Preparation method of functionalized covalent organic framework nanocomposite capable of scavenging reactive oxygen species

Abstract

The application discloses a preparation method of a functionalized covalent organic framework nanocomposite capable of removing active oxygen. Mesoporous silica nanoparticles are used as a sacrifice template, and after loading platinum nanoparticles, the covalent organic framework is wrapped with manganese porphyrin. Finally, the hollow covalent organic framework nanocomposite loaded with platinum nanoparticles is formed through strong alkali etching. Since the nanocomposite contains platinum nanoparticles and manganese-based porphyrin at the same time, the nanocomposite has hydrogen peroxidase-like activity and superoxide dismutase-like activity, and can be used for efficiently removing active oxygen. The application is simple and easy to operate, has strong repeatability, excellent morphology, uniform size, good dispersity and strong catalytic activity.

Description

Technical Field

[0001] The present invention relates to the field of new chemical materials, and in particular to a functionalized covalent organic framework nanocomposite material capable of scavenging active oxygen and a preparation method thereof. Background Art

[0002] Covalent organic framework nanomaterials are a class of functional organic polymer materials with a porous structure. Covalent organic framework nanomaterials with porphyrin monomers as synthetic ligands have special optical, acoustic, catalytic and other properties, and are widely used in cutting-edge fields of biochemistry.

[0003] Metal nanoparticles possess small size, high specific surface area, high catalytic activity, good biocompatibility, and unique electrical, optical, acoustic, thermodynamic, and magnetic properties. They are currently being applied in a wide range of fields, including disease treatment, clinical diagnosis, and pollution control. Typical metal nanoparticles include platinum nanoclusters and gold nanoclusters.

[0004] Constructing nanocomposites, that is, combining multiple types of nanozyme materials to achieve richer functions, is a widely used idea. At present, incorporating inorganic functional materials into covalent organic frameworks is one of the important strategies for constructing nanocomposites. Generally, small metal nanoparticles are loaded into the porous structure of pre-synthesized COF, or the pre-synthesized metal nanoparticles are encapsulated with COF. Summary of the Invention

[0005] In order to address the shortcomings of existing synthesis technology, the purpose of the present invention is to synthesize a porphyrin-based covalent organic framework nanocomposite material with uniform size and stable performance functionalized platinum nanoparticles, which has both catalase-like activity (CAT) and superoxide dismutase (SOD)-like activity.

[0006] In order to achieve the above-mentioned objectives, the present invention adopts the following technical solutions: in the first aspect, the present invention provides a method for preparing a functionalized covalent organic framework nanocomposite material that can scavenge active oxygen; in the second aspect, the present invention provides a functionalized covalent organic framework nanocomposite material that can scavenge active oxygen.

[0007] The present invention provides a method for preparing a functionalized covalent organic framework nanocomposite material capable of scavenging active oxygen, comprising the following steps: using mesoporous silica nanoparticles as a sacrificial template, loading platinum nanoparticles, and then wrapping a covalent organic framework of manganese porphyrin; and finally etching with a strong base to form a hollow functionalized covalent organic framework nanocomposite material loaded with platinum nanoparticles.

[0008] Further, the following steps are included:

[0009] (1) Preparation of platinum nanoparticles (PtNPs): Polyvinylpyrrolidone (PVP) was dissolved in ethanol, and an aqueous solution of chloroplatinic acid (H2PtCl6) was added. The mixture was stirred at room temperature, heated under reflux, and cooled to room temperature to obtain a PtNPs solution.

[0010] (2) Preparation of mesoporous silica nanoparticles (MSN): Hexadecyltrimethylammonium p-toluenesulfonate (CTAT) and triethanolamine were added to water and heated with stirring; tetraethyl orthosilicate and bis-[3-(triethoxysilyl)propyl]-tetrasulfide (BTES) were added dropwise and heated for reaction. After cooling to room temperature, 10% hydrochloric acid ethanol solution was added and heated. After cooling to room temperature, the mixture was centrifuged and washed to obtain a mesoporous silica nanoparticle (MSN) solution.

