Preparation method and application of rare earth-silver antibacterial material

Abstract

The invention discloses a preparation method of a rare earth-silver antibacterial material, which comprises the following steps: preparing rare earth chloride, zinc chloride and zirconium oxychloride into a mixed solution, heating the mixed solution, then adding PEG (polyethylene glycol), then adding glacial acetic acid, adding an ammonium bicarbonate solution into the mixed solution after adding, filtering after reaction to obtain a precipitate, and drying the precipitate to obtain the rare earth-silver antibacterial material. Drying to obtain a first reactant; carrying out size mixing on the first reactant by using deionized water, adding strong phosphoric acid, then adding 1-butyl-3-methylimidazole dibutyl phosphate, reacting for a period of time, filtering and drying to obtain a second reactant; and adding a silver nitrate solution into the second reactant, reacting for a period of time, filtering, washing, drying and calcining to obtain the rare earth-silver antibacterial material. According to the invention, the problems of non-uniform components and poor antibacterial property of the antibacterial material prepared by a simple physical mixing method are solved, and the problems of high reaction temperature and long reaction time when the antibacterial material is synthesized by a common liquid phase method are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of rare earth materials, and more particularly to a preparation method and application of a rare earth-silver antibacterial material. Background Art

[0002] Inorganic ion antimicrobial agents are the most widely used of the several types of antimicrobial agents currently available. Currently, commonly used inorganic ion antimicrobial agents on the market include silver ion antimicrobial agents, zinc ion antimicrobial agents, and copper ion antimicrobial agents. These agents are generally subject to high cost, poor high-temperature resistance and easy discoloration, small specific surface area, easy loss of active ingredients within the antimicrobial agent, short antimicrobial durability, and uneven composition of antimicrobial agents prepared by solid-phase mixing methods. The development and utilization of rare earth elements in the antimicrobial field dates back to the early 20th century, with potassium cerium sulfate being used as an antimicrobial agent to prevent burn infections. Subsequently, it was discovered that neodymium sulfate and praseodymium sulfate could treat tuberculosis. The antibacterial mechanism of rare earths is: rare earth ions interact with bacteria, destroying their cell walls, cell membranes, and intracellular DNA, proteins, and enzymes, hindering bacterial life activities, and inhibiting bacterial growth and reproduction; the unpaired electrons in the 4f sublayer of rare earth elements interact with the outer electrons of other elements, making the rare earths have active coordination properties, and rare earth complexes with antibacterial properties can be synthesized; rare earth elements doped into antibacterial materials can produce a synergistic antibacterial effect with other antibacterial agents, reducing the dosage of other antibacterial agents, and obtaining composite antibacterial materials with stronger antibacterial capabilities.

[0003] CN114698649A discloses a rare earth antibacterial material, its preparation method, and application. The rare earth antibacterial material is obtained by mixing tetrapod-shaped zinc oxide whiskers, polyethylene glycol 2000, lanthanum oxide, lanthanum chloride, cerium oxide, and copper chloride with water, dispersing them, drying them, and then calcining them. Although the antibacterial material prepared by this method is dispersed, the tetrapod-shaped zinc oxide whiskers, lanthanum oxide, and cerium oxide in the raw materials are insoluble in water. Even after dispersion, the problem of uneven composition still exists.

[0004] CN102763678A discloses a method for preparing cubic zirconium phosphate-loaded silver antibacterial powder. The synthesis process has a high temperature of 90°C, a long reaction cycle of 28 hours, and high energy consumption. The obtained antibacterial powder is cubic and has a small specific surface area, which affects the antibacterial effect.

[0005] CN 110934153 A discloses a zirconium phosphate carrier, a zirconium phosphate-supported copper antibacterial agent, a zirconium phosphate antibacterial agent, and its preparation and application. The synthesis reaction temperature reaches a maximum of 180°C, the reaction pressure reaches a maximum of 1 MPa, and the reaction time for step 3 alone is 5-8 seconds. This method consumes a lot of energy, and the resulting cubic antibacterial powder has a small specific surface area, which can affect the antibacterial effect during use.

