Rare earth-molybdenum antibacterial material and preparation method thereof

Abstract

The application discloses a rare earth-molybdenum antibacterial material and a preparation method thereof, and belongs to the technical field of rare earth materials. The preparation method comprises the following steps: uniformly mixing chlorinated rare earth, zinc chloride, zirconium oxychloride and water, adding PEG and glacial acetic acid after heating the mixed solution, adding an ammonium bicarbonate solution and citric acid or tartaric acid, centrifuging the reaction liquid after the reaction is completed, drying the precipitate, uniformly mixing the obtained first reaction product with deionized water, adding concentrated phosphoric acid and 1-butyl-3-methyl imidazole phosphoric acid dibutyl ester salt for heating reaction, filtering the reaction liquid, obtaining the precipitate, drying the precipitate, adding the obtained second reaction product into an ammonium molybdate solution and glacial acetic acid for reaction, filtering the reaction liquid, washing and drying the precipitate, and calcining the precipitate to obtain the rare earth-molybdenum antibacterial material. The rare earth-molybdenum antibacterial material synthesized by the liquid phase method has the advantages of short reaction time, small particle size, large specific surface area, good antibacterial effect and good aging resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of rare earth materials, in particular to a rare earth-molybdenum antibacterial material and a preparation method thereof. BACKGROUND

[0002] Nanometer antibacterial materials have been widely applied in building materials, plastics, textiles and other fields on the basis of traditional organic antibacterial products, and have greatly improved in safety, broad-spectrum, drug resistance and other aspects. MoO3 has the characteristics of small band gap, good catalytic effect under visible light, high solar energy utilization rate and other characteristics, and has important application prospects in the field of photocatalytic antibacterial. For example, molybdenum disulfide can directly act on bacteria, causing bacterial morphology distortion and cell membrane damage, thereby inhibiting bacterial growth. In addition, under the assistance of light source, the antibacterial effect of molybdenum disulfide will be better, and under ultraviolet irradiation, molybdenum disulfide particles can generate superoxide ion radicals and singlet oxygen to accelerate bacterial inactivation.

[0003] In recent years, the application of rare earth antibacterial materials in antibacterial aspects has attracted people's attention. Rare earth ions interact with bacteria, damaging their cell walls, cell membranes, and intracellular DNA, proteins and enzymes, hindering the life activities of bacteria and inhibiting the growth and reproduction of bacteria; the unpaired electrons in the 4f subshell of rare earth elements interact with the outer layer electrons of other elements, making rare earth elements have active coordination properties, and can synthesize rare earth complexes with antibacterial properties; rare earth elements doped into antibacterial materials can produce synergistic antibacterial effect with other inorganic antibacterial agents, reducing the amount of other antibacterial agents, and obtaining a composite antibacterial material with stronger antibacterial ability.

[0004] There is no report on a molybdenum antibacterial active ion synergistic antibacterial material with rare earth as a carrier.

[0005] CN114698649A discloses a rare earth antibacterial material, a preparation method and application thereof, which adopts four needle-shaped zinc oxide whiskers, polyethylene glycol 2000, lanthanum oxide, lanthanum chloride, cerium oxide, copper chloride and water to be mixed, dispersed, dried and calcined to obtain a rare earth antibacterial material. Although the antibacterial material prepared by this method is dispersed, the four needle-shaped zinc oxide whiskers, lanthanum oxide and cerium oxide in the raw materials are not soluble in water, and even after dispersion, there is still a problem of uneven composition.

[0006] CN102763678A discloses a preparation method of silver-loaded cubic zirconium phosphate antibacterial powder, which has a high synthesis temperature of 90℃ and a long reaction period of 28 hours, resulting in high energy consumption. The obtained antibacterial powder is cubic, and has a small specific surface area, which affects the antibacterial effect.

[0007] CN 110934153 A discloses a zirconium phosphate carrier, a zirconium phosphate carrier copper antibacterial agent, a zirconium phosphate antibacterial agent, and a preparation method and application thereof. The synthesis reaction temperature is as high as 180℃, the reaction process pressure is as high as 1MPa, and the reaction time of only step 3 is 5-8 hours. The method has high energy consumption, and the obtained cubic antibacterial powder has small specific surface area, which affects the antibacterial effect during use.

[0008] CN 115849325 A discloses a cubic zirconium phosphate sodium carrier and a preparation method of a silver-zinc-loaded antibacterial powder thereof. The method further improves CN 102763678 A and CN 110934153 A by reducing the reaction temperature to 60-80℃ and shortening the reaction time. However, the antibacterial powder prepared by the method is prone to agglomeration during drying due to high viscosity, and needs to be crushed before use. Moreover, the morphology is still not cubic, and the specific surface area is small, which affects the antibacterial effect during subsequent use.

