An organic-inorganic hybrid photocatalyst, a preparation method and application thereof

Abstract

This application relates to the field of materials technology, providing an organic-inorganic hybrid photocatalyst, its preparation method, and its application. The catalyst comprises an organic semiconductor component and an inorganic nanomaterial component. The organic semiconductor component is an N-substituted perylene diimide derivative with N-substituted aryl groups containing electron-withdrawing groups at both ends of its perylene core. The inorganic nanomaterial is a weakly light-absorbing, hydrophilic inorganic oxide nanoparticle. The organic semiconductor component is stably loaded onto the surface of the inorganic nanomaterial through covalent bonds, hydrogen bonds, or physical adsorption. This catalyst exhibits high photocatalytic activity and good stability, effectively solving the problems of high carrier recombination rate and insufficient active sites in pure perylene diimide derivatives. It can be applied to photocatalytic oxidation of organic synthesis reactions, especially suitable for the selective oxidation of alcohols to aldehydes or ketones in a fixed-bed continuous flow under visible light and air atmosphere. The reaction conditions are mild and highly selective, suppressing over-oxidation, and it has good prospects for industrial application.

Description

Technical Field

[0001] This application belongs to the field of materials technology, and in particular relates to an organic-inorganic hybrid photocatalyst, its preparation method and application. Background Technology

[0002] Aldehydes and ketones are widely used fine chemical intermediates with irreplaceable value in pharmaceutical synthesis, fragrance preparation, and fine chemicals. Traditional methods for preparing aldehydes and ketones by alcohol oxidation often require the use of stoichiometric oxidants, involve harsh reaction conditions, and are prone to over-oxidation, resulting in low selectivity for the target product and numerous byproducts. This not only increases production costs but also easily causes environmental pollution. Therefore, developing simple, efficient, and green routes for the preparation of aldehydes and ketones has become an urgent technical challenge to be addressed in this field.

[0003] Heterogeneous photocatalysis technology offers a green solution to the aforementioned problems. Using visible light as an energy source and air as an oxidant, it requires no additional equivalent oxidant and boasts advantages such as environmental friendliness, low energy consumption, and mild reaction conditions. Among these, heterogeneous photocatalysts, due to their ease of separation and recovery, good stability, compatibility with continuous flow reactors, and low cost, are more suitable for large-scale industrial applications and have become a research hotspot in the field of photocatalytic organic synthesis. Among numerous heterogeneous photocatalysts, perylene diimide (PDI)-based materials, due to their excellent thermal stability, photostability, and tunable electronic structure, exhibit good application potential in photocatalytic oxidation reactions and have become a key research object in the field of photocatalytic organic synthesis. However, pure perylene diimide (PDI) materials still face significant technical bottlenecks in practical applications: their strong intermolecular forces easily lead to aggregation, resulting in a small specific surface area and insufficient exposure of active sites. Simultaneously, the high recombination rate of photogenerated carriers significantly limits their photocatalytic activity, making it difficult to meet the requirements of high-efficiency catalysis.

[0004] More importantly, industrial applications place higher demands on catalysts, requiring them to simultaneously possess high catalytic activity, easy separation and recovery, low cost, and good adaptability to continuous flow processes. Currently, existing perylene diimide (PDI) photocatalysts still suffer from two major drawbacks: first, insufficient built-in electric field (BEF) leads to low photogenerated carrier separation efficiency and difficulty in improving catalytic activity; second, the material morphology is prone to aggregation, further reducing the exposure of active sites and making it difficult to adapt well to the fixed-bed application mode of continuous flow reactors, hindering industrial continuous production. Furthermore, while some catalysts can achieve certain catalytic effects, their complex preparation processes and high costs further limit their large-scale application. Therefore, developing a perylene diimide-based heterogeneous photocatalyst with high catalytic activity, stable loading, adaptability to continuous flow processes, and effective solutions to the problems of carrier separation and insufficient active sites has significant practical implications and industrial application value. Summary of the Invention

[0005] The purpose of this application is to provide an organic-inorganic hybrid photocatalyst, which aims to solve the problems of poor loading stability, harsh catalytic conditions, and difficulty in adapting to continuous flow processes of existing PDI photocatalysts, and to achieve efficient, green, and continuous photocatalytic oxidation of alcohol compounds.