[0006] CN 115849325 A discloses a method for preparing a cubic sodium zirconium phosphate carrier and its silver-zinc-loaded antibacterial powder. This method further improves upon CN 102763678A and CN 110934153 A by lowering the reaction temperature to 60-80°C and shortening the reaction time. However, the antibacterial powder prepared by this method has a high viscosity and tends to agglomerate during the drying process, requiring pulverization before use. Furthermore, the powder is not cubic in shape and has a small specific surface area, which can affect its antibacterial effectiveness during subsequent use. Summary of the Invention

[0007] In light of this, the present invention aims to provide a method for synthesizing and preparing a rare earth-silver antibacterial material with excellent antibacterial efficacy and low production cost. This method overcomes the problems of uneven composition and poor antibacterial performance associated with simple physical mixing methods, as well as the high reaction temperatures and long reaction times associated with conventional liquid-phase methods for synthesizing antibacterial materials. Furthermore, the antibacterial material obtained by the present invention has a higher specific surface area, increasing the amount and strength of silver ion adsorption by the rare earth-based adsorbent material, resulting in a more excellent antibacterial effect.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] A method for preparing a rare earth-silver antibacterial material comprises the following steps:

[0010] (1) preparing a mixed solution of rare earth chloride, zinc chloride, and zirconium oxychloride, heating the mixed solution to 40-80° C., then adding PEG, and then adding glacial acetic acid. After the addition is complete, adding ammonium bicarbonate solution to the mixed solution, reacting until the pH value of the system is 6.7-7, filtering to obtain a precipitate, and drying to obtain a first reactant;

[0011] (2) The first reactant is slurried with deionized water, concentrated phosphoric acid is added, and then 1-butyl-3-methylimidazole dibutyl phosphate is added, reacted for a period of time, filtered, and dried to obtain a second reactant;

[0012] (3) adding silver nitrate solution to the second reactant, reacting for a period of time, filtering, washing, drying, and calcining to obtain a rare earth-silver antibacterial material.

[0013] Preferably, the rare earth chloride in step 1 comprises: lanthanum chloride or cerium chloride; and the molar ratio of rare earth: zinc: zirconium in the mixed solution is (2-8): 1: (2-8).

[0014] Preferably, the rare earth ion concentration in the mixed solution is controlled at 0.3-0.9 mol / L.

[0015] Preferably, in step (1), the molecular weight of PEG is 2000-10000, the amount of PEG added is 0.05-2% of the total mass of rare earth chloride, zinc chloride and zirconium oxychloride; and the amount of glacial acetic acid added is 1%-3% of the total mass of rare earth chloride, zinc chloride and zirconium oxychloride.

[0016] Preferably, the concentration of the ammonium bicarbonate solution in step (1) is 2.53 mol / L, citric acid or tartaric acid is added to the ammonium bicarbonate solution, and the molar ratio of the added amount of citric acid and tartaric acid to the ammonium bicarbonate is 10:(1-2).

[0017] Preferably, in step (2), the mass ratio of the first reactant to deionized water is 1:(3-8); the mass ratio of concentrated phosphoric acid to the first reactant is (0.2-0.3):1; and the mass ratio of 1-butyl-3-methylimidazole dibutyl phosphate to the first reactant is (0.001-0.01):1.

[0018] Preferably, the reaction time in step (2) is 0.5-2 h at 60°C.

[0019] Preferably, the mass concentration of the silver nitrate solution in step (3) is 10%, the mass ratio of the silver nitrate solution to the second reactant is (5-10):1, the pH of the mixed solution is adjusted to 1-2 with nitric acid, and glacial acetic acid is added, with the mass ratio of the glacial acetic acid added to the silver nitrate solution being 0.01-0.02:1. The reaction temperature is 60-90°C, and the reaction time is 1-4 hours.

