A preparation method of defective perylene imide supramolecular photocatalyst and its application

Abstract

The invention discloses a method for preparing a defective perylene imide supramolecular photocatalyst and catalytic oxidation of benzylamine to synthesize N-benzylene butylamine, belonging to the field of chemistry and materials science. The method of the present invention is to use a defective perylene imide supramolecular as a catalyst for the first time, an oxygen-containing gas as an oxidant, and acetonitrile as a solvent, and catalyze benzylamine under the irradiation of visible light without affecting the active benzene ring, and the N-H bond and the C-N bond in the target amino group are respectively oxidized and broken to generate a method for N-benzylene butylamine compound. Using light as a driving force, a method for selectively oxidizing benzylamine molecules to generate N-benzylene butylamine under the promotion of a photocatalyst based on a defective perylene imide supramolecular. The inventive method has the characteristics of simple operation, green and efficient, mild reaction conditions, easy separation of catalyst and reaction system, and can realize multiple cycles of application, in line with the sustainable development energy strategy, and has broad application prospects.

Description

Technical Field

[0001] The present invention relates to the fields of chemistry and material science, and in particular to a method for synthesizing a defective perylene diimide supramolecular photocatalyst R-Ov-PDI and application of the method in photocatalytic efficient oxidation of benzylamine to prepare N-benzylbutylamine. Background Art

[0002] At present, the rapid development of human society and high fossil fuel consumption have inevitably led to environmental and energy crises. Selective oxidation reaction is one of the most effective synthetic routes for high value-added organic intermediates, including imines, which are usually carried out under high temperature and high pressure in industrial production, which will lead to a certain degree of energy consumption and environmental pollution; therefore, it is necessary to develop green methods to overcome the key bottleneck of selective oxidation reaction. Imines, also known as Schiff bases, as a class of active synthetic intermediates, can further undergo a series of transformations such as reduction, addition, condensation and cycloaddition. In recent years, some emerging methods for synthesizing imines have been developed, such as the hydrogenation coupling method of nitro compounds and the oxidative dehydrogenation reaction of secondary amines. However, these methods still have defects such as high cost and many toxic byproducts.

[0003] The route of oxidative coupling of amines to synthesize imines is highly atom-economical and environmentally friendly, and has become a hot topic of research. Metals such as ruthenium and gold have good catalytic properties, but price factors and the environmental problems they bring limit their effective development. Therefore, it is necessary to develop a green and inexpensive selective coupling catalytic system with excellent performance. Photocatalytic technology, as an efficient, safe, and low-consumption green oxidation technology, has great application potential for selective oxidation reactions. Photooxidation of benzylamine (BA) to N-benzylbutylamine (N-BA) is an attractive method that can be used for energy regeneration and energy storage, while also alleviating the increasing CO2 emissions. However, the yield or selectivity usually obtained in the prior art is low and the average reaction rate is slow. This is mainly due to the low reaction efficiency of the photocatalytic oxidation of benzylamine system due to the mild reaction conditions, which makes it impossible to produce efficiently and continuously. For example, in 2018, Mou et al. [J. Yang, C.-Y. Mou, Appl. Catal. B Environ. 2018, 231, 283-291.] used Au / TiO2 as a photocatalyst to catalyze the dehydrogenation coupling of BA. After 24 hours of reaction, the yield of N-BA was only 12%. In 2020, Lang et al. used Polyimide-TiO2 as a photocatalyst to couple 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) to catalyze the oxidative dehydrogenation of BA, and the average conversion rate of BA was 11.8 mmol g -1 ·h -1[W.Sheng, J.-L.Shi, H.Hao, X.Li, X.Lang, Chem.Eng.J.2020, 379.]. Later, Li et al. [P.Wang, X.Li, S.Fan, Z.Yin, L.Wang, M.O.Tadé, S.Liu, Nano Energy 2021, 83.] used Bi4NbO8Br as a photocatalyst to drive the catalytic photooxidation of BA. Unfortunately, the average conversion rate of BA was only 0.8 mmol g -1 ·h -1 Not long ago, Song et al. [S. Wei, H. Zhong, H. Wang, Y. Song, C. Jia, M. Anpo, L. Wu, Appl. Catal. B Environ. 2022, 305.] used Pd / BiOCl ultrathin nanosheets as photocatalysts and achieved an average BA conversion rate of 1.6 mmol·g within 12 h of reaction. -1 ·h -1 These studies have greatly promoted the development of photocatalytic imine synthesis and also showed that the effective dissociation of the CN bond is the rate-limiting step in the photocatalytic oxidation of BA to N-BA. However, due to the extremely high dissociation energy of the CN bond, the problem of photooxidatively stable benzylamine molecules under mild conditions has not yet been solved. Summary of the invention

