A copper-doped aluminum oxide cluster layered material, its preparation method and applications

Abstract

This invention provides a copper-doped aluminum oxide cluster compound, its preparation method, and its uses. The molecular formula of the copper-doped aluminum oxide cluster compound is [Al8Cu3(μ2-OH)4(A)]. 12 [(B)8(C)4], wherein μ2-OH represents a di-linked OH; A is the same or different, independently selected from residues of unsubstituted or substituted organic acids; B is the same or different, independently selected from residues of organic alcohols or derivatives containing organic alcohol groups; C is the same or different, independently selected from halide ions. Copper-doped aluminum oxide clusters are obtained by mixing reactants using a solvothermal synthesis method followed by a one-step self-assembly reaction. This method has simple synthesis requirements, low purity requirements for raw materials, readily available and inexpensive raw materials, a yield of over 40%, and can be synthesized in large quantities, facilitating large-scale production. The aluminum oxide clusters of this invention can be used in ceramics, pharmaceuticals, electronics, and other fields.

Description

Technical Field

[0001] This invention belongs to the field of crystal material preparation technology, and relates to a copper-doped aluminum oxide cluster layered material, its preparation method, synthesis, and application. Specifically, it relates to a copper-doped aluminum oxide cluster compound, its large-scale synthesis method, and its application. Background Technology

[0002] Aluminum is one of the most abundant metallic elements in the Earth's crust, playing a crucial role in environmental protection and a sustainable economy. Widely found in various soils and minerals, aluminum is extensively studied by researchers in environmental chemistry, geochemistry, and biochemistry due to its high natural abundance and excellent industrial applications. The structure-property relationship of aluminum-based materials has also been a hot research topic; however, achieving rational structural design and improving the performance of aluminum-based materials to broaden their application areas is quite challenging. Therefore, designing and synthesizing crystalline aluminum-oxygen cluster materials with atomically precise structures is of paramount importance.

[0003] Compared to the aqueous chemistry of aluminum-based materials, research on aluminum oxide clusters in organic phases is relatively limited. Aluminum salts hydrolyze rapidly and are difficult to control, readily forming aluminum hydroxides, thus making aluminum oxide clusters difficult to obtain. The synthesis of metal oxide clusters is accidental and random; due to the uncertainty of the reaction process, cluster compounds with ideal structures are often difficult to obtain. Currently, the types of reported aluminum oxide clusters are limited, and the performance development of aluminum-based materials is still incomplete. Therefore, the development of new aluminum oxide clusters is of great significance. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a copper-doped aluminum oxide cluster layered crystalline material, its preparation method, and its applications. The synthesis of the aluminum oxide cluster compound of this invention exhibits high reproducibility, and the method is simple, efficient, and meets green and environmentally friendly requirements.

[0005] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0006] This invention provides a copper-doped aluminum oxide cluster compound, the molecular formula of which is:

[0007] [Al8Cu3(μ2-OH)4(A) 12 (B)8(C)4]

[0008] Wherein, μ2-OH represents a di-linked OH;

[0009] A is the same or different, and is independently selected from residues of organic acids (such as nicotinic acid) or residues of organic acids containing substituents (such as nicotinic acid).

[0010] According to an embodiment of the present invention, the "substituent" in the residue of the nicotinic acid containing the substituent is selected from at least one of hydroxyl, C1-6 alkyl, C1-6 alkoxy, amino, nitro, and halogen atom.

[0011] According to an embodiment of the invention, the A residues are the same or different and are independently selected from residues of organic acids (such as nicotinic acid).

[0012] According to embodiments of the present invention, the B residues are the same or different and are independently selected from residues of organic alcohols or derivatives containing organic alcohol groups.

[0013] Preferably, the organic alcohol is selected from one or more combinations of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, n-butanol, tert-butanol, and n-pentanol, and more preferably n-propanol.

