Antibacterial agent, preparation method thereof and refrigerator

Abstract

The invention discloses an antibacterial agent, a preparation method thereof and a refrigerator, and belongs to the technical field of antibacterial materials. According to the technical scheme, the preparation method comprises the following steps: dispersing MoO3, 1, 3, 5-triformyl phloroglucinol and potassium hydroxide in deionized water, carrying out an oil bath reaction, adding an N, N-dimethylformamide solution containing p-phenylenediamine, continuing the reaction, washing, and drying to prepare the antibacterial agent MoO3 at TpPa-1 composite material. The preparation method is applied to the aspect of refrigerator antibacterial materials, the problems that when MoO3 is used as a photocatalytic material, the electron and hole separation efficiency is low, the stability in an aqueous solution is poor, and then the photoresponsiveness and the antibacterial durability of MoO3 are affected are solved, electron-hole pair separation of MoO3 can be effectively promoted, the aqueous solution stability of MoO3 is improved, and the preparation method is simple and easy to implement. The service life is prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of antibacterial materials, and in particular relates to an antibacterial agent, a preparation method thereof and a refrigerator. Background Art

[0002] Photocatalytic antibacterial materials can generate electrons and an equal number of holes under the excitation of light. These photogenerated electrons and holes can react with H attached to the surface of the material. 2 O or O 2 Oxidation occurs, generating highly oxidizing substances - reactive oxygen species (ROS). Photogenerated electrons can react with H 2 O reacts to generate hydroxyl radicals ·OH, while the photogenerated holes react with O 2 The reaction generates superoxide anion O 2 Once these active oxygen substances come into contact with bacteria, they will destroy the bacterial cell structure in a relatively short period of time, causing the bacterial contents to flow out and rendering the bacteria inactive.

[0003] MoO 3 It is a metal oxide photocatalytic material with good response to visible light. 3 It is an excellent antibacterial material with a broad spectrum and high efficiency in sterilization. Under the irradiation of visible light, it can absorb the energy of visible light, generate reactive oxygen species (ROS), destroy the cell structure of bacteria, and thus kill bacteria. 3 The wide band gap of MoO leads to slow migration of photogenerated carriers and low separation efficiency of electrons and holes, which limits its application in the field of photocatalysis. 3 It has poor stability in aqueous solution and easily reacts with water to generate H 3 O+ and molybdenum ions form MoO 3 The Chinese patent CN114314666A discloses an oxygen vacancy type nano molybdenum trioxide antibacterial agent and a preparation method thereof, comprising: mixing a molybdenum salt aqueous solution and an amino acid salt reducing agent solution evenly, reacting at room temperature for 12h-48h, and obtaining MoO 3 Precursor, and then calcined in stages to obtain micron-sized MoO 3 ; Micron-sized MoO 3 Ball milling was performed to obtain oxygen vacancy type nano molybdenum trioxide antibacterial agent. The technical scheme disclosed in the above Chinese patent uses amino acid hydrochloride reducing agent as green reducing agent to prepare MoO 3 The amino acid hydrochloride reducing agent itself can provide a weakly acidic environment without introducing other impurities with toxic side effects. No external acid is needed to adjust the pH value. The ball milling method is used to 3 The nanoparticle grain size is controlled while oxygen vacancies are constructed. The preparation process is simple, the cost is low, and it is easy to mass produce.

[0004] However, the above solutions still cannot solve the problem of MoO 3 When used as a photocatalytic material, it has the problems of low separation efficiency of electrons and holes and poor stability in aqueous solution, which in turn affects its light responsiveness and antibacterial durability. Summary of the invention

[0005] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is that MoO 3 As a photocatalytic material, it has the problems of low separation efficiency of electrons and holes and poor stability in aqueous solution, which affects its light responsiveness and antibacterial durability. This paper proposes a method that can effectively promote the MoO 3 An antibacterial agent which can separate electron-hole pairs, improve the stability of its aqueous solution and extend the service life, and a preparation method and a refrigerator thereof.