[0006] The embodiments of this application are implemented as follows: an organic-inorganic hybrid photocatalyst includes an organic semiconductor component and an inorganic nanomaterial component; The organic semiconductor component is an N-substituted perylene diimide derivative with the structure shown in general formula (I): R1 and R2 are each independently selected from aryl groups substituted with electron-withdrawing groups; The inorganic nanomaterials are composed of weak light-absorbing, hydrophilic inorganic oxide nanoparticles. The organic semiconductor component is loaded onto the surface of the inorganic nanomaterial component through covalent bonds, hydrogen bonds, or physical adsorption.

[0007] Another objective of this application is a method for preparing the above-mentioned organic-inorganic hybrid photocatalyst, comprising: The N-substituted perylene diimide derivative is dissolved in a good solvent to form a solution; The inorganic nanomaterials were added to the solution, and then ultrasonically dispersed and allowed to stand to allow the N-substituted perylene diimide derivatives to self-assemble and be loaded onto the surface of the inorganic nanomaterials. The solid product was separated, washed, and dried to obtain the organic-inorganic hybrid photocatalyst.

[0008] Another objective of this application is the application of the above-mentioned organic-inorganic hybrid photocatalyst in photocatalytic oxidation organic synthesis reactions.

[0009] The organic-inorganic hybrid photocatalyst provided in this application achieves complementary advantages through the combination of N-substituted perylene diimide derivatives and hydrophilic inorganic nanomaterials. The wide light absorption range and high electron mobility of the organic component and the high dispersibility and large specific surface area of ​​the inorganic component form a synergistic effect. At the same time, the introduction of electron-withdrawing groups on the aryl group effectively enhances the built-in electric field and promotes the separation of photogenerated carriers, completely solving the technical pain points of high carrier recombination rate and insufficient exposure of active sites in pure PDI materials, and significantly improving photocatalytic activity. Moreover, the organic semiconductor component and the inorganic nanomaterials are stably combined through covalent bonds, hydrogen bonds or physical adsorption, effectively avoiding the peeling and shedding of organic components during the reaction, significantly improving the stability and cycle life of the catalyst, and reducing the cost of industrial applications.

[0010] Furthermore, the preparation method of this application is simple to operate, requires no complex special equipment, and the reaction conditions are mild. The preparation can be completed simply by dissolving, ultrasonically dispersing, standing, separating and drying, resulting in low production costs and easy large-scale scaling. The obtained catalyst can be directly adapted to a continuous flow reactor in a fixed-bed form, and continuous photocatalytic oxidation of alcohols can be achieved under visible light irradiation and air atmosphere. No equivalent oxidant needs to be added during the entire reaction process, making it green, environmentally friendly and mild. At the same time, the over-oxidation of aldehydes can be effectively inhibited by precisely controlling the material residence time, which greatly improves the selectivity of aldehyde and ketone products. It has extremely high industrial application value and prospects in the fields of fine chemicals and pharmaceutical intermediate synthesis. Attached Figure Description

[0011] Figure 1 shows the XPS spectrum of the PDI-PoCa / Si hybrid photocatalyst prepared in Example 1 of this application; Figure 2 shows the EDS diagrams of the PDI-PoCa / Si and PDI-PoCN / Si hybrid photocatalysts prepared in Examples 1-2 of this application; Figure 3 shows the SEM images of the SiO2 aerogel, PDI-PoCa / Si and PDI-PoCN / Si hybrid photocatalysts used in Examples 1-2 of this application; Figure 4 is a comparison of the yields of PDI-PoCa / Si and PDI-PoCN / Si hybrid photocatalysts prepared in Examples 1-2 of this application for the photocatalytic oxidation of various alcohol compounds. Figure 5 is a schematic diagram of the photocatalytic reaction of the organic-inorganic hybrid photocatalyst provided in the embodiments of this application in a continuous flow reactor. Detailed Implementation

[0012] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0013] This application provides an organic-inorganic hybrid photocatalyst, comprising an organic semiconductor component and an inorganic nanomaterial component; The organic semiconductor component is an N-substituted perylene diimide derivative with the structure shown in general formula (I): R1 and R2 are each independently selected from aryl groups substituted with electron-withdrawing groups; the introduction of electron-withdrawing groups can regulate the electronic structure of perylene diimide derivatives, enhance the built-in electric field, promote the separation of photogenerated carriers, and improve its interfacial interaction with inorganic nanomaterials.

