Aluminum-oxygen cluster carrier catalyst material as well as macro-quantity preparation method and application thereof

Abstract

The invention provides an aluminum-oxygen cluster carrier catalyst material as well as a macro preparation method and application thereof. The molecular formula of the aluminum oxygen cluster carrier catalyst material is [Al3Ag2 (A) 4 (mu2-B) 3]. (Cn), wherein A is the same or different and is independently selected from residues of C1-C40 organic acids; b are the same or different and are independently selected from residues of C1-C40 organic alcohols; c are the same or different and are independently selected from at least one of C1-C40 organic alcohols; and n represents the number of C and is selected from 1-30. According to the aluminum-oxygen cluster carrier catalyst material, combination of aluminum-oxygen clusters and precious metal silver is achieved, and the application prospect of the aluminum-oxygen cluster material is widened. According to the preparation method, a solvothermal method is adopted, aluminum-oxygen clusters and precious metal silver are combined, synthesis is carried out through a one-step method, and aluminum-oxygen cluster crystals are loaded with precious metal sites. The preparation process is simple to operate, the product purity is high, and gram-level large-scale controllable rapid synthesis is realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of crystal material preparation, and particularly relates to an aluminum-oxygen cluster supported catalyst material, a method for its large-scale preparation, and applications thereof. Background Art

[0002] Aluminum is the most abundant metallic element in the earth's crust. Due to its low cost, easy availability, and environmental friendliness, aluminum-based materials have shown extensive applications in industrial catalysis, electro-optics, and other fields. Aluminum-based materials can serve as both catalysts and excellent catalyst supports. For example, trimethylaluminum and aluminum oxide can act as catalysts for organic reactions. Aluminum oxide can also be an excellent support for noble metal particles. For instance, the Pt-Na / Al2O3 catalyst is used for the catalytic conversion of carbon dioxide. In recent years, aluminum-oxygen clusters (AlOCs) prepared using aluminum as the metal source have received extensive attention due to their light weight, non-toxicity, strong chemical stability, etc. Using such crystalline materials as the support for catalytic particles can obtain internal molecular information through single crystal diffraction and visually study the structure-activity relationship between structure and function.

[0003] Noble metal silver has excellent physical properties and unique catalytic activity. Silver nanoparticles and silver clusters have been proven to be effective as catalytic materials for activating carbon-carbon triple bonds and converting carbon dioxide molecules. Combining aluminum-oxygen cluster molecules with excellent stability and noble metal particles may provide a good research platform for catalytic research related to carbon dioxide, which is of great significance. Summary of the Invention

[0004] To achieve the above object, the present invention provides an aluminum-oxygen cluster supported catalyst material, a method for its large-scale preparation, and applications thereof.

[0005] The technical solution of the present invention is as follows:

[0006] An aluminum-oxygen cluster supported catalyst material, the molecular formula of the aluminum-oxygen cluster supported catalyst material is:

[0007] [Al3Ag2(A)4(μ2-B)3]·(C n )

[0008] wherein, A are the same or different, and independently selected from residues of organic acids with C1-C40, and the residue of the organic acid with C1-C40 refers to the group remaining after removing all hydrogens on the carboxyl groups of the C1-C40 organic acid;

[0009] B are the same or different, and independently selected from at least one of residues of organic alcohols with C1-C40, and the residue of the organic alcohol with C1-C40 refers to the group remaining after removing the hydrogen on the alcohol hydroxyl group of the organic alcohol;

[0010] μ2-B represents the formation of a bridging coordination by two Al atoms with the O atoms in the alcohol hydroxyl groups of B;

[0011] C is the same or different and independently selected from at least one of C1-C40 organic alcohols.

[0012] n represents the number of C, selected from 1-30, for example, an integer or a decimal between 1-30.

[0013] According to an embodiment of the present invention, in the aluminoxane-supported catalyst material, the A, μ2-B, Al, and Ag form an aluminoxane support, and its periphery is coordinated by A, μ2-B, and Ag.

[0014] According to an embodiment of the present invention, in the aluminoxane-supported catalyst material, part or all of the C is in a free state. Preferably, the C exists freely inside the aluminoxane clusters in the aluminoxane-supported catalyst material or is adsorbed outside the aluminoxane clusters.