[0004] In order to solve the problems in the prior art, the present invention adopts a simple, mild and low-cost photocatalytic method. First, a defective perylene diimide supramolecular photocatalyst (R-Ov-PDI) is prepared as a recyclable heterogeneous photocatalyst, and oxygen is used as an oxidant and acetonitrile is used as a reaction medium to catalyze the selective oxidation of benzylamine to prepare N-benzylbutylamine.

[0005] The first object of the present invention is to provide a method for preparing a defective perylene imide supramolecular photocatalyst, the method steps are as follows:

[0006] Step 1: Perylene tetracarboxylic anhydride, β-alanine and imidazole are heated to react under inert gas conditions. After the reaction, the mixture is cooled and dispersed in ethanol, HCl solution is added, stirred overnight, filtered and washed until the pH of the washing liquid becomes neutral, and PDI is obtained after drying;

[0007] Step 2: Disperse the PDI in step 1 in water, add triethylamine, and then add HCl solution and stir. When the solution precipitates, filter and wash until the pH of the washing liquid becomes neutral, and dry to obtain SA-PDI;

[0008] Step 3: dissolving an inorganic salt containing bismuth and polyvinyl pyrrolidone in an N,N-dimethylformamide-ethylene glycol-water solution and stirring, then adding the SA-PDI obtained in step 2 for ultrasonic treatment, and after the ultrasonic treatment, transferring to a hydrothermal reactor for solvothermal reaction;

[0009] Step 4: After the reaction is completed, the mixture is cooled and dispersed in ethanol, HCl solution is added, stirred overnight, filtered, washed until the pH of the washing liquid becomes neutral, and dried to obtain Ov-PDI;

[0010] Step 5: Disperse the Ov-PDI in step 4 in HNO3 solution, stir overnight, filter and wash until the pH of the washing solution becomes neutral, and dry to obtain R-Ov-PDI.

[0011] In one embodiment, in step 1, the molar ratio of perylenetetracarboxylic anhydride, β-alanine, and imidazole is 1:0.8-1.2:0.8-1.2;

[0012] The inert gas is nitrogen, argon or helium;

[0013] The heating reaction temperature is 100-130° C., and the reaction time is 3-6 hours.

[0014] In one embodiment, the volume ratio of triethylamine to water in step 2 is 0.1-0.4%, and the volume ratio of HCl solution to water is 8-12%.

[0015] In one embodiment, the inorganic salt containing bismuth in step 3 includes bismuth nitrate and bismuth chloride; and the K value of polyvinyl pyrrolidone is 30.

[0016] In one embodiment, the bismuth nitrate comprises Bi(NO3)3·5H2O.

[0017] In one embodiment, the mass ratio of the inorganic salt containing bismuth to polyvinyl pyrrolidone is 5:1; the stirring reaction time of the two is 0.5-1 hour, the amount of SA-PDI added in step 3 is 1.5 times the molar mass of the inorganic salt containing bismuth, the volume ratio of the N,N-dimethylformamide-water-ethylene glycol solution is 1:1:8, the ultrasonic treatment time after adding SA-PDI is 0.2-0.5 hour, the solvent thermal reaction temperature is 180-190°C, and the reaction time is 3-5 hours.

