Rare earth-copper antibacterial material, preparation method and application

Abstract

The application belongs to the field of rare earth material preparation, and particularly relates to a rare earth-copper antibacterial material, a preparation method and application. The application provides a preparation method of the rare earth-copper antibacterial material with good antibacterial effect and low cost, which can overcome the problems of uneven composition and poor antibacterial performance of the antibacterial material prepared by a simple physical mixing method in the prior art, and can overcome the problems of high reaction temperature and long reaction time when the antibacterial material is synthesized by an ordinary liquid phase method. The antibacterial material obtained by the application has the advantages of higher specific surface area, better combination of copper ions and the matrix, and more persistent antibacterial effect, and is suitable for promotion and application.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of rare earth material preparation, and particularly relates to a rare earth-copper antibacterial material, a preparation method and application thereof. BACKGROUND

[0002] Inorganic ion antibacterial agents are the most widely used among several types of antibacterial agents. Inorganic antibacterial materials have the advantages of broad-spectrum antibacterial property, long-acting antibacterial property, heat resistance, but the commonly used inorganic ion antibacterial agents on the market generally have the problems of high cost, poor high-temperature resistance and 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 solid-phase mixing method.

[0003] Rare earth also plays an important role in the field of antibacterial agents. Rare earth ions interact with bacteria, destroy their cell walls, cell membranes, and DNA, proteins and enzymes in cells, hinder the life activities of bacteria, and inhibit the growth and reproduction of bacteria. Unpaired electrons in the 4f subshell of rare earth elements interact with the outer shell 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 antibacterial agents, reducing the amount of other antibacterial agents, and obtaining composite antibacterial materials with stronger antibacterial ability. Copper-based antibacterial materials refer to materials that use metallic copper and copper oxides (CuO, Cu2O) as antibacterial agents and have bactericidal function. The antibacterial performance of copper-based antibacterial materials is between that of silver and zinc. Due to the characteristics of high antibacterial rate and low cost, research on copper-based antibacterial materials has become more and more in-depth in recent years.

[0004] CN 117226105A discloses a preparation method of inorganic antibacterial powder. A soluble copper salt solution is heated and then mixed with a reducing agent solution such as ascorbic acid and a dispersant solution in a reaction container, and the gas in the reaction container is extracted and replaced with nitrogen or inert gas. The reaction product is cooled, solid-liquid separated, and the solid material is collected and vacuum rotary evaporated to obtain inorganic antibacterial powder. The inorganic antibacterial powder obtained by this method has large agglomerated particle size and poor high-temperature resistance.

[0005] CN 111387177A discloses a cubic zirconium phosphate carrier and a preparation method of silver or copper-silver dual-ion inorganic antibacterial powder loaded thereon. The method uses zirconium oxyfluoride, sodium fluoride, soluble phosphate and silicon dioxide as raw materials to prepare a zirconium phosphate carrier by high-pressure hydrothermal reaction, and then loads copper or silver on the zirconium phosphate carrier to obtain an antibacterial material. The preparation process of this method has high reaction temperature and high energy consumption, and requires high-pressure reaction, which has safety hazards in the production process.

[0006] CN 115517268 A discloses a silver-loaded zinc copper single-layer zirconium phosphate nanosheet and a preparation method thereof. A soluble zirconium salt is directly added to hydrofluoric acid and phosphoric acid to prepare layered zirconium phosphate, and then a betaine or other amphoteric surfactant is added to exfoliate the layered zirconium phosphate to prepare single-layer zirconium phosphate nanosheets. The zirconium phosphate prepared by directly adding phosphoric acid and hydrofluoric acid to the soluble zirconium salt is difficult to filter, and the operation is difficult.

[0007] 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 four needle-shaped zinc oxide whiskers, polyethylene glycol 2000, lanthanum oxide, lanthanum chloride, cerium oxide, copper chloride and water. 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 material are insoluble in water. Even after dispersion, there is still a problem of uneven composition.

[0008] CN102763678A discloses a preparation method of a cubic zirconium phosphate silver-loaded antibacterial powder. The synthesis process has a high temperature of 90℃ and a long reaction period of 28 hours, resulting in high energy consumption. The obtained antibacterial powder is cubic, has a small specific surface area, and affects the antibacterial effect.

[0009] CN 110934153 A discloses a zirconium phosphate carrier, a zirconium phosphate copper-loaded antibacterial agent, a zirconium phosphate antibacterial agent, and a preparation method and application thereof. The reaction temperature is as high as 180℃, and the reaction process pressure is as high as 1MPa, resulting in high energy consumption. The obtained antibacterial powder is cubic, has a small specific surface area, and affects the antibacterial effect.