[0015] According to an embodiment of the present invention, the aluminoxane support includes an aluminoxane cluster structure. Preferably, the cluster structure includes an aluminoxane cluster core, and the size of the aluminoxane cluster core is

[0016] According to an embodiment of the present invention, the aluminoxane cluster structure is a symmetric structure.

[0017] According to an embodiment of the present invention, the aluminoxane cluster structure includes at least 10 aluminoxane cluster cores.

[0018] According to an embodiment of the present invention, in the oxygen cluster support, the noble metal silver is combined with the aluminoxane cluster through a coordination bond.

[0019] According to a preferred embodiment of the present invention, A is selected from at least one of the residues of nicotinic acid and the residues of substituted nicotinic acid. Further, the "substituent" is a conventional substituent in the art, for example, selected from hydroxyl, C 1-6 alkyl, C 1-6 alkoxy, amino, nitro, carboxyl, phenyl, or halogen atom, preferably hydroxyl. Preferably, A is selected from the residues of nicotinic acid.

[0020] Exemplarily, A is selected from at least one of the residues of 2-hydroxy nicotinic acid, 4-hydroxy nicotinic acid, 5-hydroxy nicotinic acid, 6-hydroxy nicotinic acid, 2-amino nicotinic acid, 2-methyl nicotinic acid, 4-amino nicotinic acid, and 2-nitro nicotinic acid, preferably the residue of 2-hydroxy nicotinic acid.

[0021] According to a preferred embodiment of the present invention, n is an integer selected from 1 to 30; more preferably, n is an integer selected from 1 to 6; further preferably, n is an integer selected from 1 to 4; still more preferably, n is 1 or 2.

[0022] According to an embodiment of the present invention, B is selected from at least one of the residues of benzyl alcohol, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, butanol, and pentanol; preferably, it is at least one of the residues of benzyl alcohol, methanol, ethanol, and butanol.

[0023] According to an embodiment of the present invention, C is selected from at least one of benzyl alcohol, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, butanol, and pentanol; preferably, it is at least one of benzyl alcohol, methanol, ethanol, and butanol.

[0024] According to an embodiment of the present invention, the aluminoxane-supported catalyst material is a pure phase, preferably a pure phase with a crystal structure.

[0025] According to an embodiment of the present invention, the aluminoxane-supported catalyst material is an organic-inorganic hybrid compound.

[0026] According to an embodiment of the present invention, the aluminoxane-supported catalyst material includes pores, and the pore diameter of the pores is 0.5 - 1 nm, for example, 0.78 nm.

[0027] According to a preferred embodiment of the present invention, the molecular formula of the aluminoxane-supported catalyst material is:

[0028] [Al3Ag2(A)4(μ2-B)3]·(C n )

[0029] wherein A is the residue of 2-hydroxy nicotinic acid; B is selected from one of the residues of benzyl alcohol, methanol, ethanol, and butanol; C is selected from one of benzyl alcohol, methanol, ethanol, and butanol;

[0030] n is an integer selected from 1 to 30, preferably, n is 1 or 2.

[0031] According to an exemplary embodiment of the present invention, the molecular formula of the aluminoxane-supported catalyst material is [Al3Ag2(C6NO3H3)4(OCH3)3]·(CH3OH) (denoted as C 28 H 25 Ag2Al3N4O 16 ), its crystal system is trigonal system, space group is R-3, and the unit cell parameter a is b is c is α is 90°, β is 90°, and γ is 120°; the relative molecular mass Mr of the catalyst material is 970.20. Preferably, the aluminoxane-supported catalyst material C 28 H 25 Ag2Al3N4O 16 has a crystal structure substantially as Figure 1 shown.

[0032] Preferably, the crystal structure packing of the aluminoxane-supported catalyst material C 28 H 25 Ag2Al3N4O 16 is substantially as shown in the left figure of Figure 2 .

[0033] Preferably, the aluminoxane-supported catalyst material C 28 H 25 Ag2Al3N4O 16 has an X-ray powder diffraction pattern substantially as Figure 3 shown.

[0034] Preferably, the crystal parameters of the crystalline substance of the aluminoxane-supported catalyst material C 28 H 25 Ag2Al3N4O 16 are shown in Table 1.

