Preparation method of rare earth antibacterial material

Abstract

The application discloses a preparation method of a rare earth antibacterial material, and specifically comprises the following steps: (1) first, a mixed solution of chlorinated rare earth and zirconium oxychloride is prepared, heated, then polyethylene glycol, glacial acetic acid and ammonium bicarbonate solution are added, reacted, filtered, and dried; (2) water, concentrated phosphoric acid and 1-butyl-3-methyl imidazole phosphoric acid dibutyl ester salt are added, reacted, filtered, and dried; (3) zinc nitrate solution is added into the second reactant, reacted, filtered, washed, dried, calcined, and the rare earth-zinc antibacterial material is obtained. The rare earth-zinc antibacterial material prepared by the method has good uniformity, can be obtained without crushing, has a particle size of 500-1500nm, a large specific surface area (15-150m 2 / g), increased adsorption amount (1.5-4.5g / 100g) and adsorption strength of zinc ions, good aging resistance, excellent antibacterial effect, and the antibacterial rate of the material reaches 99.99% on staphylococcus aureus, escherichia coli and klebsiella pneumoniae, and the antibacterial rate of the material reaches more than 99% on candida albicans and pseudomonas aeruginosa.

Description

TECHNICAL FIELD

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

[0002] Inorganic ion antibacterial agents are the most widely used among several types of antibacterial agents. Currently, the inorganic ion antibacterial agents commonly used on the market include silver ion antibacterial agents, zinc ion antibacterial agents, copper ion antibacterial agents and the like, but there are problems such as high cost, poor high-temperature resistance, easy discoloration, small specific surface area, easy loss of active ingredients in the antibacterial agent, short antibacterial durability, and uneven composition of the antibacterial agent prepared by a solid-phase mixing method.

[0003] Rare earth ion antibacterial agents are relatively common inorganic ion antibacterial agents. Rare earth ions interact with bacteria, destroy the cell wall, cell membrane and DNA, protein and enzyme in the cell, hinder the life activities of the bacteria and inhibit the growth and reproduction of the bacteria. Unpaired electrons in the 4f subshell of the rare earth element interact with the outer layer electrons of other elements, so that the rare earth has active coordination properties, and a rare earth complex with antibacterial properties can be synthesized. The rare earth element doped into the antibacterial material can produce a synergistic antibacterial effect with other antibacterial agents, reducing the amount of other antibacterial agents and obtaining a composite antibacterial material with stronger antibacterial ability. In addition, zinc-containing nanomaterials can easily produce active oxygen, zinc ions can not only be effectively used as antibacterial agents for a variety of microorganisms, but also be widely explored as anticancer agents in the absence of ultraviolet light and visible light, and thus are considered as potential materials with antibacterial and anticancer effects in the next generation of biomedical applications. The high oxidation-reduction potential, chemical stability and high surface reactivity also make it more attractive in a wide range of applications, especially in biomedical applications.

[0004] CN114698649A discloses a rare earth antibacterial material, a preparation method and application thereof. The rare earth antibacterial material is obtained by mixing, dispersing, drying and calcining tetrapod-shaped zinc oxide whiskers, polyethylene glycol 2000, lanthanum oxide, lanthanum chloride, cerium oxide and copper chloride with water. 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, and even after dispersion, the problem of uneven composition still exists.

[0005] CN102763678A discloses a preparation method of silver-loaded cubic zirconium phosphate antibacterial powder. The synthesis process has a high temperature of 90 DEG C 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.

[0006] CN110934153A discloses a kind of zirconium phosphate carrier, zirconium phosphate carrier copper antibacterial agent, preparation method and application of zirconium phosphate antibacterial agent.The highest synthesis reaction temperature reaches 180 DEG C, the highest reaction process pressure reaches 1MPa, and only the reaction time of step 3 reaches 5-8, this method is high in energy consumption, and the specific surface area of the cubic antibacterial powder obtained is small, which will affect the antibacterial effect during use.

[0007] CN 115849325A discloses a kind of cubic zirconium phosphate sodium carrier and preparation method of silver zinc antibacterial powder carried by it, which further improves CN102763678A and CN110934153A by reducing the reaction temperature to 60-80 DEG C and shortening the reaction time, but the antibacterial powder prepared by this method is prone to agglomeration during drying due to its high viscosity, and still needs to be crushed before use, and the morphology is still cubic, the specific surface area is small, which will affect the antibacterial effect during subsequent use.