[0010] CN 115849325 A discloses a cubic zirconium phosphate sodium carrier and a preparation method of a silver-loaded zinc antibacterial powder thereof. Although the method further improves CN102763678A and CN 110934153 A by reducing the reaction temperature to 60-80℃ and shortening the reaction time, the antibacterial powder prepared by the method has a large viscosity and is prone to agglomeration during the drying process, and thus needs to be crushed before use. The morphology of the antibacterial powder is still cubic, the specific surface area is small, and the antibacterial effect is affected in the subsequent use process.

[0011] Therefore, how to provide a preparation method of a rare earth-copper antibacterial material with good antibacterial effect and low cost is a technical problem to be solved by those skilled in the art. SUMMARY

[0012] Therefore, the present application provides a rare earth-copper antibacterial material, a preparation method and application thereof.

[0013] It should be noted that the present application provides a preparation method of a rare earth-copper antibacterial material with good antibacterial effect and low cost, so as to overcome the problems of uneven composition and poor antibacterial performance of the antibacterial material prepared by a simple physical mixing method in the prior art, and overcome the problems of high reaction temperature and long reaction time of the antibacterial material synthesized by an ordinary liquid phase method. The antibacterial material obtained by the present application has a higher specific surface area, a better combination ability of copper ions and a substrate, and a more durable antibacterial effect.

[0014] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0015] The first technical purpose of the present application is to provide a preparation method of a rare earth-copper antibacterial material, which specifically comprises the following steps:

[0016] The rare earth chloride (preferably lanthanum cerium), zinc chloride and zirconium oxychloride are prepared into a mixed solution, the mixed solution is heated to 40-80℃, PEG and glacial acetic acid are added; after the addition is completed, ammonium bicarbonate solution is added to the mixed solution, the reaction is carried out until the pH value of the system is 6.7-7, then the first reactant is obtained by filtering and drying;

[0017] The first reactant is slurried with deionized water, then concentrated phosphoric acid is added, followed by the addition of 1-butyl-3-methyl imidazole phosphoric acid dibutyl ester salt, then the second reactant is obtained by filtering and drying;

[0018] Copper nitrate or copper acetate solution is added to the second reactant, and the pH value is adjusted to 1-2 with nitric acid, then the antibacterial material is obtained by adding glacial acetic acid dispersion, reaction, filtering, washing, drying and calcining.

[0019] Optionally, the molar ratio of rare earth, zinc and zirconium in the mixed solution is (2-8):1:(2-8), preferably 5:2:5; the concentration of rare earth ions in the mixed solution is 0.3-0.9mol / L, preferably 0.6mol / L.

[0020] Further, the molecular weight of PEG is 2000-10000, preferably 6000; the addition amount of PEG is 0.05-2% of the total mass of rare earth chloride, zinc chloride and zirconium oxychloride, preferably 1%; the addition amount of glacial acetic acid is 1%-3% of the total mass of rare earth chloride, zinc chloride and zirconium oxychloride.

[0021] Further, the concentration of ammonium bicarbonate solution is 1.5-2.8mol / L, preferably 2.53mol / L, and citric acid or tartaric acid is added to the ammonium bicarbonate solution to form organic rare earth salt such as citric acid or tartaric acid, thereby reducing the agglomeration of the powder during calcination; the molar ratio of citric acid or tartaric acid to ammonium bicarbonate is 10:1-2.

[0022] Optionally, the mass ratio of the first reactant to deionized water is 1:3-8, preferably 1:5; the mass ratio of concentrated phosphoric acid to the first reactant is 0.2-0.3:1, preferably 0.25:1; and the mass ratio of 1-butyl-3-methyl imidazole phosphoric acid dibutyl ester salt to the first reactant is 0.001-0.01:1.

[0023] Further, the reaction time is 0.5-2h, and the reaction temperature is 60℃.

[0024] Optionally, the concentration of the copper nitrate or copper acetate solution is 8-20%, and the mass ratio of the volume of the added glacial acetic acid to the mass of the copper nitrate solute is 0.01-0.02:1; and if copper acetate is used, glacial acetic acid need not be added.

[0025] Further, the reaction time is 4h, the calcination temperature is 400-600℃, the temperature rising rate is 10℃ / min, and the temperature is kept at 150℃ for 30min before being raised to the required temperature.

[0026] The second technical object of the present application is to provide a rare earth-copper antibacterial material prepared by the above method.

