Application of Ti3C2@NH2-MIL-101 material in photocatalytic degradation of bifenthrin in insect-resistant cable

Abstract

This invention discloses the application of Ti3C2@NH2-MIL-101 material in the photocatalytic degradation of bifenthrin in insect-proof cables, belonging to the technical fields of composite material applications and environmental protection. This invention utilizes Ti3C2@NH2-MIL-101 material at different concentrations under light irradiation to catalytically degrade bifenthrin, effectively degrading bifenthrin, which is environmentally toxic and difficult to degrade naturally. This invention leverages the large specific surface area, good hydrophilicity, excellent electronic conductivity, and surface group characteristics of Ti3C2MXene to grow NH2-MIL-101 in situ on Ti3C2MXene. The two work synergistically to photocatalytically degrade bifenthrin, resulting in high degradation efficiency and a fast rate.

Description

Technical Field

[0001] This invention belongs to the technical field of composite material application and environmental protection, specifically relating to the application of a Ti3C2@NH2-MIL-101 material in the photocatalytic degradation of bifenthrin in insect-proof cables. Background Technology

[0002] Insect-proof cables are widely used in applications requiring protection against rodents, insects, and other pests, such as agriculture, landscaping, urban public facilities, construction, power, communications, mining, and oil fields. The design and manufacture of insect-proof cables utilize special technologies and materials, such as the addition of bifenthrin, which has both contact and stomach poison effects, providing rapid knockdown, long-lasting effectiveness, and a broad insecticidal spectrum, ensuring excellent performance in terms of insect protection, corrosion resistance, water resistance, abrasion resistance, and aging resistance.

[0003] In summary, insect-proof cables are cable products with characteristics such as insect resistance, corrosion resistance, fire resistance, water resistance, wear resistance, and aging resistance. They are widely used in various fields, providing reliable protection for people's production and daily life. However, while existing insect-proof cables can repel rodents and insects after adding bifenthrin, their degradation rate under natural conditions is very slow, making it difficult to degrade them in a timely and effective manner. Bifenthrin is highly toxic to fish, and once it seeps into water, it can cause serious harm to aquatic animals. The inability to degrade bifenthrin in a timely and effective manner is inconsistent with the expectations of environmentally friendly development.

[0004] Bifenthrin is widely used to control pests on cotton, vegetables, fruit trees, and tea trees, as well as termites, mites, and other household pests. Bifenthrin is stable to light and heat, and has a long half-life in the environment (411 days in sandy soil and 522 days in organic soil with 20% moisture content). Therefore, it is difficult to degrade rapidly under natural conditions. Coupled with long-term and frequent use, the problem of excessive pesticide residues is becoming increasingly serious. The quality and safety of agricultural products are increasingly attracting widespread social attention. Therefore, there is an urgent need for a new material that can efficiently degrade bifenthrin under natural conditions (such as light) to prevent it from poisoning organisms and polluting the environment. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention aims to provide an application of Ti3C2@NH2-MIL-101 material in the photocatalytic degradation of bifenthrin in insect-proof cables.

[0006] To solve the above problems, the technical solution adopted by the present invention is as follows:

[0007] An application of Ti3C2@NH2-MIL-101 material in the photocatalytic degradation of bifenthrin in insect-proof cables includes: using Ti3C2@NH2-MIL-101 material to effectively catalyze the degradation of bifenthrin, which is toxic to the environment and difficult to degrade under natural conditions, under light irradiation.

[0008] Furthermore, the steps of catalytic degradation of bifenthrin include: material absorption of visible light; photogenerated electron migration; spatial electron enrichment; photoexcitation to generate free radicals, which participate in the degradation of bifenthrin as the main active substances.

[0009] Furthermore, the preparation method of the Ti3C2@NH2-MIL-101 material includes: using lithium fluoride and HCl as raw materials, adding Ti3AlC2 to react and obtain Ti3C2; then adding the obtained Ti3C2 to a stirring solution of ferric chloride hexahydrate and 2-aminoterephthalic acid, and after vacuum low-temperature stirring and ultrasonic treatment, the Ti3C2@NH2-MIL-101 material is obtained after hydrothermal reaction and centrifugal drying.

