4-propylphenol@Cu-btc-tmib composite material, and preparation method and application thereof

Abstract

The application discloses a 4-propylphenol@Cu-BTC-TMIB composite material and a preparation method and application thereof, and relates to the technical field of agricultural fungicides and material chemistry. The 4-propylphenol is first loaded in Cu-BTC channels to obtain a 4-propylphenol@Cu-BTC composite precursor, then the composite precursor is subjected to coordination assembly with a nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazole-1-yl)benzene, and after a post-modification reaction, the 4-propylphenol@Cu-BTC-TMIB composite material is prepared. The film damage effect of the plant source fungicide 4-propylphenol is organically combined with the strong oxidizing sterilization effect of the free radical-based advanced oxidation technology, the inhibition activity on main pathogenic bacteria such as apple anthracnose fungi and apple ring rot fungi is greatly improved, and the problems of limited effect and short effective period existing in single sterilization mode are overcome.

Description

Technical Field

[0001] This invention relates to the fields of agricultural fungicides and materials chemistry, and in particular to a 4-propylphenol@Cu-BTC-TMIB composite material, its preparation method, and its application. Background Technology

[0002] Apples are an important economic crop in my country, but they are susceptible to infection by various pathogenic fungi during their growth, such as apple anthracnose caused by *Alternaria alternata* and apple ring rot caused by *Alternaria solani*. These diseases severely affect apple yield and quality, causing huge economic losses. Currently, agricultural production mainly relies on chemical fungicides for disease control. However, the long-term and large-scale use of traditional chemical fungicides has led to a series of problems, including the increasing resistance of pathogens leading to decreased efficacy, pesticide residues threatening food safety, and negative impacts on non-target organisms and the environment. Therefore, the development of highly efficient, low-toxicity, and environmentally friendly new fungicides has become an urgent need in the field of green pest control in agriculture.

[0003] Plant-derived fungicides are considered a key area for development as alternatives to traditional chemical pesticides due to their natural origin, good environmental compatibility, and unique mechanisms of action. Studies have shown that plant-derived phenolic compounds, such as 4-propylphenol (also known as tetrapropylphenol), possess excellent antifungal activity. For example, 4-propylphenol can disrupt the cell membrane integrity of pathogenic fungi such as *Fusarium oxysporum* and *Fusarium oxysporum*, demonstrating its potential as an environmentally friendly fungicide. 4-propylphenol can also exert its inhibitory effect by inducing reactive oxygen species stress, damaging the cell membrane and DNA of *Fusarium graminearum*, the causal agent of wheat blight. However, single plant-derived fungicides may suffer from poor stability, slow action, or short-lasting effects in practical applications.

[0004] Metal-organic frameworks (MOFs) are a class of porous crystalline materials formed by the self-assembly of metal ions or clusters with organic ligands through coordination bonds. Due to their large specific surface area, tunable pore structure, and ease of functionalization, they show broad application prospects in gas storage, catalysis, sensing, and biomedicine. Among them, Cu-BTC, a copper-based MOF, can exert antibacterial effects by releasing copper ions or interacting with bacterial cell membranes through surface active sites. Furthermore, advanced oxidation technologies based on persulfate have been extensively studied in water treatment and disinfection. The principle behind this is the use of transition metal ions (such as Fe) to... 2+ Co 2+ MOF materials activate persulfate, generating highly reactive sulfate and hydroxyl radicals. Studies have shown that these radicals can effectively disrupt the cell structure of microorganisms, leading to their death. Currently, there are no reports on using MOF materials as heterogeneous catalysts to activate persulfate for agricultural sterilization, or on combining them with plant-derived fungicides to achieve synergistic effects. Summary of the Invention