[0014] According to embodiments of the present invention, the C may be the same or different and is independently selected from inorganic acid radical ions; for example, selected from anaerobic inorganic acid radical ions; for example, selected from halide ions.

[0015] According to an embodiment of the present invention, the C may be the same or different, and is independently selected from one or more combinations of chloride ions, bromide ions, and iodide ions, more preferably chloride ions.

[0016] According to an exemplary embodiment of the present invention, the molecular formula of the aluminum oxide cluster is [Al8Cu3(μ2-OH)4(A)]. 12 (B)8(C)4]

[0017] Where A is a residue of nicotinic acid; B is a residue of n-propanol; and C is a chloride ion.

[0018] Specifically, the molecular formula of the copper-doped aluminum oxide cluster is C2. 96 H 104 O 36 N 12 Cl4Al8Cu3, denoted as aluminum oxide cluster a, has a Mr of 2550.20.

[0019] According to an embodiment of the present invention, the copper-doped aluminum oxide cluster compound is an organic-inorganic hybrid compound.

[0020] This invention also provides a copper-doped aluminum oxide cluster crystal, the molecular formula of which is:

[0021] [Al8Cu3(μ2-OH)4(A) 12 (B)8(C)4]

[0022] Wherein, μ2-OH represents a di-linked OH;

[0023] A is the same or different, and is independently selected from residues of organic acids (such as nicotinic acid) or residues of organic acids containing substituents (such as nicotinic acid).

[0024] According to an embodiment of the present invention, the "substituent" in the residue of the nicotinic acid containing the substituent is selected from at least one of hydroxyl, C1-6 alkyl, C1-6 alkoxy, amino, nitro, and halogen atom.

[0025] According to an embodiment of the invention, the A residues are the same or different and are independently selected from residues of organic acids (such as nicotinic acid).

[0026] According to embodiments of the present invention, the B residues are the same or different and are independently selected from residues of organic alcohols or derivatives containing organic alcohol groups.

[0027] Preferably, the organic alcohol is selected from one or more combinations of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, n-butanol, tert-butanol, and n-pentanol, and more preferably n-propanol.

[0028] According to embodiments of the present invention, the C may be the same or different and is independently selected from inorganic acid radical ions; for example, selected from anaerobic inorganic acid radical ions; for example, selected from halide ions.

[0029] According to an embodiment of the present invention, the C may be the same or different, and is independently selected from one or more combinations of chloride ions, bromide ions, and iodide ions, more preferably chloride ions.

[0030] According to an embodiment of the present invention, the aluminum oxide cluster crystal has substantially the following characteristics: Figure 5 The shape shown.

[0031] According to an embodiment of the present invention, the aluminum oxide cluster crystal is assembled from an octet of aluminum oxide rings and copper halide clusters connected by organic acid A.

[0032] Preferably, the octet aluminum oxide ring cluster is coordinated with organic acid residue A and organic alcohol B.

[0033] Preferably, the copper halide cluster is a combination of copper atoms and halogen atoms.

[0034] According to an exemplary embodiment of the present invention, the molecular formula of the aluminum oxide cluster crystal is:

[0035] [Al8Cu3(μ2-OH)4(A) 12 (B)8(C)4]

[0036] Where A is a residue of nicotinic acid; B is a residue of n-propanol; and C is a chloride ion.

[0037] Specifically, the molecular formula of the copper-doped aluminum oxide cluster crystal is C0. 96 H104 O 36 N 12 Cl4Al8Cu3, denoted as aluminum oxide cluster a, has a Mr of 2550.20.

[0038] According to an embodiment of the present invention, the aluminum-oxygen cluster crystal has a monoclinic crystal system, a space group of P21 / n, and a cell parameter a. b is c is α is 90°, β is 90.55°, γ is 90°, and V is...

[0039] According to an embodiment of the present invention, the copper-doped aluminum oxide cluster crystal has substantially the following properties: Figure 2 The X-ray powder diffraction pattern shown.