[0027] The copper adsorption amount of the rare earth-copper antibacterial material prepared by the present application is 1.5-8g / 100g, the agglomerated particle size is 500nm-2000nm, the specific surface area is 25-150m 2 / g, the antibacterial rate against Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae reaches 99.9%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa is more than 99%. After being irradiated by an ultraviolet lamp for 2000h, the antibacterial rate against Staphylococcus aureus is 99.9%, the antibacterial rate against Escherichia coli is more than 99.5%, the antibacterial rate against Pseudomonas aeruginosa is more than 99%, the antibacterial rate against Klebsiella pneumoniae is more than 98%, and the antibacterial rate against Candida albicans is more than 97%.

[0028] The third technical object of the present application is to provide an application of the rare earth-copper antibacterial material prepared by the above method in the fields of fibers, ceramics, paints, plastics and the like.

[0029] Compared with the prior art, the present application has the following beneficial effects:

[0030] The rare earth-copper antibacterial material prepared by the liquid phase method has the advantages of short reaction time, small particle size, large specific surface area, large copper adsorption amount, good antibacterial effect and long-lasting antibacterial property. BRIEF DESCRIPTION OF DRAWINGS

[0031] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description only represent some embodiments of the present application, and for those skilled in the art, other drawings can be obtained without creative effort based on the provided drawings.

[0032] Figure 1 Figure is a particle size distribution diagram of the rare earth-copper antibacterial material prepared by the present application. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments only represent some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative effort fall within the scope of the present application.

[0034] The special word "embodiment" in this application is not necessarily interpreted as superior or better than other embodiments as explained by "exemplary". In the performance index test of the embodiments of the present application, unless otherwise specified, the conventional test method in the art is adopted. It should be understood that the terms described in the present application are only for describing the specific embodiments, and are not used to limit the disclosure of the present application.

[0035] Unless otherwise specified, the technical and scientific terms used in this application have the same meaning as generally understood by those skilled in the art to which the present application belongs; as the experimental methods and technical means not specially noted in the present application are all the experimental methods and technical means generally used by those skilled in the art.

[0036] In order to better illustrate the content of the present application, a large number of specific details are given in the specific embodiments below. Those skilled in the art should understand that without some specific details, the present application can also be implemented. In the embodiments, some methods, means, instruments, equipment and the like which are well known to those skilled in the art are not described in detail, in order to highlight the main idea of the present application.

[0037] The technical features disclosed in the embodiments of the present application can be combined in any way without conflict, and the technical solutions obtained belong to the disclosure of the embodiments of the present application.

[0038] The present application discloses a rare earth-copper antibacterial material and a preparation method thereof.

[0039] For better understanding of the present application, the following examples are further illustrated in detail, but can not be understood as limiting the present application, and some non-essential improvements and adjustments made by those skilled in the art according to the above content of the application are also regarded as falling within the scope of the present application.

[0040] Example 1

[0041] Take cerium chloride 293g, zinc chloride 26g, zirconium oxychloride 242g, add water 1000ml, heat to 55℃, add 3.7g PEG 6000 and 5ml glacial acetic acid, and add ammonium bicarbonate solution (ammonium bicarbonate solution concentration is 2.53mol / L, the molar ratio of citric acid to ammonium bicarbonate in ammonium bicarbonate solution is 10:1.1) to the system pH value is 6.7-7, filter, wash, dry at 80℃, get the first reactant;

[0042] Take 100g first reactant with 450g water slurry, add 30g concentrated phosphoric acid, then add 0.2g 1-butyl-3-methylimidazole phosphoric acid dibutyl ester salt, react at 60℃ for 1.5h, filter, wash, dry to get the second reactant;

[0043] In the second reactant, add copper acetate solution with a concentration of 12%, react for 4h, filter, wash, dry and calcine at 400℃ for 4h to obtain rare earth-copper antibacterial material.

[0044] The copper adsorption capacity of the prepared rare earth-copper antibacterial material is 4.2g / 100g, the agglomerated particle size is 1500nm, and the specific surface area is 136.72m 2 / g. The antibacterial rate against Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae is greater than 99.97%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa is greater than 99.8%. After irradiation by ultraviolet lamp for 2000h, the antibacterial rate against Staphylococcus aureus reaches 99.99%, the antibacterial rate against Escherichia coli reaches 99.96%, the antibacterial rate against Pseudomonas aeruginosa reaches 99.1%, the antibacterial rate against Klebsiella pneumoniae reaches 98.12%, and the antibacterial rate against Candida albicans reaches 97.56%.