[0005] To address the aforementioned limitations of existing technologies, the present invention aims to provide a 4-propylphenol@Cu-BTC-TMIB composite material, its preparation method, and its applications. The present invention first loads 4-propylphenol into the pores of Cu-BTC to obtain a 4-propylphenol@Cu-BTC composite precursor. Then, this precursor is coordinated and assembled with the nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene. Following a post-modification reaction, the 4-propylphenol@Cu-BTC-TMIB composite material is obtained. This invention organically combines the membrane-disrupting effect of the plant-derived fungicide 4-propylphenol with the strong oxidative fungicidal effect of advanced free radical oxidation technology, significantly enhancing its inhibitory activity against major pathogens such as apple anthracnose fungus and ring rot fungus, overcoming the problems of limited effectiveness and slow action associated with single fungicidal methods.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a method for preparing a 4-propylphenol@Cu-BTC-TMIB composite material, comprising the following steps: (1) 4-Propylphenol was loaded into the pores of Cu-BTC by impregnation method to obtain 4-Propylphenol@Cu-BTC composite precursor; (2) The 4-propylphenol@Cu-BTC composite precursor was dispersed in an organic solvent to obtain a dispersion; the nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene was added to the dispersion for reaction. After the reaction was completed, the mixture was cooled, centrifuged, and the solid after centrifugation was collected. After washing and drying, the 4-propylphenol@Cu-BTC-TMIB composite material was obtained.

[0007] Preferably, in step (1), the mass ratio of 4-propylphenol to Cu-BTC is (0.1-1):(1-5).

[0008] Preferably, in step (1), the specific steps for loading 4-propylphenol into the channels of Cu-BTC using the impregnation method are as follows: Cu-BTC was added to a methanol solution of 4-propylphenol, and after ultrasonic dispersion, it was reacted at 25-55℃ and 100-200rpm for 6-24h. After the reaction was completed, the precipitate was separated by centrifugation, washed and dried to obtain the 4-propylphenol@Cu-BTC composite precursor.

[0009] Furthermore, the methanol solution of 4-propylphenol is prepared by mixing 4-propylphenol and anhydrous methanol at a material-to-liquid ratio of (0.05-0.15) g: 20 mL, with ultrasonic dispersion time of 5-15 min, and drying method of vacuum drying at 50-70℃ for 10-16 h.

[0010] Preferably, in step (2), the molar ratio of the nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene and the 4-propylphenol@Cu-BTC composite precursor is (0.1-1):1.

[0011] Preferably, in step (2), the organic solvent is one or more of N,N-dimethylformamide, methanol, or ethanol.

[0012] Preferably, in step (2), the ratio of 4-propylphenol@Cu-BTC composite precursor to organic solvent is (0.05-0.15) g: 10 mL.

[0013] Preferably, in step (2), the reaction temperature is 50-100℃ and the reaction time is 12-48h.

[0014] Preferably, in step (2), the drying method is vacuum drying, the drying temperature is 50-70℃, and the drying time is 10-16h.

[0015] In a second aspect, the present invention provides a 4-propylphenol@Cu-BTC-TMIB composite material prepared by the above preparation method.

[0016] A third aspect of the present invention provides the use of the above-described 4-propylphenol@Cu-BTC-TMIB composite material in any one of the following (1)-(4): (1) Prevention and control of apple anthracnose; (2) Prepare products for the prevention and control of apple anthracnose; (3) Prevention and control of apple ring rot; (4) Prepare products for the prevention and control of apple ring rot.

[0017] As a preferred method, the specific application method is as follows: mix the above-mentioned 4-propylphenol@Cu-BTC-TMIB composite material, persulfate and water to obtain a mixture; apply the mixture to apple plants or spray it on apple fruits.

[0018] Preferably, the concentration of 4-propylphenol@Cu-BTC-TMIB composite material in the mixture is 20-200 mg / L, and the concentration of persulfate is 2-5 mM.

[0019] Preferably, the persulfate is one of sodium persulfate, potassium persulfate, or ammonium persulfate.

[0020] The beneficial effects of this invention are: 1. In this invention, 4-propylphenol is first loaded into the pores of Cu-BTC to obtain a 4-propylphenol@Cu-BTC composite precursor. Then, it is coordinated and assembled with the nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene. After a post-modification reaction, a 4-propylphenol@Cu-BTC-TMIB composite material is obtained.

