A two-dimensional aluminum phosphate material and its preparation method and application

Abstract

The present invention belongs to the technical field of molecular sieves and open frameworks, and specifically relates to a two-dimensional aluminum phosphate material ZHKU-2 prepared based on a novel carbazole derivative template, wherein the asymmetric unit molecular formula is [C 17 H 21 N 2 ] 3 [Al 3 (PO 4 ) 4 ](H 2 O) 5 , its crystal form is monoclinic P 2 1 / c space group; [C 17 H 21 N 2 ] + It is 2-(9H-carbazole-9-yl)-N,N,N-trimethylethyl-1-ammonium ion. The material has excellent fluorescence performance and extremely obvious color change, and has good application prospects in the fields of optical switches, optical storage, and anti-counterfeiting labels. The present invention also provides a preparation method with low cost and simple process.

Description

Technical Field

[0001] The invention belongs to the technical field of molecular sieves and open frameworks, and specifically relates to a two-dimensional aluminum phosphate material prepared based on a novel carbazole derivative template, a method thereof, and a fluorescence application thereof. Background Art

[0002] Since Wilson and Flanigen discovered the first microporous aluminum phosphate in 1982, the synthesis of new aluminum phosphate materials with novel frameworks and the study of their potential adsorption, catalytic, separation and other properties have always been an area of ​​great interest to researchers. Aluminophosphate materials show rich structural diversity from zero-dimensional clusters, one-dimensional chains, two-dimensional layers to three-dimensional frameworks. As the main family of aluminum phosphate materials, two-dimensional layered materials include neutral and anionic frameworks with complex structures and diverse compositions. The neutral framework of layered aluminum phosphate is composed of AlO 4 and PO 4 The tetrahedrons are strictly alternating, while the anion framework is composed of Al polyhedra (AlO 4 、AlO 5 、AlO 6 ) and P tetrahedron P(O b ) n (O t ) 4-n (n = 1, 2, 3, 4; b: indicates bridging, t: indicates terminal) alternately form different stoichiometries with P / Al ratios between 1 and 2, including 1:1, 1:2, 2:3, 3:4, 4:5, 13:18, etc.

[0003] Organic structure-directing agents, also called templates, direct the formation of specific secondary structural units to form a crystalline open framework. Their size, shape and orientation affect the crystallization and stacking mode of the molecular sieve. In the two-dimensional phosphate structure, the template also plays two additional roles, namely balancing the framework and stabilizing the gaps. To date, more than 100 templates have been successfully used. Typical templates are quaternary ammonium cations and various organic amines, including primary amines, secondary amines, tertiary amines, cyclic amines, and alkanolamines.

[0004] In the synthesis of new open framework materials, the use of photoactive templates with specific structures is of great significance. In recent years, 4, 4'-bipyridine (also known as methyl viologen) derivatives have been proposed as functional structure-directing agents for the synthesis of a series of open framework phospho / phosphonates, including JU98, JU99, JU101, JU104 and NTHU-9-MV, which have very interesting properties in fluorescence, optoelectronics and photochromism. For example, using methyl-anthrone as a photoactive template, a layered aluminum phosphate SYSU-2 with fluorescent properties was prepared. However, the current types of new fluorescent aluminum phosphate materials are far from enough, and aluminum phosphate materials with high fluorescence mass yield are urgently needed. Summary of the invention

[0005] In response to the above technical problems, the present invention provides a two-dimensional aluminum phosphate material ZHKU-2, which has excellent fluorescence properties and extremely obvious color changes. It has good application prospects in the fields of optical switches, optical storage, and anti-counterfeiting marks. The material has a low synthesis cost and a simple synthesis process.

[0006] To achieve the above object, the present invention is implemented through the following technical solutions:

[0007] The present invention uses a large and rigid template agent carbazolyl quaternary ammonium base (Caza) to synthesize a new two-dimensional aluminum phosphate material ZHKU-2 with a P / Al ratio of 3 / 4, and its asymmetric unit molecular formula is [C 17 H 21 N 2 ] 3 [Al 3 (PO 4 ) 4 ](H 2 O) 5 .

[0008] Wherein, the carbazole-based quaternary ammonium base is 2-(9H-carbazole-9-yl)-N, N, N-trimethylethyl-1-ammonium hydroxide, and its molecular structure is shown in Formula I, and the [C 17 H 21 N 2 ] + It is 2-(9H-carbazol-9-yl)-N, N, N-trimethylethyl-1-ammonium ion, which is the cation of the template agent carbazolyl quaternary ammonium base.