[0009] Therefore, how to develop a rare earth-molybdenum antibacterial material with good antibacterial effect and low preparation cost and a preparation method thereof is a technical problem that needs to be solved by those skilled in the art. SUMMARY

[0010] Therefore, the present application provides a rare earth-molybdenum antibacterial material and a preparation method thereof.

[0011] In order to achieve the above purpose, the present application adopts the following technical solutions:

[0012] A preparation method of a rare earth-molybdenum antibacterial material, comprising the following steps:

[0013] (1) uniformly mixing chlorinated rare earth, zinc chloride, zirconium oxychloride and water to obtain a mixed solution, heating the mixed solution, then adding PEG and glacial acetic acid, and then adding ammonium bicarbonate solution and citric acid or tartaric acid, centrifuging the reaction liquid after the reaction is completed to obtain a precipitate, and drying the precipitate to obtain a first reaction product;

[0014] (2) uniformly mixing the first reaction product with deionized water, then adding concentrated phosphoric acid and 1-butyl-3-methylimidazolium phosphoric acid dibutyl ester, and heating the reaction, filtering the reaction liquid to obtain a precipitate, and drying the precipitate to obtain a second reaction product;

[0015] (3) adding the second reaction product into an ammonium molybdate solution and glacial acetic acid, filtering the reaction liquid to obtain a precipitate, washing, drying and calcining the precipitate to obtain a rare earth-molybdenum antibacterial material.

[0016] Further, in step (1), the chlorinated rare earth is lanthanum cerium chloride.

[0017] Furthermore, in step (1), the molar ratio of rare earth chloride, zinc chloride and zirconium oxychloride is (2-8):1:(2-8), and the concentration of rare earth ions in the above mixed solution is 0.3-0.9 mol / L.

[0018] Preferably, in step (1), the molar ratio of rare earth chloride, zinc chloride, and zirconium oxychloride is 5:2:5, and the concentration of rare earth ions in the above mixed solution is 0.6 mol / L.

[0019] Further, in step (1), the amount of PEG added is 0.05-2% of the total mass of rare earth chloride, zinc chloride and zirconium oxychloride, the amount of glacial acetic acid added is 1%-3% of the total mass of rare earth chloride, zinc chloride and zirconium oxychloride, and ammonium bicarbonate solution and citric acid or tartaric acid are added until the pH of the system is 6.7-7 and the reaction is completed. The concentration of ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of the amount of citric acid or tartaric acid added to the amount of ammonium bicarbonate in the ammonium bicarbonate solution is 10:(1-2).

[0020] Preferably, in step (1), the amount of PEG added is 1% of the total mass of rare earth chloride, zinc chloride and zirconium oxychloride.

[0021] Furthermore, the molecular weight of PEG is 2000-10000, preferably 6000.

[0022] Further, in step (1), after heating the mixed solution to 40-80°C, PEG and glacial acetic acid are added, and the precipitate is dried at 80°C.

[0023] Furthermore, in step (2), the mass ratio of the first reactant, deionized water, concentrated phosphoric acid, and 1-butyl-3-methylimidazolium dibutyl phosphate salt is 1:(3-8):(0.2-0.3):(0.001-0.01).

[0024] Preferably, in step (2), the mass ratio of the first reactant, deionized water, concentrated phosphoric acid and 1-butyl-3-methylimidazolium dibutyl phosphate is 1:5:0.25:(0.001-0.01), and the concentration of concentrated phosphoric acid is 14.63 mol / L.

[0025] Furthermore, in step (2), the heating temperature is 60℃, the reaction time is 0.5-2h, and the precipitate is dried at 80℃.

[0026] Furthermore, in step (3), the mass ratio of the second reactant to the ammonium molybdate solution is 1:(6-10), the concentration of the ammonium molybdate solution is 10wt%-15wt%, and the mass ratio of glacial acetic acid to the ammonium molybdate solution is (0.01-0.02):1.

[0027] Furthermore, in step (3), the reaction time is 4 hours, the drying temperature is 80°C, the calcination temperature is 400-1000°C, and the calcination time is 4 hours.

[0028] This invention also provides a rare earth-molybdenum antibacterial material prepared by the above method, wherein the particle size of the rare earth-molybdenum antibacterial material is 10 nm-1500 nm and the specific surface area is 10-100 m². 2 / g, molybdenum adsorption capacity is 1.0-4.0g / 100g.