[0035] Table 1

[0036]

[0037] The present invention also provides a method for the bulk preparation of the above aluminoxane-supported catalyst material, and the bulk preparation method includes the following steps: mixing reaction raw materials, heating for reaction, and preparing the aluminoxane-supported catalyst material; wherein, the reaction raw materials include an aluminum salt, a silver salt, an organic acid, and an organic alcohol;

[0038] wherein, the residue of the organic acid forms A in the molecular formula of the aluminoxane-supported catalyst material, the residue of the organic alcohol forms B in the molecular formula of the aluminoxane-supported catalyst material, and the organic alcohol forms C in the molecular formula of the aluminoxane-supported catalyst material.

[0039] According to the embodiments of the present invention, the bulk preparation method specifically includes the following steps:

[0040] 1) Mix the aluminum salt, silver salt, organic acid, and organic alcohol, and carry out a heating reaction to obtain a mixture;

[0041] 2) Separate the mixture obtained after the reaction in step 1) to obtain the aluminoxane-supported catalyst material.

[0042] According to an embodiment of the present invention, the aluminum salt is selected from compounds formed by aluminum ions and alcohols after removing the hydrogen on the alcohol hydroxyl group.

[0043] According to an embodiment of the present invention, the aluminum salt is selected from at least one of aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, and aluminum tert-butoxide, and preferably aluminum isopropoxide.

[0044] According to an embodiment of the present invention, the silver salt is selected from at least one of silver chloride, silver bromide, silver nitrate, silver fluoride, silver chlorate, silver trifluoromethanesulfonate, and silver perchlorate, and preferably silver trifluoromethanesulfonate.

[0045] According to an embodiment of the present invention, the organic acid has the selection as shown above, for example, it is selected from organic acids with C1-C40.

[0046] According to an embodiment of the present invention, the organic alcohol has the selection as shown above, for example, it is selected from organic alcohols with C1-C40.

[0047] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the silver salt is 1:(0.01-10), for example, 1:(0.1-5), and also 1:(0.2-3).

[0048] According to an embodiment of the present invention, the molar ratio of the aluminum salt to the organic acid is 1:(0.01-10), for example, 1:(0.1-5), and also 1:(0.2-3).

[0049] 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:(0.1-80), and also 1:(1-50).

[0050] According to an embodiment of the present invention, the temperature of the heating reaction is 50-150 °C; preferably 60-120 °C, for example 70-120 °C, such as 80 °C. If the temperature of the heating reaction is too low, it will lead to a longer reaction time and smaller crystal size.

[0051] According to an embodiment of the present invention, the time of the heating reaction is 24-240 hours; preferably 36-180 hours, such as 72 hours, 96 hours.

[0052] Exemplarily, the heating reaction can be carried out at 80 °C for 72 hours or 96 hours.

[0053] According to an embodiment of the present invention, step 1) specifically includes: mixing the aluminum salt, silver salt, organic acid, and alcohol, stirring, carrying out a constant-temperature reaction, and then cooling to room temperature.

[0054] Preferably, the constant-temperature reaction refers to a static reaction at a constant temperature. For example, after mixing an aluminum salt, a silver salt, an organic acid, and an alcohol, the mixture is placed in an oven for heating and reaction.

[0055] According to an embodiment of the present invention, in step 2), the separated solid is washed and dried.

[0056] Preferably, water or an alcohol is used to wash the separated solid, and it is air-dried at room temperature. Among them, the alcohol selected for washing can be at least one of methanol, ethanol, and n-propanol.

[0057] The present invention also provides an aluminoxane-supported catalyst material, which is obtained by the above-mentioned macroscale preparation method; the aluminoxane-supported catalyst material has the meaning as described above.

[0058] The present invention also provides the application of the above aluminoxane-supported catalyst material in the field of catalysis.

[0059] Beneficial effects

[0060] The aluminoxane-supported catalyst material of the present invention realizes the combination of aluminoxane clusters and noble metal silver, broadening the application prospects of aluminoxane cluster materials. The present invention uses a solvothermal method to combine aluminoxane clusters with noble metal silver, and through a one-step synthesis, aluminoxane cluster crystals are loaded with noble metal sites. The preparation process of this process is simple, the product purity is relatively high, and gram-scale large-scale controllable and rapid synthesis is achieved.