[0014] The inorganic nanomaterial component is a weak light-absorbing, hydrophilic inorganic oxide nanoparticle, which can avoid competing with the light absorption of the organic semiconductor component, while improving the dispersion of the catalyst in the polar reaction system and increasing the exposure of active sites.

[0015] The organic semiconductor component is loaded onto the surface of the inorganic nanomaterial through covalent bonds, hydrogen bonds, or physical adsorption, thereby achieving a stable combination of organic and inorganic components, preventing the organic component from peeling off, and improving the catalyst's service life.

[0016] Further, the aryl group is any one of benzene, naphthalene, thiophene, furan, pyrrole, pyrazole, pyridine, pyridazine, pyrimidine, etc. The electron-withdrawing group (EWG) is selected from at least one of carboxyl (-COOH), cyano (-CN), halogen (-F, -Cl, -Br), nitro (-NO2). For N-containing heterocycles such as pyrrole, pyrazole, pyridine, pyridazine, and pyrimidine, the N atom can be prepared into an electron-withdrawing quaternary ammonium salt form as the electron-withdrawing group.

[0017] Furthermore, to improve catalytic efficiency and catalytic stability, the number of electron-withdrawing groups substituted on the aryl group is 1-3, and the corresponding N-substituted perylene diimide derivative can be selected from any one of PDI-PCa (p-carboxyphenyl substituted), PDI-PCN (p-cyanophenyl substituted), PDI-PoCa (meta / p-dicarboxyphenyl substituted), PDI-PoCN (cyanophenyl disubstituted), and PDI-PTCa (meta / p / meta-tricarboxyphenyl substituted). Based on previous functional group design and screening experiments, this application confirms that linking electron-withdrawing groups to the perylene nucleus via the benzene ring is an effective strategy for regulating the photocatalytic performance of PDI derivatives. Furthermore, when 1-3 electron-withdrawing groups are introduced onto the aryl group, the photogenerated carrier separation efficiency and catalytic activity of the PDI derivatives reach the optimal level. Among them, PDI-PoCa and PDI-PoCN, which contain 2 electron-withdrawing groups, exhibit the most outstanding catalytic activity, while PDI-PCa and PDI-PCN, which contain 1 electron-withdrawing group, and PDI-PTCa, which contain 3 electron-withdrawing groups, also possess excellent catalytic performance.

[0018] Furthermore, the inorganic nanomaterial is a nanoparticle of silicon dioxide (SiO2), aluminum oxide (Al2O3), titanium oxide (TiO2), or zinc oxide (ZnO), preferably a hydrophilic SiO2 aerogel nanoparticle or a SiO2 nanoparticle.

[0019] This application also provides a method for preparing the above-mentioned organic-inorganic hybrid photocatalyst, including the following steps: Dissolution: The N-substituted perylene diimide derivative is dissolved in a good solvent to form a homogeneous solution, ensuring complete dissolution of the organic components and avoiding agglomeration; Loading: The inorganic nanomaterials are added to the solution and subjected to ultrasonic dispersion and static treatment. Ultrasonic dispersion can make the inorganic nanomaterials uniformly dispersed in the solution and promote full contact between the organic semiconductor components and the inorganic nanomaterials. Static treatment promotes the self-assembly of N-substituted perylene diimide derivatives and stabilizes them on the surface of inorganic nanomaterials through covalent bonds, hydrogen bonds or physical adsorption. Separation and drying: Separate the solid product, wash and dry it to obtain the organic-inorganic hybrid photocatalyst.

[0020] Further, the good solvent is concentrated sulfuric acid or an alkaline solvent. When the good solvent is concentrated sulfuric acid, the step of separating the solid product includes: slowly adding deionized water to the mixture to precipitate the solid; when the good solvent is an alkaline solvent, such as an aqueous solution of triethylamine or an aqueous solution of sodium carbonate, the step of separating the solid product includes: slowly adding an aqueous solution of dilute hydrochloric acid to the mixture to precipitate the solid.

[0021] Furthermore, the mass ratio of the N-substituted perylene diimide derivative to the inorganic nanomaterial is 1:(20~300).

[0022] This application also provides the application of the above-mentioned organic-inorganic hybrid photocatalyst, which is used in photocatalytic oxidation of organic synthesis reactions, and is particularly suitable for the selective oxidation of alcohols.