[0011] (3) Mesoporous silica nanoparticles loaded with platinum nanoparticles MPt: MSN and PtNPs were mixed, ultrasonically shaken, and centrifuged to obtain MPt solution;

[0012] (4) Modification of polyethylenimine (PEI) on PtNPs-loaded MSNs (MPtP): 10% polyethylenimine (PEI) aqueous solution was slowly added to the MPt solution, stirred at room temperature, and centrifuged to obtain the MPtP solution.

[0013] (5) Coating the covalent organic framework MPtC on the mesoporous silica modified with PEI: PVP was dissolved in o-dichlorobenzene and n-hexanol, and sonicated. The MPtP solution was centrifuged and dissolved in the upper solution, and sonicated. 5,10,15,20-tetrakis(4-aminophenyl) manganese porphyrin TAPP-Mn and 2,5-dihydroxyterephthalaldehyde were weighed and added. Glacial acetic acid was added and heated. After cooling to room temperature, the solution was centrifuged and washed to obtain the MPtC solution.

[0014] (6) Etching silicon to generate a platinum-loaded hollow covalent organic framework HPtC: The MPtC solution was centrifuged and added with a 2-5 mol / L strong base solution and stirred; the solution was centrifuged and washed, and freeze-dried to obtain a green powder solid, thereby preparing a functionalized covalent organic framework nanocomposite material HPtC.

[0015] Furthermore, in step (1), tetraethyl orthosilicate and bis-[3-(triethoxysilyl)propyl]-tetrasulfide (BTES) are used as silicon sources in a volume ratio of 4:1 to synthesize mesoporous silica.

[0016] In step (2), the volume ratio of tetraethyl orthosilicate to bis-[3-(triethoxysilyl)propyl]-tetrasulfide BTES is 3-5:1.

[0017] In step (2), MSNs stabilized with cetyltrimethylammonium p-toluenesulfonate (CTAT) as a surfactant were mixed with PVP-stabilized PtNPs and successfully loaded. PVP-stabilized platinum nanoparticles were synthesized using PVP as a substrate; cetyltrimethylammonium p-toluenesulfonate (CTAT) was used as a surfactant to stabilize mesoporous silica nanoparticles.

[0018] In step (3), the mixing ratio of mesoporous silica nanoparticles MSN and platinum nanoparticles PtNPs is 0.5-5 mg:1 μmol.

[0019] Furthermore, in step (5), the mass ratio of 5,10,15,20-tetrakis(4-aminophenyl)manganeseporphyrin TAPP-Mn to 2,5-dihydroxyterephthalaldehyde is 2-3:1.

[0020] In step (1), platinum nanoparticles (PtNPs) are prepared by dissolving 15-20 mg of polyvinylpyrrolidone (PVP) in ethanol, adding 3-8 mL (6 mM) of chloroplatinic acid (H2PtCl6) aqueous solution, stirring at room temperature, heating under reflux, and cooling to room temperature to obtain a PtNPs solution;

[0021] Furthermore, in step (2), mesoporous silica nanoparticles (MSN) are prepared by adding 200-400 mg of hexadecyltrimethylammonium p-toluenesulfonate (CTAT) and 70-80 mg of triethanolamine to water, heating and stirring; adding 2-3 mL of tetraethyl orthosilicate and bis-[3-(triethoxysilyl)propyl]-tetrasulfide (BTES) dropwise, heating for reaction, cooling to room temperature, adding 10% hydrochloric acid ethanol solution, heating, cooling to room temperature, and centrifuging and washing to obtain a mesoporous silica nanoparticle MSN solution;

[0022] Furthermore, in step (3), mesoporous silica nanoparticles are loaded with platinum nanoparticles (MPt): 10-100 mg of MSN and 10-50 μmol of PtNPs are mixed, ultrasonically shaken, and centrifuged to obtain an MPt solution;

[0023] Furthermore, in step (4), polyethylenimine PEI (MPtP) was modified on the PtNPs-loaded MSN: 100-300 μL of a 10% polyethylenimine (PEI) aqueous solution was slowly added to 4-5.5 mL of the MPt solution, stirred at room temperature, and centrifuged to obtain an MPtP solution;