[0006] In order to solve the technical problem, the technical solution adopted by the present invention is:

[0007] In one aspect, the present invention provides a method for preparing an antibacterial agent, comprising: 3 , 1,3,5-triformylphloroglucinol and potassium hydroxide were dispersed in deionized water, and after oil bath reaction, N,N-dimethylformamide solution containing p-phenylenediamine was added to continue the reaction, and then washed and dried to prepare the antibacterial agent MoO 3 @TpPa-1 composite material.

[0008] Preferably, the MoO 3 Prepared by hydrothermal method or calcination.

[0009] Preferably, the MoO 3 The MoO is prepared by the following method: adding nitric acid to an aqueous solution of ammonium molybdate to adjust the pH value to 1.1, transferring the mixed solution to a reactor, performing a hydrothermal reaction, washing and drying, and obtaining the MoO 3 .

[0010] Preferably, the mass ratio of the 1,3,5-triformylphloroglucinol to the p-phenylenediamine is 21:16.

[0011] Preferably, the oil bath temperature of the oil bath reaction is 140°C.

[0012] Preferably, the reaction time of the oil bath reaction is 15-20 min; the continued reaction time of adding the N,N-dimethylformamide solution containing p-phenylenediamine to continue the reaction is 24 h.

[0013] Preferably, the antibacterial agent MoO 3 MoO in @TpPa-1 composites 3The mass ratio to TpPa-1 is 3:2-4.5.

[0014] Preferably, the antibacterial agent MoO 3 MoO in @TpPa-1 composites 3 The mass ratio with TpPa-1 is 3:3.

[0015] Another aspect of the present invention provides an antibacterial agent prepared by the method for preparing an antibacterial agent according to any of the above technical solutions, wherein the antibacterial agent MoO 3 In @TpPa-1 composite materials, MoO 3 and TpPa-1 to form a heterojunction, and the TpPa-1 covers the MoO 3 .

[0016] The present invention also provides a refrigerator, wherein the plastic raw material of the refrigerator includes the antibacterial agent described in the above technical solution.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The present invention provides a method for preparing an antibacterial agent, and specifically defines the steps of first adding MoO 3 and 1,3,5-triformylphloroglucinol, so that a monomer of TpPa-1, 1,3,5-triformylphloroglucinol, is first adsorbed on MoO 3 After a period of time, another monomer, p-phenylenediamine, is added to ensure that TpPa-1 can self-assemble (grow) on the MoO 3 At the same time, due to the excellent crystallinity of TpPa-1, even in MoO 3 In the case of fewer active sites on the surface, a high crystallinity structure can also be formed. High crystallinity can not only reduce the recombination center and promote the transmission of photogenerated carriers, but also expand the π-π conjugated system, improve the light absorption capacity and photocatalytic performance. At the same time, the TpPa-1 in the antibacterial agent prepared by the preparation method has a large surface MoO 3 Self-growth, MoO 3 The modification improves its stability in aqueous solution, inhibits the photoinduced electron and hole recombination, improves the separation efficiency of photogenerated carriers, promotes the generation of ROS, and enhances the antibacterial function. DETAILED DESCRIPTION

[0019] The technical scheme in the specific embodiment of the present invention is described in detail and completely below. Obviously, the described embodiment is only a part of the specific implementation of the overall technical scheme of the present invention, rather than all implementations. Based on the overall concept of the present invention, all other embodiments obtained by ordinary technicians in this field fall within the scope of protection of the present invention.

[0020] The present invention provides a method for preparing an antibacterial agent, comprising: 3 , 1,3,5-triformylphloroglucinol and potassium hydroxide were dispersed in deionized water, and after oil bath reaction, N,N-dimethylformamide solution containing p-phenylenediamine was added to continue the reaction, and then washed and dried to prepare the antibacterial agent MoO 3 @TpPa-1 composite material. The preparation method of the antibacterial agent specifically defines the addition of MoO 3 and 1,3,5-triformylphloroglucinol, so that a monomer of TpPa-1, 1,3,5-triformylphloroglucinol, is first adsorbed on MoO 3 After a period of time, another monomer, p-phenylenediamine, is added to ensure that TpPa-1 can self-assemble (grow) on the MoO 3 At the same time, due to the excellent crystallinity of TpPa-1, even in MoO 3 In the case of fewer active sites on the surface, a high crystallinity structure can also be formed. High crystallinity can not only reduce the recombination center and promote the transmission of photogenerated carriers, but also expand the π-π conjugated system, improve the light absorption capacity and photocatalytic performance. At the same time, the TpPa-1 in the antibacterial agent prepared by the preparation method has a large surface MoO 3 Self-growth, MoO 3 The modification improves its stability in aqueous solution, inhibits the recombination of photoinduced electrons and holes, improves the separation efficiency of photogenerated carriers, promotes the generation of ROS, and enhances the antibacterial function. In addition, the above preparation method uses KOH as a catalyst to reduce the Schiff base reaction time from the conventional 72h to 24h, effectively improving the reaction efficiency.