[0061] The preparation process of the aluminoxane-supported catalyst material of the present invention is simple, the product purity is relatively high, the reaction time is short, and it is convenient for large-scale production. Moreover, the post-treatment process of the macroscale preparation method of the present invention is simple, and only by washing and separating and natural air-drying, a crystalline product can be obtained. At the same time, the raw materials of the macroscale preparation method of the present invention are low-toxic, inexpensive, less polluting, and meet the requirements of green environmental protection.

[0062] The present invention establishes a synthesis method of a porous cluster crystal-supported noble metal catalyst, realizing the application of aluminoxane cluster crystalline products in the field of catalysis.

[0063] Term definitions and explanations

[0064] Unless otherwise specified, the group and term definitions recorded in the specification and claims of this application, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, definitions of specific compounds in examples, etc., can be combined and combined with each other arbitrarily. The group definitions and compound structures after such combination and combination should be understood to be within the scope recorded in the specification and / or claims of this application.

[0065] The "cluster" is a relatively stable microscopic or submicroscopic aggregate composed of several to thousands of atoms, molecules or ions through physical or chemical binding forces, and its physical and chemical properties vary with the number of atoms contained therein. If the cluster is electrically neutral, it is a cluster molecule. If the cluster carries a positive or negative charge, it is a cluster ion.

[0066] It should be understood that in the description of one or more, "a plurality" should mean greater than 1, for example, an integer greater than or equal to 2, such as 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0067] The term "C 1-6 alkyl" means a straight-chain and branched-chain alkyl having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, etc. or their isomers.

[0068] The above definition of the term "alkyl", such as "C 1-6 alkyl", also applies to other terms containing "C 1-6 alkyl", such as the term "C 1-6 alkoxy", etc.

[0069] The term "organic alcohol of C1-C40" or "organic acid of C1-C40" means an organic alcohol or organic acid having 1, 2, 3, 4, 5, …, 38, 39 or 40 carbon atoms. Description of the Drawings

[0070] Figure 1 It is a schematic diagram of the crystal structure of the aluminum oxide cluster supported catalyst material prepared in Example 1;

[0071] Figure 2 It is a schematic diagram of the crystal structure stacking and pore channels of the aluminum oxide cluster supported catalyst material prepared in Example 1;

[0072] Figure 3 It is an X-ray powder diffraction pattern of the aluminum oxide cluster supported catalyst material prepared in Example 1; wherein, the "simulated diagram" is the X-ray powder diffraction pattern simulated according to the crystal structure; the "experimental diagram" is the X-ray powder diffraction pattern tested on an X-ray powder diffractometer;

[0073] Figure 4Infrared spectrum of the aluminum oxo cluster supported catalyst material prepared in Example 1.

[0074] Figure 5 Process of using the aluminum oxo cluster supported catalyst material prepared in Example 1 for the catalytic fixation of carbon dioxide. Detailed implementation mode

[0075] The technical solution of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only illustrative explanations of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0076] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

[0077] The single crystal structure analysis of the present invention uses a Rigaku Metal Jet D2 single crystal diffractometer.

[0078] The X-ray powder diffraction pattern uses Cu-Kα rays as the radiation source.

[0079] Example 1

[0080] Preparation of aluminum oxo cluster supported catalyst material (C 28 H 25 Ag2Al3N4O 16 )

[0081] The specific preparation method is as follows: Put aluminum isopropoxide (0.25 mmol), silver trifluoromethanesulfonate (0.2 mmol), 2-hydroxynicotinic acid (0.4 mmol), acetonitrile (2 mL), methanol (5 mL), and DMF (1 mL) into a 20 mL glass bottle, mix well at room temperature, keep it at a constant temperature of 80 °C in an oven for 3 days, take it out, naturally cool it to room temperature, separate the solid phase, rinse it with ethanol, and naturally dry it in the air to obtain the colorless cubic crystalline target product aluminum oxo cluster supported catalyst material (C 28 H 25 Ag2Al3N4O 16 ). The yield is about 37.4% (based on the mass of aluminum isopropoxide).

[0082] From Figure 1It can be seen that the smallest asymmetric unit in the aluminoxane-supported catalyst material contains 4 C6NO3H3 ligands, 3 Al atoms, 2 Ag atoms, 3 μ2-OCH3, and 1 free CH3OH. Therefore, it can be expressed as [Al3Ag2(C6NO3H3)4(OCH3)3]·(CH3OH). The cluster monomer contains 4 C6NO3H3 ligands, 3 Al atoms, 2 Ag atoms, 3 μ2-OCH3, and 1 free CH3OH, and its size is

[0083] From Figure 2 it can be seen the crystal structure packing diagram (left figure) of the aluminoxane-supported catalyst material and the channels formed after the crystal structure packing (middle and right figures). The pore diameter of the channels is about 0.78 nm.