[0009]

[0010] Formula I.

[0011] Preferably, the two-dimensional aluminum phosphate material of the present invention is in a crystal form, a monoclinic system, P 2 1 / c space group, unit cell parameters are: a =24.1785(12) Å, b =14.5847(6) Å, c =17.9856(9) Å, β =111.698(6)°. Its structure consists of AlO 4 Tetrahedron and PO 3 The 4.6.8-network characterized by a capped 6-membered ring composed of (=O) tetrahedra, forming [Al 3 P 4 O 16 ]3- The inorganic layers are stacked into a two-dimensional structure by AA method.

[0012] The two-dimensional aluminum phosphate material of the present invention uses carbazole quaternary ammonium base as a template, and comprises the following steps:

[0013] A certain amount of carbazole quaternary ammonium base solution and pseudo-boehmite are mixed evenly, stirred for 0.5-1.5 hours, and then a certain amount of phosphoric acid is added, stirred for 0.5-1.0 hours, and then dried into a gel, and the gel is transferred to a reactor and reacted at 120-180°C for 3-5 days; after the reaction is completed, crystals or microcrystalline powders are separated, washed (with deionized water and acetone), and dried to obtain a two-dimensional aluminum phosphate material.

[0014] Preferably, the carbazole-based quaternary ammonium base solution is a carbazole-based quaternary ammonium base aqueous solution with a concentration of 0.1-0.3 mol / kg.

[0015] Preferably, Al in the pseudo-boehmite 2 O 3 The content is not less than 65wt%.

[0016] Preferably, the drying is carried out under an infrared lamp at 45-60°C.

[0017] Preferably, the raw materials used in the above reaction are such that the gel has the following molar ratios: Al / P = 0.7-1.2, Caza / (P+Al) = 0.2-0.4, H 2 O / (P+Al) = 5-50. That is, the amount of the pseudo-boehmite and phosphoric acid is such that the molar ratio of Al to P in the system reaches 0.7-1.2; the amount of the carbazole quaternary ammonium base solution is such that the molar ratio of the amount of the carbazole quaternary ammonium base to the sum of the amount of Al and P in the system reaches 0.2-0.4.

[0018] Preferably, the carbazole-based quaternary ammonium base is prepared by the following steps:

[0019] (1) In an argon atmosphere at -70 - -80°C, slowly add a hexane solution of n-butyl lithium and triisobutyl aluminum to toluene containing carbazole and stir for 45-90 min to obtain an initial amine solution I;

[0020] The molar ratio of carbazole, n-butyl lithium and triisobutyl aluminum is 8-12:8-12:1.

[0021] (2) dissolving dimethylaminoethyl chloride hydrochloride in an appropriate amount of toluene, adding a hexane solution of n-butyl lithium and triisobutylaluminum, and continuing stirring for 45-90 min to obtain a mixture II;

[0022] The molar ratio of dimethylaminoethyl chloride hydrochloride, n-butyl lithium and triisobutylaluminum is 8-12:8-12:1.

[0023] (3) Under argon protection at -70 to -80°C, slowly add the mixture II to the amine solution I, heat under reflux, and react for 6 to 10 hours. After the reaction is completed, cool and filter to obtain a crude product of carbazole tertiary amine;

[0024] The amounts of the mixture II and the amine solution I used in this step are such that the molar ratio of carbazole to dimethylaminoethyl chloride hydrochloride in the reaction system reaches 1:(0.8-1.2).

[0025] (4) extracting and purifying the obtained crude carbazole tertiary amine product, washing the obtained organic phase with brine, drying, and concentrating under reduced pressure to obtain an oily crude product, and separating the oily crude product through a silica gel column with a solvent of chloroform: methanol = 10:1 and 5:1 (volume ratio) to obtain a pure carbazole tertiary amine;

[0026] The solvents used for extraction in this step are ethyl acetate and saturated NaHCO 3 solution, the volume ratio of the two is (4-6):1.

[0027] (5) Adding methyl iodide to the carbazole tertiary amine to carry out a quaternization reaction;

[0028] (6) After quaternization, the anion resin is exchanged to obtain a carbazole-based quaternary ammonium base, 2-(9H-carbazole-9-yl)-N, N, N-trimethylethyl-1-ammonium hydroxide aqueous solution.

