MXene@PCN-224 composite material and preparation method and application thereof

Abstract

The application discloses a kind of MXene@PCN-224 composite material and its preparation method and application, the preparation method includes the following steps: S1: respectively prepare premix A and premix B, the premix A includes MXene material, metal ion chelating agent, solvent, the solvent is the solvent required for synthesis PCN-224 material, and the premix B is the mixture of other raw materials required for synthesis PCN-224 material except solvent;S2: the premix A and the premix B are mixed uniformly and then put into reaction vessel, under normal temperature and pressure, using dielectric barrier discharge method to make the mixture in the reaction vessel react;S3: the reaction product is collected by centrifugal washing, and the reaction product is the MXene@PCN-224 composite material.The MXene@PCN-224 composite material can be safely and controllably, simply and quickly prepared.

Description

Technical Field

[0001] This invention relates to the field of composite material technology, and in particular to an MXene@PCN-224 composite material, its preparation method, and its application. Background Technology

[0002] Composite materials come in a wide variety of types. Due to their customizable structures, controllable synthesis processes, and predictable functions, they are widely used in many fields such as bio-antibacterial applications. Among them, the novel MXene material has attracted much attention. MXene is a type of 2D sheet-like material. It is an inorganic compound with advantages such as large specific surface area, ease of modification, and photothermal antibacterial capabilities. Therefore, it is often selected as a base material in antibacterial composite materials.

[0003] Currently, when preparing composite materials based on MXene materials, researchers often use electrostatic adsorption. This method utilizes the difference in surface charge between the MXene material and the modified material, and through the interaction between the charges, achieves a tight bond between the two materials. However, while electrostatic adsorption is convenient, this physical adsorption method suffers from drawbacks such as unstable bonding and susceptibility to damage. Furthermore, it places high demands on the difference in surface charge between the MXene material and the modified material.

[0004] Besides electrostatic adsorption, composite materials are also often synthesized using chemical doping. However, although the stability of composite materials synthesized by chemical doping is improved compared to electrostatic adsorption, the synthesis process is extremely complex and lengthy, and the reaction process is difficult to control and adjust, thus making it inconvenient for subsequent use. Summary of the Invention

[0005] To address the aforementioned issues, this invention aims to provide an MXene@PCN-224 composite material, its preparation method, and its applications.

[0006] The technical solution of the present invention is as follows:

[0007] On the one hand, a method for preparing MXene@PCN-224 composite material is provided, which uses in-situ growth to grow PCN-224 material on the surface of MXene material to obtain the MXene@PCN-224 composite material.

[0008] Preferably, the in-situ growth of PCN-224 material on the surface of MXene material is achieved by dielectric barrier discharge method.

[0009] As a preferred option, the following steps are included:

[0010] S1: Prepare premix A and premix B respectively. Premix A includes MXene material, metal ion chelating agent and solvent. Premix B is a mixture of raw materials other than solvent required for the synthesis of PCN-224 material.

[0011] S2: After the premix A and the premix B are mixed evenly, they are put into a reaction vessel. Under normal temperature and pressure conditions, the mixture in the reaction vessel is reacted by dielectric barrier discharge method.

[0012] S3: Collect the reaction product by centrifugation and washing. The reaction product is the MXene@PCN-224 composite material.

[0013] Preferably, in step S1, the premix A comprises, by weight, 5-10 parts of MXene material, 5-20 parts of metal ion chelating agent, and 50 parts of solvent, wherein the solvent is the solvent required for synthesizing PCN-224 material, and the premix B comprises 15-60 parts of zirconium oxychloride octahydrate, 5-20 parts of tetracarboxyphenylporphyrin, and 50-300 parts of benzoic acid.

[0014] Preferably, in step S1, the metal ion chelating agent is polyvinylpyrrolidone.

[0015] Preferably, in step S1, the solvent is N,N-dimethylformamide.

[0016] Preferably, in step S1, the prepared premix A and premix B are stored under sealed, light-protected, and room-temperature conditions.

