Preparation method of rare earth antibacterial material

Abstract

The invention discloses a preparation method of a rare earth antibacterial material, which specifically comprises the following steps: (1) preparing rare earth chloride and zirconium oxychloride into a mixed solution, heating, then adding polyethylene glycol, glacial acetic acid and an ammonium bicarbonate solution, reacting, filtering and drying; (2) adding water, concentrated phosphoric acid and 1-butyl-3-methylimidazole dibutyl phosphate salt, reacting, filtering and drying; and (3) adding a zinc nitrate solution into the second reactant, reacting, filtering, washing, drying and calcining to obtain the catalyst. The prepared rare earth-zinc antibacterial material is good in uniformity, the material with the particle size of 500-1500 nm can be obtained without crushing, the specific surface area is large (15-150 m < 2 > / g), the adsorption capacity (1.5-4.5 g / 100 g) and the adsorption strength on zinc ions are increased, the aging resistance is good, the antibacterial effect is excellent, the antibacterial rate on staphylococcus aureus, escherichia coli and klebsiella pneumoniae reaches 99.99%, and the antibacterial effect is good. The antibacterial rate on candida albicans and pseudomonas aeruginosa reaches 99% or above.

Description

Technical Field

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

[0002] Inorganic ion antimicrobial agents are the most widely used of several types of antimicrobial agents. Currently, commonly used inorganic ion antimicrobial agents on the market include silver ion antimicrobial agents, zinc ion antimicrobial agents, and copper ion antimicrobial agents. However, they generally suffer from high costs, poor high-temperature resistance, 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.

[0003] Rare earth ion antimicrobial agents are common inorganic ion antimicrobial agents. Rare earth ions interact with bacteria, damaging their cell walls, membranes, and intracellular DNA, proteins, and enzymes, hindering their vital activities and inhibiting their growth and reproduction. The unpaired electrons in the 4f subshell of rare earth elements interact with the outer-shell electrons of other elements, giving them active coordination properties, enabling the synthesis of rare earth complexes with antimicrobial properties. Rare earth element doping in antimicrobial materials can produce synergistic antimicrobial effects with other antimicrobial agents, reducing the dosage of other antimicrobial agents and yielding composite antimicrobial materials with enhanced antimicrobial potency. Furthermore, zinc-containing nanomaterials readily generate reactive oxygen species. Zinc ions are not only effective antimicrobial agents against a wide range of microorganisms but are also being widely explored as anticancer agents in the absence of ultraviolet and visible light. Therefore, they are considered promising materials with antimicrobial and anticancer properties in next-generation biomedicine. Their high redox potential, chemical stability, and high surface reactivity also make them attractive for a wide range of applications, particularly in biomedicine.

[0004] 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.

[0005] 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.

[0006] CN110934153A discloses a method for preparing and using a zirconium phosphate carrier, a zirconium phosphate-supported copper antibacterial agent, and a zirconium phosphate antibacterial agent. 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.

[0007] CN 115849325A discloses a method for preparing a cubic sodium zirconium phosphate carrier and its silver-zinc-loaded antibacterial powder. This method further improves upon CN102763678A and CN110934153A 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 is prone to agglomeration during the drying process, requiring pulverization before use. Furthermore, the powder is not cubic in shape and has a small specific surface area, which may affect its antibacterial effect during subsequent use.

[0008] CN114698647A discloses a method for preparing a zinc oxide / metal antibacterial powder. The method involves adding a metal core of zinc, copper, or aluminum to a zinc salt and an alkali metal salt. The zinc salt is then precipitated with an alkali metal salt, causing it to grow on the surface of the metal core. The antibacterial material obtained by this method has poor high-temperature resistance. When used in paints, coatings, fibers, and other applications, the heating process can affect the material's performance. Furthermore, the antibacterial rate against Escherichia coli and Staphylococcus aureus achieved by this method is only 80%.

[0009] CN114853054A discloses a method for preparing silver-doped zinc oxide antibacterial and antiviral nanopowders, as well as their product and application. The method involves directly adding silver nitrate to a simple zinc salt solution, followed by precipitation and preparation of a zinc and silver sol, which is then dried to produce the antibacterial material. However, the antibacterial agent prepared by this method is unstable, and the silver oxide obtained by direct silver precipitation is prone to discoloration and blackening during subsequent use.