[0029] The present invention has the following positive and beneficial effects:

[0030] The present invention provides a two-dimensional aluminum phosphate material ZHKU-2 and a simple synthesis process. The two-dimensional aluminum phosphate material emits purple fluorescence under ultraviolet irradiation with high fluorescence quantum yield, can realize the ultraviolet-specific fluorescence response of aluminum phosphate molecular sieves, provides more value for the development of aluminum phosphate molecular sieves and open frameworks and their fluorescence benefits, and has great application prospects in the fields of optical switches, optical storage, and anti-counterfeiting labels. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 : Schematic diagram of the synthesis of the template 2-(9H-carbazole-9-yl)-N, N, N-trimethylethyl-1-ammonium hydroxide.

[0032] Figure 2 : Thermal ellipsoid diagram of the asymmetric unit of the ZHKU-2 crystal obtained in Example 1 (50% possible level).

[0033] Figure 3: A comparison diagram of the structure simulation X-ray powder diffraction spectrum (PXRD) of the aluminum phosphate molecular sieve ZHKU-2 obtained in Example 1 and the experimental PXRD diagram, indicating that the synthesized sample in Example 1 is a pure phase.

[0034] Figure 4 : is a scanning electron microscope image of the aluminum phosphate ZHKU-2 crystal obtained in Example 1, showing its long strip morphology.

[0035] Figure 5 : Diagram of the layered structure of the 8-membered ring window formed along the

[011] direction of crystal ZHKU-2.

[0036] Figure 6 : This is the interlayer structure diagram of the carbazole-based template formed along the

[001] direction of the crystal ZHKU-2.

[0037] Figure 7 :For the same coordination order [Al 3 P 4 O 16 ] 3- Comparison chart of layered aluminum phosphate ZHKU-2 and AlPO-CJ17.

[0038] Figure 8 : The excitation spectrum of ZHKU-2 at 402 nm emission wavelength and the emission spectrum at 348 nm excitation wavelength.

[0039] Fig. 9 : Quantum yield diagram of ZHKU-2. Implementation

[0040] The carbazole-based quaternary ammonium base used in the following examples is 2-(9H-carbazole-9-yl)-N, N, N-trimethylethyl-1-ammonium hydroxide, which is prepared by the following steps:

[0041] (1) In an argon atmosphere at -78 °C, slowly add 6.5 mL of a hexane solution of n-butyl lithium (concentration 1.6 mol / L) and triisobutylaluminum (TIBA, 1 mmol, 0.20 g) to a toluene (70 ml) solution of carbazole (10 mmol, 1.67 g), and stir for 60 min to obtain the initial amine solution I.

[0042] (2) Mix 1.43 g of dimethylaminoethyl chloride hydrochloride and 30 mL of toluene, then add 6.5 mL of a hexane solution of n-butyl lithium (concentration 1.6 mol / L) and 0.2 g of triisobutylaluminum, and continue stirring for 60 min to obtain a mixture II;

[0043] (3) Under argon protection at -78 °C, slowly add the mixture II to the amine solution I, heat and reflux, and react for 8 hours. After the reaction is completed, cool the reactants to 0 °C and filter to obtain a crude product of carbazole tertiary amine;

[0044] (4) The obtained crude carbazolyl tertiary amine product is extracted and purified (the solvent is ethyl acetate and saturated NaHCO 3 solution, the volume ratio of the two was 10:2), the obtained organic phase was washed with brine, anhydrous Na 2 SO 4 Drying and concentrating under reduced pressure to obtain an oily crude product, the oily crude product was separated by silica gel column using chloroform:methanol = 10:1 and 5:1 volume ratio solvents to obtain pure carbazolyl tertiary amine (1.9 g, yield 80%);

[0045] (5) Carbazole tertiary amine (4.7 g, 0.02 mol) was dissolved in 20 mL of acetone, and iodomethane (2.5 mL, 0.04 mol) was slowly added dropwise and stirred at room temperature overnight. After the reaction was completed, acetone was removed by rotary evaporation, and the mixture was washed with ether and filtered to obtain a colorless powder of carbazole quaternary ammonium salt (7.1 g, yield: ~93%).