[0021] This invention organically combines the membrane-disrupting effect of the plant-derived fungicide 4-propylphenol with the strong oxidative bactericidal effect of advanced free radical oxidation technology, which significantly improves the inhibitory activity against major pathogens such as apple anthracnose fungus and ring rot fungus, overcoming the problems of limited effect and slow action of single bactericidal methods.

[0022] Among them, 4-propylphenol exerts its antibacterial effect by disrupting the cell membrane integrity of pathogenic bacteria; the TMIB ligand introduced through post-modification synthesis interacts with Cu in Cu-BTC. 2+ The microenvironment formed by coordination endows the composite material with highly efficient catalytic activity, which can activate persulfate to generate highly active sulfate radicals and hydroxyl radicals. These radicals can rapidly and non-selectively oxidize and destroy key structures such as cell membranes and DNA of pathogens, thereby achieving rapid and efficient killing of pathogens.

[0023] When in use, the 4-propylphenol@Cu-BTC-TMIB composite material of the present invention can be mixed with persulfate and then applied. The Cu-BTC-TMIB active center in the composite material catalyzes the decomposition of persulfate, continuously generating sulfate free radicals and hydroxyl free radicals, which work together with the 4-propylphenol slowly released from the Cu-BTC channels to act on pathogens, achieving a synergistic effect of dual bactericidal mechanism and playing an excellent role in the prevention and control of apple diseases.

[0024] 2. This invention utilizes the porous structure of Cu-BTC as a carrier to not only achieve the loading of 4-propylphenol and protect the active component of the plant-derived fungicide 4-propylphenol, but also achieves the slow release of 4-propylphenol through the spatial confinement effect of the pores, allowing it to continuously act on pathogens and destroy their cell membrane structure, effectively prolonging the duration of the agent's effect, reducing the frequency of application, and lowering the amount of pesticide used.

[0025] 3. The preparation method provided by this invention is simple, mild, and easy to operate and control. Furthermore, the resulting 4-propylphenol@Cu-BTC-TMIB composite material combines the low toxicity and environmentally friendly properties of plant-derived fungicides with the rapid and efficient fungicidal advantages of advanced free radical oxidation technology. It has a broad range of targets and is less likely to induce drug resistance in pathogens, showing promising application prospects and significant economic and ecological value in the field of green control of apple diseases. Attached Figure Description

[0026] Figure 1 X-ray diffraction characterization of the 4-propylphenol@Cu-BTC-TMIB composite material and Cu-BTC prepared in Example 1; Figure 2 Nitrogen adsorption-desorption test of Cu-BTC and 4-propylphenol@Cu-BTC composite precursor prepared in Example 1. Detailed Implementation

[0027] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0028] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0029] The experimental materials used in the embodiments of this invention are all conventional experimental materials in the art and can be purchased through commercial channels.

[0030] In this invention, the CAS number of 4-propylphenol is 645-56-7, and the CAS number of 1,3,5-tris(1H-imidazol-1-yl)benzene is 528543-96-6.

[0031] Cu-BTC is prepared by the following method: Cu(NO3)2·3H2O and methanol are mixed at a ratio of 2.416g:50mL to obtain a copper nitrate solution; terephthalic acid and methanol are mixed at a ratio of 1.051g:50mL to obtain a terephthalic acid solution; the terephthalic acid solution is added to the copper nitrate solution under stirring, and PVP is added, wherein the mass ratio of PVP to terephthalic acid is 0.5:1.051g. After stirring evenly, the mixture is allowed to stand for 24 hours, and the precipitate is collected by centrifugation, which is Cu-BTC.