[0024] Furthermore, in step (5), a covalent organic framework (MPtC) is coated on the mesoporous silica modified with PEI: 150-250 mg of PVP is dissolved in o-dichlorobenzene and n-hexanol, ultrasonically dissolved, the MPtP solution is centrifuged, dissolved in the upper solution, ultrasonicated, 10-30 mg of 5,10,15,20-tetrakis(4-aminophenyl)manganese porphyrin (TAPP-Mn) and 5-10 mg of 2,5-dihydroxyterephthalaldehyde are weighed and added, glacial acetic acid is added and heated; after cooling to room temperature, the solution is centrifuged and washed to obtain an MPtC solution;

[0025] Furthermore, in step (6), silicon is etched to generate a platinum-loaded hollow covalent organic framework (HPtC): the MPtC solution is centrifuged and added with a 2-5 mol / L strong base solution and stirred; the mixture is centrifuged, washed, and freeze-dried to obtain a green powdery solid, thereby preparing a functionalized covalent organic framework nanocomposite material HPtC.

[0026] The functionalized covalent organic framework nanocomposite material is prepared by the method for preparing the functionalized covalent organic framework nanocomposite material capable of scavenging active oxygen.

[0027] Beneficial effects: The platinum nanoparticle-functionalized porphyrin-based covalent organic framework nanocomposite material of the present invention stably combines platinum nanoparticles and a porphyrin-based covalent organic framework. This nanocomposite material can serve as a platform to simultaneously exhibit catalase-like activity (CAT) and superoxide dismutase (SOD)-like activity, and can be used to scavenge hydrogen peroxide and superoxide anions in reactive oxygen species, thereby improving the efficiency of scavenging reactive oxygen species.

[0028] Compared with the prior art, the present invention has the following advantages:

[0029] The synthesis method of the platinum nanoparticle-functionalized porphyrin-based covalent organic framework nanocomposite material of the present invention is simple and easy, and the independent synthesis of each part improves the fault tolerance and has strong repeatability; the morphology is excellent, the size is uniform, and the dispersion is good. Both dynamic light scattering (DLS) analysis and electron microscopy characterization show good morphological characteristics; it has two types of enzyme activities and the catalytic activity is relatively strong; the platinum nanoparticles are encapsulated in the hollow covalent organic framework, the platinum nanoparticles are not easy to seep out, the catalytic activity of the material is stable, and the local catalytic activity can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments or descriptions of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0031] Figure 1Schematic diagram of the synthesis of Example 1 and Example 2 of the present invention;

[0032] Figure 2 Schematic diagram of the working principle of the HPtC of the present invention;

[0033] Figure 3 Transmission electron microscope images of Examples 1 and 2 of the present invention are shown;

[0034] Figure 4 The scanning electron microscope images of Examples 1 and 2 of the present invention are used;

[0035] Figure 5 The particle size distribution diagrams of Examples 1 and 2 of the present invention are shown below;

[0036] Figure 6 Zeta potential diagrams of Examples 1 and 2 of the present invention are used;

[0037] Figure 7 The following are Fourier infrared absorption spectra of Examples 1 and 2 of the present invention;

[0038] Figure 8 This is an X-ray photoelectron spectrum diagram using Example 2 of the present invention;

[0039] Figure 9 This is a graph showing the activity detection of the catalase-like enzyme of Example 2 of the present invention;

[0040] Figure 10 This is a graph showing the activity detection using the superoxide dismutase-like activity of Example 2 of the present invention. DETAILED DESCRIPTION

[0041] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0042] A first aspect of an embodiment of the present invention provides a method for preparing a functionalized covalent organic framework nanocomposite material capable of scavenging reactive oxygen species, comprising the following steps: using mesoporous silica nanoparticles as a sacrificial template, loading platinum nanoparticles and then wrapping a covalent organic framework of manganese porphyrin, and finally etching with a strong base to form a hollow functionalized covalent organic framework nanocomposite material loaded with platinum nanoparticles.

[0043] The present invention provides a method for preparing a functionalized covalent organic framework nanocomposite material capable of scavenging active oxygen, comprising the following steps:

[0044] (1) Preparation of platinum nanoparticles (PtNPs): Polyvinylpyrrolidone (PVP) was weighed and dissolved in ethanol. Aqueous chloroplatinic acid (H2PtCl6) solution was added, stirred at room temperature, heated under reflux, and cooled to room temperature to obtain a PtNPs solution. Mesoporous silica was synthesized using tetraethyl orthosilicate and bis-[3-(triethoxysilyl)propyl]-tetrasulfide (BTES) in a volume ratio of 4:1 as silicon sources. Hexadecyltrimethylammonium p-toluenesulfonate (CTAT) was used as a surfactant to stabilize the mesoporous silica nanoparticles.