[0020] Preferably, the calcination temperature in step (3) is 400-1000°C.

[0021] Another object of the present invention is to provide the use of the rare earth-silver antibacterial material prepared by the above-mentioned preparation method of the rare earth-silver antibacterial material in antibacterial paint and antibacterial paper.

[0022] It can be seen from the above technical solutions that compared with the prior art, the present invention has the following beneficial effects:

[0023] The rare earth-silver 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.

[0024] The silver adsorption capacity is 1.5-4g / 100g, the particle size is 500nm-1500nm, and the specific surface area is 15-150m 2 / g, with an antibacterial rate of 99.99% against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae, and over 99.9% against Candida albicans and Pseudomonas aeruginosa. After 2000 hours of UV light irradiation, the antibacterial rate against Staphylococcus aureus reached 99.99%, the antibacterial rate against Escherichia coli was greater than 99.95%, the antibacterial rate against Pseudomonas aeruginosa was greater than 99.9%, the antibacterial rate against Klebsiella pneumoniae was greater than 99%, and the antibacterial rate against Candida albicans was greater than 99%.

[0025] Rare earth antibacterial materials are added to paint or pulp at a rate of 1-4% to obtain antibacterial paint and antibacterial pulp. The paint is applied to glass and metal surfaces. The antibacterial rate against Staphylococcus aureus and Escherichia coli reaches 99%, and the antibacterial rate against Candida albicans reaches 95%, which complies with the "Medical Antibacterial Functional Finishing Materials T / CADBM35-2021"; the antibacterial paper prepared from antibacterial pulp has an antibacterial rate of 99% against Staphylococcus aureus, Escherichia coli, and Candida albicans. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0027] Figure 1 This is a scanning electron microscope image of the product of the present invention. DETAILED DESCRIPTION

[0028] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0029] Example 1

[0030] (1) Take 195.6 g of cerium chloride, 17 g of zinc chloride, and 161.25 g of zirconium oxychloride, add 700 ml of water, heat to 60° C., add 3.7 g of PEG6000, add 5 g of glacial acetic acid, and add ammonium bicarbonate solution (the concentration of ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of tartaric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:1.25) until the system pH value is 6.7-7, centrifuge, and dry at 80° C. to obtain the first reactant.

[0031] (2) 40 g of the first reactant was slurried with 200 g of water, 12 g of concentrated phosphoric acid was added, and 0.08 g of 1-butyl-3-methylimidazole dibutyl phosphate was added. The mixture was reacted at 60° C. for 1 h, filtered, washed, and dried to obtain the second reactant.

[0032] (3) 40 g of the second reactant was added to 320 g of a 10% silver nitrate solution (the pH value of the nitric acid was 1-2, and glacial acetic acid was added, and the mass ratio of the glacial acetic acid to the silver nitrate solution was 0.01:1), and the mixture was reacted at 80 ° C for 4 h, filtered, washed, dried, and calcined at 900 ° C for 4 h to obtain a cerium zirconium zinc phosphate silver-loaded antibacterial material with a silver adsorption capacity of 3.3 g / 100 g, a particle size of 815 nm, and a specific surface area of 41.08 m 2 / g. The antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae is 99.99%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa is 99.9%. After 2000 hours of UV light irradiation, the antibacterial rate against Staphylococcus aureus reached 99.99%, the antibacterial rate against Escherichia coli reached 99.98%, the antibacterial rate against Pseudomonas aeruginosa reached 99.95%, the antibacterial rate against Klebsiella pneumoniae reached 99.64%, and the antibacterial rate against Candida albicans reached greater than 98.96%.

[0033] Example 2

[0034] (1) Take 384.1 g of lanthanum cerium chloride, 27.2 g of zinc chloride, and 300 g of zirconium oxychloride, add 1800 ml of water, heat to 80° C., add 7.2 g of PEG4000, add 15 g of glacial acetic acid, and add ammonium bicarbonate solution (the concentration of the ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of citric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:1.8) until the pH value of the system is 6.7-7, centrifuge, and dry at 80° C. to obtain the first reactant.