[0010] Therefore, how to develop a rare earth antibacterial material with good antibacterial effect and low preparation cost is an urgent problem that needs to be solved by those skilled in the art. Summary of the Invention

[0011] In view of this, the object of the present invention is to provide a method for preparing a rare earth antibacterial material to address the deficiencies in the prior art.

[0012] In order to achieve the above object, the present invention adopts the following technical solutions:

[0013] A method for preparing a rare earth antibacterial material comprises the following steps:

[0014] (1) first preparing a mixed solution of rare earth chloride and zirconium oxychloride, heating the solution, then adding polyethylene glycol, glacial acetic acid and ammonium bicarbonate solution, reacting the solution, filtering the solution, and drying the solution to obtain a first reactant;

[0015] (2) adding water, concentrated phosphoric acid and 1-butyl-3-methylimidazole dibutyl phosphate to the first reactant, reacting, filtering, and drying to obtain a second reactant;

[0016] (3) adding zinc nitrate solution to the second reactant, reacting, filtering, washing, drying, and calcining to obtain a rare earth antibacterial material.

[0017] Furthermore, in the above step (1), the molar ratio of rare earth ions to zirconium ions in the mixed solution is 1:(0.2-3), preferably 1:1; the concentration of rare earth ions in the mixed solution is 0.3-0.9 mol / L, preferably 0.6 mol / L; and the rare earth chloride is lanthanum chloride or cerium chloride.

[0018] A further beneficial effect of the above method is that rare earth chloride and zirconium oxychloride can form a rare earth-zirconium composite with a high specific surface area, which is easy to filter and easy to implement industrially.

[0019] Furthermore, in the above step (1), the molecular weight of polyethylene glycol (PEG) is 2000-10000, preferably 6000; the amount of polyethylene glycol added is 0.05%-2% of the total mass of the rare earth chloride and zirconium oxychloride, preferably 1%; the amount of glacial acetic acid added is 1%-3% of the total mass of the rare earth chloride and zirconium oxychloride; the concentration of the ammonium bicarbonate solution is 2.53 mol / L, and the pH value of the system is 6.7-7.0; citric acid or tartaric acid is added to the ammonium bicarbonate solution, and the molar ratio of citric acid or tartaric acid to ammonium bicarbonate is 10:(1-2).

[0020] A further beneficial effect of the above method is that polyethylene glycol and glacial acetic acid serve as organic and inorganic dispersants, respectively. Adding citric acid or tartaric acid to ammonium bicarbonate can form organic complex salts with rare earth and other metal ions, inhibiting powder agglomeration during calcination and facilitating the production of a precursor with a larger specific surface area.

[0021] Furthermore, in the above step (1), the temperature is heated to 40-70°C, preferably 50°C; the reaction is carried out until the pH value of the system reaches 6.7-7.0; and the drying temperature is 80°C.

[0022] Furthermore, in the above step (2), the mass ratio of the first reactant, water, concentrated phosphoric acid and 1-butyl-3-methylimidazole dibutyl phosphate is 1:(3-8):(0.2-0.3):(0.001-0.01), preferably 1:5:0.25:0.002.

[0023] A further beneficial effect of the above method is that 1-butyl-3-methylimidazole dibutyl phosphate salt is used as a dispersant for organophosphorus, which can prevent agglomeration.

[0024] Furthermore, in the above step (2), the reaction temperature is 60°C, the reaction time is 0.5-2h, and the drying temperature is 80°C.

[0025] Furthermore, in the above step (3), the mass concentration of the zinc nitrate solution is 15%-20%, and the added amount is 5-10 times the mass of the second reactant; nitric acid is added to the zinc nitrate solution until the pH value of the system is 1-2; glacial acetic acid is added to the zinc nitrate solution in an amount of 1%-2% of the mass of the zinc nitrate solute.

[0026] A further beneficial effect of the above method is that zinc nitrate is a carrier of active zinc ions. The addition of nitric acid can prevent the hydrolysis of zinc nitrate during the heating reaction. In addition, it can ensure that the zinc ions are adsorbed into the antibacterial material in the form of active ions rather than precipitated into the antibacterial material, thereby ensuring the antibacterial effect.

[0027] Furthermore, in the above step (3), the reaction time is 2-4 hours; the calcination temperature is 400-1000° C., and the calcination time is 4 hours.

[0028] It can be seen from the above technical solution that compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] 1. The present invention discloses a high-load rare earth-zinc antibacterial material with good antibacterial effect and low preparation cost. It overcomes the problems of uneven composition and poor antibacterial performance of antibacterial materials prepared by simple physical mixing methods. It also overcomes the problems of high reaction temperature and long reaction time when synthesizing antibacterial materials by ordinary liquid phase method.