[0008] CN114698647A discloses a preparation method of zinc oxide / metal antibacterial powder, which adds zinc, copper and aluminum metal cores in zinc salt and alkali metal salt, and precipitates zinc salt on the surface of the metal core with alkali metal salt. The antibacterial material obtained by this method has poor high temperature resistance, and the performance of the material will be affected during heating in the fields of paint, coating and fiber. And the antibacterial material prepared by this method has an antibacterial rate of only 80% on escherichia coli and staphylococcus aureus.

[0009] CN114853054A discloses a preparation method, product and application of silver-doped zinc oxide antibacterial and antiviral nano powder, which directly adds silver nitrate in a simple zinc salt solution, then adds a precipitate and a zinc and silver sol to prepare an antibacterial material. The antibacterial agent prepared by this method is unstable, and the silver oxide obtained by directly precipitating silver in the subsequent use process is prone to discoloration and blackening.

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

[0011] Therefore, the purpose of the present application is to provide a preparation method of a rare earth antibacterial material to solve the problems in the prior art.

[0012] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0013] A preparation method of a rare earth antibacterial material, specifically comprising the following steps:

[0014] (1) first, the rare earth chloride and zirconium oxychloride are prepared into a mixed solution, heated, then polyethylene glycol, glacial acetic acid and ammonium bicarbonate solution are added, reacted, filtered, dried, to obtain the first reactant;

[0015] (2) water, concentrated phosphoric acid and 1-butyl-3-methyl imidazole dibutyl phosphate salt are added to the first reactant, reacted, filtered, dried, to obtain the second reactant;

[0016] (3) zinc nitrate solution is added to the second reactant, reacted, filtered, washed, dried, calcined, to obtain the rare earth antibacterial material.

[0017] Further, in the 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; the rare earth chloride is lanthanum chloride or cerium chloride.

[0018] The above further beneficial effects are that the rare earth chloride and zirconium oxychloride can form a high specific surface area rare earth-zirconium composite, and it is easy to filter and easy to implement in industry.

[0019] Further, in the 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 rare earth chloride and zirconium oxychloride, preferably 1%; the amount of glacial acetic acid added is 1%-3% of the total mass of rare earth chloride and zirconium oxychloride; the concentration of 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] The above further beneficial effects are that polyethylene glycol and glacial acetic acid are used as organic and inorganic dispersants respectively. The addition of citric acid or tartaric acid to ammonium bicarbonate can form organic complex salt with metal ions such as rare earth ions, which can inhibit the agglomeration of the powder during calcination and is beneficial to obtain a precursor with larger specific surface area.

[0021] Further, in the step (1), the heating temperature is 40-70℃, preferably 50℃; the reaction is carried out until the pH value of the system is 6.7-7.0; the drying temperature is 80℃.

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

[0023] The further beneficial effect of the above is that 1-butyl-3-methyl imidazole dibutyl phosphate salt as a dispersant of organic phosphorus can prevent agglomeration.

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

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

[0026] The further beneficial effect of the above is that zinc nitrate is a carrier of active zinc ions, and the addition of nitric acid can prevent the hydrolysis of zinc nitrate during the heating reaction, and can ensure that the zinc ions are adsorbed into the antibacterial material in the form of active ions rather than being precipitated into the antibacterial material, so as to ensure the antibacterial effect.

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

[0028] The beneficial effects of the present application compared with the prior art are as follows:

[0029] 1. The present application discloses a high-loading rare earth-zinc antibacterial material with good antibacterial effect and low preparation cost, which overcomes the problems of uneven composition and poor antibacterial performance of the antibacterial material prepared by simple physical mixing method, and also overcomes the problems of high reaction temperature and long reaction time in the synthesis of the antibacterial material by ordinary liquid phase method.

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

[0031] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0032] Example 1

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

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

[0035] (2) 72 g of the first reactant is first slurried with 350 g of water, then 21 g of concentrated phosphoric acid and 0.15 g of 1-butyl-3-methylimidazolium dibutyl phosphate are added, and the mixture is reacted at 60°C for 1 h, filtered, dried at 80°C, and the second reactant is obtained;

[0036] (3) 5 times the mass concentration of 20% zinc nitrate solution is added to the second reactant, and nitric acid is added to the zinc nitrate solution to a pH value of 1.0; glacial acetic acid is added to the zinc nitrate solution, and the amount of glacial acetic acid added is 1% of the mass of the zinc nitrate solution, and the mixture is reacted for 4 h, filtered, washed, dried, and calcined at 400°C for 4 h to obtain the rare earth antibacterial material (cerium-zirconium-zinc phosphate zinc-loaded antibacterial material).