[0045] (2) Preparation of mesoporous silica nanoparticles (MSN): Hexadecyltrimethylammonium p-toluenesulfonate (CTAT) and triethanolamine were weighed and added to water, heated and stirred; tetraethyl orthosilicate and bis-[3-(triethoxysilyl)propyl]-tetrasulfide (BTES) were added dropwise to the above solution, heated for reaction, cooled to room temperature, added with 10% hydrochloric acid ethanol solution and heated, cooled to room temperature, and centrifuged and washed to obtain mesoporous silica nanoparticles MSN solution; PVP was used as a substrate to synthesize PVP-stabilized platinum nanoparticles.

[0046] (3) Mesoporous silica nanoparticles loaded with platinum nanoparticles (MPt): MSNs and PtNPs were mixed, ultrasonically shaken, and centrifuged to obtain an MPt solution. Hexadecyltrimethylammonium p-toluenesulfonate (CTAT)-stabilized mesoporous silica nanoparticles and PVP-stabilized platinum nanoparticles were mixed at a ratio of 10-100 mg MSNs to 10-50 μmol PtNPs. The mixing ratio of mesoporous silica nanoparticles (MSNs) to platinum nanoparticles (PtNPs) was 0.5-5 mg:1 μmol.

[0047] (4) Modification of polyethylenimine PEI (MPtP) on PtNPs-loaded MSNs: Slowly add 10% polyethylenimine (PEI) aqueous solution to the MPt solution, stir at room temperature, and centrifuge to obtain MPtP solution; PEI is modified on PtNPs-loaded MSNs.

[0048] (5) Coating a covalent organic framework (MPtC) on mesoporous silica modified with PEI: PVP was dissolved in o-dichlorobenzene and n-hexanol, and ultrasonically dissolved. The MPtP solution was centrifuged and dissolved in the supernatant, and ultrasonicated for 0.5 h. 5,10,15,20-tetrakis(4-aminophenyl)manganeseporphyrin (TAPP-Mn) and 2,5-dihydroxyterephthalaldehyde were weighed and added to the supernatant, and glacial acetic acid was added and heated; after cooling to room temperature, the solution was centrifuged and washed to obtain an MPtC solution; in the process of coating a covalent organic framework on mesoporous silica modified with PEI, 5,10,15,20-tetrakis(4-aminophenyl)manganeseporphyrin and 2,5-dihydroxyterephthalaldehyde were used as ligands to synthesize the covalent organic framework. The mass ratio of 5,10,15,20-tetrakis(4-aminophenyl)manganeseporphyrin TAPP-Mn and 2,5-dihydroxyterephthalaldehyde was 2-3:1.

[0049] (6) Etching silicon to form a platinum-loaded hollow covalent organic framework (HPtC): 15 mL of MPtC solution was centrifuged and stirred in a strong alkaline solution. The solution was washed by centrifugation and freeze-dried to obtain a green powdery solid, thus preparing the functionalized covalent organic framework nanocomposite HPtC. Etching silicon produced a hollow bowl-shaped covalent organic framework HPtC, which contained a large number of stable platinum nanoparticles.

[0050] A second aspect of the embodiments of the present invention provides a functionalized covalent organic framework nanocomposite material that can scavenge active oxygen, obtained by a method for preparing the functionalized covalent organic framework nanocomposite material.

[0051] Example 1

[0052] This example is used to illustrate the preparation of platinum nanoparticles (PtNPs)

[0053] Using polyvinylpyrrolidone (PVP) as a substrate, chloroplatinic acid was reduced to PVP-stabilized platinum nanoparticles (PtNPs) by heating under reflux at 80°C. Weigh 16.6 mg of polyvinylpyrrolidone (PVP) (Mw = 58,000) and dissolve it in 45 mL of ethanol. Prepare 5 mL of a 6 mM aqueous solution of chloroplatinic acid (HPtCl) and add the solution dropwise. Stir at room temperature for 2 minutes. Heat under reflux at 80°C for 3 hours. After cooling to room temperature, store at 4°C without further treatment.