[0040] According to an embodiment of the present invention, the crystal parameters of the copper-doped aluminum oxide cluster crystal are shown in Table 1:

[0041] Table 1

[0042]

[0043] According to an embodiment of the present invention, the copper-doped aluminum oxide cluster crystal is a pure-phase transparent yellow layered crystalline material.

[0044] According to an embodiment of the present invention, the copper-doped aluminum oxide cluster crystal has a symmetrical structure.

[0045] The present invention also provides a method for preparing the above-mentioned copper-doped aluminum oxide clusters and / or copper-doped aluminum oxide cluster crystals, wherein the preparation method includes mixing aluminum salt, copper salt, organic acid A, quaternary ammonium salt, organic alcohol, oxygen-containing six-membered heterocyclic compound, and organic amine, and then reacting them with a solvothermal reaction to obtain copper-doped aluminum oxide clusters and / or copper-doped aluminum oxide cluster crystals.

[0046] Wherein, the residues of the organic acid form A in the molecular formula, the organic alcohol forms B in the molecular formula, and the anion in the copper salt forms C in the molecular formula.

[0047] According to an embodiment of the present invention, the aluminum salt is a compound formed by aluminum ions and the removal of hydrogen from the hydroxyl group of an alcohol.

[0048] According to an embodiment of the present invention, the aluminum salt is one or more combinations of aluminum ethoxide, aluminum tert-butoxide, aluminum isobutoxide, aluminum n-butoxide, aluminum n-propoxide, and aluminum isopropoxide, preferably aluminum isopropoxide.

[0049] According to an embodiment of the present invention, the copper salt is one or more combinations of copper chloride, cuprous chloride, copper fluoride, copper iodide, and cuprous iodide, preferably cuprous chloride.

[0050] According to an embodiment of the present invention, the organic acid A is selected from carboxylic acids or mixtures of carboxylic acids containing nitrogen-containing five- or six-membered organic aromatic rings (e.g., nitrogen-containing six-membered organic aromatic rings, nitrogen-containing six-membered organic aromatic rings containing substituents) without substitution or with substituents, preferably nicotinic acid.

[0051] According to an embodiment of the present invention, the quaternary ammonium salt is one or more combinations of tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium hydroxide, hexamethylenetetramine tribromide, and hexamethylenetetramine, preferably hexamethylenetetramine.

[0052] According to an embodiment of the present invention, the organic alcohol is one or more combinations of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, n-butanol, tert-butanol, and n-pentanol, preferably n-propanol.

[0053] According to an embodiment of the present invention, the oxygen-containing six-membered heterocyclic compound is selected from 1,4-dioxane.

[0054] According to an embodiment of the present invention, the organic amine is selected from one or more combinations of methylamine aqueous solution, methylamine ethanol solution, ethylenediamine, triethylamine, n-propylamine, 1,2-propanediamine, and isopropylamine, preferably methylamine ethanol solution.

[0055] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the copper salt is 1:(0.01-3), for example 1:(0.05-2), preferably 1:(0.1-1.5), and exemplary ratios are 1:0.01, 1:0.05, 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, and 1:3.

[0056] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the organic acid A is 1:(0.01-3), for example 1:(0.05-2), preferably 1:(0.1-1.5), and exemplary ratios are 1:0.01, 1:0.05, 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, and 1:3.

[0057] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the quaternary ammonium salt is 1:(0.01-3), for example 1:(0.05-2), preferably 1:(0.1-1.5), and exemplary ratios are 1:0.01, 1:0.05, 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, and 1:3.

[0058] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the oxygen-containing six-membered heterocyclic compound is 1:(0.01-50), for example 1:(0.1-50), preferably 1:(1-40), and exemplary ratios are 1:0.01, 1:0.1, 1:0.5, 1:1, 1:2, 1:5, 1:10, 1:20, 1:40, and 1:50.

