip-shaped crystalline substance
State object；The crystallographic system of the crystalline state object of the titanyl cluster compound b is anorthic system, and space group isCell parameter a isB isC isα is 74.3 °, and β is 81.9 °, and γ is 75.6 °, and V is
The crystal parameter of the crystalline state object of the titanyl cluster compound b is as shown in table 2:
Table 2
6. titanyl cluster compound according to claim 1-5, which is characterized in that the titanyl cluster compound is pure phase
Without color strip-shaped crystalline state object.
Preferably, the titanyl cluster compound is hybrid inorganic-organic compound.
Preferably, the cluster core of the crystalline state object of the titanyl cluster compound is having a size of 2.8 ± 0.2nm.
Preferably, the crystalline state object of the titanyl cluster compound has symmetrical structure.
7. a kind of method for preparing titanyl cluster compound described in any one of claims 1-6, the described method comprises the following steps: will
Titanium salt, organic acid A and organic acid B mixing carry out solvent thermal reaction to get the titanyl cluster compound is arrived.
Preferably, the method specifically includes the following steps:
1) titanium salt, organic acid A and organic acid B are mixed, carries out solvent thermal reaction, obtains mixture；
2) mixture obtained after step 1) reaction is separated, solid phase therein is titanyl cluster compound.
8. preparation method according to claim 7, which is characterized in that the titanium salt is titanium ethanolate, tert-butyl alcohol titanium, isobutanol
One of titanium, n-butyl titanium, normal propyl alcohol titanium and isopropyl titanate or multiple combinations, preferably isopropyl titanate.
Preferably, the organic acid A is selected from that (such as 1-30 carbon atom, 1-20 carbon atom, 1-10 are a containing 1-40 carbon atom
Carbon atom, 1-6 carbon atom) acid or acid mixture.
Preferably, the organic acid A is selected from one of formic acid, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid or glutaric acid etc.
Or two kinds；Preferably formic acid and/or glutaric acid.
Preferably, the organic acid B is selected from that (such as 1-20 carbon atom, 1-10 carbon atom, 1-6 are a containing 1-30 carbon atom
Carbon atom) acid or acid mixture.
Preferably, the organic acid B be selected from formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, n-caproic acid, octanoic acid, oneself two
Acid, ethanedioic acid, malonic acid, succinic acid or in which two or more any mixture.
Preferably, the molar ratio of the titanium salt and the organic acid A are 1:(0.01-1), for example, 1:(0.1-0.8), specifically such as
1:(0.2-0.5)；The molar ratio of the titanium salt and the organic acid B are 1:(0.01-1), for example, 1:(0.02-0.5), specifically
Such as 1:(0.03-0.3).
Preferably, the temperature of the solvent thermal reaction is 40~160 DEG C；Preferably 60~100 DEG C, such as 70~90 DEG C, such as 80
℃；The time of the solvent thermal reaction is 24~240 hours；Preferably 48~150 hours, such as 72 hours, 120 hours.
Preferably, it can react at 80 DEG C 72 hours or 96 hours, or be reacted 48 hours or 72 hours at 100 DEG C.
Preferably, can also be added into the mixed system of titanium salt, organic acid A and organic acid B sodium hydroxide, potassium chloride, water or
Hydrogen peroxide.
9. titanyl cluster compound described in any one of claims 1-6 is prepared by any one of claim 7-8 the method
It arrives.
10. the purposes of the described in any item titanyl cluster compounds of claim 1-6 or 9, can be used for splitting water, degradation of contaminant or
In electronic device (such as solar battery).
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| CN112029212A (en) * | 2020-08-10 | 2020-12-04 | 厦门大学 | Gel polymer electrolyte containing ligand-modified cluster and preparation method thereof |
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| CN110975860A (en) * | 2019-11-12 | 2020-04-10 | 河北地质大学 | Chromium-doped titanium-oxygen cluster nano catalytic material, preparation method and application |
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| CN111573773A (en) * | 2020-05-27 | 2020-08-25 | 齐鲁工业大学 | Application of titanium-based coordination polymer in photocatalytic degradation of dye wastewater |
| CN111786024A (en) * | 2020-06-22 | 2020-10-16 | 厦门大学 | Titanium oxygen cluster based solid polymer electrolyte and preparation method and application thereof |
| CN111804344A (en) * | 2020-07-15 | 2020-10-23 | 江苏师范大学 | Calixarene-based titanium oxide cluster compound, preparation method thereof and application thereof in dye photodegradation |
| 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 |
| CN111790451A (en) * | 2020-08-04 | 2020-10-20 | 江苏师范大学 | Dissimilar metal titanium-oxygen cluster crystalline material, preparation method thereof and application thereof in dye photodegradation |
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| CN111943976A (en) * | 2020-08-07 | 2020-11-17 | 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 |
| 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 |
| CN112029212A (en) * | 2020-08-10 | 2020-12-04 | 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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