[0021] It should be noted that the covalent organic framework is a type of porous polymer constructed by organic units connected by covalent bonds. Its skeleton is composed of light elements such as C, H, N, O, B, etc., and has the characteristics of low density, excellent thermal stability and chemical stability. There are many types of covalent organic frameworks, which can be roughly divided into four categories according to the type of covalent bond formation: boron-containing COF, imine COF, triazine COF and other types of COF. Among them, the triazine covalent organic framework has high chemical stability, but there is a problem of low material crystallinity; TpPa-1 defined in the present invention is an imine covalent organic framework, which has high crystallinity and thermal stability. Chinese patent CN118577304A discloses a composite photocatalyst doped with a metal organic framework and a covalent organic framework, and its preparation method and application, wherein the triazine covalent organic framework is based on a carrier PEI-coated NH 2 The amino groups on the surface of -UIO-67-Fe react with the aldehyde groups of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine, a monomer of COF, to form COF on the PEI-coated NH 2-UIO-67-Fe surface self-assembles to form a highly crystalline COF material. However, triazine COF itself does not have high crystallinity. When the carrier material is changed to MoO 3 When MoO 3 The COF generated on the surface has a low crystallinity. Low crystallinity leads to high-density structural defects in the COF, which hinders the migration of photogenerated carriers inside the material and thus reduces the photocatalytic effect.

[0022] TpPa-1 is a typical covalent organic framework material with good responsiveness to visible light and is considered to be a semiconductor material with great potential. TpPa-1 has a conjugated structure constructed by benzene rings, which is conducive to the transmission of electrons. Its high specific surface area and porous structure can provide more active sites for photocatalytic reactions and promote electron transmission. TpPa-1 can be combined with inorganic materials to form a heterojunction, improve the separation efficiency of photogenerated electron-hole pairs, and at the same time make the photoelectrons and photogenerated holes of the heterojunction show stronger redox ability at different active sites. The present invention controls the synthesis method, first adsorbs a monomer 1,3,5-triformylphloroglucinol on MoO 3 After a period of time, another monomer, p-phenylenediamine, is added to ensure that TpPa-1 can self-assemble (grow) on the MoO 3 At the same time, due to the excellent crystallinity of imine COF itself, even in MoO 3 A high crystallinity structure can be formed even when there are fewer active sites on the surface. High crystallinity can not only reduce the recombination center and promote the transmission of photogenerated carriers, but also expand the π-π conjugated system and improve the light absorption capacity and photocatalytic performance.

[0023] In a preferred embodiment, the MoO 3 It is prepared by a hydrothermal method or calcination. Specifically, it is prepared by the following method: adding nitric acid to an aqueous solution of ammonium molybdate to adjust the pH value to 1.1, transferring the mixed solution to a reactor, performing a hydrothermal reaction, washing and drying to obtain the MoO 3 .

[0024] In a preferred embodiment, the mass ratio of the 1,3,5-triformylphloroglucinol to the p-phenylenediamine is 21:16. In a preferred embodiment, the oil bath temperature of the oil bath reaction is 140°C. In a preferred embodiment, the reaction time of the oil bath reaction is 15-20min; the continued reaction time of adding the N,N-dimethylformamide solution containing p-phenylenediamine to continue the reaction is 24h. This technical solution specifically defines the amount of raw materials used in the preparation process of the antibacterial agent, the reaction temperature of each stage, and the reaction time. The reason is that the control of each parameter of the reaction process is the premise and key to ensure the structural composition and performance requirements of the prepared composite material.