[0023] Furthermore, the specific application involves filling the illumination zone of a continuous flow reactor in the form of a fixed bed of the organic-inorganic hybrid photocatalyst under visible light irradiation and an air atmosphere, catalyzing the selective oxidation of alcohols to the corresponding aldehydes or ketones. This application scenario requires no additional oxidant, using air as the oxidant and visible light as the energy source, aligning with the concept of green catalysis. The combination of the fixed bed configuration and the continuous flow reactor enables catalyst recycling, and the reaction process can be strictly controlled by adjusting the reactant residence time, effectively suppressing the over-oxidation of aldehydes, improving the selectivity of the target product, and making it suitable for industrial continuous production.

[0024] The following detailed embodiments illustrate the organic-inorganic hybrid photocatalyst, its preparation method, and its application provided in this application. Unless otherwise specified, the experimental methods used in the embodiments are conventional methods; and the materials and reagents used, unless otherwise specified, are commercially available conventional products.

[0025] Example 1: Preparation of PDI-PoCa / Si hybrid photocatalyst 50 mg of PDI-PoCa (structural formula as shown in formula (1) above) was dissolved in 50 mL of concentrated sulfuric acid. After complete dissolution, 2.5 g of hydrophilic SiO2 aerogel (PDI:SiO2 mass ratio 1:50) was added. The mixture was sonicated for 30 minutes and allowed to stand for 24 hours. Subsequently, a large amount of deionized water was slowly added to the mixture, and a solid precipitated out. The precipitate was collected by centrifugation, repeatedly washed with deionized water until the pH of the supernatant was neutral, and finally dried under vacuum to obtain the PDI-PoCa / Si hybrid photocatalyst.

[0026] Example 2: Preparation of PDI-PoCN / Si hybrid photocatalyst The preparation method is the same as in Example 1, except that PDI-PoCa is replaced with PDI-PoCN (structural formula as shown in formula (2) above). The resulting product is a PDI-PoCN / Si hybrid photocatalyst.

[0027] The PDI-PoCa / Si and PDI-PoCN / Si hybrid photocatalysts prepared in Examples 1-2 above were characterized in structure and tested in photocatalytic performance. The specific test results are analyzed in conjunction with the attached figures below: Figure 1 The XPS spectrum of the PDI-PoCa / Si hybrid photocatalyst prepared in Example 1 shows a new bonding environment in its O 1s spectrum, confirming the synergistic interaction between hydrogen bonds and covalent bonds between the organic semiconductor component and the inorganic nanomaterial, achieving a stable combination of the two.

[0028] Figure 2 The images show the EDS spectra of the PDI-PoCa / Si and PDI-PoCN / Si hybrid photocatalysts prepared in Examples 1-2. The energy dispersive spectroscopy analysis results show that the carbon elements on the surface of both hybrid materials are uniformly distributed. The relative atomic content of carbon elements on the surface of PDI-PoCa / Si is about 49.2%, which directly proves that the perylene diimide derivative has been effectively loaded on the surface of SiO2 nanomaterials.

[0029] Figure 3The images show SEM images of the SiO2 aerogel, PDI-PoCa / Si and PDI-PoCN / Si hybrid photocatalysts used in Examples 1-2. It can be clearly observed from the morphology images that the organic components are uniformly loaded on the surface of the inorganic nanomaterials without obvious agglomeration, which ensures the full exposure of active sites in the catalytic reaction.

[0030] Figure 4 This is a comparison of the yields of the PDI-PoCa / Si and PDI-PoCN / Si hybrid photocatalysts prepared in Examples 1-2 for the photocatalytic oxidation of various alcohol compounds. Black text represents the yield of PDI-PoCa / Si, and blue text represents the yield of PDI-PoCN / Si. Taking the PDI-PoCa / Si from Example 1 as an example, its intermittent photocatalytic performance was tested as follows: 15 mg of the hybrid catalyst (PDI-PoCa equivalent) was dispersed with 0.3 mmol of benzyl alcohol derivative in 10 mL of a mixed solvent (acetonitrile / 6M HCl = 4:1, v / v). The mixture was first stirred in the dark for 30 min to ensure sufficient contact between the substrate and the catalyst, and then irradiated with a 25 W blue LED for 18 h. After the reaction, the catalyst was separated by filtration, and the filtrate was extracted, dried, and then... 1 The product yield was determined by H NMR. The results showed that the catalyst exhibited excellent performance in the oxidation of various aromatic alcohols, and the yields of the corresponding aldehyde / ketone products could reach more than 90%.