[0037] Example 2

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

[0039] (1) 352 g of cerium chloride and 290 g of zirconium oxychloride are dissolved in 1260 mL of deionized water to prepare a mixed solution, heated to 50°C, then 7 g of PEG-6000, 10 g of glacial acetic acid and a 2.53 mol / L ammonium bicarbonate solution are added to the system to a pH value of 6.7 (citric acid is added to the ammonium bicarbonate solution, and the molar ratio of citric acid to ammonium bicarbonate is 10:1.5), filtered, dried at 80°C, and the first reactant is obtained;

[0040] (2) 72 g of the first reactant is first slurried with 350 g of water, then 21 g of concentrated phosphoric acid and 0.15 g of 1-butyl-3-methylimidazolium dibutyl phosphate are added, and the mixture is reacted at 60°C for 1 h, filtered, dried at 80°C, and the second reactant is obtained;

[0041] (3) to the second reactant, 5 times mass concentration of 20% zinc nitrate solution was added, and nitric acid was added to the zinc nitrate solution until the pH value of the system was 1.0; 1% of the mass of the zinc nitrate solution was added to the zinc nitrate solution, and ice acetic acid was added, and the reaction was carried out for 4 h, filtration, washing, drying, and calcination at 800°C for 4 h to obtain the rare earth antibacterial material (zinc-loaded cerium-zirconium-zinc phosphate antibacterial material).

[0042] Example 3

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

[0044] (1) 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 ice acetic acid, and a 2.53 mol / L ammonium bicarbonate solution were added to the system until the pH value was 6.7 (the ammonium bicarbonate solution was added with citric acid, and the molar ratio of citric acid to ammonium bicarbonate was 10:1.5), filtration, drying at 80°C, and obtaining the first reactant;

[0045] (2) 72 g of the first reactant was slurried with 350 g of water, and then 21 g of concentrated phosphoric acid and 0.15 g of 1-butyl-3-methylimidazolium dibutyl phosphate were added, and the reaction was carried out at 60°C for 1 h, filtration, drying at 80°C, and obtaining the second reactant;

[0046] (3) to the second reactant, 5 times mass concentration of 20% zinc nitrate solution was added, and nitric acid was added to the zinc nitrate solution until the pH value of the system was 1.0; 1% of the mass of the zinc nitrate solution was added to the zinc nitrate solution, and ice acetic acid was added, and the reaction was carried out for 4 h, filtration, washing, drying, and calcination at 800°C for 4 h to obtain the rare earth antibacterial material (zinc-loaded cerium-zirconium-zinc phosphate antibacterial material).

[0047] Example 4

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

[0049] (1) 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 ice acetic acid, and a 2.53 mol / L ammonium bicarbonate solution were added to the system until the pH value was 7 (the ammonium bicarbonate solution was added with tartaric acid, and the molar ratio of tartaric acid to ammonium bicarbonate was 10:1.4), filtration, drying at 80°C, and obtaining the first reactant;

[0050] (2) First, add 230g of water to 46.8g of the first reactant to make a slurry, then add 12g of concentrated phosphoric acid and 0.1g of 1-butyl-3-methylimidazolium dibutyl phosphate salt, react at 60℃ for 2h, filter, and dry at 80℃ to obtain the 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, the amount of which is 2% of the mass of zinc nitrate solute, react for 4 hours, filter, wash, dry, calcine at 600℃ for 4 hours to obtain rare earth antibacterial material (zinc-loaded antibacterial material of cerium zirconium zinc phosphate).

[0052] Comparative Example 1

[0053] The preparation method of rare earth antibacterial materials specifically includes the following steps:

[0054] (1) First, dissolve 352g of cerium chloride and 290g of zirconium oxychloride in 1260mL of deionized water to prepare a mixed solution, heat to 50℃, then add 7g of PEG-6000, 10mL of glacial acetic acid and 2.53mol / L ammonium bicarbonate solution until the pH of the system is 7.0 (no citric acid or tartaric acid is added to the ammonium bicarbonate solution), filter, dry at 80℃ to obtain the first reactant;

[0055] (2) First, add 350g of water to 72g of the first reactant to make a slurry, then add 21mL of concentrated phosphoric acid and 0.15g of 1-butyl-3-methylimidazolium dibutyl phosphate salt, react at 60℃ for 1h, filter, and dry at 80℃ to obtain the 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, the amount of which is 1% of the mass of zinc nitrate solute, react for 4 hours, filter, wash, dry, calcine at 400℃ for 4 hours to obtain rare earth antibacterial material (zinc-loaded antibacterial material of cerium zirconium zinc phosphate).