[0018] In one embodiment, the mass ratio of Bi(NO3)3·5H2O to polyvinyl pyrrolidone is 5:1; the stirring reaction time of the two is 0.5-1 hour, and the amount of SA-PDI added in step 3 is 1.5 times the molar mass of Bi(NO3)3·5H2O.

[0019] In one embodiment, the volume ratio of the HCl solution to water in step 4 is 8-12%; and the volume ratio of the HNO3 solution to water in step 5 is 10-15%.

[0020] The second object of the present invention is to provide a defective perylene imide supramolecular photocatalyst.

[0021] The third object of the present invention is to provide an application of a defective perylene imide supramolecular photocatalyst, characterized in that it is applied to the selective oxidation of benzylamine to N-benzylbutylamine.

[0022] In one embodiment, the specific application method is:

[0023] Step 2-1: adding the defective perylene imide supramolecular photocatalyst to benzylamine and acetonitrile, degassing with oxygen, stirring, and sealing;

[0024] Step 2-2: react the reaction system obtained in step 1 under visible light to obtain N-benzylbutylamine.

[0025] In one embodiment, in step 2-1, the mass ratio of the defective perylene imide supramolecular photocatalyst to benzylamine is 1:1.3-1.5; the mass volume ratio of the defective perylene imide supramolecular photocatalyst to acetonitrile is 0.8-1:1 (mg / ml), and the stirring time is 0.3-1 hour; the reaction time in step 2-2 is 4-5 hours.

[0026] Beneficial Effects

[0027] 1. The defective perylene imide supramolecular catalyst prepared by the present invention is stable, the preparation method is simple, and the operability is strong. The obtained defective perylene imide supramolecular improves the interface microenvironment of the catalyst, greatly improves the utilization efficiency of the photoinduced charge, and has higher photocatalytic activity than other types of non-precious metal modified composite photocatalysts.

[0028] 2. The defective perylene imide supramolecular photocatalyst of the present invention is metal-free, inexpensive, and has mild conditions. It plays a vital role in the selective oxidation of benzylamino groups and has high stability. It can be used for photocatalytic generation of corresponding imine compounds from benzylamine.

[0029] 3. The present invention uses acetonitrile as solvent and cheap raw materials to realize the process of photocatalytic heterogeneous oxidation of benzylamine to generate corresponding imine at room temperature.

[0030] 4. Compared with the prior art, the advantage of the present invention is that it avoids the use of difficult-to-recycle homogeneous catalysts. For the first time, by using defective perylene imide supramolecules as photocatalysts, it successfully provides a new, cheap, efficient, mild and rapid green method for selective oxidation of benzylamine to prepare the corresponding imine.

[0031] 5. The photocatalyst prepared by the present invention can be used repeatedly and the effect remains basically unchanged. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is the XRD spectrum of the photocatalyst prepared in Example 1-1.

[0033] Figure 2 This is the IR spectrum of the photocatalyst prepared in Example 1-1.

[0034] Figure 3 This is the Raman spectrum of the photocatalyst prepared in Example 1-1.

[0035] Figure 4 This is the 13CNMR spectrum of the photocatalyst prepared in Example 1-1.

[0036] Figure 5 This is the ESR spectrum of the photocatalyst prepared in Example 1-1.

[0037] Figure 6 This is the XPS spectrum of the photocatalyst prepared in Example 1-1.

[0038] Figure 7 This is a test chart of the catalytic performance of the catalyst prepared in Example 1-1 in different atmospheres.

[0039] Figure 8 This is a test chart of the catalytic performance of the catalyst prepared in Example 1-1 under different light sources.

[0040] Fig. 9 This is a test chart of the catalytic performance of the catalyst prepared in Example 1-1 on different substrates.