[0029] The beneficial effects of this invention are as follows: The purpose of this invention is to provide a method for synthesizing a rare earth-molybdenum antibacterial material with good antibacterial effect and low preparation cost. This method overcomes the problems of uneven composition and poor antibacterial performance in antibacterial materials prepared by simple physical mixing methods, and also overcomes the problems of high reaction temperature and long reaction time in the synthesis of antibacterial materials by ordinary liquid-phase methods. Furthermore, the antibacterial material obtained by this invention has a higher specific surface area, higher adsorption capacity and adsorption strength for molybdenum ions, and excellent antibacterial effect. No reports have yet described synergistic antibacterial materials using rare earth elements as a carrier and molybdenum as the antibacterial active ion.

[0030] The rare earth-molybdenum antibacterial material synthesized by the liquid phase method in this invention has the advantages of short reaction time, small particle size, large specific surface area, good antibacterial effect, and good aging resistance. Attached Figure Description

[0031] Figure 1 This is an electron microscope image of the rare earth-molybdenum antibacterial material from Example 1. Detailed Implementation

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] Example 1

[0034] The preparation method of rare earth-molybdenum antibacterial materials includes the following steps:

[0035] (1) Mix 430.3g lanthanum chloride, 37.4g zinc chloride, 354.75g zirconium oxychloride and 1500mL water evenly. The rare earth ion concentration in the mixed solution is 0.75mol / L. Heat the mixed solution to 60℃, add 8.0g PEG and 11g glacial acetic acid. The molecular weight of PEG is 6000. Then add ammonium bicarbonate solution and tartaric acid until the pH of the system is 6.7 and the reaction is complete (the concentration of ammonium bicarbonate solution is 2.53mol / L, and the molar ratio of the amount of tartaric acid added to the amount of ammonium bicarbonate in the ammonium bicarbonate solution is 10:1.5). After the reaction is complete, centrifuge the reaction solution at 3000r / min for 10min to obtain a precipitate. Dry the precipitate at 80℃ to obtain the first reactant.

[0036] (2) Add 90g of the first reactant to 450g of deionized water and mix well. Then add 22.5g of concentrated phosphoric acid and 0.18g of 1-butyl-3-methylimidazolium dibutyl phosphate salt and heat to react. The concentration of concentrated phosphoric acid is 14.63mol / L, the heating temperature is 60℃, and the reaction time is 1h. Filter the reaction solution through a filter membrane with a pore size of 1-3 micrometers to obtain a precipitate. Dry the precipitate at 80℃ to obtain the second reactant.

[0037] (3) Add 100g of the second reactant to 800g of ammonium molybdate solution and 8g of glacial acetic acid. The mass concentration of the ammonium molybdate solution is 10%, and the reaction time is 4h. Filter the reaction solution with a filter membrane with a pore size of 1-3 micrometers to obtain a precipitate. Wash the precipitate with pure water. The mass ratio of pure water to the second reactant is 8:1. Dry the precipitate at 80℃ and calcine it at 900℃ for 4h to obtain rare earth-molybdenum antibacterial material.

[0038] The rare earth-molybdenum antibacterial material has a particle size of 20 nm, an aggregate size of 600 nm, and a specific surface area of ​​41.08 m². 2 / g, molybdenum adsorption capacity is 2.8g / 100g.

[0039] The antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae was 99.99%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa was 99.9%. After 2000 hours of UV irradiation, the antibacterial rate against Staphylococcus aureus reached 99.99%, against Escherichia coli 99.98%, against Pseudomonas aeruginosa 99.96%, against Klebsiella pneumoniae 99.54%, and against Candida albicans greater than 99.06%.

[0040] Example 2

[0041] The preparation method of rare earth-molybdenum antibacterial materials includes the following steps:

[0042] (1) Mix 430.3g of lanthanum chloride, 37.4g of zinc chloride, 354.75g of zirconium oxychloride and 1500mL of water evenly. The concentration of rare earth ions in the mixed solution is 0.75mol / L. Heat the mixed solution to 80℃, add 8.0g of PEG and 11g of glacial acetic acid. The molecular weight of PEG is 6000. Then add ammonium bicarbonate solution and tartaric acid until the pH of the system is 7. The reaction is complete. The concentration of ammonium bicarbonate solution is 2.53mol / L. The molar ratio of the amount of tartaric acid added to the amount of ammonium bicarbonate in the ammonium bicarbonate solution is 10:1.8. After the reaction is complete, centrifuge the reaction solution at 3000r / min for 10min to obtain a precipitate. Dry the precipitate at 80℃ to obtain the first reactant.