[0030] 2. The rare earth-zinc antibacterial material prepared by the present invention has good uniformity and can obtain a material with a particle size of 500-1500nm without crushing, and has a large specific surface area (15-150m 2 / g), increases the adsorption capacity (1.5-4.5g / 100g) and adsorption strength of zinc ions, has good aging resistance and excellent antibacterial effect. The antibacterial rate against Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae reaches 99.99%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa reaches more than 99%. DETAILED DESCRIPTION

[0031] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. 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 any creative efforts are within the scope of protection of the present invention.

[0032] Example 1

[0033] The preparation method of rare earth antibacterial material specifically comprises the following steps:

[0034] (1) First, 352 g of cerium chloride and 290 g of zirconium oxychloride were dissolved in 1260 mL of deionized water to prepare a mixed solution, which was heated to 50° C., and then 7 g of PEG-6000, 10 g of glacial acetic acid, and a 2.53 mol / L ammonium bicarbonate solution were added until the pH value of the system was 6.7 (citric acid was added to the ammonium bicarbonate solution, and the molar ratio of citric acid to ammonium bicarbonate was 10:1.5). The mixture was filtered and dried at 80° C. to obtain a first reactant;

[0035] (2) First, 350 g of water was added to 72 g of the first reactant to prepare a slurry, and then 21 g of concentrated phosphoric acid and 0.15 g of 1-butyl-3-methylimidazole dibutyl phosphate were added. The mixture was reacted at 60° C. for 1 h, filtered, and dried at 80° C. to obtain a second reactant.

[0036] (3) Add 5 times the mass concentration of 20% zinc nitrate solution to the second reactant, add nitric acid to the zinc nitrate solution until the pH value of the system is 1.0; add glacial acetic acid to the zinc nitrate solution in an amount of 1% of the mass of the zinc nitrate solute, react for 4 hours, filter, wash, dry, and calcine at 400°C for 4 hours to obtain a rare earth antibacterial material (cerium zirconium zinc phosphate loaded zinc antibacterial material).

[0037] Example 2

[0038] The preparation method of rare earth antibacterial material specifically comprises the following steps:

[0039] (1) First, 352 g of cerium chloride and 290 g of zirconium oxychloride were dissolved in 1500 mL of deionized water to prepare a mixed solution, which was heated to 60° C., and then 5.8 g of PEG-4000, 12.8 g of glacial acetic acid, and a 2.53 mol / L ammonium bicarbonate solution were added until the pH value of the system was 7.0 (citric acid was added to the ammonium bicarbonate solution, and the molar ratio of citric acid to ammonium bicarbonate was 10:1.8). The mixture was filtered and dried at 80° C. to obtain a first reactant;

[0040] (2) First, 500 g of water was added to 72 g of the first reactant to prepare a slurry, and then 15 g of concentrated phosphoric acid and 0.35 g of 1-butyl-3-methylimidazole dibutyl phosphate were added. The mixture was reacted at 60° C. for 2 h, filtered, and dried at 80° C. to obtain a second reactant.

[0041] (3) Add 10 times the mass concentration of 15% zinc nitrate solution to the second reactant, add nitric acid to the zinc nitrate solution until the pH value of the system is 1.0; add glacial acetic acid to the zinc nitrate solution in an amount of 1% of the mass of the zinc nitrate solute, react for 4 hours, filter, wash, dry, and calcine at 400°C for 4 hours to obtain a rare earth antibacterial material (cerium zirconium zinc phosphate loaded zinc antibacterial material).

[0042] Example 3

[0043] The preparation method of rare earth antibacterial material specifically comprises the following steps:

[0044] (1) First, 352 g of cerium chloride and 290 g of zirconium oxychloride were dissolved in 1260 mL of deionized water to prepare a mixed solution, which was heated to 50° C., and then 7 g of PEG-6000, 10 g of glacial acetic acid, and a 2.53 mol / L ammonium bicarbonate solution were added until the pH value of the system was 6.7 (citric acid was added to the ammonium bicarbonate solution, and the molar ratio of citric acid to ammonium bicarbonate was 10:1.5). The mixture was filtered and dried at 80° C. to obtain a first reactant;

[0045] (2) First, 350 g of water was added to 72 g of the first reactant to prepare a slurry, and then 21 g of concentrated phosphoric acid and 0.15 g of 1-butyl-3-methylimidazole dibutyl phosphate were added. The mixture was reacted at 60° C. for 1 h, filtered, and dried at 80° C. to obtain a second reactant.