[0059] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the organic alcohol is 1:(0.01-100), for example 1:(0.1-90), preferably 1:(1-90), and exemplary ratios are 1:0.01, 1:0.1, 1:0.5, 1:1, 1:2, 1:5, 1:10, 1:20, 1:40, 1:50, 1:90, and 1:100.

[0060] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the organic ammonium is 1:(0.01-10), for example 1:(0.05-5), preferably 1:(0.1-5), and exemplary ratios are 1:0.01, 1:0.05, 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:3, 1:4, 1:5, 1:8, and 1:10.

[0061] According to an embodiment of the present invention, the temperature of the solvothermal reaction is 40–160°C; preferably 60–130°C, for example 70–100°C, with exemplary values ​​of 60°C, 70°C, 80°C, 100°C, and 130°C. If the reaction temperature is too low, the reaction time will be longer and the crystal size will be smaller.

[0062] According to an embodiment of the present invention, the solvothermal reaction time is 48 to 168 hours; preferably 48 to 150 hours, such as 48 hours, 60 hours, 72 hours, 96 hours, 120 hours, or 168 hours.

[0063] In a preferred embodiment of the present invention, the solvothermal reaction can be carried out at 80°C for 120 hours or 168 hours, or at 100°C for 72 hours or 96 hours.

[0064] According to an embodiment of the present invention, step 1) specifically includes: mixing the aluminum salt, copper salt, organic acid A, quaternary ammonium salt, oxygen-containing six-membered heterocyclic compound, organic alcohol, and organic amine, stirring, and reacting at a constant temperature in a glass bottle or polytetrafluoroethylene pressure vessel, and then cooling to room temperature.

[0065] Preferably, a isothermal reaction refers to a reaction that is allowed to stand at a constant temperature, such as a reaction in a heating device (e.g., an oven) with a constant temperature.

[0066] According to an embodiment of the present invention, the preparation method further includes separating the product obtained from the solvothermal reaction to obtain a crystalline substance, and then washing it.

[0067] Preferably, the separated crystalline material is washed with water or alcohol and then air-dried at room temperature.

[0068] Preferably, the alcohol is selected from at least one of low-boiling-point alcohols, such as at least one of methanol, ethanol, or n-propanol.

[0069] According to embodiments of the present invention, the yield of the copper-doped aluminum oxide cluster compound can reach 30% or more, for example, 40%, 50%, 60%, 70%, 80%, or 90%.

[0070] According to an embodiment of the present invention, the method for preparing the copper-doped aluminum oxide cluster compound and / or the above-mentioned copper-doped aluminum oxide cluster compound crystal includes the following steps:

[0071] 1) The aluminum salt, copper salt, organic acid A, quaternary ammonium salt, organic alcohol, oxygen-containing six-membered heterocyclic compound, and organic amine are mixed and subjected to a solvothermal reaction to obtain a mixture;

[0072] 2) The mixture obtained after the reaction in step 1) is separated and washed to obtain (yellow transparent layered crystals) copper-doped aluminum oxide clusters and / or copper-doped aluminum oxide cluster crystals.

[0073] The present invention also provides aluminum oxide clusters and / or copper-doped aluminum oxide cluster crystals prepared by the above preparation method.

[0074] The present invention also provides applications of the above-mentioned aluminum oxide clusters and / or copper-doped aluminum oxide cluster crystals in ceramics, medicine, electronics and other fields.

[0075] According to embodiments of the present invention, the aluminum oxide clusters and / or copper-doped aluminum oxide cluster crystals are used as nonlinear optical materials, adsorbents, or catalysts (supports).

[0076] The present invention also provides a nonlinear optical material, the nonlinear optical material comprising the above-mentioned copper-doped aluminum oxide clusters and / or copper-doped aluminum oxide cluster crystals.