[0017] Preferably, in step S2, the discharge voltage of the dielectric barrier discharge method is 35-37V, the current is 1.20-1.29A, and the reaction time is 20-30min.

[0018] On the other hand, an MXene@PCN-224 composite material is also provided, which is prepared by any of the above-described methods for preparing MXene@PCN-224 composite materials.

[0019] On the other hand, the application of the above-described MXene@PCN-224 composite material in bio-antibacterial applications is also provided.

[0020] The beneficial effects of this invention are:

[0021] This invention combines MXene, a material with photothermal antibacterial capabilities, with PCN-224, a material with photocatalytic antibacterial capabilities, to obtain an MXene@PCN-224 composite material with excellent antibacterial properties. Furthermore, the composite material is prepared by in-situ growth, which makes the preparation process safer, more controllable, simpler, and faster, effectively improving preparation efficiency and reducing production costs. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 This is a schematic diagram comparing scanning electron microscope (SEM) images of MXene material and MXene@PCN-224 composite material in a specific embodiment.

[0024] Figure 2 This is a schematic diagram comparing the transmission electron microscopy results of MXene material and MXene@PCN-224 composite material in a specific embodiment.

[0025] Figure 3 This is a schematic diagram of the scanning electron microscope (SEM) of the MXene@PCN-224 composite material prepared in Comparative Example 1.

[0026] Figure 4 This is a schematic diagram of the N2 isothermal adsorption-desorption curves and pore size distribution of the MXene@PCN-224 composite material in a specific embodiment.

[0027] Figure 5 This is a schematic diagram showing the test results of the antibacterial performance of the MXene@PCN-224 composite material against Staphylococcus aureus in a specific embodiment.

[0028] Figure 6 A schematic diagram showing the test results of the antibacterial performance of MXene@PCN-224 composite material against Escherichia coli in a specific embodiment;

[0029] Figure 7 This is a schematic diagram of the cytotoxicity test results of the MXene@PCN-224 composite material in a specific embodiment. Detailed Implementation

[0030] The present invention will be further described below with reference to the accompanying drawings and embodiments. It should be noted that, unless otherwise specified, the embodiments and technical features described in this application can be combined with each other. It should also be pointed out that, unless otherwise indicated, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. The terms "comprising" or "including" and similar words used in this invention refer to elements or objects preceding the word that encompass the elements or objects listed following the word and their equivalents, without excluding other elements or objects.

[0031] On the one hand, the present invention provides a method for preparing MXene@PCN-224 composite material, which uses in-situ growth to grow PCN-224 material on the surface of MXene material to obtain the MXene@PCN-224 composite material.

[0032] In one specific embodiment, the in-situ growth of PCN-224 material on the surface of MXene material is achieved using the dielectric barrier discharge method. Optionally, the preparation method includes the following steps:

[0033] S1: Prepare premix A and premix B respectively. Premix A includes MXene material, metal ion chelating agent and solvent. The solvent is the solvent required for synthesizing PCN-224 material. Premix B is a mixture of other raw materials required for synthesizing PCN-224 material except for the solvent.

[0034] In one specific embodiment, by weight, premix A comprises 5-10 parts of MXene material, 5-20 parts of a metal ion chelating agent, and 50 parts of a solvent; premix B comprises 15-60 parts of zirconium oxychloride octahydrate, 5-20 parts of tetracarboxyphenylporphyrin, and 50-300 parts of benzoic acid. Optionally, the metal ion chelating agent is polyvinylpyrrolidone, and the solvent is N,N-dimethylformamide.

[0035] In one specific embodiment, the prepared premix A and premix B are stored under sealed, light-protected, and room-temperature conditions. It should be noted that storing the premixes under these conditions can prevent the decomposition of the compounds within the premixes and extend their shelf life. If the premixes are prepared and proceed directly to subsequent steps, this storage step can be omitted.