[0046] (3) Add 5 times the mass concentration of 20% zinc nitrate solution to the second reactant, add nitric acid to the zinc nitrate solution until the pH value of the system is 1.0; add glacial acetic acid to the zinc nitrate solution in an amount of 1% of the mass of the zinc nitrate solute, react for 4 hours, filter, wash, dry, and calcined at 800°C for 4 hours to obtain a rare earth antibacterial material (cerium zirconium zinc phosphate loaded zinc antibacterial material).

[0047] Example 4

[0048] The preparation method of rare earth antibacterial material specifically comprises the following steps:

[0049] (1) First, 230 g of cerium chloride and 150 g of zirconium oxychloride were dissolved in 1110 mL of deionized water to prepare a mixed solution, which was heated to 60° C., and then 4.2 g of PEG-4000, 8 g of glacial acetic acid, and a 2.53 mol / L ammonium bicarbonate solution were added until the pH value of the system was 7 (tartaric acid was added to the ammonium bicarbonate solution, and the molar ratio of tartaric acid to ammonium bicarbonate was 10:1.4). The mixture was filtered and dried at 80° C. to obtain a first reactant;

[0050] (2) First, 230 g of water was added to 46.8 g of the first reactant to prepare a slurry, and then 12 g of concentrated phosphoric acid and 0.1 g of 1-butyl-3-methylimidazole dibutyl phosphate were added. The mixture was reacted at 60° C. for 2 h, filtered, and dried at 80° C. to obtain a second reactant.

[0051] (3) Add 8 times the mass concentration of 15% zinc nitrate solution to the second reactant, add nitric acid to the zinc nitrate solution until the pH value of the system is 1.0; add glacial acetic acid to the zinc nitrate solution in an amount of 2% of the mass of the zinc nitrate solute, react for 4 hours, filter, wash, dry, and calcined at 600°C for 4 hours to obtain a rare earth antibacterial material (cerium zirconium zinc phosphate loaded zinc antibacterial material).

[0052] Comparative Example 1

[0053] The preparation method of rare earth antibacterial material specifically comprises the following steps:

[0054] (1) First, 352 g of cerium chloride and 290 g of zirconium oxychloride were dissolved in 1260 mL of deionized water to prepare a mixed solution, which was heated to 50° C., and then 7 g of PEG-6000, 10 mL of glacial acetic acid, and a 2.53 mol / L ammonium bicarbonate solution were added until the pH value of the system was 7.0 (no citric acid or tartaric acid was added to the ammonium bicarbonate solution), filtered, and dried at 80° C. to obtain a first reactant;

[0055] (2) First, 350 g of water was added to 72 g of the first reactant to prepare a slurry, and then 21 mL of concentrated phosphoric acid and 0.15 g of 1-butyl-3-methylimidazole dibutyl phosphate were added. The mixture was reacted at 60° C. for 1 h, filtered, and dried at 80° C. to obtain a second reactant.

[0056] (3) Add 10 times the mass concentration of 20% zinc nitrate solution to the second reactant, add nitric acid to the zinc nitrate solution until the pH value of the system is 2.0; add glacial acetic acid to the zinc nitrate solution in an amount of 1% of the mass of the zinc nitrate solute, react for 4 hours, filter, wash, dry, and calcine at 400°C for 4 hours to obtain a rare earth antibacterial material (cerium zirconium zinc phosphate loaded zinc antibacterial material).

[0057] Comparative Example 2

[0058] The preparation method of rare earth antibacterial material specifically comprises the following steps:

[0059] (1) First, 352 g of cerium chloride and 290 g of zirconium oxychloride were dissolved in 1260 mL of deionized water to prepare a mixed solution, which was heated to 50° C., and then 7 g of PEG-6000, 10 mL of glacial acetic acid, and a 2.53 mol / L ammonium bicarbonate solution were added until the pH value of the system was 7.0 (no citric acid or tartaric acid was added to the ammonium bicarbonate solution), filtered, and dried at 80° C. to obtain a first reactant;

[0060] (2) First, 350 g of water was added to 72 g of the first reactant to prepare a slurry, and then 21 mL of concentrated phosphoric acid was added. The mixture was reacted at 60° C. for 1 h, filtered, and dried at 80° C. to obtain the second reactant.