[0077] Beneficial effects:

[0078] Copper atoms possess high symmetry and readily coordinate with atoms such as N, O, and S, with coordination numbers ranging from three to six coordinations, and even extending to Cu-Cu bonds. Furthermore, copper is inexpensive and readily available, and exhibits diverse coordination geometries. Research on aluminum-oxygen clusters doped with other metal elements contributes to a deeper understanding of their structure-property relationships. Therefore, this invention develops a copper-doped aluminum-oxygen cluster with high reproducibility and a novel structure. Specifically:

[0079] This invention provides a novel type of organic-inorganic hybrid copper-doped aluminum oxide cluster compound with a symmetrical structure. The aluminum oxide cluster compound can be used as a nonlinear optical material, catalyst (support) or adsorbent, and can be applied in ceramics, medicine, electronics and other fields.

[0080] This invention also provides a method for preparing copper-doped aluminum oxide clusters, particularly a method for their large-scale preparation. This invention utilizes a solvothermal synthesis method, where a heated reaction is carried out in a solvent. The reactants are simply mixed, and the copper-doped aluminum oxide clusters are obtained through a one-step self-assembly reaction. The synthesis method of this invention is simple, has low purity requirements for the raw materials, and the raw materials are readily available and inexpensive. All raw materials can be purchased with chemically pure reagents, eliminating the need for further purification, thus facilitating large-scale production. Furthermore, the post-processing of this method is simple and easy to perform, requiring only simple alcohol washing and separation, followed by air drying at room temperature to obtain a pure-phase crystalline product. Moreover, the method uses inexpensive raw materials, produces minimal pollution, and meets green environmental protection requirements. Attached Figure Description

[0081] Figure 1 This is a schematic diagram of the crystal structure of the crystalline product prepared in Example 1;

[0082] Figure 2 X-ray powder diffraction pattern of the crystalline product prepared in Example 1; wherein, the theoretical value is the X-ray powder diffraction pattern obtained by simulating the crystal structure; and the experimental value is the X-ray powder diffraction pattern obtained by testing on an X-ray powder diffractometer.

[0083] Figure 3 The infrared spectrum of the crystalline product prepared in Example 1;

[0084] Figure 4 Thermogravimetric analysis (TGA) diagram of the crystalline product prepared in Example 1;

[0085] Figure 5 X-ray photoelectron spectroscopy analysis of the crystalline product prepared in Example 1;

[0086] Figure 6 A photograph of the crystalline product prepared in Example 1;

[0087] Figure 7The image shown is a scanning electron microscope image of the crystalline product prepared in Example 1.

[0088] Figure 8 It is the aluminum oxide cluster compound a(C) prepared in Example 1. 96 H 104 O 36 N 12 A figure showing the third-order nonlinear optical properties of Cl4Al8Cu3.

[0089] Figure 9 This is a schematic diagram of the crystal structure of the crystalline product prepared in Example 2;

[0090] Figure 10 The infrared spectrum of the crystalline product prepared in Example 2;

[0091] Figure 11 Thermogravimetric analysis (TGA) diagram of the crystalline product prepared in Example 2;

[0092] Figure 12 X-ray photoelectron spectroscopy analysis of the crystalline product prepared in Example 2;

[0093] Figure 13 A photograph of the crystalline product prepared in Example 2;

[0094] Figure 14 The image shown is a scanning electron microscope image of the crystalline product prepared in Example 2. Detailed Implementation

[0095] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Furthermore, it should be understood that after reading the disclosure of this invention, those skilled in the art can make various modifications or alterations to the present invention, and these equivalent forms also fall within the scope of protection defined by this invention.

[0096] Unless otherwise stated, all reagents used in this invention are commercially available.

[0097] The single-crystal structure analysis of this invention was performed using a Rigaku Metal Jet D2 single-crystal diffractometer from Japan.

[0098] The X-ray source used in the powder diffraction pattern was Cu-Kα rays.