[0032] Anthrax bacillus fusiformis ( Colletotrichum acutatum Purchased from the China Agricultural Microbial Culture Collection Center, accession number ACCC 38939; *Berenger* spp. pear-specific type ( B.berengeriana f.sp.piricola Purchased from the China Forestry Microbial Culture Collection Center, strain number CFCC 51744. Example 1: Preparation of 4-propylphenol@Cu-BTC-TMIB composite material (1) Dissolve 0.5g of 4-propylphenol in 100mL of anhydrous methanol to obtain a methanol solution of 4-propylphenol; add 1g of Cu-BTC to the above methanol solution of 4-propylphenol and disperse by ultrasonication for 10min to obtain a mixture; place the mixture at 40℃ and 150rpm for 12h of shaking reaction. After the reaction is completed, centrifuge to separate the precipitate, wash the precipitate three times with methanol to remove the 4-propylphenol on its surface, and then place the washed solid at 60℃ for vacuum drying for 12h to obtain the 4-propylphenol@Cu-BTC composite precursor, wherein the drug loading of the 4-propylphenol@Cu-BTC composite precursor is 80%; (2) 0.3 g of 4-propylphenol@Cu-BTC composite precursor was dispersed in 30 mL of N,N-dimethylformamide to obtain a dispersion. The nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene was added to the above dispersion, wherein the molar ratio of 1,3,5-tris(1H-imidazol-1-yl)benzene and 4-propylphenol@Cu-BTC composite precursor was 0.5:1. After ultrasonic dispersion to completely dissolve it, it was placed at 80 °C for 24 h. After the reaction was completed, it was naturally cooled to room temperature, centrifuged and the solid product was collected. It was washed three times each with N,N-dimethylamide and methanol to remove unreacted ligands and solvents. Finally, the washed solid was placed at 60 °C for vacuum drying for 12 h to obtain 4-propylphenol@Cu-BTC-TMIB composite material.

[0033] Example 2: Preparation of 4-propylphenol@Cu-BTC-TMIB composite material (1) Dissolve 0.05 g of 4-propylphenol in 20 mL of anhydrous methanol to obtain a methanol solution of 4-propylphenol; add 2 g of Cu-BTC to the above methanol solution of 4-propylphenol and disperse by ultrasonication for 5 min to obtain a mixture; place the mixture at 25 °C and 100 rpm for 6 h of shaking reaction; after the reaction is completed, centrifuge to separate the precipitate, wash the precipitate three times with methanol to remove the 4-propylphenol on its surface, and then place the washed solid at 50 °C for vacuum drying for 10 h to obtain the 4-propylphenol@Cu-BTC composite precursor; (2) 0.05 g of 4-propylphenol@Cu-BTC composite precursor was dispersed in 20 mL of N,N-dimethylformamide to obtain a dispersion; 0.5 mmol of nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene was added to the above dispersion, and ultrasonically dispersed to completely dissolve it. The mixture was then placed at 50 °C for 12 h. After the reaction was completed, the mixture was naturally cooled to room temperature, centrifuged and the solid product was collected. The solid product was washed three times each with N,N-dimethylamide and methanol to remove unreacted ligands and solvents. Finally, the washed solid was placed at 50 °C and vacuum dried for 10 h to obtain the 4-propylphenol@Cu-BTC-TMIB composite material.

[0034] Example 3: Preparation of 4-propylphenol@Cu-BTC-TMIB composite material (1) Dissolve 0.15g of 4-propylphenol in 20mL of anhydrous methanol to obtain a methanol solution of 4-propylphenol; add 0.15g of Cu-BTC to the above methanol solution of 4-propylphenol and disperse by ultrasonication for 15min to obtain a mixture; place the mixture at 55℃ and 200rpm for 24h of shaking reaction. After the reaction is completed, centrifuge to separate the precipitate, wash the precipitate three times with methanol to remove the 4-propylphenol on its surface, and then place the washed solid at 70℃ for vacuum drying for 16h to obtain the 4-propylphenol@Cu-BTC composite precursor. (2) 0.15 g of 4-propylphenol@Cu-BTC composite precursor was dispersed in 20 mL of N,N-dimethylformamide to obtain a dispersion. 1 mmol of nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene was added to the above dispersion. After ultrasonic dispersion to completely dissolve it, it was placed at 100 °C for 48 h. After the reaction was completed, it was naturally cooled to room temperature, centrifuged and the solid product was collected. It was washed three times each with N,N-dimethylamide and methanol to remove unreacted ligands and solvents. Finally, the washed solid was placed at 70 °C and vacuum dried for 16 h to obtain the 4-propylphenol@Cu-BTC-TMIB composite material.