[0035] (2) 100 g of the first reactant was slurried with 800 g of water, 20 g of concentrated phosphoric acid was added, and 0.50 g of 1-butyl-3-methylimidazole dibutyl phosphate was added. The mixture was reacted at 60° C. for 1 h, filtered, washed, and dried to obtain the second reactant.

[0036] (3) Take 50g of the second reactant, add 10% mass concentration of silver nitrate solution (the pH value of adding nitric acid is 1-2, add glacial acetic acid, and the mass ratio of glacial acetic acid added volume to silver nitrate solute is 0.01:1), react at 90℃ for 4h, filter, wash, dry, and calcine at 500℃ for 4h to obtain lanthanum cerium zirconium zinc phosphate silver-loaded antibacterial material with a silver adsorption capacity of 3.5g / 100g, a particle size of 736nm, and a specific surface area of 122.19m 2 / g. The antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae is 99.99%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa is 99.9%. After 2000 hours of UV light irradiation, the antibacterial rate against Staphylococcus aureus and Escherichia coli reaches 99.99%, the antibacterial rate against Pseudomonas aeruginosa reaches 99.9%, the antibacterial rate against Klebsiella pneumoniae reaches 99.78%, and the antibacterial rate against Candida albicans reaches greater than 98.86%.

[0037] Example 3

[0038] (1) Take 192 g of lanthanum chloride, 27.2 g of zinc chloride, and 161 g of zirconium oxychloride, add 900 ml of water, heat to 50° C., add 5.7 g of PEG6000, add 7.6 g of glacial acetic acid, and add ammonium bicarbonate solution (the concentration of the ammonium bicarbonate solution is 2.53 mol / L, and the molar ratio of citric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:1.6) until the pH value of the system is 6.7-7, centrifuge, and dry at 80° C. to obtain the first reactant.

[0039] (2) 100 g of the first reactant was slurried with 600 g of water, 21.5 g of concentrated phosphoric acid was added, and 0.30 g of 1-butyl-3-methylimidazole dibutyl phosphate was added. The mixture was reacted at 60° C. for 2 h, filtered, washed, and dried to obtain the second reactant.

[0040] (3) Take 50g of the second reactant, add 10% mass concentration of silver nitrate solution (the pH value of adding nitric acid is 1-2, add glacial acetic acid, and the mass ratio of glacial acetic acid added volume to silver nitrate solute is 0.02:1), react at 90℃ for 3h, filter, wash, dry, and calcine at 600℃ for 4h to obtain lanthanum zirconium zinc phosphate silver-loaded antibacterial material with a silver adsorption capacity of 2.9g / 100g, a particle size of 789nm, and a specific surface area of 79.5m 2 / g. It has an antibacterial rate of 99.99% against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae, and 99.9% against Candida albicans and Pseudomonas aeruginosa. After 2000 hours of UV irradiation, the antibacterial rate against Staphylococcus aureus and Escherichia coli reached 99.99%, against Pseudomonas aeruginosa 99.9%, against Klebsiella pneumoniae 99.58%, and against Candida albicans greater than 98.26%.

[0041] Example 4

[0042] Compared with Example 1, other conditions remain unchanged, the calcination temperature is changed to 500℃, and the specific surface area of the material is 98.65m 2 / g

[0043] Comparative Example 1

[0044] Compared with Example 1, other conditions remained unchanged, and 1-butyl-3-methylimidazole dibutyl phosphate was not added. The particle size of the antibacterial material was 12.3 μm, and agglomeration was serious.