[0025] In a preferred embodiment, the antibacterial agent MoO 3 MoO in @TpPa-1 composites 3 The mass ratio of the antibacterial agent MoO to TpPa-1 is 3:2-4.5. 3 MoO in @TpPa-1 composites 3 The mass ratio of MoO to TpPa-1 is 3:3. 3 MoO in @TpPa-1 composites 3 The mass ratio with TpPa-1 is beneficial to ensure the antibacterial property and the durability of antibacterial. 3 @TpPa-1Key factors in the structural composition of composite materials.

[0026] Another aspect of the present invention provides an antibacterial agent prepared by the method for preparing an antibacterial agent according to any of the above technical solutions, wherein the antibacterial agent MoO 3 In @TpPa-1 composite materials, MoO 3 and TpPa-1 to form a heterojunction, and the TpPa-1 covers the MoO 3 The antibacterial agent component prepared by the above preparation method is MoO 3 @TpPa-1 composite material, compared with pure MoO 3 Compared with other materials, it has better light absorption ability, better photocatalytic antibacterial effect, stronger stability and longer-lasting antibacterial effect.

[0027] MoO 3 Compounded with TpPa-1 to form heterojunction MoO 3 @TpPa-1, the construction of heterojunction can effectively inhibit the recombination of photogenerated electrons and holes, improve the efficiency of carrier separation and transmission, and at the same time, TpPa-1 has a large number of active sites with a high specific surface area, which can effectively promote interfacial charge transfer and improve photocatalytic activity; MoO 3@TpPa-1 The energy required for electrons to transition to the conduction band is low. Under the excitation of visible light, reactive oxygen free radicals (ROS) (hydroxyl free radicals and superoxide free radicals) can be generated on the surface; MoO 3 @TpPa-1 has a broad-spectrum antibacterial function and can have a good bactericidal effect on both Gram-positive and Gram-negative bacteria. The cell structure of Gram-positive and Gram-negative bacteria contains thick peptidoglycan and lipids. ROS can oxidize peptidoglycan and lipids, destroy the cell structure of bacteria and cause bacterial death, thus playing an antibacterial effect; in addition, MoO 3 @TpPa-1 has a long-lasting antibacterial effect. 3 The coating can improve the MoO 3 Stability, avoid MoO 3 Dissolves when in contact with water, reducing the service life of the antibacterial agent.

[0028] The present invention also provides a refrigerator, wherein the plastic raw material of the refrigerator includes the antibacterial agent described in the above technical solution. Specifically, the antibacterial agent can be added to the refrigerator plastic raw materials such as polypropylene, polystyrene, acrylonitrile-styrene-butadiene copolymer, etc., to give the raw materials antibacterial function.

[0029] In order to more clearly and in detail introduce the antibacterial agent, the preparation method thereof and the refrigerator provided in the embodiments of the present invention, they will be described below in conjunction with specific embodiments.

[0030] Example 1

[0031] An antibacterial agent and a preparation method thereof, wherein the antibacterial agent comprises MoO 3 @TpPa-1, where MoO 3 The mass ratio of TpPa-1 is 3:3, comprising the following steps:

[0032] (1) MoO 3 Preparation

[0033] Weigh 1g of ammonium molybdate and dissolve it in 50mL of deionized water. Add nitric acid solution dropwise to adjust the pH value of the solution to 1.1. Transfer the mixed solution to the inner lining of the reactor and perform hydrothermal reaction at 180℃ for 20h. Then, wash it with deionized water several times and dry it at 60℃ for 12h to obtain MoO 3 powder.

[0034] (2) MoO 3 Preparation of @TpPa-1

[0035] Weigh 118.4 mg MoO 3, 84 mg 1,3,5-triformylphloroglucinol and 88.5 mg potassium hydroxide were placed in a beaker, 10 mL deionized water was poured in, and ultrasonic was used to make them uniformly dispersed. The mixed solution was transferred to a conical flask, inert gas was introduced, and the reaction was carried out in an oil bath at 140 ° C. The whole process was accompanied by continuous stirring. After 15 minutes, 20 mL of N, N-dimethylformamide solution containing 64 mg p-phenylenediamine was poured into the above mixed solution and the reaction was continued for 24 hours. The suspension after the reaction was washed several times with N, N-dimethylformamide and acetone to remove the unreacted reactants, and dried at 60 ° C for 12 hours to obtain MoO 3 @TpPa-1 composite material.