[0041] Fig.10 This is a test chart of the cyclic stability of the catalyst prepared in Example 1-1. DETAILED DESCRIPTION

[0042] In order to facilitate further understanding of the present invention, the following examples are provided to illustrate it in more detail. However, these examples are only provided to provide a better understanding of the invention and are not intended to limit the scope or implementation principles of the present invention. The implementation methods of the present invention are not limited to the following contents.

[0043] Example 1-1 Preparation of a defective perylene diimide supramolecular photocatalyst R-Ov-PDI

[0044] Step 1: Place a certain amount of perylene tetracarboxylic anhydride, β-alanine, and imidazole in a three-necked flask and heat at 110°C for 4 hours under inert gas. After cooling the reaction mixture, disperse it in 100 mL of ethanol, then add 300 M of 2.0 M HCl solution, stir overnight, filter, wash until the pH of the washing liquid becomes neutral, and dry in an oven at 60°C.

[0045] Step 2: Take a certain amount of the above PDI and disperse it in 300 mL of water, add 850 μL of triethylamine and stir. Then add 28 mL of 4.0 M HCl and stir. When the solution precipitates, filter and wash until the pH of the washing liquid becomes neutral, and dry in an oven at 60°C.

[0046] Step 3: Dissolve a certain amount of Bi(NO3)2·6H2O and PVP in 50mL aqueous solution (volume ratio DMF: ethylene glycol: water = 1:8:1), stir for 0.5h, then add a certain amount of the above SA-PDI and ultrasonically treat for 0.5h. Solvothermal treatment at 190℃ for 4h, after the reaction is completed, cool the mixture and disperse it in ethanol, add HCl solution, stir overnight, filter and wash until the pH of the washing liquid becomes neutral, and dry to obtain Ov-PDI;

[0047] Step 4: Disperse the Ov-PDI in step 3 in HNO3 solution, stir overnight, filter and wash until the pH of the washing solution becomes neutral, and dry to obtain R-Ov-PDI.

[0048] like Figure 1 As shown in the XRD spectrum of the photocatalyst, all diffraction peaks of R-Ov-PDI are in good agreement with the XRD spectrum of the corresponding PDI, and due to the introduction of defects, the crystallization properties and stacking mode of R-Ov-PDI are affected to a certain extent.

[0049] like Figure 2 The IR spectrum of the photocatalyst shows that PDI is at 1681, 1645 and 1236 cm -1 The characteristic bands are attributed to the stretching vibrations of O=C, C=C and CO. -1 The characteristic bands are attributed to the stretching vibration of the -OH group of the carboxylic acid, and the disappearance of these -COOH-related bands indicates the cleavage of the C=O in the carboxyl group in the bulk phase.

[0050] like Figure 3 The Raman spectrum of the photocatalyst shows that the Raman spectrum of R-Ov-PDI shows that it still maintains a molecular structure similar to that of PDI.

[0051] like Figure 4The 13C NMR spectrum of the photocatalyst shows that the signal of R-Ov-PDI at 172ppm in the 13C NMR spectrum confirms the formation of a new CO bond, and similar results are obviously absent in PDI. Ov exists in the carbonyl position of some PDI monomer side chains, and its physical and chemical properties are significantly changed after the introduction of Ov.

[0052] like Figure 5 As shown in the ESR spectrum of the photocatalyst, R-Ov-PDI exhibits a stronger EPR signal than P-Ov-PDI and PDI, which directly verifies the existence of OVs.

[0053] like Figure 6 As shown in the XPS spectrum of the photocatalyst, as shown in the XPS full spectrum scanning analysis results, the elemental composition consistent with that of PDI was confirmed in R-Ov-PDI.

[0054] like Figure 7 As shown in the catalytic performance test chart of the catalyst in different atmospheres, under oxygen atmosphere, R-Ov-PDI achieved nearly complete photooxidation of BA to prepare N-BA in about 4 hours, while maintaining nearly 100% selectivity for N-BA; under air atmosphere, R-Ov-PDI achieved a BA conversion rate of 57% after four hours of illumination, maintaining nearly 100% selectivity for N-BA; in nitrogen atmosphere, there was almost no conversion (conversion rate 0.63%).