[0084] The aluminoxane-supported catalyst material was subjected to X-ray powder diffraction and infrared spectroscopy tests respectively:

[0085] From Figure 3 it can be seen that the X-ray powder diffraction pattern of the aluminoxane-supported catalyst material is consistent with the theoretical simulation. The aluminoxane-supported catalyst material has a high purity (95%) and is stable in air. Its crystal form parameters are as follows: The crystal system of the aluminoxane-supported catalyst material is trigonal system, the space group is R-3, and the unit cell parameter a is b is c is α is 90°, β is 90°, γ is 120°, and V is

[0086] Through single-crystal X-ray analysis, the crystal parameters of the aluminoxane-supported catalyst material are shown in Table 1:

[0087] Table 1

[0088]

[0089] From Figure 4 it can be seen that the aluminoxane-supported catalyst material has obvious vibration peaks of organic carboxylic acid.

[0090] 2. Catalytic performance test for carbon dioxide

[0091] Phenylacetylene (0.5 mmol), Cs2CO3 (1.5 mmol), CO2, the above-prepared aluminoxane-supported catalyst material (20 mg), acetonitrile (3 mL), etc. were mixed and reacted at 60 °C for 12 hours to obtain phenylpropiolic acid with a yield of about 73%. The reaction process is shown in Figure 5 .

[0092] Example 2

[0093] Macroscopic Preparation of Alumina Cluster Supported Catalyst Material

[0094] The specific preparation method is as follows: Put aluminum isopropoxide (12.5 mmol), silver trifluoromethanesulfonate (10 mmol), 2-hydroxy nicotinic acid (20 mmol), acetonitrile (100 mL), methanol (250 mL), and DMF (50 mL) into a 500 mL glass bottle, mix well at room temperature, keep it at a constant temperature of 80 °C in an oven for 3 days, take it out, naturally cool it to room temperature, separate the solid phase, rinse it with ethanol, and naturally dry it in air to obtain the colorless cubic crystalline target product alumina cluster supported catalyst material (C 28 H 25 Ag2Al3N4O 16 ). The yield is about 43% (based on the mass of aluminum isopropoxide).

[0095] It can be seen that the preparation method of the present invention can obtain the alumina cluster supported catalyst material through macroscopic preparation.

[0096] The above describes the exemplary embodiments of the present invention. However, the protection scope of this application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. An aluminum oxide cluster-supported catalyst material, characterized in that, The molecular formula of the aluminoxane-supported catalyst material is: [Al3Ag2(A)4(μ2-B)3]·(C n ) Among them, A are the same or different, and are independently selected from the residues of C1-C40 organic acids, and the residue of the C1-C40 organic acid refers to the group remaining after removing the hydrogen on all carboxyl groups of the C1-C40 organic acid; B are the same or different, and are independently selected from at least one of the residues of C1-C40 organic alcohols, and the residue of the C1-C40 organic alcohol refers to the group remaining after removing the hydrogen on the alcohol hydroxyl group of the organic alcohol; C are the same or different, and are independently selected from at least one of C1-C40 organic alcohols; μ2-B represents that two Al form a bridging coordination with the bidentate O atom in the alcohol hydroxyl group of B; n represents the number of C, and is selected from 1-30.

2. The aluminoxane-supported catalyst material according to claim 1, characterized in that, In the aluminoxane-supported catalyst material, A, μ2-B, Al, and Ag form an aluminoxane support, and its periphery is coordinated by A, μ2-B, and Ag. Preferably, in the aluminoxane-supported catalyst material, part or all of C is in a free state. Preferably, C exists freely inside the aluminoxane in the aluminoxane-supported catalyst material or is adsorbed outside the aluminoxane. Preferably, the aluminoxane carrier includes an aluminoxane cluster structure. Preferably, the cluster structure includes an aluminoxane cluster core, and the size of the aluminoxane cluster core is Preferably, the aluminoxane cluster structure is a symmetric structure. Preferably, the aluminoxane cluster structure includes at least 10 aluminoxane cluster cores. Preferably, in the oxygen cluster support, the noble metal silver is bonded to the aluminoxane cluster through a coordination bond.