[0046] (6) Weigh 19 g of anionic resin (1 g of resin for every 1 mmol of quaternary ammonium salt), wash it three times with deionized water, then add quaternary ammonium salt (7.1 g) and 200 g of deionized water, stir and exchange overnight in the dark to obtain a carbazole quaternary ammonium base aqueous solution, i.e., 2-(9H-carbazole-9-yl)-N,N,N-trimethylethyl-1-ammonium hydroxide aqueous solution. The carbazole quaternary ammonium base concentration was obtained by acid-base titration twice, and was 0.14 mol / kg and 0.2 mol / kg respectively. Example

[0047] A novel two-dimensional aluminum phosphate material modified with a carbazole-based template is synthesized by pseudoboehmite, phosphoric acid, quaternary ammonium base and water. The molar ratio of synthesis is: P+Al = 0.0035 mol, Al / P = 1.1, Caza / (P+Al) = 0.3, H 2 O / (P+Al) = 20.

[0048] 7.4468 g of 0.14 mol / kg carbazole quaternary ammonium base aqueous solution was added to the beaker, and then 0.1336 g of pseudo-boehmite (Al 2 O 3The mixture was stirred evenly for 1 hour, and then 0.1953 g of 85% phosphoric acid solution was added and stirred for 0.5 hour. The water was evaporated by heating under an infrared lamp (~50°C). The synthetic molar ratio was controlled by weighing. Finally, the gel with the above ratio was transferred to a 23 mL polytetrafluoroethylene liner and placed in a stainless steel reactor. The reaction was sealed and placed in an oven at 150°C for 5 days under the reactor's own pressure.

[0049] After the reaction is completed, the reactor is taken out and naturally cooled at room temperature. The crystals generated in the reactor are repeatedly washed three times with deionized water and acetone. The sample is naturally dried to obtain the two-dimensional aluminum phosphate material of the present invention. Example

[0050] A novel carbazole-based template-modified two-dimensional aluminum phosphate material was synthesized from pseudoboehmite, phosphoric acid, quaternary ammonium base and water. The molar ratio of synthesis was: P+Al = 0.0035, Al / P = 0.8, Caza / (P+Al) = 0.2, H 2 O / (P+Al) = 9.

[0051] 4.9645 g of 0.14 mol / kg aqueous solution of carbazole quaternary ammonium base was added to a beaker, 0.1336 g of pseudo-boehmite was added and stirred evenly for 1 hour, and then 0.1911 g of 85% phosphoric acid solution was added and stirred for 0.5 hour, and the water was heated under an infrared lamp (~50°C) to evaporate the water, and the synthetic molar ratio was controlled by weighing. Finally, the gel with the above ratio was transferred to a 23 mL polytetrafluoroethylene liner and placed in a stainless steel reactor, which was sealed and placed in an oven at 150°C, and reacted for 5 days under the reactor's own pressure.

[0052] After the reaction is completed, the reactor is taken out and cooled naturally at room temperature. The crystals generated in the reactor are repeatedly washed three times with deionized water and acetone. The sample is dried naturally to obtain the two-dimensional aluminum phosphate material of the present invention. Example

[0053] A novel carbazole-based template-modified two-dimensional aluminum phosphate material was synthesized from pseudoboehmite, phosphoric acid, quaternary ammonium base and water. The synthesis molar ratio was: P+Al=0.0010, Al / P = 1.1, Caza / (P+Al) = 0.2, H 2 O / (P+Al) =10.

[0054] 1013.7 g of 0.2 mol / kg aqueous solution of carbazole quaternary ammonium base was added to a beaker, 0.0382 g of pseudo-boehmite was added and stirred evenly for 1 hour, and then 0.0617 g of 85% phosphoric acid solution was added and stirred for 0.5 hour. The water was heated under an infrared lamp (~50°C) to evaporate the water, and the synthetic molar ratio was controlled by weighing. Finally, the gel with the above ratio was transferred to a 23 mL polytetrafluoroethylene liner and placed in a stainless steel reactor, which was sealed and placed in an oven at 150°C to react for 3 days under the reactor's own pressure.

[0055] After the reaction is completed, the reactor is taken out and cooled naturally at room temperature. The crystals generated in the reactor are repeatedly washed three times with deionized water and acetone. The sample is dried naturally to obtain the two-dimensional aluminum phosphate material of the present invention.

[0056] In the above embodiment, we used carbazole quaternary ammonium base as template and synthesized a new two-dimensional layered structure ZHKU-2 under hydrothermal conditions. Figure 2 As shown in the SEM image, the material has a long flake morphology, and its X-ray powder diffraction pattern is consistent with the simulation data, indicating that the synthesized sample is pure phase ( Figure 3 ).