[0055] like Figure 8 As shown in the catalytic performance test chart of the catalyst under different light sources, under visible light, simulated sunlight and full light, R-Ov-PDI achieved nearly complete photooxidation of BA to prepare N-BA within about 4 hours, while maintaining nearly 100% selectivity for N-BA.

[0056] like Fig. 9 The catalytic performance test of the catalyst on different substrates shows that in the process of photooxidation of BA to prepare N-BA on R-Ov-PDI, the electron-withdrawing group is more conducive to the reaction.

[0057] Example 1

[0058] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, and 103 mg of benzylamine and 10 mL of acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under visible light (300 W xenon lamp with cut 420 filter) for 4 hours. GC detection of the reaction solution showed that the oxidation conversion rate of benzylamine was 99% and the selectivity of N-benzylbutylamine was about 99%.

[0059] Example 2

[0060] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, and 10.3 mg of benzylamine and 10 mL of acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp with AM1.5 cutoff filter) for 4 hours. GC detection of the reaction solution showed that the oxidation conversion rate of benzylamine was 99%, and the selectivity for N-benzylbutylamine was about 99%.

[0061] Example 3

[0062] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, and 10.3 mg of benzylamine and 10 mL of acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under light (300 W xenon lamp) for 4 hours. GC detection of the reaction solution showed that the oxidation conversion rate of benzylamine was 99%, and the selectivity for N-benzylbutylamine was about 99%.

[0063] Example 4

[0064] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, and 17.5 mg of 4-(trifluoromethyl)benzylamine and 10 mL of acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and sealed. The reaction was carried out under visible light (300 W xenon lamp with cut 420 filter) for 4 hours. The reaction solution was tested by GC and the oxidation conversion rate of benzylamine was 99%, and the selectivity for N-benzylbutylamine was about 99%.

[0065] Example 5

[0066] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, and 14.1 mg of 4-chlorobenzylamine and 10 mL of acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and sealed. The reaction was carried out under visible light (300 W xenon lamp plus cut 420 filter) for 4 hours. The reaction solution was tested by GC and found that the oxidation conversion rate of 4-chlorobenzylamine was 99%, and the selectivity of N-benzylbutylamine was about 99%.

[0067] Example 6

[0068] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, and 13.7 mg of 4-methoxybenzylamine and 10 mL of acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under visible light (300 W xenon lamp with cut 420 filter) for 4 hours. GC analysis of the reaction solution showed that the oxidation conversion rate of 4-methoxybenzylamine was 85%, and the selectivity of N-benzylbutylamine was about 99%.

[0069] Example 7

[0070] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, and 12.1 mg of 4-methylbenzylamine and 10 mL of acetonitrile were added. The mixture was degassed with oxygen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under visible light (300 W xenon lamp with cut 420 filter) for 4 hours. GC detection of the reaction solution showed that the oxidation conversion rate of 4-methylbenzylamine was 76%, and the selectivity of N-benzylbutylamine was about 99%.

[0071] Example 8

[0072] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, and 10.3 mg of benzylamine and 10 mL of acetonitrile were added. The mixture was degassed with nitrogen and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under visible light (300 W xenon lamp with cut 420 filter) for 4 hours. The reaction solution was tested by GC and the oxidation conversion rate of benzylamine was 0.63%, and the selectivity for N-benzylbutylamine was about 99%.

[0073] Example 9

[0074] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, and 10.3 mg of benzylamine and 10 mL of acetonitrile were added. The mixture was degassed with air and stirred for 0.5 h in the dark and then sealed. The reaction was carried out under visible light (300 W xenon lamp with cut 420 filter) for 4 hours. The reaction solution was tested by GC and found to have an oxidation conversion rate of benzylamine of 57%, and a selectivity of about 99% for N-benzylbutylamine.