[0035] Comparative Example 1: The difference between this comparative example and Example 1 is that the post-modification reaction with the nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene was not carried out during the preparation of the composite material. The specific steps are as follows: 0.1 g of 4-propylphenol was dissolved in 20 mL of anhydrous methanol to obtain a methanol solution of 4-propylphenol; 0.5 g of Cu-BTC was added to the above addition solution of 4-propylphenol and ultrasonically dispersed for 10 min to obtain a mixture; the mixture was placed at 40 °C and 150 rpm for 12 h of shaking reaction. After the reaction was completed, the precipitate was separated by centrifugation and washed three times with methanol to remove 4-propylphenol from its surface. The washed solid was then placed at 60 °C and vacuum dried for 12 h to obtain the 4-propylphenol@Cu-BTC composite material.

[0036] Comparative Example 2: The difference between this comparative example and Example 1 is that 4-propylphenol was not used in the preparation of the composite material. The specific steps are as follows: 0.3 g Cu-BTC was dispersed in 30 mL of N,N-dimethylformamide to obtain a dispersion. 0.1 mmol of nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene was added to the above dispersion. After ultrasonic dispersion to ensure complete dissolution, the mixture was placed at 80 °C for 24 h. After the reaction was completed, the mixture was naturally cooled to room temperature, centrifuged, and the solid product was collected. The solid was washed three times each with N,N-dimethylformamide and methanol to remove unreacted ligands and solvents. Finally, the washed solid was vacuum dried at 60 °C for 12 h to obtain the Cu-BTC-TMIB composite material.

[0037] Experimental Example 1: Structural Characterization 1. X-ray diffraction analysis was performed on the 4-propylphenol@Cu-BTC-TMIB composite material prepared in Example 1, as follows: Figure 1 As shown in the figure. The sample in the figure is the 4-propylphenol@Cu-BTC-TMIB composite material prepared in Example 1, and the standard is Cu-BTC. Figure 1 It can be seen that the prepared composite material is basically consistent with Cu-BTC in the main diffraction peak positions, indicating that the crystal structure of Cu-BTC is well maintained during the loading and post-synthesis modification process. 2. Nitrogen adsorption-desorption tests were performed on the 4-propylphenol@Cu-BTC composite precursor prepared in Example 1, and the results are as follows: Figure 2 As shown.

[0038] Since TMIB modification is surface-based and does not affect the porosity of Cu-BTC, while 4-propylphenol occupies the internal channels of Cu-BTC, nitrogen adsorption-desorption tests were performed only on the Cu-BTC and 4-propylphenol@Cu-BTC composite precursors. Figure 2 It can be seen that, compared with pure Cu-BTC, the specific surface area and pore volume of tetrapropylphenol@Cu-BTC and 4-propylphenol@Cu-BTC-TMIB are reduced, further confirming that tetrapropylphenol was successfully loaded into the pores.

[0039] Experimental Example 2: Persulfate Catalytic Activity Test At room temperature, 20 mg of each of the following composite materials were added to 50 mL of a solution containing 0.5 mM persulfate and 10 mg / L rhodamine B as simulated pollutants: 4-propylphenol@Cu-BTC-TMIB composite material prepared in Example 1, Cu-BTC, 4-propylphenol@Cu-BTC composite material prepared in Comparative Example 1, and Cu-BTC-TMIB composite material prepared in Comparative Example 2. Samples were taken at regular intervals (5 min, 10 min), centrifuged, and the absorbance change of rhodamine B at 554 nm was measured using a UV-Vis spectrophotometer. The degradation rate was calculated, and the results are shown in Table 1.