[0057] Comparative Example 2

[0058] The preparation method of rare earth antibacterial materials specifically includes the following steps:

[0059] (1) First, dissolve 352g of cerium chloride and 290g of zirconium oxychloride in 1260mL of deionized water to prepare a mixed solution, heat to 50℃, then add 7g of PEG-6000, 10mL of glacial acetic acid and 2.53mol / L ammonium bicarbonate solution until the pH of the system is 7.0 (no citric acid or tartaric acid is added to the ammonium bicarbonate solution), filter, dry at 80℃ to obtain the first reactant;

[0060] (2) first reactant 72 g, add 350 g water, then add 21 mL of concentrated phosphoric acid, 60 ℃ reaction 1 h, filter, 80 ℃ drying, to get the second reactant;

[0061] (3) to the second reactant, add 10 times mass concentration of 20% zinc nitrate solution, add nitric acid in the zinc nitrate solution, until the pH value of the system is 2.0; add glacial acetic acid in the zinc nitrate solution, the amount is 1% of the mass of the zinc nitrate solution, reaction 4 h, filter, wash, dry, calcine at 400 ℃ for 4 h, to get the rare earth antibacterial material (cerium zinc zirconium phosphate zinc antibacterial material).

[0062] Performance test

[0063] Each of the rare earth antibacterial materials prepared in examples 1-4 and comparative examples 1-2 is tested for zinc adsorption, particle size, specific surface area, and antibacterial rate against staphylococcus aureus, escherichia coli, klebsiella pneumoniae, candida albicans, and pseudomonas aeruginosa.

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

[0065] The particle size is tested by a laser particle size instrument;

[0066] The specific surface area is tested by a gas adsorption method;

[0067] The antibacterial performance is tested by GB / T21510-2008 Nanometer Inorganic Material Antibacterial Performance Test - Oscillation Method.

[0068] The results are shown in Table 1.

[0069] Table 1 Zinc adsorption, particle size, specific surface area, and antibacterial rate of the 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 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 disclosed examples enables one of ordinary skill in the art to make or use the application. Various modifications to these examples will be readily apparent to those of ordinary skill in the art, and the generic principles defined herein can be applied to other examples without departing from the spirit or scope of the application. Therefore, the application is not to be limited to the examples shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for producing a rare earth antibacterial material, characterized by comprising the steps of: The application specifically comprises the following steps: ​ (1) first prepare a mixed solution of chlorinated rare earth and zirconium oxychloride, heat, then add polyethylene glycol, glacial acetic acid and ammonium bicarbonate solution, react, filter, dry to obtain a first reactant; 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; the chlorinated rare earth is lanthanum chloride or cerium chloride; The molecular weight of the polyethylene glycol is 2000-10000, and the added amount is 0.05%-2% of the total mass of the chlorinated rare earth and zirconium oxychloride; the added amount of the glacial acetic acid is 1%-3% of the total mass of the chlorinated rare earth 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 after adding the ammonium bicarbonate solution; citric acid or tartaric acid is added in the ammonium bicarbonate solution, and the molar ratio of citric acid or tartaric acid to ammonium bicarbonate is 10:(1-2); (2) add water, concentrated phosphoric acid and 1-butyl-3-methylimidazole dibutyl phosphate salt to the first reactant, react, filter, dry to obtain a second reactant; The mass ratio of the first reactant, water, concentrated phosphoric acid and 1-butyl-3-methylimidazole dibutyl phosphate salt is 1:(3-8):(0.2-0.3):(0.001-0.01); The reaction temperature is 60℃, and the reaction time is 0.5-2h; (3) add zinc nitrate solution to the second reactant, react, filter, wash, dry, calcine to obtain the rare earth antibacterial material; The mass concentration of the zinc nitrate solution is 15%-20%, and the added amount is 5-10 times of the mass of the second reactant; nitric acid is added in the zinc nitrate solution to make the pH value of the system 1-2; glacial acetic acid is added in the zinc nitrate solution, and the added amount is 1%-2% of the mass of the zinc nitrate solution.

2. The method for preparing a rare earth antibacterial material according to claim 1, characterized in that, In step (1), the heating is to 40-70℃; the reaction is to make the pH value of the system 6.7-7.0; and the drying temperature is 80℃.

3. The method for preparing a rare earth antibacterial material according to claim 1, characterized in that, In step (2), the drying temperature is 80℃.

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

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