[0036] Example 2

[0037] An antibacterial agent and a preparation method thereof, wherein the antibacterial agent comprises MoO 3 @TpPa-1, where MoO 3 The mass ratio of TpPa-1 is 3:4.5. It includes the following steps:

[0038] (1) MoO 3 Preparation

[0039] Weigh 1g of ammonium molybdate and dissolve it in 50mL of deionized water. Add nitric acid solution dropwise to adjust the pH value of the solution to 1.1. Transfer the mixed solution to the inner lining of the reactor and perform hydrothermal reaction at 180℃ for 20h. Then, wash it with deionized water several times and dry it at 60℃ for 12h to obtain MoO 3 powder.

[0040] (2) MoO 3 Preparation of @TpPa-1

[0041] Weigh 78.8 mg MoO 3 , 84 mg 1,3,5-triformylphloroglucinol and 88.5 mg potassium hydroxide were placed in a beaker, 10 mL deionized water was poured in, and ultrasonic was used to make them uniformly dispersed. The mixed solution was transferred to a conical flask, inert gas was introduced, and the reaction was carried out in an oil bath at 140 ° C. The whole process was accompanied by continuous stirring. After 15 minutes, 20 mL of N, N-dimethylformamide solution containing 64 mg p-phenylenediamine was poured into the above mixed solution and the reaction was continued for 24 hours. The suspension after the reaction was washed several times with N, N-dimethylformamide and acetone to remove the unreacted reactants, and dried at 60 ° C for 12 hours to obtain MoO 3 @TpPa-1 composite material.

[0042] The difference from Example 1 is that in step (2), MoO 3 The amount added was 78.8 mg.

[0043] Example 3

[0044] An antibacterial agent and a preparation method thereof, wherein the antibacterial agent comprises MoO 3 @TpPa-1, where MoO 3 The mass ratio of TpPa-1 is 3:2. It includes the following steps:

[0045] (1) MoO 3 Preparation

[0046] Weigh 1g of ammonium molybdate and dissolve it in 50mL of deionized water. Add nitric acid solution dropwise to adjust the pH value of the solution to 1.1. Transfer the mixed solution to the inner lining of the reactor and perform hydrothermal reaction at 180℃ for 20h. Then, wash it with deionized water several times and dry it at 60℃ for 12h to obtain MoO 3 powder.

[0047] (2) MoO 3 Preparation of @TpPa-1

[0048] Weigh 177.6 mg MoO 3 , 84 mg 1,3,5-triformylphloroglucinol and 88.5 mg potassium hydroxide were placed in a beaker, 10 mL deionized water was poured in, and ultrasonic was used to make them uniformly dispersed. The mixed solution was transferred to a conical flask, inert gas was introduced, and the reaction was carried out in an oil bath at 140 ° C. The whole process was accompanied by continuous stirring. After 15 minutes, 20 mL of N, N-dimethylformamide solution containing 64 mg p-phenylenediamine was poured into the above mixed solution and the reaction was continued for 24 hours. The suspension after the reaction was washed several times with N, N-dimethylformamide and acetone to remove the unreacted reactants, and dried at 60 ° C for 12 hours to obtain MoO 3 @TpPa-1 composite material.

[0049] The difference from Example 1 is that in step (2), MoO 3 The amount added was 177.6 mg.

[0050] Comparative Example 1

[0051] An antibacterial agent and a preparation method thereof, wherein the antibacterial agent comprises MoO 3 , including the following steps:

[0052] Weigh 1g of ammonium molybdate and dissolve it in 50mL of deionized water. Add nitric acid solution dropwise to adjust the pH value of the solution to 1.1. Transfer the mixed solution to the inner lining of the reactor and perform hydrothermal reaction at 180℃ for 20h. Then, wash it with deionized water several times and dry it at 60℃ for 12h to obtain MoO 3 powder.