[0040] The degradation rate is calculated using the following formula: Degradation rate = [(A0-A...]] t ) / A0]×100%; In the formula, A0 is the absorbance of Rhodamine B at 554 nm at the initial time (t=0); A t The absorbance is the value measured at time t during the reaction.

[0041] Table 1. Degradation rates (%) for different treatments As shown in Table 1, the system with added 4-propylphenol@Cu-BTC-TMIB achieved a degradation rate of over 99% for Rhodamine B within 10 minutes, which is higher than that of the Cu-BTC system (10%) and the tetrapropylphenol@Cu-BTC system (12%). Therefore, the 4-propylphenol@Cu-BTC-TMIB composite material prepared in this invention exhibits excellent persulfate catalytic activity. Example 3: Antibacterial activity test of apple anthracnose bacterium. The mycelial growth rate method was used to test the inhibitory activity of 4-propylphenol@Cu-BTC-TMIB composite material prepared in Example 1, the composite materials prepared in Comparative Examples 1-2, and Cu-BTC against apple anthracnose. The specific steps are as follows: (1) Different samples were added to the PDA medium to make the final drug concentration 100 mg / L (based on the composite material). At the same time, a PDA medium without samples was set up as a blank control group. In addition, a treatment group was set up with only sodium persulfate (1 mM).

[0042] (2) Bacillus caudatus ( ) Colletotrichum acutatum As the pathogen causing apple anthracnose, activated bacterial cakes (5 mm in diameter) were inoculated into the center of PDA medium and incubated at 25°C for 5 days. The colony diameter was then measured using the cross-hatching method to calculate the inhibition rate. Some treatment groups received an additional 1 mL of 1 mM sodium persulfate in the medium. The results are shown in Table 2.

[0043] The inhibition rate (%) is calculated as follows: [(control colony diameter - treated colony diameter) / (control colony diameter - mycelial cake diameter)] × 100%.

[0044] Table 2. Results of antibacterial activity tests in different treatment groups As shown in Table 2, persulfate alone has almost no antibacterial effect. Adding only the 4-propylphenol@Cu-BTC-TMIB prepared in this invention, without adding persulfate, results in an antibacterial effect of only 40.9%. This is because the 4-propylphenol in the composite material is released slowly, exhibiting certain antibacterial activity, and its antibacterial effect is superior to Cu-BTC. Combining the 4-propylphenol@Cu-BTC-TMIB prepared in this invention with persulfate results in an antibacterial effect of 86.7%, which is higher than the combined antibacterial rate of the two treatment groups: persulfate alone and the combination of only adding the 4-propylphenol@Cu-BTC-TMIB prepared in this invention without adding persulfate.

[0045] Furthermore, compared to Cu-BTC, the antibacterial rate of the 4-propylphenol@Cu-BTC composite material in Comparative Example 1 was increased by 19.7%, and the antibacterial rate of the Cu-BTC-TMIB composite material in Comparative Example 2 was increased by 48.3%. In contrast, the antibacterial rate of the 4-propylphenol@Cu-BTC-TMIB composite material of the present invention was increased by 69.7%. Therefore, the present invention utilizes 4-propylphenol loading and TMIB post-modification to achieve a synergistic effect in improving the antibacterial rate of the composite material.

[0046] Experiment Example 4: Antibacterial Activity Test of *Rhizoctonia solani* Using the pear-specific type of Staphylococcus berengeri ( B.berengeriana f.sp.piricola As the pathogen of apple ring rot, the 4-propylphenol@Cu-BTC-TMIB composite material prepared in Example 1 was used as a sample, and its inhibitory activity against the apple ring rot pathogen was tested using the mycelial growth rate method. The specific steps are as follows: (1) Add the sample to the PDA medium to make the final drug concentration 100 mg / L (based on the composite material), and set up a PDA medium without adding the sample as a blank control group.