[0031] Figure 5This diagram illustrates the photocatalytic reaction of the organic-inorganic hybrid photocatalyst provided in this application within a continuous flow reactor. The photocatalytic performance was tested using thiophene-2-methanol as the substrate. The specific operation was as follows: The hybrid catalyst was filled into the right-side illumination chamber of a U-shaped tube (10 cm long, 1.3 cm in diameter), with a fixed catalyst bed formed by sand core support at the bottom of the chamber. The reaction solution containing the substrate was pumped into the catalyst bed through a constant-pressure dropping funnel at a flow rate of 8.5 mL / h. The right-side chamber underwent photocatalytic reaction under continuous blue LED irradiation. The effluent was collected and post-processed to analyze the formation rate of the product thiophene-2-carboxaldehyde. The test results showed that the PDI-PoCa / Si hybrid catalyst with a PDI to SiO2 mass ratio of 1:50 maintained a stable product formation rate of 0.15 mmol / h, demonstrating good potential for industrial application. When the mass ratio was adjusted to 1:100, the catalytic performance of the catalyst decreased, with the product formation rate dropping to 0.06 mmol / h. After replacing the catalyst with the PDI-PoCN / Si prepared in Example 2, the continuous flow catalytic performance was further tested. The results showed that when the mass ratio of PDI to SiO2 was 1:50, the product formation rate was stable at 0.05 mmol / h; when the mass ratio was 1:100, the product formation rate was only 0.02 mmol / h. It is speculated that the main reason for this performance difference is that the adsorption capacity of SiO2 nanomaterials for PDI-PoCN is weaker than that for PDI-PoCa, resulting in a decrease in both its loading capacity and loading stability.

[0032] Example 3: Preparation of PDI-PCa / Si hybrid photocatalyst The preparation method is the same as in Example 1, except that PDI-PoCa is replaced with PDI-PCa, which has only a carboxyl group modified at the para position on the benzene ring. The resulting product is a PDI-PCa / Si hybrid photocatalyst.

[0033] Example 4: Preparation of PDI-PoCa / Ti hybrid photocatalyst The preparation method is the same as in Example 1, except that SiO2 aerogel is replaced with TiO2. The resulting product is a PDI-PoCa / Ti hybrid photocatalyst.

[0034] Example 5: Preparation of PDI-PoCa / Al hybrid photocatalyst The preparation method is the same as in Example 1, except that the SiO2 aerogel is replaced with high-purity α-Al2O3. The resulting product is a PDI-PoCa / Al hybrid photocatalyst.

[0035] Example 6: Preparation of PDI-PoCa / Si hybrid photocatalyst The preparation method is the same as in Example 1, except that the good solvent is replaced with the alkaline solvent triethylamine aqueous solution (99wt%), and the deionized water added in the step of separating the solid product is replaced with dilute hydrochloric acid aqueous solution (1mol / L).

[0036] Example 7: Preparation of PDI-PoCa / Si hybrid photocatalyst The preparation method is the same as in Example 1, except that the good solvent is replaced with an alkaline solvent sodium carbonate aqueous solution (1 mol / L), and the deionized water added in the step of separating the solid product is replaced with a dilute hydrochloric acid aqueous solution (1 mol / L).

[0037] The hybrid photocatalysts prepared in Examples 3-7 were subjected to performance testing using the same continuous flow reaction testing method as described above. The test results are as follows: When the PDI-PCa / Si hybrid photocatalyst prepared in Example 3 with a PDI to SiO2 mass ratio of 1:50 was filled into the reactor, the formation rate of the product thiophene-2-carboxaldehyde was found to be stable at 0.03 mmol / h; when the PDI-PoCa / Ti hybrid photocatalyst prepared in Example 4 with a PDI to TiO2 mass ratio of 1:50 was filled, the formation rate of the product thiophene-2-carboxaldehyde was stable at 0.13 mmol / h; when the PDI-PoCa / Al hybrid photocatalyst prepared in Example 5 with a PDI to Al2O3 mass ratio of 1:50 was filled, the formation rate of the product thiophene-2-carboxaldehyde was stable at 0.12 mmol / h. The PDI-PoCa / Si hybrid photocatalysts prepared in Examples 6-7 with a PDI to SiO2 mass ratio of 1:50 were filled with 0.13 mmol / h. The generation rate of the product thiophene-2-carboxaldehyde was stable at 0.13 mmol / h.