[0057] As shown in Table 1 and Figure 2 As shown, ZHKU-2 crystallizes in the monoclinic space group P 2 1 / c, a = 24.1785(12) Å, b =14.5847(6) Å, c = 17.9856(9) Å, α = 90°, β = 111.698(6)°, γ = 90°. Its asymmetric unit molecular formula is [C 17 H 21 N 2 ] 3 [Al 3 (PO 4 ) 4 ](H 2 O) 5 , containing three different Al sites, four P sites, three carbazolyl quaternary ammonium ions and five water molecules. The Al atom is bonded to the four adjacent P atoms through coordinated oxygen atoms to form a tetrahedron. The Al–O bond length and O–Al–O bond angle ranges from 1.700(3)–1.733(3) Å and 105.7(2)-112.92, respectively, which are typical characteristics of tetracoordinated Al in aluminum phosphate. Each P atom shares oxygen atoms with three adjacent Al atoms to form a P–O bThe bond length range is 1.522(4)-1.541(3)Å. However, the fourth P leaves a terminal oxygen atom (P=O t ), the terminal P=Ot bond length is in the range of 1.465(4)-1.483(3)Å, which is significantly shorter than that of P–O b key, indicating P=O t The bond has a double bond nature. Therefore, the terminal P=Ot group prevents Al-OP from further extending and connecting to the three-dimensional network, thus forming a two-dimensional layered structure.

[0058] Table 1. Crystallographic and refinement data of ZHKU-2

[0059]

[0060] like Figure 5 As shown in Figure 2, the ZHKU-2 structure contains a topological network of 4-, 6-, and 8-membered rings, which is a distinctive capped 6-membered ring secondary structural unit. 4 Tetrahedron and PO 3 (=O) tetrahedra are connected alternately to form [Al 3 P 4 O 16 ] 3- Inorganic layer. The charge of the inorganic anion layer is balanced by the carbazolyl quaternary ammonium cation, and it forms a two-dimensional layered structure in an AAAA stacking manner along the

[010] direction. The adjacent inorganic layers are connected by water molecules, quaternary ammonium ions and terminal P=O t The inorganic layers are completely separated by templates and water molecules, forming a mesoporous space with a distance of ~21.9 Å ( Figure 6 ).

[0061] ZHKU-2 is characterized by an 8-membered network with a capped 6-ring SBU. It is noteworthy that similar 4, 6, 8-networks with the same topology are found in reported layered aluminum phosphate compounds with an Al:P ratio of 3:4, namely 2.3.4.11.00, 2.3.4.14.00, 2.3.4.14.002, 2.3.4.14.007, 2.3.4.19.001, 2.3.4.2.003, 2.3.4.4002 and AlPO-CJ17. However, as Figure 7 As shown in a, in the capped 6-membered ring secondary structural unit of ZHKU-2 layer, the top terminal P=O t The group points upward (U) and the terminal P in the 6-ring is O tThe groups point downward (D), upward (U), and downward (D), respectively, with a UDUD pattern. In all other aluminum phosphate compounds mentioned above with the same coordination sequence, the capped 6-membered ring secondary structural unit shows another pattern, namely UDDD ( Figure 7 b). That is, the terminal P=O in the 6-ring of the secondary structural unit t The groups point in the same direction, down, down, and down, and the P at the top end is O t The groups point in the opposite direction (upward). Therefore, the terminal P=O t The different arrangements of the groups confirmed that ZHKU-2 is a new aluminum phosphate structure.

[0062] As shown in the figure, the fluorescence properties of ZHKU-2 were studied and it was found that the maximum absorption spectrum peaks were at 438 nm and 354 nm ( Figure 8 ). Under ultraviolet light (365 nm), ZHKU-2 changes from white to purple fluorescence, and the color change is obvious. In addition, its luminescence wavelength coincides with its emission spectrum, which has two absorption peaks at 402 nm and 425 nm. Fig. 9 As shown in the figure, the fluorescence lifetime of ZHKU-2 is 17.6 ns, and the fluorescence quantum yield is as high as 40.05%. Compared with the currently reported luminescent open-framework phosphates, such as JU104 (12.70%), NTHU-3 (10%), NTHU-10 (11%) and NTHU-14 (8%-10%), ZHKU-2 has a fairly high quantum yield. The excellent fluorescence performance of ZHKU-2 is attributed to the π-π interaction of offset stacking and edge-face stacking between the carbazole-based template molecules encapsulated in the inorganic layer.