[0099] Example 1

[0100] Preparation of aluminum oxide cluster compound a

[0101] Aluminum isopropoxide (1.47 mmol), cuprous chloride (1 mmol), nicotinic acid (1.62 mmol), hexamethylenetetramine (1.07 mmol), 1,4-dioxane (3 mL), n-propanol (5 mL), and methylamine ethanol solution (300 μL) were placed in a 20 mL glass bottle and mixed thoroughly at room temperature. The mixture was then incubated at 100 °C for 3 days. After incubation, the mixture was removed, allowed to cool naturally to room temperature, and the crystalline product was separated. The product was then washed with n-propanol and air-dried to obtain the yellow layered crystalline target product. The yield was approximately 60% (based on the mass of aluminum isopropoxide).

[0102] Figure 1 This is a schematic diagram of the crystal structure of the crystalline product prepared in Example 1; from Figure 1 As can be seen from the data, this compound has 8 aluminum atoms and 3 copper atoms. The ligands around the aluminum atom ring are nicotinic acid and n-propanol, and the copper atoms are connected to the aluminum atom ring through nicotinic acid.

[0103] Figure 2 The image shows the X-ray powder diffraction pattern of the crystalline product prepared in Example 1; where the theoretical value is the X-ray powder diffraction pattern obtained from crystal structure simulation; and the experimental value is the X-ray powder diffraction pattern obtained by testing on an X-ray powder diffractometer. Figure 2 As can be seen, the compound has high purity and is stable in solvents.

[0104] Figure 3 The infrared spectrum of the crystalline product prepared in Example 1; from Figure 3 The vibrational characteristic peaks of the Al-O cluster nucleus in this compound can be seen to be in the range of 1000-500 cm⁻¹. -1 The vibrational characteristic peaks of organic ligands are in the range of 3500-1000 cm⁻¹. -1 .

[0105] Figure 4 Thermogravimetric analysis (TGA) curve of the crystalline product prepared in Example 1; from Figure 4 As can be seen from the above, if the aluminum oxide cluster prepared in Example 1 is used as a material, its optimal temperature range should be below 100°C. High temperature may cause the aluminum oxide cluster to be unstable.

[0106] Figure 5 X-ray photoelectron spectroscopy analysis of the crystalline product prepared in Example 1; from Figure 5 It can be seen from the data that this compound contains aluminum, copper, carbon, nitrogen, and oxygen.

[0107] Figure 6 A photograph of the crystalline product prepared in Example 1; from Figure 6 As can be seen from the example, the aluminum oxide cluster compound a prepared in Example 1 is a yellow layered crystalline material.

[0108] Figure 7 The image shown is a scanning electron microscope (SEM) image of the crystalline product prepared in Example 1; from Figure 7 The layered morphology of this crystalline material can be seen in the image.

[0109] Example 2

[0110] Preparation of aluminum oxide cluster b

[0111] Aluminum isopropoxide (1.47 mmol), cuprous chloride (1 mmol), nicotinic acid (1.62 mmol), hexamethylenetetramine (1.07 mmol), 1,4-dioxane (3 mL), n-propanol (5 mL), and triethylamine (300 μL) were placed in a 20 mL glass bottle and mixed thoroughly at room temperature. The mixture was then incubated at 100 °C for 3 days. After incubation, the mixture was removed, allowed to cool naturally to room temperature, and the crystalline product was separated. The crystalline product was then washed with n-propanol and air-dried to obtain the green layered crystalline target product. The yield was approximately 30% (based on the mass of aluminum isopropoxide).

[0112] Figure 9 This is a schematic diagram of the crystal structure of the crystalline product prepared in Example 2;

[0113] Figure 10 The infrared spectrum of the crystalline product prepared in Example 2; from Figure 10 The vibrational characteristic peaks of the Al-O cluster nucleus in this compound can be seen to be in the range of 1000-500 cm⁻¹. -1 The vibrational characteristic peaks of organic ligands are in the range of 3500-1000 cm⁻¹. -1 .