[0053] Comparative Example 2

[0054] An antibacterial agent and a preparation method thereof, wherein the antibacterial agent comprises MoO 3 @COF, where MoO 3 The mass ratio of the COF is 3:3, and the COF is constructed by covalent bonds of two monomers, 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and p-phenylenediamine, and comprises the following steps:

[0055] (1) MoO 3 Preparation

[0056] Weigh 1g of ammonium molybdate and dissolve it in 50mL of deionized water. Add nitric acid solution dropwise to adjust the pH value of the solution to 1.1. Transfer the mixed solution to the inner lining of the reactor and perform hydrothermal reaction at 180℃ for 20h. Then, wash it with deionized water several times and dry it at 60℃ for 12h to obtain MoO 3 powder.

[0057] (2) MoO 3 Preparation of @COF

[0058] Weigh 118.4 mg MoO 3 , 106 mg of 1,3,5-triformylphloroglucinol was placed in a beaker, 1 mL of o-dichlorobenzene and 1 mL of n-butanol were added dropwise, and the mixture was evenly dispersed by ultrasound. The mixed solution was transferred to a conical flask, 44 mg of p-phenylenediamine and 0.25 mL of 6 mol / L acetic acid solution were added to the conical flask, inert gas was introduced, and the reaction was carried out in an oil bath at 120 ° C for 72 hours, and the whole process was accompanied by continuous stirring. The suspension after the reaction was washed several times with acetone and tetrahydrofuran to remove the unreacted reactants, and dried at 60 ° C for 12 hours to obtain MoO 3 @COF composite materials.

[0059] Performance Testing

[0060] (1) Antibacterial test

[0061] Gram-negative bacteria Escherichia coli and Gram-positive bacteria Staphylococcus aureus were selected as experimental strains. The strains were inoculated into sterile agar medium, cultured and activated at 37°C, and the activated bacteria were diluted to 1х106CFU / mL with sterile phosphate solution as inoculated bacterial solution. The antibacterial agent aqueous dispersion with a concentration of 1 mg / mL and the inoculated bacterial solution were placed in a centrifuge tube with a pipette, and the centrifuge tube was placed in a 37°C shaker for cultivation for 20 minutes. After the cultivation was completed, the centrifuge tube was irradiated with simulated visible light (xenon lamp with a power of 300W) for 20 minutes. The supernatant was added dropwise to the solid culture medium, and the bacterial solution was evenly coated on the surface of the culture medium by coating. After the culture medium was placed in a 37°C constant temperature incubator for 24 hours, the antibacterial rate was calculated by the colony counting method. The setting of adding the antibacterial agent described in the embodiment and the comparative example was used as an experimental sample, and the blank sample without any addition was used. The experimental results are shown in Table 1.

[0062] The antibacterial rate calculation formula is as follows:

[0063] Antibacterial rate (%) = ((N 0 -N 1 ) / N 0 )х100%

[0064] Among them, N 0 is the number of bacteria in the blank group; N 1 is the number of bacteria in the experimental group.

[0065] Table 1 Antibacterial test results

[0066] Antibacterial rate Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Escherichia coli 99.21％ 93.39％ 87.83％ 50.44％ 67.62％ Staphylococcus aureus 97.48％ 91.17％ 83.9％ 47.56％ 61.35％

[0067] It can be seen from the experimental results that the lethality of the antibacterial agents in the examples and comparative examples to Escherichia coli is higher than that to Staphylococcus aureus. This is because the peptidoglycan in the cell wall of Staphylococcus aureus is thicker than that of Escherichia coli, and it takes longer for the ROS generated by the photocatalysis of the antibacterial agent to oxidize the peptidoglycan of Staphylococcus aureus. The antibacterial rates of Examples 1-3 are significantly higher than those of Comparative Example 1, and compared with the simple MoO 3 In comparison, MoO 3 @TpPa-1 greatly improves the separation efficiency of photogenerated electrons and holes under visible light by forming a heterojunction, promotes the release of ROS, and significantly increases the antibacterial efficiency. The antibacterial rate of Example 1 is the highest, indicating that 3:3 is MoO 3 The preferred mass ratio of MoO2 to TpPa-1 is the highest at this time, and the antibacterial rate of Example 3 is significantly reduced. 3 When the doping concentration is too high, the recombination velocity between carriers increases, resulting in a decrease in carrier lifetime.