[0061] (3) Add 10 times the mass concentration of 20% zinc nitrate solution to the second reactant, add nitric acid to the zinc nitrate solution until the pH value of the system is 2.0; add glacial acetic acid to the zinc nitrate solution in an amount of 1% of the mass of the zinc nitrate solute, react for 4 hours, filter, wash, dry, and calcine at 400°C for 4 hours to obtain a rare earth antibacterial material (cerium zirconium zinc phosphate loaded zinc antibacterial material).

[0062] Performance Testing

[0063] The rare earth antibacterial materials prepared in Examples 1-4 and Comparative Examples 1-2 were respectively tested for their zinc adsorption capacity, particle size and specific surface area, as well as their antibacterial rates against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Candida albicans and Pseudomonas aeruginosa.

[0064] Among them, the zinc adsorption capacity was tested by ICP;

[0065] The particle size test was performed using a laser particle size analyzer;

[0066] The specific surface area was tested using the gas adsorption method;

[0067] The antibacterial performance test adopted GB / T21510-2008 nano-inorganic material antibacterial performance test-oscillation method.

[0068] The results are shown in Table 1.

[0069] Table 1 Zinc adsorption capacity, particle size, specific surface area and antibacterial rate of rare earth antibacterial materials of Examples 1-4 and Comparative Examples 1-2

[0070]

[0071] As can be seen from Table 1, compared with Comparative Examples 1-2, the zinc adsorption capacity of the rare earth antibacterial materials prepared by adding citric acid or tartaric acid in Examples 1-4 is significantly improved, the particle size is significantly reduced, the specific surface area is significantly increased, and the antibacterial rate against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Candida albicans and Pseudomonas aeruginosa is significantly improved.

[0072] 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 antibacterial material, characterized in that: The specific steps include: (1) first preparing a mixed solution of rare earth chloride and zirconium oxychloride, heating the solution, then adding polyethylene glycol, glacial acetic acid and ammonium bicarbonate solution, reacting the solution, filtering the solution, and drying the solution to obtain a first reactant; (2) adding water, concentrated phosphoric acid and 1-butyl-3-methylimidazole dibutyl phosphate to the first reactant, reacting, filtering, and drying to obtain a second reactant; (3) adding zinc nitrate solution to the second reactant, reacting, filtering, washing, drying, and calcining to obtain the rare earth antibacterial material.

2. The method for preparing a rare earth antibacterial material according to claim 1, characterized in that: In step (1), in the mixed solution, the molar ratio of rare earth ions to zirconium ions is 1:(0.2-3), and the concentration of rare earth ions is 0.3-0.9 mol / L; and the rare earth chloride is lanthanum chloride or cerium chloride.

3. The method for preparing a rare earth antibacterial material according to claim 1 or 2, characterized in that: In step (1), the molecular weight of the polyethylene glycol is 2000-10000, and the added amount is 0.05%-2% of the total mass of the rare earth chloride and zirconium oxychloride; the added amount of the glacial acetic acid is 1%-3% of the total mass of the rare earth chloride and zirconium oxychloride; the concentration of the ammonium bicarbonate solution is 2.53 mol / L, and the pH value of the system is 6.7-7.0; citric acid or tartaric acid is added to the ammonium bicarbonate solution, and the molar ratio of citric acid or tartaric acid to ammonium bicarbonate is 10:(1-2).

4. The method for preparing a rare earth antibacterial material according to claim 1, characterized in that: In step (1), the heating temperature is 40-70°C; the reaction is carried out until the pH value of the system reaches 6.7-7.0; and the drying temperature is 80°C.

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

6. The method for preparing a rare earth antibacterial material according to claim 1, characterized in that: In step (2), the reaction temperature is 60°C and the reaction time is 0.5-2h; the drying temperature is 80°C.

7. The method for preparing a rare earth antibacterial material according to claim 1, characterized in that: In step (3), the mass concentration of the zinc nitrate solution is 15%-20%, and the added amount is 5-10 times the mass of the second reactant; nitric acid is added to the zinc nitrate solution until the pH value of the system is 1-2; glacial acetic acid is added to the zinc nitrate solution in an amount of 1%-2% of the mass of the zinc nitrate solute.

8. The method for preparing a rare earth antibacterial material according to claim 1, characterized in that: In step (3), the reaction time is 2-4 hours; the calcination temperature is 400-1000° C., and the calcination time is 4 hours.

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