[0045] Comparative Example 2

[0046] Compared with Example 1, other conditions remain unchanged, and tartaric acid is not added to the ammonium bicarbonate solution. The specific surface area of the material obtained is 10.84m 2 / g, the silver adsorption capacity dropped to 1.2g / 100g. 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 99.32%. After 2000h of UV light irradiation, the antibacterial rate against Staphylococcus aureus reached 99.86%, the antibacterial rate against Escherichia coli reached 97.24%, the antibacterial rate against Pseudomonas aeruginosa reached 96.56%, the antibacterial rate against Klebsiella pneumoniae reached 96.18%, and the antibacterial rate against Candida albicans reached more than 94.32%.

[0047] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. Reference can be made to the common and similar parts between the various embodiments. For the devices disclosed in the embodiments, since they correspond to the methods disclosed in the embodiments, the description is relatively simple, and the relevant parts can be referred to the method description.

[0048] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one 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 present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a rare earth-silver antibacterial material, characterized in that: The following steps are involved: (1) preparing a mixed solution of rare earth chloride, zinc chloride, and zirconium oxychloride, heating the mixed solution to 40-80° C., then adding PEG, and then adding glacial acetic acid. After the addition is complete, adding ammonium bicarbonate solution to the mixed solution, reacting until the pH value of the system is 6.7-7, filtering to obtain a precipitate, and drying to obtain a first reactant; (2) The first reactant is slurried with deionized water, concentrated phosphoric acid is added, and then 1-butyl-3-methylimidazole dibutyl phosphate is added, reacted for a period of time, filtered, and dried to obtain a second reactant; (3) adding silver nitrate solution to the second reactant, reacting for a period of time, filtering, washing, drying, and calcining to obtain a rare earth-silver antibacterial material.

2. The method for preparing a rare earth-silver antibacterial material according to claim 1, characterized in that: The rare earth chloride in step 1 includes: lanthanum chloride or cerium chloride; the molar ratio of rare earth: zinc: zirconium in the mixed solution is (2-8): 1: (2-8).

3. The method for preparing a rare earth-silver antibacterial material according to claim 2, characterized in that: The rare earth ion concentration in the mixed solution is controlled at 0.3-0.9 mol / L.

4. The method for preparing a rare earth-silver antibacterial material according to claim 1, characterized in that: In step (1), the molecular weight of PEG is 2000-10000, and 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.

5. The method for preparing a rare earth-silver antibacterial material according to claim 1, characterized in that: The concentration of the ammonium bicarbonate solution in step (1) is 2.53 mol / L, and citric acid or tartaric acid is added to the ammonium bicarbonate solution, and the molar ratio of the added amount of citric acid and tartaric acid to the ammonium bicarbonate is 10:(1-2).

6. The method for preparing a rare earth-silver antibacterial material according to claim 1, characterized in that: In step (2), the mass ratio of the first reactant to deionized water is 1:(3-8); the mass ratio of concentrated phosphoric acid to the first reactant is (0.2-0.3):1; and the mass ratio of 1-butyl-3-methylimidazole dibutyl phosphate to the first reactant is (0.001-0.01):

1.

7. The method for preparing a rare earth-silver antibacterial material according to claim 1, characterized in that: The reaction time in step (2) is 0.5-2h at 60°C.

8. The method for preparing a rare earth-silver antibacterial material according to claim 1, characterized in that: The mass concentration of the silver nitrate solution in step (3) is 10%, the mass ratio of the silver nitrate solution to the second reactant is (5-10):1, the pH value of the mixed solution is adjusted to 1-2 with nitric acid, glacial acetic acid is added, the mass ratio of the glacial acetic acid added to the silver nitrate solution is 0.01-0.02:1, the reaction temperature is 60-90°C, and the reaction time is 1-4h.

9. The method for preparing a rare earth-silver antibacterial material according to claim 1, characterized in that: The calcination temperature in step (3) is 400-1000°C.

10. Use of the rare earth-silver antibacterial material prepared by the method for preparing the rare earth-silver antibacterial material according to any one of claims 1 to 9 in antibacterial paint and antibacterial paper.

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