[0075] Comparative Example 1

[0076] The defective TiO2 catalyst was prepared according to the literature Q. Chen, H. Wang, C. Wang, R. Guan, R. Duan, Y. Fang, X. Hu, Applied Catalysis B: Environmental, 2020, 262, 118258.

[0077] Comparative Example 2

[0078] V-Bi2O2CO3 catalyst was prepared according to the literature Y.Zhao, W.Liu, W.Shao, L.Li, M.Zuo, J.Hu, J.Zhu, H.Wang, X.Zhang, Journal of Materials Chemistry A, 2023, 11, 3594–3598.

[0079] Comparative Example 3

[0080] The polyimide-TiO2 hybrid catalyst was prepared according to the literature W. Sheng, J. Shi, H. Hao, X. Li, X. Lang, Chemical Engineering Journal, 2020, 379, 122399.

[0081] Comparative Example 4

[0082] The BiVO4 catalyst was prepared according to the literature ML, F. Tong, Z. Wang, Y. Liu, P. Wang, H. Cheng, Y. Dai, Z. Zheng, B. Huang, Journal of Materials Chemistry A, 2022, 10, 19699-19709.

[0083] Comparative Example 5

[0084] Au-TiO2 catalyst was prepared according to the literature J.Yang, C.Mou, Applied Catalysis B:Environmental, 2018, 231, 283–291.

[0085] Comparative Example 6

[0086] The Pd / BiOCl catalyst was prepared according to the literature S. Wei, H. Zhong, H. Wang, Y. Song, C. Jia, M. Anpo, L. Wu, Applied Catalysis B: Environmental 2022, 305, 121032.

[0087] Comparative Example 7

[0088] Bi4NbO8Br catalyst was prepared according to the literature P.Wang, X.Li, S.Fan, Z.Yin, L.Wang, M.Tad′e, S Liu, Nano Energy, 2021, 83, 105831.

[0089] Comparative Example 8

[0090] The ZrS3 catalyst was prepared according to the literature Z.Tian, ​​C.Han, Y.Zhao, W.Dai, X.Lian, Y.Wang, Y.Zheng, Y.Shi, X Pan, Z.Huang, H.Li, W.Chen, Nature Communications 2021,12,2039.

[0091] Comparative Example 9

[0092] Pd@MIL-125 was prepared according to the literature H. Wang, J. Yu, S. Wei, M. Lin, Y. Song, L. Wu, Chemical Engineering Journal, 2022, 441, 136020.

[0093] Table 1. Reaction results of light-driven catalytic oxidation of BA in Examples 1-9 and Comparative Examples 1-15

[0094]

[0095] Example 10

[0096] 8 mg of R-Ov-PDI was added to a round-bottom reaction bottle, 10.3 mg of benzylamine and 10 mL of acetonitrile were added, the mixture was degassed in air and stirred for 0.5 h in the dark, and then sealed; the mixture was reacted for 4 h under visible light (300 W xenon lamp with cut 420 filter), the reaction solution was detected by GC, the catalyst was centrifuged, washed and dried, and the cycle was repeated 4 times under the same conditions. The circulating reaction solution was analyzed by GC, and the results are shown in Fig.10 , showing that the BA conversion rate and selectivity for N-benzylbutylamine did not change significantly during the four cycles, indicating that the R-Ov-PDI catalyst can be recycled. After four cycles of selective oxidation of BA under light, the composite catalyst R-Ov-PDI still showed good catalytic ability.