[0068] The antibacterial rate of comparative example 2 is higher than that of comparative example 1, which is due to the COF and MoO 3A heterojunction is formed, which promotes the transport of photogenerated carriers. 3 Failure to provide sufficient active sites for COF leads to 3 The COF generated on the surface has a low crystallinity. Low crystallinity will lead to high-density structural defects in the COF, hindering the migration of photogenerated carriers inside the material, thereby reducing the photocatalytic effect and the antibacterial effect is lower than that in the embodiment.

[0069] (2) Immersion stability test

[0070] 20 mg of the antibacterial agent described in the embodiment and the comparative example were dissolved in 20 mL of deionized water, respectively, and placed in a dark environment for 24 h to test the pH and Mo of the solution. 3+ The pH of the solution was measured using a benchtop pH meter. 3+ The concentration was measured by electron coupled emission spectrometry.

[0071] Table 2 Immersion stability test results

[0072] project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 pH 7.5 7.3 7.9 5.1 7.4 <![CDATA[Mo 3+ Concentration]]> Ignore Ignore Ignore 4.8mmol / L Ignore

[0073] From the data in Table 2, it can be seen that the pH of Comparative Example 1 is 5.1, and the solution is acidic, indicating that MoO 3 The aqueous solution has poor stability, which will lead to H 3 O + At the same time, MoO 3 After being placed in water for 24 hours, Mo appeared in the solution. 3+ .MoO 3 Poor water stability will cause quality loss and reduce its service life. 3 @TpPa-1 contains a large number of primary amine groups, resulting in a pH value of the embodiment slightly greater than 7. No Mo was detected after immersion in aqueous solution 3+ The existence of TpPa-1 on MoO 3 The modification is effective and can improve the MoO 3 The aqueous solution stability of MoO 3 @TpPa-1 has excellent water stability, which can ensure its long-lasting antibacterial function. Triazine COF has high chemical stability and aqueous solution stability. 3 Modification of MoO 3 stability in aqueous solution.

Claims

1. A method for preparing an antibacterial agent, characterized in that: include: MoO3, 1,3,5-triformylphloroglucinol and potassium hydroxide were dispersed in deionized water. After oil bath reaction, N,N-dimethylformamide solution containing p-phenylenediamine was added to continue the reaction. The mixture was washed and dried to prepare the antibacterial agent MoO3@TpPa-1 composite material.

2. The method for preparing the antibacterial agent according to claim 1, characterized in that: The MoO3 is prepared by a hydrothermal method or calcination.

3. The method for preparing the antibacterial agent according to claim 1, characterized in that: The MoO3 is prepared by the following method: adding nitric acid to an aqueous solution of ammonium molybdate to adjust the pH value to 1.1, transferring the mixed solution to a reactor, performing a hydrothermal reaction, washing and drying to obtain the MoO3.

4. The method for preparing the antibacterial agent according to claim 1, characterized in that: The mass ratio of the 1,3,5-triformylphloroglucinol to the p-phenylenediamine is 21:

16.

5. The method for preparing the antibacterial agent according to claim 1, characterized in that: The oil bath temperature of the oil bath reaction is 140°C.

6. The method for preparing the antibacterial agent according to claim 1, characterized in that: The reaction time of the oil bath reaction is 15-20 minutes; the continued reaction time of adding the N,N-dimethylformamide solution containing p-phenylenediamine to continue the reaction is 24 hours.

7. The method for preparing the antibacterial agent according to claim 1, characterized in that: The mass ratio of MoO3 to TpPa-1 in the antibacterial agent MoO3@TpPa-1 composite material is 3:2-4.

5.

8. The method for preparing the antibacterial agent according to claim 7, characterized in that: The mass ratio of MoO3 to TpPa-1 in the antibacterial agent MoO3@TpPa-1 composite material is 3:

3.

9. The antibacterial agent prepared by the method for preparing an antibacterial agent according to any one of claims 1 to 8, characterized in that: In the antibacterial agent MoO3@TpPa-1 composite material, MoO3 and TpPa-1 form a heterojunction, and the TpPa-1 covers the MoO3.

10. A refrigerator, characterized in that: The plastic raw material of the refrigerator includes the antibacterial agent according to claim 9.