[0054] This example is used to illustrate the preparation of mesoporous silica nanoparticles (MSN).

[0055] Synthesis Method: Mesoporous silica nanoparticles were synthesized using tetraethyl orthosilicate doped with bis-[3-(triethoxysilyl)propyl]-tetrasulfide (BTES) as a silicon source and cetyltrimethylammonium p-toluenesulfonate (CTAT) as a surfactant. 300 mg of CTAT and 74 mg of triethanolamine were added to 20 mL of water, stirred at 300 rpm, and heated at 80°C for 0.5 h. The mixture was then adjusted to 1000 rpm, and 2 mL of tetraethyl orthosilicate and 0.5 mL of BTES were mixed and added dropwise to the supernatant. The mixture was then heated at 80°C for 4 h. After cooling to room temperature, an equal volume of ethanol was added, and the mixture was centrifuged at 10,000 rpm for 5 minutes. The supernatant was removed, and 20 mL of 10% hydrochloric acid in ethanol was added. The mixture was then heated at 80°C for 12 h. The supernatant was removed, and ethanol was added. The mixture was centrifuged at 12,000 rpm for 5 minutes, and the supernatant was removed. This process was repeated three times, and the mixture was dissolved in 40 mL of ethanol and stored at room temperature. A portion of the sample can be dried and quantified, and the product concentration is approximately 4 mg / mL.

[0056] Example 2

[0057] This example is used to illustrate mesoporous silica nanoparticles loaded with platinum nanoparticles (MPt).

[0058] Mix 12 mL of MSN (4 mg / mL) and 45 mL of PtNPs (0.6 mM) and sonicate for 1 hour. Centrifuge at 12,000 rpm for 5 minutes and discard the supernatant. The product will be a uniform brown color. Add ethanol and centrifuge at 12,000 rpm for 5 minutes. Wash twice by centrifugation. Dissolve the product in 4.8 mL of water to a concentration of 10 mg / mL and store at 4°C.

[0059] This example is used to illustrate the modification of PEI (MPtP) on MSNs loaded with PtNPs.

[0060] Slowly add 200 μL of 10% polyethyleneimine (PEI) aqueous solution to 4.8 mL of MPt (10 mg / mL) and stir at room temperature for 1 hour. Centrifuge at 12,000 rpm for 7 minutes, wash twice with water and ethanol, then remove the supernatant and dissolve in 10 mL of ethanol to a concentration of approximately 5 mg / mL.

[0061] This example is used to illustrate the encapsulation of a covalent organic framework (MPtC) on mesoporous silica modified with PEI.

[0062] Weigh 200 mg of PVP (Mw = 58,000) and dissolve it in 10 mL of o-dichlorobenzene and 10 mL of n-hexanol, then sonicate. Centrifuge 3 mL of MPtP (5 mg / mL) (approximately 15 mg of product) and dissolve it in the supernatant. Sonicate for 0.5 h. Weigh 17 mg of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP-Mn) and 8.2 mg of 2,5-dihydroxyterephthalaldehyde, add them to the supernatant, and sonicate. Transfer the supernatant to a three-necked flask, protect from light, and purge with nitrogen at a flow rate of approximately 80 mL / min. Stir at 300 rpm for 5 min. Add 200 μL of glacial acetic acid and react at room temperature for 4 h. Add 600 μL of glacial acetic acid, heat in an oil bath at 120°C, and reflux under condensation for 24 h. After cooling to room temperature, the solution was centrifuged at 12,000 rpm for 7 min, washed twice with methanol, dissolved in 15 mL of water to a concentration of 1 mg / mL, and stored at 4°C.

[0063] This example is used to illustrate the formation of a platinum-loaded hollow covalent organic framework (HPtC) by etching silicon.

[0064] 15 mL of MPtC (1 mg / mL) was centrifuged and added to 15 mL of sodium hydroxide solution (2 mol / L). The mixture was stirred for 12 hours. After centrifugation at 12,000 rpm for 7 minutes, the mixture was washed twice with water and freeze-dried to obtain a green powdery solid, the functionalized covalent organic framework nanocomposite (HPtC).

[0065] Test Example 1

[0066] This test example is used to illustrate the material characterization of HPtC.