[0114] Figure 11 Thermogravimetric analysis (TGA) curve of the crystalline product prepared in Example 2; from Figure 11 As can be seen from the above, if the aluminum oxide cluster prepared in Example 2 is used as a material, its optimal temperature range should be below 100°C. High temperature may cause the aluminum oxide cluster to be unstable.

[0115] Figure 12 X-ray photoelectron spectroscopy analysis of the crystalline product prepared in Example 2; from Figure 12 It can be seen from the data that this compound contains aluminum, copper, carbon, nitrogen, and oxygen.

[0116] Figure 13 A photograph of the crystalline product prepared in Example 2; from Figure 13 As can be seen from the data, the aluminum oxide cluster compound b prepared in Example 1 is a green layered crystalline material.

[0117] Figure 14 The image shown is a scanning electron microscope (SEM) image of the crystalline product prepared in Example 2; from Figure 14 The layered morphology of this crystalline material can be seen in the image.

[0118] Example 3

[0119] Large-scale preparation of aluminum oxide cluster a

[0120] Aluminum isopropoxide (14.7 mmol), cuprous chloride (10 mmol), nicotinic acid (16.2 mmol), hexamethylenetetramine (10.7 mmol), 1,4-dioxane (30 mL), n-propanol (50 mL), and methylamine ethanol solution (3 mL) were placed in a 100 mL glass bottle and mixed thoroughly at room temperature. The mixture was then incubated at 100 °C for 3 days. After removal, the mixture was allowed to cool naturally to room temperature. The crystalline product was separated, washed with n-propanol, and then air-dried to obtain the yellow layered crystalline target product. The yield was approximately 50% (based on the mass of aluminum isopropoxide).

[0121] As can be seen from Examples 1 and 3, the large-scale preparation method of aluminum oxide cluster a of the present invention is simple and easy to operate. It only requires increasing the amount of feed proportionally, which facilitates large-scale production.

[0122] Example 4

[0123] Applications of aluminum oxide clusters a in nonlinear optics

[0124] Five mg of the aluminum oxide cluster a crystal prepared in Example 1 was ultrasonically dispersed in 1 mL of n-propanol solvent to obtain a suspension (with partial dissolution of the crystals) as the sample to be tested. The aperture Z-scan technique was used, with an instrument model NLO-MZ. An Nd:YAG laser was used as the excitation source (repetition frequency 10 Hz, period 8.5 ns, wavelength 532 nm). All measurements were performed at room temperature. The third-order nonlinear optical properties of the crystal dispersed in n-propanol were measured, see [reference needed]. Figure 8 .

[0125] from Figure 8 As can be seen from the data, the Z-scan curve of the sample prepared in Example 2 shows a downward peak, exhibiting anti-saturation absorption characteristics. Its normalized transmittance is 87%, so it can be used as a potential nonlinear optical material (optical limiting material).

[0126] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A copper-doped aluminum oxide cluster compound, characterized in that, The molecular formula of the aluminum oxide cluster is: [Al8Cu3(μ2-OH)4(A) 12 (B)8(C)4] Wherein, μ2-OH represents a di-linked OH; A, whether the residues are the same or different, are independently selected from nicotinic acid residues; B may be the same or different, and are independently selected from n-propanol; C, whether the same or different, are independently selected from chloride ions.

2. A copper-doped aluminum oxide cluster crystal, characterized in that, The molecular formula of the aluminum oxide cluster crystal is: [Al8Cu3(μ2-OH)4(A) 12 (B)8(C)4] Wherein, μ2-OH represents a di-linked OH; A, whether the residues are the same or different, are independently selected from nicotinic acid residues; B may be the same or different, and are independently selected from n-propanol; C, whether the same or different, are independently selected from chloride ions.