[0047] (2) The activated apple ring rot fungus (5 mm in diameter) was inoculated in the center of PDA medium and 1 mL of 1 mM sodium persulfate was added. After culturing in a 25°C incubator for 5 days, the colony diameter was measured by the cross-cross method and the inhibition rate was calculated. The results are shown in Table 3.

[0048] Table 3 4-Propylphenol@Cu-BTC-TMIB Composite Materials As shown in Table 3, the 4-propylphenol@Cu-BTC-TMIB composite material prepared in this invention achieved an inhibition rate of 82.5% against apple ring rot fungus in a culture medium containing 1 mM persulfate, demonstrating excellent control effect.

[0049] Experiment 5: Pot Experiment (1) The 4-propylphenol@Cu-BTC-TMIB composite material prepared in Example 1, sodium persulfate, and water were mixed to obtain a mixture; wherein, the concentration of the 4-propylphenol@Cu-BTC-TMIB composite material in the mixture was 100 mg / mL, and the concentration of sodium persulfate was 3.5 mM; it and 80% mancozeb wettable powder (600 times dilution) were sprayed on the front and back of the leaves of 2-3 year old apple trees, until the solution began to drip, and the spraying amount per pot was 10-15 ml / pot; wherein, An equal amount of water was sprayed as a control group; (2) The anthracnose pathogen of apples—Anthracnose fusiforme ( Colletotrichum acutatum Inoculate onto PDA plates and incubate at 25°C for 7-10 days. After a large number of conidia are produced, wash away the conidia with sterile water, filter through double-layer gauze, centrifuge and wash, and then adjust the conidia concentration to 1×10⁻⁶ with sterile water. 5 spores / mL, to obtain a spore suspension; Apple leaves were collected 1, 3, 7, 14 and 21 days after application of the pesticide. The spore suspension was inoculated onto the apple leaves using the drip inoculation method. Four points were inoculated on the back of the leaves. After 5 days of moist culture, the size of the lesions was investigated. Each treatment was set up with 3 replicates, and the average value was taken.

[0050] The relative efficacy was calculated using lesion area as an indicator. The results are shown in Table 4, and the calculation formula is as follows. .

[0051] The method for determining the lesion area is as follows: measure the major axis (a) and minor axis (b) of each lesion, and calculate the area using the ellipse area formula: S = πxaxb / 4. At least 10 lesions are investigated for each treatment, and the average value is taken.

[0052] Table 4. Relative efficacy of 4-propylphenol@Cu-BTC-TMIB composite and mancozeb. As shown in Table 4, one day after application, the efficacy of both was similar (approximately 86-88%), indicating that the 4-propylphenol@Cu-BTC-TMIB composite material prepared in this invention, when used in combination with persulfate, can rapidly generate free radicals, with an onset speed comparable to conventional chemical agents. Seven days after application, the efficacy of mancozeb significantly decreased to 62%, indicating a short duration of effectiveness; the efficacy of the 4-propylphenol@Cu-BTC-TMIB composite material prepared in this invention remained above 79%, demonstrating the sustained release effect of Cu-BTC channels on tetrapropylphenol and the continuous free radical generation capacity of catalytic active sites. Fourteen days after application, the efficacy of mancozeb had decreased to below 40%, losing its effective protective effect; the efficacy of the 4-propylphenol@Cu-BTC-TMIB composite material prepared in this invention remained above 65%, significantly superior to conventional agents. 21 days after application: Mancozeb had a control efficacy of only 24%, essentially ineffective; 4-propylphenol@Cu-BTC-TMIB composite material still had a control efficacy of 56%, maintaining a moderate control level, proving that it has long-lasting slow release and continuous catalytic activity.