[0038] In summary, the organic-inorganic hybrid photocatalyst preparation process provided in this application is simple, uses low-cost raw materials, and can be mass-produced. The catalyst possesses high photocatalytic activity, high selectivity, excellent stability, and good cycle performance. It requires no precious metal doping or the addition of equivalent oxidants, achieving selective oxidation of alcohols using only visible light as energy and air as the oxidant. Furthermore, this catalyst can be directly adapted to a continuous flow reactor in a fixed-bed configuration, solving the problem of the difficulty in industrial continuous production of traditional PDI-based catalysts. During the reaction, the residence time can be precisely controlled by adjusting the material flow rate, effectively inhibiting the over-oxidation of aldehydes and significantly improving the yield of the target product. The catalyst and application process of this application are suitable for the green synthesis of aldehydes and ketones in pharmaceutical intermediates, fragrances, and fine chemicals, possessing significant economic value and environmental benefits, and showing broad prospects for industrial application.

[0039] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of this patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. An organic-inorganic hybrid photocatalyst, characterized in that, Includes organic semiconductor components and inorganic nanomaterial components; The organic semiconductor component is an N-substituted perylene diimide derivative with the structure shown in general formula (I): R1 and R2 are each independently selected from aryl groups substituted with electron-withdrawing groups; The inorganic nanomaterials are composed of weak light-absorbing, hydrophilic inorganic oxide nanoparticles. The organic semiconductor component is loaded onto the surface of the inorganic nanomaterial component through covalent bonds, hydrogen bonds, or physical adsorption.

2. The organic-inorganic hybrid photocatalyst according to claim 1, characterized in that, The aryl group is any one of benzene, naphthalene, thiophene, furan, pyrrole, pyrazole, pyridine, pyridazine, and pyrimidine; The electron-withdrawing group is selected from carboxyl, cyano, halogen, nitro, or electron-withdrawing quaternary ammonium salts formed by quaternization of N atoms of N heterocyclic aryl groups such as pyrrole, pyrazole, pyridine, pyridazine, and pyrimidine.

3. The organic-inorganic hybrid photocatalyst according to claim 2, characterized in that, The number of electron-withdrawing groups is 1-3.

4. The organic-inorganic hybrid photocatalyst according to claim 2, characterized in that, The N-substituted perylene diimide derivative is selected from any one of p-carboxyphenyl-substituted perylene diimide, p-cyanophenyl-substituted perylene diimide, meta / para-dicarboxyphenyl-substituted perylene diimide, cyanophenyl disubstituted perylene diimide, and meta / para / meta-tricarboxyphenyl-substituted perylene diimide.

5. The organic-inorganic hybrid photocatalyst according to claim 1, characterized in that, The inorganic nanomaterial components are selected from nanoparticles of silicon dioxide, aluminum oxide, titanium oxide, or zinc oxide.

6. A method for preparing an organic-inorganic hybrid photocatalyst as described in any one of claims 1-5, characterized in that, include: The N-substituted perylene diimide derivative is dissolved in a good solvent to form a solution; The inorganic nanomaterials were added to the solution, and then ultrasonically dispersed and allowed to stand to allow the N-substituted perylene diimide derivatives to self-assemble and be loaded onto the surface of the inorganic nanomaterials. The solid product was separated, washed, and dried to obtain the organic-inorganic hybrid photocatalyst.

7. The preparation method according to claim 6, characterized in that, The good solvent is concentrated sulfuric acid or an alkaline solvent; when the good solvent is concentrated sulfuric acid, the step of separating the solid product includes: slowly adding deionized water to the mixture to precipitate the solid; when the good solvent is an alkaline solvent, the step of separating the solid product includes: slowly adding dilute hydrochloric acid aqueous solution to the mixture to precipitate the solid.

8. The preparation method according to claim 6, characterized in that, The mass ratio of the N-substituted perylene diimide derivative to the inorganic nanomaterial is 1:(20~300).

9. The application of an organic-inorganic hybrid photocatalyst as described in any one of claims 1-5 in photocatalytic oxidation of organic synthesis reactions.

10. The application according to claim 9, characterized in that, Under visible light irradiation and an air atmosphere, the organic-inorganic hybrid photocatalyst is filled in the irradiation zone of a continuous flow reactor in the form of a fixed bed, catalyzing the selective oxidation of alcohol compounds to the corresponding aldehydes or ketones.

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