[0036] S2: After the premix A and the premix B are mixed evenly, they are put into a reaction vessel. Under normal temperature and pressure conditions, the mixture in the reaction vessel is reacted by dielectric barrier discharge method.

[0037] In one specific embodiment, the discharge voltage of the dielectric barrier discharge method is 35-37V, the current is 1.20-1.29A, and the reaction time is 20-30min. It should be noted that the parameters in this embodiment are only preferred embodiment parameters, and those skilled in the art can adjust these parameters according to the performance of the MXene@PCN-224 composite material as needed.

[0038] S3: Collect the reaction product by centrifugation and washing. The reaction product is the MXene@PCN-224 composite material.

[0039] On the other hand, the present invention also provides an MXene@PCN-224 composite material prepared by any of the above-described methods, and the application of the MXene@PCN-224 composite material in bio-antibacterial applications.

[0040] Example 1

[0041] An MXene@PCN-224 composite material was prepared using the following steps:

[0042] (1) Prepare premix A

[0043] Five parts of MXene material and five parts of polyvinylpyrrolidone were added to 50 parts of N,N-dimethylformamide. The mixture was shaken under normal temperature and pressure conditions, and after being mixed and dispersed evenly, it was stored in a sealed, light-proof, and room-temperature environment.

[0044] (2) Prepare premix B

[0045] Mix 15 parts zirconium oxychloride octahydrate, 5 parts tetracarboxyphenylporphyrin, and 140 parts benzoic acid thoroughly, and then store in a sealed, light-proof, room-temperature environment.

[0046] (3) MXene@PCN-224 composite material was prepared by dielectric barrier discharge method.

[0047] Prepare the production equipment required for the dielectric barrier discharge method. In this embodiment, the reaction vessel of the production equipment is a glass tube. After the premix A and the premix B are mixed evenly, they are put into the reaction vessel. Under normal temperature and pressure conditions, adjust the external power supply to adjust the discharge voltage to 35-37V and the current to 1.20-1.29A. The reaction is carried out for 20-30 minutes. After the reaction is completed, the centrifuged precipitate is collected by centrifugation and washing. The centrifuged precipitate is the MXene@PCN-224 composite material.

[0048] Example 2

[0049] Unlike Example 1, in this example, the premix A contains 10 parts of MXene material and 20 parts of polyvinylpyrrolidone.

[0050] Example 3

[0051] Unlike Example 1, in this example, the premix A contains 8 parts of MXene material and 15 parts of polyvinylpyrrolidone.

[0052] Example 4

[0053] Unlike Example 1, in this example, the amount of benzoic acid in premix B is 50 parts.

[0054] Example 5

[0055] Unlike Example 1, in this example, the premix B contains 60 parts of zirconium oxychloride octahydrate, 20 parts of tetracarboxyphenylporphyrin, and 300 parts of benzoic acid.

[0056] Comparative Example 1

[0057] Unlike Example 1, this comparative example combines PCN-224 and MXene materials through electrostatic interaction to obtain an MXene@PCN-224 composite material.

[0058] Experimental Example 1

[0059] The structures of the MXene@PCN-224 composite materials obtained in each example were observed using scanning electron microscopy and transmission electron microscopy. The comparative results of the MXene@PCN-224 composite material of Example 1 and the original MXene material are shown below. Figure 1 and Figure 2 As shown; the composite material structure obtained in Comparative Example 1 was observed using a scanning electron microscope, and the results are as follows. Figure 3 As shown. From Figure 1 and Figure 2 It can be seen that the MXene@PCN-224 composite material prepared by this invention has a good morphology, with abundant, uniformly distributed, and moderately sized in-situ grown PCN-224, possessing excellent application value. Figure 3 It can be seen that when preparing MXene@PCN-224 composite materials using electrostatic adsorption, a large amount of PCN-224 does not grow on the MXene sheet, resulting in poor stability.