3. The aluminoxane-supported catalyst material according to claim 1 or 2, characterized in that, A is selected from at least one of the residue of nicotinic acid and the residue of substituted nicotinic acid. Preferably, n is selected from integers from 1 to 30. Preferably, B is selected from at least one of the residues of benzyl alcohol, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, butanol, and pentanol. Preferably, C is selected from at least one of benzyl alcohol, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, butanol, pentanol, and benzyl alcohol. Preferably, the aluminoxane-supported catalyst material is a pure phase. Preferably, the aluminoxane-supported catalyst material is an organic-inorganic hybrid compound. Preferably, the aluminoxane-supported catalyst material includes pores, and the pore diameter of the pores is 0.5-1 nm.

4. The aluminum oxide cluster supported catalyst material according to any one of claims 1-3, characterized in that, The molecular formula of the aluminoxane-supported catalyst material is: [Al3Ag2(A)4(μ2-B)3]·(C n ) Among them, A is the residue of 2-hydroxy nicotinic acid; B is selected from one of the residues of benzyl alcohol, methanol, ethanol, and butanol; C is selected from one of benzyl alcohol, methanol, ethanol, and butanol. n is selected from integers from 1 to 30. Exemplarily, the molecular formula of the aluminoxane-supported catalyst material is [Al3Ag2(C6NO3H3)4(OCH3)3]·(CH3OH) (denoted as C 28 H 25 Ag2Al3N4O 16 ), its crystal system is trigonal, the space group is R-3, and the unit cell parameters are a b is c is α is 90°, β is 90°, γ is 120°; the relative molecular mass Mr of the catalyst material is 970.

20.

5. The method for large-scale preparation of the aluminoxane-supported catalyst material according to any one of claims 1-4, characterized in that, The bulk preparation method includes the following steps: mixing reaction raw materials, heating and reacting to prepare the aluminoxane-supported catalyst material; wherein, the reaction raw materials include an aluminum salt, a silver salt, an organic acid, and an organic alcohol; Among them, the residue of the organic acid forms A in the molecular formula of the aluminoxane-supported catalyst material, and the residue of the organic alcohol forms B in the molecular formula of the aluminoxane-supported catalyst material.

6. The large-scale preparation method according to claim 5, characterized in that, The bulk preparation method specifically includes the following steps: 1) Mix the aluminum salt, silver salt, organic acid, and organic alcohol, and carry out a heating reaction to obtain a mixture; 2) Separate the mixture obtained after the reaction in step 1) to obtain the aluminoxane-supported catalyst material.

7. The large-scale preparation method according to claim 5 or 6, characterized in that, The aluminum salt is selected from the compound formed by the aluminum ion and the alcohol after removing the hydrogen on the alcohol hydroxyl group. Preferably, the aluminum salt is selected from at least one of aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, and aluminum tert-butoxide. Preferably, the silver salt is selected from at least one of silver chloride, silver bromide, silver nitrate, silver fluoride, silver chlorate, silver trifluoromethanesulfonate, and silver perchlorate. Preferably, the organic acid is selected from C1-C40 organic acids. Preferably, the organic alcohol is selected from C1-C40 organic alcohols.

8. The large-scale preparation method according to any one of claims 5-7, characterized in that, The molar ratio of the aluminum salt to the silver salt is 1:(0.01-10). Preferably, the molar ratio of the aluminum salt to the organic acid is 1:(0.01-10). Preferably, the molar ratio of the aluminum salt to the organic alcohol is 1:(0.01-100). Preferably, the temperature of the heating reaction is 50-150 °C. Preferably, the time of the heating reaction is 24-240 hours.

9. The bulk preparation method according to any one of claims 5-8, characterized in that, Step 1) specifically includes: after mixing the aluminum salt, silver salt, organic acid, and alcohol, stirring, carrying out a constant-temperature reaction, and then cooling to room temperature. Preferably, the constant-temperature reaction means standing and reacting at a constant temperature. Preferably, in step 2), the separated solid is washed and dried.

10. Use of the aluminoxane-supported catalyst material according to any one of claims 1-4 in the catalytic field.

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