[0010] Furthermore, the specific steps for preparing the novel Ti3C2@NH2-MIL-101 material are as follows:

[0011] 1) Preparation of Ti3C2: Weigh 1~2g of lithium fluoride and 15~30mL of 9M HCl, stir evenly in a polytetrafluoroethylene container, and stir at 40℃ for 5min; then slowly add 1~2g of Ti3AlC2 to the LiF / HCl mixed solution over 5min, stir at 40℃ for 48h, wash the reactants with deionized water until pH=7, filter to form a film, and vacuum dry at 40℃ for 12h to obtain Ti3C2;

[0012] 2) Preparation of Ti3C2@ NH2-MIL-101: Weigh 2.025~4.050g FeCl3·6H2O and 0.618~1.236g 2-aminoterephthalic acid and stir in 45mL of N,N-dimethylformamide solution until fully dissolved, then sonicate; add Ti3C2, stir under vacuum at low temperature for 2h, and sonicate again; hydrothermally react in a polytetrafluoroethylene container for 24h, centrifuge three times with N,N-dimethylformamide solution, and vacuum dry at 40℃ for 12h to obtain Ti3C2@ NH2-MIL-101 material.

[0013] Furthermore, the photocatalytic degradation occurs at room temperature.

[0014] Furthermore, the specific steps of the photocatalytic degradation are as follows: NH2-MIL-101 absorbs visible light, photogenerated electrons rapidly migrate from NH2-MIL-101 to Ti3C2, and spatially hinder the recombination of photogenerated charge carriers, resulting in an electron-rich environment on the Ti3C2 surface. After photoexcitation, holes (h) on the material surface... + ) and superoxide radicals (·O2) - ) and hydroxyl radicals (·OH) are the main active substances involved in the degradation of bifenthrin.

[0015] Compared with existing technologies, the advantages of this invention are:

[0016] (1) The Schottky junction formed between MXene and NH2-MIL-101 due to the internal electric field promotes the separation of photogenerated carriers in the semiconductor, thereby suppressing the recombination of charge carriers and improving the photocatalytic efficiency.

[0017] (2) In this invention, NH2-MIL-101 is grown in situ on Ti3C2 Mxene to obtain an excellent environmentally friendly photocatalytic degradation material. The two work together to photocatalytically degrade bifenthrin, resulting in high degradation efficiency, fast rate, and no pollution.

[0018] (3) The presence of a large number of hydrophilic groups on the surface of MXene enables MXene to establish a close contact with NH2-MIL-101, which promotes the rapid transfer of charge from NH2-MIL-101 to MXene.

[0019] (4) Two-dimensional MXene has a large specific surface area, which can provide sufficient reaction sites and shorten the diffusion path of photogenerated carriers.

[0020] (5) The dark color of Ti3C2 can enhance light absorption. In addition, the photothermal conversion properties of black Ti3C2 also contribute to the improvement of photocatalytic activity.

[0021] (6) Currently, there are few photocatalytic materials that can photocatalytically degrade bifenthrin at room temperature under sunlight. This invention provides a new approach. Attached Figure Description

[0022] Figure 1 XRD patterns of Ti3C2, NH2-MIL-101, and 3wt% Ti3C2@NH2-MIL-101;

[0023] Figure 2 : SEM image of 1wt% Ti3C2@NH2-MIL-101;

[0024] Figure 3 : SEM image of 3wt% Ti3C2@NH2-MIL-101;

[0025] Figure 4 : SEM image of 5wt% Ti3C2@NH2-MIL-101;

[0026] Figure 5 : Efficiency of photocatalytic degradation of 10 mg / L bifenthrin by 10 mg Ti3C2@ NH2-MIL-101 with different mass fractions. Detailed Implementation

[0027] To make the above-mentioned objectives, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to specific examples.

[0028] In the examples, lithium fluoride (LiF) was obtained from McLean Pharmaceuticals; HCl was purchased from Sinopharm Group; 2-aminoterephthalic acid was purchased from Aladdin Biochemical Technology Co., Ltd. (Shanghai); N,N-dimethylformamide (DMF) was purchased from Nanjing Peptide Biotechnology Co., Ltd.; and Ti3AlC2 was purchased from Nanjing Mingchang New Materials Co., Ltd.

[0029] Example 1

[0030] A method for preparing a 3wt% Ti3C2@NH2-MIL-101 material includes the following steps:

[0031] 1) Preparation of Ti3C2: Weigh 1g of lithium fluoride (LiF) and 15mL of 9M HCl, stir evenly in a polytetrafluoroethylene container, and stir at 40℃ for 5min; then slowly add 1g of Ti3AlC2 to the LiF / HCl mixed solution over 5min, stir at 40℃ for 48h, centrifuge the reactants with deionized water until pH=7, filter to form a film, and vacuum dry at 40℃ for 12h to obtain (0.8g) Ti3C2;

[0032] 2) Preparation of Ti3C2@NH2-MIL-101: Weigh 2.025g of ferric chloride hexahydrate (FeCl3·6H2O) and 0.618g of 2-aminoterephthalic acid and stir in 45mL of N,N-dimethylformamide (DMF) solution until fully dissolved, then sonicate for 10min; add 0.0225g of Ti3C2, stir under vacuum at low temperature for 2h, and sonicate for 10min; hydrothermally react at 110℃ for 24h in a polytetrafluoroethylene container, centrifuge three times with DMF solution, and vacuum dry at 40℃ for 12h to obtain (0.7725g) 3wt% Ti3C2@NH2-MIL-101.