[0043] (2) Add 100g of the first reactant to 600g of deionized water and mix well. Then add 25g of concentrated phosphoric acid and 0.2g of 1-butyl-3-methylimidazolium dibutyl phosphate salt and heat to react. The concentration of concentrated phosphoric acid is 14.63mol / L, the heating temperature is 60℃, and the reaction time is 1h. Filter the reaction solution through a filter membrane with a pore size of 1-3 micrometers to obtain a precipitate. Dry the precipitate at 80℃ to obtain the second reactant.

[0044] (3) Add 100g of the second reactant to 600g of ammonium molybdate solution and 10g of glacial acetic acid for reaction. The concentration of the ammonium molybdate solution is 12wt%. The reaction time is 4h. Filter the reaction solution with a filter membrane with a pore size of 1-3 micrometers to obtain a precipitate. Wash the precipitate, dry it at 80℃, and calcine it at 400℃ for 4h to obtain rare earth-molybdenum antibacterial material.

[0045] The rare earth-molybdenum antibacterial material has a particle size of 50 nm, an aggregate size of 632 nm, and a specific surface area of ​​189.5 m². 2 / g, molybdenum adsorption capacity is 3.0g / 100g.

[0046] The antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae was 99.99%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa was 99.96%. After 2000 hours of UV irradiation, the antibacterial rate against Staphylococcus aureus reached 99.99%, against Escherichia coli 99.98%, against Pseudomonas aeruginosa 99.97%, against Klebsiella pneumoniae 99.65%, and against Candida albicans greater than 99.76%.

[0047] Example 3

[0048] (1) Mix 391.2g cerium chloride, 27.3g zinc chloride, 322.3g zirconium oxychloride and 1800mL water evenly. The rare earth ion concentration in the mixed solution is 0.55mol / L. Heat the mixed solution to 50℃, add 7.4g PEG and 13.5g glacial acetic acid. The molecular weight of PEG is 6000. Then add ammonium bicarbonate solution and citric acid until the pH of the system is 7. The reaction is complete. The concentration of ammonium bicarbonate solution is 2.53mol / L. The molar ratio of the amount of citric acid added to the amount of ammonium bicarbonate in the ammonium bicarbonate solution is 10:1.6. After the reaction is complete, centrifuge the reaction solution at 3000r / min for 10min to obtain a precipitate. Dry the precipitate at 80℃ to obtain the first reactant.

[0049] (2) Add 100g of the first reactant to 800g of deionized water and mix well. Then add 26g of concentrated phosphoric acid and 0.36g of 1-butyl-3-methylimidazolium dibutyl phosphate salt and heat to react. The concentration of concentrated phosphoric acid is 14.63mol / L, the heating temperature is 60℃, and the reaction time is 1.5h. Filter the reaction solution through a filter membrane with a pore size of 1-3 micrometers to obtain a precipitate. Dry the precipitate at 80℃ to obtain the second reactant.

[0050] (3) Add 50g of the second reactant to 300g of ammonium molybdate solution and 6g of glacial acetic acid. The mass concentration of the ammonium molybdate solution is 10%, and the reaction time is 4h. Filter the reaction solution with a filter membrane with a pore size of 1-3 micrometers to obtain a precipitate. Wash the precipitate with pure water. The mass ratio of pure water to the second reactant is 8:1. Dry the precipitate at 80℃ and calcine it at 900℃ for 4h to obtain rare earth-molybdenum antibacterial material.

[0051] The rare earth-molybdenum antibacterial material has a particle size of 15 nm, an agglomerated particle size of 520 nm, and a specific surface area of ​​51.08 m². 2 / g, the molybdenum adsorption capacity is 2.9g / 100g.

[0052] The antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae was 99.99%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa was 99.9%. After 2000 hours of UV irradiation, the antibacterial rate against Staphylococcus aureus reached 99.99%, against Escherichia coli 99.98%, against Pseudomonas aeruginosa 99.96%, against Klebsiella pneumoniae 99.60%, and against Candida albicans greater than 99.11%.

[0053] Comparative Example 1

[0054] The preparation method of rare earth-molybdenum antibacterial material, compared with Example 1, except that tartaric acid is not added when adding ammonium bicarbonate solution in step (1), other conditions remain unchanged. The final rare earth-molybdenum antibacterial material has a particle size of 15 nm, an agglomeration particle size of 16.5 μm, and a specific surface area of ​​30.59 m². 2 / g, the molybdenum adsorption capacity is 2.2g / 100g.

[0055] The antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae was 99.08%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa was 98.67%. After 2000 hours of UV irradiation, the antibacterial rate against Staphylococcus aureus reached 99.45%, against Escherichia coli 98.12%, against Pseudomonas aeruginosa 98.76%, against Klebsiella pneumoniae 99.01%, and against Candida albicans greater than 97.55%.