[0067] In order to verify the feasibility of the synthesis of Example 1, the present invention used a transmission electron microscope (TEM, JEM-2800, JEOL Japan Electronics) and a scanning electron microscope (SEM, JSM-7800F, JEOL Japan Electronics) to characterize the morphology of HPtC. The test results are as follows: Figure 3 、 Figure 4 shown.

[0068] In order to further verify the synthesis results of Example 1 and Example 2, the particle size distribution of Example 1 and Example 2 was measured, and the test results are as follows: Figure 5 shown.

[0069] The Zeta potential of Example 1 and Example 2 was measured, and the test results are as follows: Figure 6 shown.

[0070] The Fourier infrared absorption spectra of Example 1 and Example 2 were measured, and the test results are as follows: Figure 7 shown.

[0071] The X-ray photoelectron spectrum of Example 2 was measured, and the test results are as follows: Figure 8 shown.

[0072] Test Example 2

[0073] This test example is used to illustrate and verify the catalase-like activity and superoxide dismutase-like activity of HPtC.

[0074] The CAT activity of HPtC was measured using the Solebo Catalase (CAT) activity assay kit (ammonium molybdate method). The CAT activity of HPtC increased with increasing concentration. The experimental results confirmed that HPtC has good CAT activity. The test results are as follows: Figure 9 shown.

[0075] The SOD activity of HPtC was measured using the Biyuntian Total SOD Activity Detection Kit (WST-8 method). The SOD activity of HPtC increased with increasing concentration. The experimental results confirmed that HPtC had good SOD activity. The test results are as follows: Figure 10 shown.

[0076] The basic principles, main features and advantages of the present invention are shown and described above. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and improvements may be made to the present invention without departing from the spirit and scope of the present invention. The scope of protection claimed in the present invention is defined by the appended claims, the description and their equivalents.

Claims

1. A method for preparing a functionalized covalent organic framework nanocomposite material for scavenging active oxygen, characterized in that The method comprises the following steps: using mesoporous silica nanoparticles as a sacrificial template, loading platinum nanoparticles and then wrapping a covalent organic framework of manganese porphyrin, and finally etching with a strong base to form a hollow functionalized covalent organic framework nanocomposite material loaded with platinum nanoparticles. The method specifically comprises the following steps: (1) Preparation of platinum nanoparticles (PtNPs): Dissolve polyvinylpyrrolidone (PVP) in ethanol, add chloroplatinic acid (H2PtCl6) aqueous solution, stir at room temperature, heat under reflux, and cool to room temperature to obtain a PtNPs solution. (2) Preparation of mesoporous silica nanoparticles MSN: add hexadecyltrimethylammonium p-toluenesulfonate (CTAT) and triethanolamine to water, heat and stir; add tetraethyl orthosilicate and bis-[3-(triethoxysilyl)propyl]-tetrasulfide (BTES) dropwise, heat to react, cool to room temperature, add 10% hydrochloric acid ethanol solution and heat, cool to room temperature, centrifuge and wash to obtain mesoporous silica nanoparticles MSN solution; (3) Mesoporous silica nanoparticles loaded with platinum nanoparticles MPt: MSN and PtNPs were mixed, ultrasonically shaken, and centrifuged to obtain MPt solution; (4) Modification of PEI polyethylenimine MPtP on PtNPs-loaded MSN: Slowly add 10% polyethyleneimine PEI aqueous solution to MPt solution, stir at room temperature, and centrifuge to obtain MPtP solution; (5) Coating the covalent organic framework MPtC on the mesoporous silica modified with PEI: PVP was dissolved in o-dichlorobenzene and n-hexanol, and sonicated to obtain solution A. The MPtP solution was centrifuged and dissolved in solution A, and sonicated. 5,10,15,20-tetrakis(4-aminophenyl) manganese porphyrin TAPP-Mn and 2,5-dihydroxyterephthalaldehyde were weighed and added, and glacial acetic acid was added and heated; after cooling to room temperature, the solution was centrifuged and washed to obtain the MPtC solution; (6) Etching MSN to generate platinum-loaded hollow covalent organic framework HPtC: Take the MPtC solution and centrifuge it, add 2-5 mol / L strong alkaline solution and stir; centrifuge and wash, freeze-dry to obtain a green powder solid, and prepare a functionalized covalent organic framework nanocomposite material HPtC.