[0060] Experimental Example 2

[0061] The N2 isotherm adsorption-desorption curves and pore size distribution of the MXene@PCN-224 composite materials obtained in each example were tested. The results for the MXene@PCN-224 composite material in Example 1 are as follows: Figure 4 As shown. From Figure 4 It can be seen that the MXene@PCN-224 composite material prepared by this invention exhibits a two-dimensional lamellar morphology, with a large specific surface area and a wide pore size distribution, containing micropores with a diameter of 0-2 nanometers and mesopores with a diameter of 2-50 nanometers.

[0062] Experimental Example 3

[0063] The antibacterial properties of the MXene@PCN-224 composite materials obtained in each embodiment were tested, with the results for the MXene@PCN-224 composite material in Example 1 as follows: Figure 5 and Figure 6 As shown. From Figure 5 and Figure 6 It can be seen that the MXene@PCN-224 composite material prepared by this invention has good antibacterial properties. Under the synergistic treatment of 10 min of visible light and 5 min of infrared light, the concentration of bacteria is greatly reduced.

[0064] Test Example 4

[0065] The cytotoxicity of the MXene@PCN-224 composite materials obtained in each example was tested, with the results for the MXene@PCN-224 composite material in Example 1 as follows: Figure 7 As shown, the Control group represents the growth state without the composite material of this invention. From Figure 7 It can be seen that the MXene@PCN-224 composite material prepared by this invention has very low cytotoxicity and has virtually no effect on cell activity after use.

[0066] It should be noted that the conclusions obtained from the other embodiments in the above-mentioned experimental examples are similar to those obtained from the results of Embodiment 1. Therefore, the corresponding results of other embodiments are omitted here.

[0067] In addition to the above embodiments, other raw materials used in the prior art for preparing PCN-224 materials can also be applied to this invention. For example, PDA can be used as the metal ion chelating agent, and acetic acid can be replaced with benzoic acid to adjust the morphology of PCN-224.

[0068] In summary, this invention enables the simple, safe, and rapid preparation of MXene@PCN-224 composite materials. Compared with existing technologies, this invention represents a significant advancement.

[0069] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing MXene@PCN-224 composite material, characterized in that, The MXene@PCN-224 composite material is obtained by growing PCN-224 material on the surface of MXene material using an in-situ growth method, specifically including the following steps: S1: Prepare premix A and premix B respectively. Premix A includes MXene material, metal ion chelating agent, and solvent. The solvent is the solvent required for synthesizing PCN-224 material. Premix B is a mixture of other raw materials required for synthesizing PCN-224 material, excluding the solvent. The metal ion chelating agent is polyvinylpyrrolidone, and the solvent is N,N-dimethylformamide. S2: After the premix A and the premix B are mixed evenly, they are added to the reaction vessel. Under normal temperature and pressure conditions, the mixture in the reaction vessel is reacted using the dielectric barrier discharge method. The discharge voltage of the dielectric barrier discharge method is 35-37V, the current is 1.20-1.29A, and the reaction time is 20-30min. S3: Collect the reaction product by centrifugation and washing. The reaction product is the MXene@PCN-224 composite material.

2. The method for preparing the MXene@PCN-224 composite material according to claim 1, characterized in that, In step S1, by weight, the premix A includes 5-10 parts of MXene material, 5-20 parts of metal ion chelating agent, and 50 parts of solvent, and the premix B includes 15-60 parts of zirconium oxychloride octahydrate, 5-20 parts of tetracarboxyphenylporphyrin, and 50-300 parts of benzoic acid.

3. The method for preparing the MXene@PCN-224 composite material according to claim 1, characterized in that, In step S1, the prepared premix A and premix B are stored under sealed, light-protected, and room-temperature conditions.

4. An MXene@PCN-224 composite material, characterized in that, It was prepared using the preparation method of the MXene@PCN-224 composite material according to any one of claims 1-3.

5. The application of the MXene@PCN-224 composite material as described in claim 4 in non-therapeutic biological antibacterial applications.

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