[0033] Example 2

[0034] A method for preparing a 1wt% Ti3C2@NH2-MIL-101 material includes the following steps:

[0035] 1) Preparation of Ti3C2: Weigh 1g of lithium fluoride (LiF) and 15mL of 9M HCl, stir evenly in a polytetrafluoroethylene container, and stir at 40℃ for 5min; then slowly add 1g of Ti3AlC2 to the LiF / HCl mixed solution over 5min, stir at 40℃ for 48h, centrifuge the reactants with deionized water until pH=7, filter to form a film, and vacuum dry at 40℃ for 12h to obtain (0.8g) Ti3C2;

[0036] 2) Preparation of Ti3C2@NH2-MIL-101: Weigh 2.025g of ferric chloride hexahydrate (FeCl3·6H2O) and 0.618g of 2-aminoterephthalic acid and stir in 45mL of N,N-dimethylformamide (DMF) solution until fully dissolved, then sonicate for 10min; add 0.0075g of Ti3C2, stir under vacuum at low temperature for 2h, and sonicate for 10min; hydrothermally react at 110℃ for 24h in a polytetrafluoroethylene container, centrifuge three times with DMF solution, and vacuum dry at 40℃ for 12h to obtain (0.7575g) 1wt% Ti3C2@NH2-MIL-101.

[0037] Example 3

[0038] A method for preparing a 5wt% Ti3C2@NH2-MIL-101 material includes the following steps:

[0039] 1) Preparation of Ti3C2: Weigh 1g of lithium fluoride (LiF) and 15mL of 9M HCl, stir evenly in a polytetrafluoroethylene container, and stir at 40℃ for 5min; then slowly add 1g of Ti3AlC2 to the LiF / HCl mixed solution over 5min, stir at 40℃ for 48h, centrifuge the reactants with deionized water until pH=7, filter to form a film, and vacuum dry at 40℃ for 12h to obtain (0.8g) Ti3C2;

[0040] 2) Preparation of Ti3C2@NH2-MIL-101: Weigh 2.025g of ferric chloride hexahydrate (FeCl3·6H2O) and 0.618g of 2-aminoterephthalic acid and stir in 45mL of N,N-dimethylformamide (DMF) solution until fully dissolved, then sonicate for 10min; add 0.0375g of Ti3C2, stir under vacuum at low temperature for 2h, and sonicate for 10min; hydrothermally react at 110℃ for 24h in a polytetrafluoroethylene container, centrifuge three times with DMF solution, and vacuum dry at 40℃ for 12h to obtain (0.7875g) 5wt% Ti3C2@NH2-MIL-101.

[0041] Example 4

[0042] Morphological characterization is performed using SEM Figure 2 3, 4: XRD tests were performed, and the characteristic peaks of the XRD indicate the successful synthesis of the material.

[0043] Example 5

[0044] Experiment on photocatalytic degradation of bifenthrin: Prepare a 10 mg / L bifenthrin solution, disperse it by ultrasonication, add 10 mg of 3 wt% Ti3C2@ NH2-MIL-101, disperse it by ultrasonication again, and use a xenon lamp to simulate sunlight to photocatalytically degrade bifenthrin at room temperature.

[0045] Example 6

[0046] Prepare a 10 mg / L bifenthrin solution, disperse it by ultrasonication, add 10 mg of 1 wt% Ti3C2@ NH2-MIL-101, disperse it by ultrasonication again, and use a xenon lamp to simulate sunlight to photocatalytically degrade bifenthrin at room temperature.

[0047] Example 7

[0048] Prepare a 10 mg / L bifenthrin solution, disperse it by ultrasonication, add 10 mg of 5 wt% Ti3C2@ NH2-MIL-101, disperse it by ultrasonication again, and use a xenon lamp to simulate sunlight to photocatalytically degrade bifenthrin at room temperature.

[0049] Comparative Example 1

[0050] Prepare a 10 mg / L bifenthrin solution, disperse it by sonication, add 10 mg of pure NH2-MIL-101, disperse it by sonication again, and use a xenon lamp to simulate sunlight to photocatalytically degrade bifenthrin at room temperature.