[0053] The 4-propylphenol@Cu-BTC-TMIB composite material prepared in Example 1 was mixed with persulfate to obtain a mixture. This mixture, along with a conventional chemical fungicide (mancozeb), was applied to the leaves of potted apples. Leaves were collected 1, 3, 7, 14, and 21 days after application, inoculated with apple anthracnose spore suspension, and cultured in a moist environment for 5 days. The size of the lesions was then investigated, and the relative control efficacy was calculated.

[0054] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing a 4-propylphenol@Cu-BTC-TMIB composite material, characterized in that, Includes the following steps: (1) 4-Propylphenol was loaded into the pores of Cu-BTC by impregnation method to obtain 4-Propylphenol@Cu-BTC composite precursor; (2) The 4-propylphenol@Cu-BTC composite precursor was dispersed in an organic solvent to obtain a dispersion; the nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene was added to the dispersion for reaction. After the reaction was completed, the mixture was cooled, centrifuged, and the solid after centrifugation was collected. After washing and drying, the 4-propylphenol@Cu-BTC-TMIB composite material was obtained.

2. The preparation method of the 4-propylphenol@Cu-BTC-TMIB composite material as described in claim 1, characterized in that, The mass ratio of 4-propylphenol to Cu-BTC is (0.1-1):(1-5); the molar ratio of the nitrogen-containing heterocyclic ligand 1,3,5-tris(1H-imidazol-1-yl)benzene to the 4-propylphenol@Cu-BTC composite precursor is (0.1-1):

1.

3. The preparation method of the 4-propylphenol@Cu-BTC-TMIB composite material as described in claim 1, characterized in that, In step (1), the specific steps for loading 4-propylphenol into the channels of Cu-BTC using the impregnation method are as follows: Cu-BTC was added to a methanol solution of 4-propylphenol, and after ultrasonic dispersion, it was reacted at 25-55℃ and 100-200rpm for 6-24h. After the reaction was completed, the precipitate was separated by centrifugation, washed and dried to obtain the 4-propylphenol@Cu-BTC composite precursor.

4. The preparation method of the 4-propylphenol@Cu-BTC-TMIB composite material as described in claim 3, characterized in that, The methanol solution of 4-propylphenol is prepared by mixing 4-propylphenol and anhydrous methanol at a material-to-liquid ratio of (0.05-0.15) g: 20 mL, and the ultrasonic dispersion time is 5-15 min; the drying method is vacuum drying, the drying temperature is 50-70℃, and the drying time is 10-16 h.

5. The method for preparing the 4-propylphenol@Cu-BTC-TMIB composite material as described in claim 1, characterized in that, In step (2), the organic solvent is one or more of N,N-dimethylformamide, methanol or ethanol; the ratio of 4-propylphenol@Cu-BTC composite precursor to organic solvent is (0.05-0.15) g: 10 mL.

6. The method for preparing the 4-propylphenol@Cu-BTC-TMIB composite material as described in claim 1, characterized in that, In step (2), the reaction temperature is 50-100℃ and the reaction time is 12-48h; the drying method is vacuum drying, the drying temperature is 50-70℃ and the drying time is 10-16h.

7. The 4-propylphenol@Cu-BTC-TMIB composite material prepared by the preparation method according to any one of claims 1-6.

8. The use of the 4-propylphenol@Cu-BTC-TMIB composite material of claim 7 in any one of the following (1)-(4): (1) Prevention and control of apple anthracnose; (2) Prepare products for the prevention and control of apple anthracnose; (3) Prevention and control of apple ring rot; (4) Prepare products for the prevention and control of apple ring rot.

9. The application as described in claim 8, characterized in that, The specific application method is as follows: after mixing the above-mentioned 4-propylphenol@Cu-BTC-TMIB composite material with persulfate, a mixture is obtained; the mixture is then applied to apple plants or sprayed onto apple fruits.

10. The application as described in claim 9, characterized in that, In the mixture, the concentration of 4-propylphenol@Cu-BTC-TMIB composite material is 20-200 mg / L, and the concentration of persulfate is 2-5 mM; the persulfate is one of sodium persulfate, potassium persulfate, and ammonium persulfate.

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