2. The method for preparing a functionalized covalent organic framework nanocomposite material for scavenging active oxygen according to claim 1, characterized in that: In step (2), the volume ratio of tetraethyl orthosilicate and bis-[3-(triethoxysilyl)propyl]-tetrasulfide (BTES) is 3-5:

1.

3. The method for preparing a functionalized covalent organic framework nanocomposite material for scavenging active oxygen according to claim 1, characterized in that: In step (3), MSNs stabilized by cetyltrimethylammonium p-toluenesulfonate (CTAT) as a surfactant were mixed with PVP-stabilized PtNPs and successfully loaded.

4. The method for preparing a functionalized covalent organic framework nanocomposite material for scavenging active oxygen according to claim 1, characterized in that: In step (3), the mixing ratio of mesoporous silica nanoparticles MSN and platinum nanoparticles PtNPs is 0.5-5 mg:1 μmol.

5. The method for preparing a functionalized covalent organic framework nanocomposite material for scavenging active oxygen according to claim 1, characterized in that: In step (5), the mass ratio of 5,10,15,20-tetrakis(4-aminophenyl)manganeseporphyrin TAPP-Mn and 2,5-dihydroxyterephthalaldehyde is 2-3:

1.

6. The method for preparing a functionalized covalent organic framework nanocomposite material for scavenging active oxygen according to claim 1, characterized in that: In step (1), platinum nanoparticles (PtNPs) are prepared by dissolving 15-20 mg of polyvinylpyrrolidone (PVP) in ethanol, adding 3-8 mL of a 6 mM aqueous solution of chloroplatinic acid (H2PtCl6), stirring at room temperature, heating under reflux, and cooling to room temperature to obtain a PtNPs solution. In step (2), mesoporous silica nanoparticles MSN are prepared by adding 200-400 mg of hexadecyltrimethylammonium p-toluenesulfonate (CTAT) and 70-80 mg of triethanolamine to water, heating and stirring; adding 2-3 mL of tetraethyl orthosilicate and bis-[3-(triethoxysilyl)propyl]-tetrasulfide (BTES) dropwise, heating for reaction, cooling to room temperature, adding 10% hydrochloric acid ethanol solution, heating, cooling to room temperature, and centrifuging and washing to obtain a mesoporous silica nanoparticle MSN solution; In step (3), mesoporous silica nanoparticles loaded with platinum nanoparticles MPt: 10-100 mg of MSN and 10-50 μmol of PtNPs were mixed, ultrasonically shaken, and centrifuged to obtain an MPt solution; In step (4), MPtP polyethyleneimine PEI is modified on the PtNPs-loaded MSN: 100-300 μL of a 10% polyethyleneimine PEI aqueous solution is slowly added to 4-5.5 mL of MPt solution, stirred at room temperature, and centrifuged to obtain MPtP solution; In step (5), a covalent organic framework MPtC is coated on the mesoporous silica modified with PEI: 150-250 mg of PVP is dissolved in o-dichlorobenzene and n-hexanol, and dissolved by ultrasonication to obtain solution B. The MPtP solution is centrifuged and dissolved in solution B, and ultrasonicated. 10-30 mg of 5,10,15,20-tetrakis(4-aminophenyl) manganese porphyrin TAPP-Mn and 5-10 mg of 2,5-dihydroxyterephthalaldehyde are weighed, and glacial acetic acid is added and heated; after cooling to room temperature, the mixture is centrifuged and washed to obtain an MPtC solution; In step (6), silicon is etched to generate a platinum-loaded hollow covalent organic framework HPtC: the MPtC solution is centrifuged and added with a 2-5 mol / L strong base solution and stirred; the solution is centrifuged, washed, and freeze-dried to obtain a green powder solid, thereby preparing a functionalized covalent organic framework nanocomposite material HPtC.

7. The method for preparing a functionalized covalent organic framework nanocomposite material for scavenging active oxygen according to claim 6, characterized in that: In step (6), silicon is etched to form a hollow bowl-shaped covalent organic framework HPtC, which contains a large number of platinum nanoparticles and exists stably.

8. The functionalized covalent organic framework nanocomposite material obtained by the method for preparing the functionalized covalent organic framework nanocomposite material for scavenging active oxygen according to any one of claims 1 to 7.

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