3. The copper-doped aluminum oxide cluster crystal according to claim 2, characterized in that... The aluminum oxide cluster crystal is a pure-phase yellow layered crystalline material; And / or, the aluminum oxide cluster crystal has a symmetrical structure; And / or, the aluminum oxide cluster crystal is assembled from an octet of aluminum oxide rings and copper halide clusters connected by organic acid A; And / or, the octanuclear aluminum oxide ring cluster is coordinated with nicotinic acid residue A and n-propanol B on its periphery; And / or, copper halide clusters are coordinated by copper and chlorine atoms.

4. The aluminum oxide cluster crystal according to claim 3, characterized in that, The molecular formula of the aluminum oxide cluster crystal is C 96 H 104 O 36 N 12 Cl4Al8Cu3.

5. The aluminum oxide cluster crystal according to any one of claims 2-4, characterized in that, The crystal system of the aluminum oxide cluster compound is monoclinic, and the space group is [space group number missing]. P2 1 / n The unit cell parameters are a = 12.55 Å, b = 22.17 Å, and c = 24.04 Å. α For 90 o , β It is 90.55 o , γ For 90 o V is 6598.52 Å 3 .

6. The aluminum oxide cluster crystal according to any one of claims 2-4, characterized in that, The relative molecular mass of the aluminum oxide cluster crystal is 2550.

20.

7. The method for preparing the copper-doped aluminum oxide cluster crystal according to claim 1 and / or according to any one of claims 2-6, characterized in that, The preparation method includes: mixing the aluminum salt, copper salt, organic acid A, quaternary ammonium salt, organic alcohol, oxygen-containing six-membered heterocyclic compound, and organic amine, and then reacting them with a solvothermal reaction to prepare copper-doped aluminum oxide clusters and / or copper-doped aluminum oxide cluster crystals. The organic acid A is selected from nicotinic acid; The organic alcohol is n-propanol; The copper salt is copper chloride or cuprous chloride.

8. The preparation method according to claim 7, characterized in that, The aluminum salt is one or more combinations of aluminum ethoxide, aluminum tert-butoxide, aluminum isobutoxide, aluminum n-butoxide, aluminum n-propoxide, and aluminum isopropoxide. And / or, the quaternary ammonium salt is one or more combinations of tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium hydroxide, hexamethylenetetramine tribromide, and hexamethylenetetramine. And / or, the oxygen-containing six-membered heterocyclic compound is selected from 1,4-dioxane; And / or, the organic amine is selected from one or more combinations of aqueous methylamine, ethanolic methylamine, ethylenediamine, triethylamine, n-propylamine, 1,2-propanediamine, and isopropylamine.

9. The preparation method according to claim 7, characterized in that, The molar ratio of the aluminum salt to the copper salt is 1:(0.01-3); And / or, the molar ratio of the aluminum salt to the organic acid A is 1:(0.01-3); And / or, the molar ratio of the aluminum salt to the quaternary ammonium salt is 1:(0.01-3); And / or, the molar ratio of the aluminum salt to the oxygen-containing six-membered heterocyclic compound is 1:(0.01-50); And / or, the molar ratio of the aluminum salt to the organic alcohol is 1:(0.01-100); And / or, the molar ratio of the aluminum salt to the organic ammonium is 1:(0.01-10); And / or, the temperature of the solvothermal reaction is 40~160℃; the time of the solvothermal reaction is 48~168 hours.

10. An aluminum oxide cluster compound and / or copper-doped aluminum oxide cluster compound crystal, characterized in that, It is prepared by the preparation method described in any one of claims 7-9.

11. The use of the aluminum oxide cluster compound of claim 1 and / or the copper-doped aluminum oxide cluster compound crystal of any one of claims 2-6 as a nonlinear optical material.

12. A nonlinear optical material, characterized in that, The nonlinear optical material includes the aluminum oxide cluster as described in claim 1 and / or the copper-doped aluminum oxide cluster crystal as described in any one of claims 2-6.

Images