[0056] Comparative Example 2

[0057] The preparation method of rare earth-molybdenum antibacterial material, compared with Example 1, except that 1-butyl-3-methylimidazolium dibutyl phosphate salt is not added in step (2), and other conditions remain unchanged, the final rare earth-molybdenum antibacterial material has a particle size of 10 nm, an agglomeration particle size of 18.3 μm, and a specific surface area of ​​25.36 m². 2 / g, the molybdenum adsorption capacity is 1.1g / 100g.

[0058] The antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae was 99.85%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa was 99.15%. After 2000 hours of UV irradiation, the antibacterial rate against Staphylococcus aureus reached 98.96%, against Escherichia coli 96.56%, against Pseudomonas aeruginosa 95.77%, against Klebsiella pneumoniae 94.23%, and against Candida albicans greater than 88.12%.

[0059] Conclusion: In this invention, tartaric acid is added to the ammonium bicarbonate solution during the reaction process. This tartaric acid can form organic complexes such as rare earth tartaric acid with metal ions, which can prevent powder agglomeration during the calcination process, increase the specific surface area of ​​the powder, and improve the antibacterial effect. Butyl-3-methylimidazolium phosphate dibutyl ester salt, as an organic surfactant, can effectively reduce inter-particle agglomeration and lower the particle size of the material.

[0060] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a rare earth-molybdenum antibacterial material, characterized in that, Includes the following steps: (1) Mix rare earth chloride, zinc chloride, zirconium oxychloride and water evenly to obtain a mixed solution. Heat the mixed solution and add PEG and glacial acetic acid. Then add ammonium bicarbonate solution and citric acid or tartaric acid. After the reaction is complete, centrifuge the reaction solution to obtain a precipitate. Dry the precipitate to obtain the first reactant. (2) Add the first reactant to deionized water and mix well. Then add concentrated phosphoric acid and 1-butyl-3-methylimidazolium dibutyl phosphate salt and heat to react. Filter the reaction solution to obtain a precipitate. Dry the precipitate to obtain the second reactant. (3) The second reactant was added to ammonium molybdate solution and glacial acetic acid to react. The reaction solution was filtered to obtain a precipitate. The precipitate was washed, dried and calcined to obtain rare earth-molybdenum antibacterial material. In step (1), rare earth chloride is lanthanum chloride or cerium chloride; In step (1), the molar ratio of rare earth chloride, zinc chloride and zirconium oxychloride is (2-8):1:(2-8), and the concentration of rare earth ions in the mixed solution is 0.3-0.9 mol / L; In step (1), the amount of PEG added is 0.05-2% of the total mass of rare earth chloride, zinc chloride and zirconium oxychloride, the amount of glacial acetic acid added is 1%-3% of the total mass of rare earth chloride, zinc chloride and zirconium oxychloride, and ammonium bicarbonate solution and citric acid or tartaric acid are added until the pH of the system is 6.7-7 and the reaction is completed. The concentration of ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of the amount of citric acid or tartaric acid added to the amount of ammonium bicarbonate in the ammonium bicarbonate solution is 10:(1-2). In step (2), the mass ratio of the first reactant, deionized water, concentrated phosphoric acid and 1-butyl-3-methylimidazolium dibutyl phosphate salt is 1:(3-8):(0.2-0.3):(0.001-0.01), and the concentration of concentrated phosphoric acid is 14.63 mol / L; In step (2), the heating temperature is 60℃, the reaction time is 0.5-2h, and the precipitate is dried at 80℃. In step (3), the mass ratio of the second reactant to the ammonium molybdate solution is 1:(6-10), the concentration of the ammonium molybdate solution is 10wt%-15wt%, and the mass ratio of glacial acetic acid to the ammonium molybdate solution is (0.01-0.02):

1.

2. The preparation method of a rare earth-molybdenum antibacterial material according to claim 1, characterized in that, In step (1), the mixed solution is heated to 40-80℃, PEG and glacial acetic acid are added, and the precipitate is dried at 80℃.

3. The method for preparing a rare earth-molybdenum antibacterial material according to claim 1, characterized in that, In step (3), the reaction time is 4 hours, the drying temperature is 80°C, the calcination temperature is 400-1000°C, and the calcination time is 4 hours.

4. A rare earth-molybdenum antibacterial material prepared by the method according to any one of claims 1-3, characterized in that, The rare earth-molybdenum antibacterial material has a particle size of 10nm-1500nm and a specific surface area of ​​10-100 m². 2 / g, molybdenum adsorption capacity is 1.0-4.0g / 100g.

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