[0051] Comparative Example 2

[0052] Prepare a 10 mg / L bifenthrin solution, disperse it by ultrasonication, add 10 mg of pure Ti3C2, disperse it by ultrasonication again, and use a xenon lamp to simulate sunlight to photocatalytically degrade bifenthrin at room temperature.

[0053] Through Examples 5, 6, and 7 and Comparative Examples 1 and 2, and in combination Figure 5(The horizontal axis represents the photocatalytic reaction time, and the vertical axis represents the ratio of bifenthrin concentration at the corresponding time to the initial bifenthrin concentration.) It can be seen that after adding Ti3C2@NH2-MIL-101 material, bifenthrin can be effectively degraded under visible light, reducing its harmful effects. (In Ti3C2@NH2-MIL-101 material, NH2-MIL-101 absorbs visible light, and photogenerated electrons rapidly migrate from NH2-MIL-101 to Ti3C2, spatially hindering the recombination of photogenerated charge carriers, resulting in an electron-rich environment on the Ti3C2 surface. After photoexcitation, the number of holes (h) on the material surface increases.) + ) and superoxide radicals (·O2) - ( ) and hydroxyl radicals (·OH) participate as the main active substances in the degradation of bifenthrin. ) ) With the increase of Ti3C2 content, the photocatalytic degradation efficiency continuously improves (a heterojunction is formed between Ti3C2 and NH2-MIL-101, and the photocatalytic degradation efficiency of the 3wt% Ti3C2@NH2-MIL-101 material is better than that of the 1wt% Ti3C2@NH2-MIL-101 material), with the 3wt% Ti3C2@NH2-MIL-101 material showing the best photocatalytic effect. However, with further increases in the amount of Ti3C2 added, the photocatalytic degradation efficiency decreases, because excessive Ti3C2 will block the pores and produce a light-blocking effect.

[0054] Example 8

[0055] Taking 3wt% Ti3C2@NH2-MIL-101 material as an example, the effects of different masses of Ti3C2@NH2-MIL-101 material on the photocatalytic degradation of bifenthrin were investigated. The experimental results are shown in Table 1.

[0056] Table 1: Efficiency of photocatalytic degradation of bifenthrin by 3wt% Ti3C2@NH2-MIL-101 at different masses

[0057]

[0058] As shown in Table 1, the photocatalytic efficiency increases with the increase in the mass of Ti3C2@NH2-MIL-101 material. The photocatalytic degradation efficiency is best with 10 mg of 3wt% Ti3C2@NH2-MIL-101. However, when there is an excess of Ti3C2@NH2-MIL-101 material, it will aggregate, preventing visible light photons from being exposed to the sample surface and reducing the possibility of generating active substances during the photocatalytic process.

[0059] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. The application of a Ti3C2@NH2-MIL-101 material in the photocatalytic degradation of bifenthrin in insect- and ant-proof cables, characterized in that, The Ti3C2@NH2-MIL-101 material can effectively catalyze the degradation of bifenthrin under light irradiation; the photocatalytic degradation is carried out at room temperature; the specific steps of the preparation method of the Ti3C2@NH2-MIL-101 material are as follows: 1) Preparation of Ti3C2: Weigh 1g of lithium fluoride and 15mL of 9M HCl, stir evenly in a polytetrafluoroethylene container, and stir at 40℃ for 5min; then slowly add 1g of Ti3AlC2 to the LiF / HCl mixed solution over 5min, stir at 40℃ for 48h, wash the reactants with deionized water until pH=7, filter to form a film, and vacuum dry at 40℃ for 12h to obtain 0.8g of Ti3C2; 2) Preparation of Ti3C2@NH2-MIL-101: Weigh 2.025g FeCl3·6H2O and 0.618g 2-aminoterephthalic acid and stir in 45mL N,N-dimethylformamide solution until fully dissolved, then sonicate for 10min; add 0.0225g Ti3C2, stir under vacuum at low temperature for 2h, and sonicate for 10min; hydrothermally react in a polytetrafluoroethylene container at 110℃ for 24h, centrifuge three times with DMF solution, and vacuum dry at 40℃ for 12h to obtain 0.7725g 3wt% Ti3C2@NH2-MIL-101; The specific steps of the photocatalytic degradation are as follows: NH2-MIL-101 absorbs visible light, and photogenerated electrons migrate rapidly from NH2-MIL-101 to Ti3C2, spatially hindering the recombination of photogenerated charge carriers. This results in an electron-rich environment on the Ti3C2 surface. After photoexcitation, holes, superoxide radicals, and hydroxyl radicals on the material surface participate as the main active substances in the degradation of bifenthrin.

Images