[0063] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A two-dimensional aluminum phosphate material, the asymmetric unit molecular formula of which is [C 17 H 21 N2]3[Al3(PO4)4](H2O)5; [C 17 H 21 N2] + is 2-(9H-carbazol-9-yl)-N, N, N-trimethylethyl-1-ammonium ion; The two-dimensional aluminum phosphate material is prepared by the following steps: A certain amount of carbazole quaternary ammonium base solution and pseudo-boehmite are mixed evenly, stirred for 0.5-1.5 hours, and then a certain amount of phosphoric acid is added, stirred for 0.5-1.0 hours, and then dried into a gel, and the gel is transferred to a reactor and reacted at 120-180° C. for 3-5 days; after the reaction is completed, crystals or microcrystalline powders are separated, washed, and dried to obtain a two-dimensional aluminum phosphate material.

2. The two-dimensional aluminum phosphate material according to claim 1, characterized in that: The two-dimensional aluminum phosphate material is in a crystalline form, a monoclinic system, P 21 / c space group.

3. The two-dimensional aluminum phosphate material according to claim 2, characterized in that: The unit cell parameters of the two-dimensional aluminum phosphate material are: a =24.1785(12) Å, b =14.5847(6) Å, c =17.9856(9) Å, β =111.698(6)°.

4. The two-dimensional aluminum phosphate material according to claim 1, characterized in that: The carbazole-based quaternary ammonium alkali solution is a carbazole-based quaternary ammonium alkali aqueous solution with a concentration of 0.1-0.3 mol / kg; the Al2O3 content in the pseudo-boehmite is not less than 65wt%.

5. The two-dimensional aluminum phosphate material according to claim 1, characterized in that: The raw materials used in the reaction are such that the molar ratio of Al to P elements in the gel reaches 0.7-1.2; the molar ratio of the amount of carbazole quaternary ammonium base to the sum of Al and P elements reaches 0.2-0.4; and the degree of drying is such that the molar ratio of H2O / (P+Al) in the gel reaches 5-50.

6. The two-dimensional aluminum phosphate material according to claim 1, characterized in that: The carbazole-based quaternary ammonium base is 2-(9H-carbazole-9-yl)-N, N, N-trimethylethyl-1-ammonium hydroxide.

7. The two-dimensional aluminum phosphate material according to claim 1, characterized in that: The carbazole-based quaternary ammonium base is prepared by the following steps: (1) In an argon atmosphere at -70- -80°C, slowly add a hexane solution of n-butyl lithium and triisobutyl aluminum to toluene containing carbazole, and stir for 45-90 minutes to obtain an initial amine solution I; (2) dissolving dimethylaminoethyl chloride hydrochloride in an appropriate amount of toluene, adding a hexane solution of n-butyl lithium and triisobutylaluminum, and continuing stirring for 45-90 minutes to obtain a mixture II; (3) Under argon protection at -70- -80°C, slowly add the mixture II to the amine solution I, heat under reflux, and react for 6-10 hours. After the reaction is completed, cool and filter to obtain a crude product of carbazole tertiary amine; (4) extracting and purifying the obtained crude carbazole tertiary amine product, washing the obtained organic phase with brine, drying, and concentrating under reduced pressure to obtain an oily crude product, and separating the oily crude product through a silica gel column using a solvent with a volume ratio of chloroform:methanol = 10:1 and 5:1 to obtain a pure carbazole tertiary amine; (5) Adding methyl iodide to the carbazole tertiary amine to carry out a quaternization reaction; (6) After quaternization, the quaternary ammonium salt is exchanged through an anion resin to obtain a carbazolyl quaternary ammonium base aqueous solution.

8. The two-dimensional aluminum phosphate material according to claim 7, characterized in that: In step (1), the molar ratio of carbazole, n-butyl lithium and triisobutyl aluminum is 8-12:8-12:1; in step (2), the molar ratio of dimethylaminochloroethane hydrochloride, n-butyl lithium and triisobutyl aluminum is 8-12:8-12:1; in step (3), the amounts of mixture II and amine solution I used are such that the molar ratio of carbazole and dimethylaminochloroethane hydrochloride in the reaction system reaches 1:(0.8-1.2); in step (4), the solvent used for extraction is ethyl acetate and saturated NaHCO3 solution, and the volume ratio of the two is (4-6):

1.

9. Use of the two-dimensional aluminum phosphate material according to any one of claims 1 to 3 in fluorescent materials.

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