Claims

1. A method for preparing a defective perylene imide supramolecular photocatalyst, characterized in that: The steps are as follows: Step 1: Perylene tetracarboxylic anhydride, β-alanine and imidazole are heated to react under inert gas conditions. After the reaction, the mixture is cooled and dispersed in ethanol, HCl solution is added, stirred overnight, filtered and washed until the pH of the washing liquid becomes neutral, and PDI is obtained after drying; Step 2: Disperse the PDI in step 1 in water, add triethylamine, and then add HCl solution and stir. When the solution precipitates, filter and wash until the pH of the washing liquid becomes neutral, and dry to obtain SA-PDI; Step 3: dissolving an inorganic salt containing bismuth and polyvinyl pyrrolidone in an N,N-dimethylformamide-ethylene glycol-water solution and stirring, then adding the SA-PDI obtained in step 2 for ultrasonic treatment, and after the ultrasonic treatment, transferring to a hydrothermal reactor for solvothermal reaction; Step 4: After the solvothermal reaction is completed, the mixture is cooled and dispersed in ethanol, HCl solution is added, stirred overnight, filtered and washed until the pH of the washing liquid becomes neutral, and Ov-PDI is obtained after drying; Step 5: Disperse the Ov-PDI in step 4 in a HNO3 solution, stir overnight, filter and wash until the pH of the washing solution becomes neutral, and dry to obtain the defective perylene imide supramolecular photocatalyst R-Ov-PDI.

2. The method for preparing a defective perylene imide supramolecular photocatalyst according to claim 1, characterized in that: In the step 1, the molar ratio of perylenetetracarboxylic anhydride, β-alanine, and imidazole is 1:0.8-1.2:0.8-1.2; The inert gas is nitrogen, argon or helium; The heating reaction temperature is 100-130° C., and the heating reaction time is 3-6 hours.

3. The method for preparing a defective perylene imide supramolecular photocatalyst according to claim 1, characterized in that: The volume ratio of triethylamine to water in step 2 is 0.1-0.4%, and the volume ratio of HCl solution to water is 8-12%.

4. The method for preparing a defective perylene imide supramolecular photocatalyst according to claim 1, characterized in that: The inorganic salt containing bismuth in step 3 is Bi(NO3)3·5H2O; the K value of polyvinyl pyrrolidone is 30.

5. The method for preparing a defective perylene imide supramolecular photocatalyst according to claim 1 or 4, characterized in that: In step 3, the mass ratio of the inorganic salt containing bismuth to polyvinyl pyrrolidone is 5:1; the stirring reaction time of the two is 0.5-1 hour, the amount of SA-PDI added in step 3 is 1.5 times the molar mass of the inorganic salt containing bismuth, the volume ratio of N,N-dimethylformamide: water: ethylene glycol in the N,N-dimethylformamide-water-ethylene glycol solution is 1:1:8, the ultrasonic treatment time after adding SA-PDI is 0.2-0.5 hour, the solvent thermal reaction temperature is 180-190°C, and the solvent thermal reaction time is 3-5 hours.

6. The method for preparing a defective perylene imide supramolecular photocatalyst according to claim 1, characterized in that: In step 4, the volume ratio of HCl solution to water is 8-12%; in step 5, the volume ratio of HNO3 solution to water is 10-15%.

7. A defective perylene imide supramolecular photocatalyst prepared according to any one of the preparation methods of claims 1-6.

8. The use of a defective perylene imide supramolecular photocatalyst according to claim 7, characterized in that: The photocatalyst is used for selectively oxidizing benzylamine to N-benzylbutylamine.

9. The use of a defective perylene imide supramolecular photocatalyst according to claim 8, characterized in that: The specific application method is: Step 2-1: adding the defective perylene imide supramolecular photocatalyst to benzylamine and acetonitrile, degassing with oxygen, stirring, and sealing; Step 2-2: react the reaction system obtained in step 2-1 under visible light to obtain N-benzylbutylamine.

10. The use of a defective perylene imide supramolecular photocatalyst according to claim 8, characterized in that: In the step 2-1, the mass ratio of the defective perylene imide supramolecular photocatalyst to benzylamine is 1:1.3-1.5; the mass volume ratio of the defective perylene imide supramolecular photocatalyst to acetonitrile is 0.8-1:1 (mg / ml), and the stirring time is 0.3-1 hour; the reaction time in step 2-2 is 4-5 hours.

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