[0045] Example 2

[0046] Take cerium chloride 316g, zinc chloride 26g, zirconium oxychloride 230g, add water 1100ml, heat to 60℃, add 4.0g PEG4000 and 5ml glacial acetic acid, and add ammonium bicarbonate solution (ammonium bicarbonate solution concentration is 2.53mol / L, the molar ratio of citric acid to ammonium bicarbonate in ammonium bicarbonate solution is 10:1.5) to the system pH value is 6.7-7, filter, wash, dry at 80℃, get the first reactant;

[0047] Take 100 g of the first reactant with 550 g of water, add 32 g of concentrated phosphoric acid, then add 0.18 g of 1-butyl-3-methylimidazole phosphoric acid dibutyl ester salt, react at 60°C for 1 h, filter, wash, and dry to obtain the second reactant;

[0048] Add a copper nitrate solution with a concentration of 15% (add 2 g of glacial acetic acid) to the second reactant, react for 4 h, filter, wash, and dry, then calcine at 400°C for 4 h to obtain the rare earth-copper antibacterial material.

[0049] The copper adsorption amount of the prepared rare earth-copper antibacterial material is 4.4 g / 100 g, the agglomerated particle size is 1200 nm, and the specific surface area is 153.54 m 2 / g. The antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae is greater than 99.98%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa is greater than 99.89%. After 2000 h of ultraviolet lamp irradiation, the antibacterial rate against Staphylococcus aureus reaches 99.99%, the antibacterial rate against Escherichia coli reaches 99.97%, the antibacterial rate against Pseudomonas aeruginosa reaches 99.23%, the antibacterial rate against Klebsiella pneumoniae reaches 97.87%, and the antibacterial rate against Candida albicans reaches 98.21%.

[0050] Example 3

[0051] Take 475 g of cerium chloride, 43 g of zinc chloride, and 350 g of zirconium oxychloride, add 1800 ml of water, heat to 60°C, add 6.25 g of PEG4000 and 8 ml of glacial acetic acid, and add an ammonium bicarbonate solution (ammonium bicarbonate solution concentration is 2.53 mol / L, and the molar ratio of citric acid to ammonium bicarbonate in the ammonium bicarbonate solution is 10:1.8) to the system to a pH value of 6.7-7, filter, wash, and dry at 80°C to obtain the first reactant;

[0052] Take 100 g of the first reactant with 750 g of water, add 36.5 ml of concentrated phosphoric acid, then add 0.25 g of 1-butyl-3-methylimidazole phosphoric acid dibutyl ester salt, react at 60°C for 2 h, filter, wash, and dry to obtain the second reactant;

[0053] Add a copper acetate solution with a concentration of 10% to the second reactant, react for 4 h, filter, wash, and dry, then calcine at 400°C for 4 h to obtain the rare earth-copper antibacterial material.

[0054] The copper adsorption amount of the prepared rare earth-copper antibacterial material is 3.7 g / 100 g, the agglomerated particle size is 650 nm, and the specific surface area is 145.67 m 2The antibacterial rate against Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae is greater than 99.96%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa is greater than 99.34%. After irradiation by the ultraviolet lamp for 2000h, the antibacterial rate against Staphylococcus aureus reaches 99.99%, the antibacterial rate against Escherichia coli reaches 99.98%, the antibacterial rate against Pseudomonas aeruginosa reaches 99.45%, the antibacterial rate against Klebsiella pneumoniae reaches 98.53%, and the antibacterial rate against Candida albicans reaches 98.79%.

[0055] Example 4

[0056] Take cerium chloride 475g, zinc chloride 43g, zirconium oxychloride 350g, add water 1800ml, heat to 60℃, add 6.25g PEG4000 and 8ml glacial acetic acid, and add ammonium bicarbonate solution (ammonium bicarbonate solution concentration is 2.53mol / L, the molar ratio of tartaric acid to ammonium bicarbonate in ammonium bicarbonate solution is 10:1.1) to the system pH value is 6.7-7, filter, wash, dry at 80℃, get the first reactant;

[0057] Take 100g of the first reactant and mix it with 750g of water, add 36.5ml of concentrated phosphoric acid, then add 0.25g of 1-butyl-3-methylimidazole phosphoric acid dibutyl ester salt, react at 60℃ for 2h, filter, wash, and dry to get the second reactant;

[0058] Add copper acetate solution with a concentration of 10% to the second reactant, react for 4h, filter, wash, and dry, then calcine at 400℃ for 4h to get the rare earth-copper antibacterial material.

[0059] The copper adsorption capacity of the prepared rare earth-copper antibacterial material is 3.2g / 100g, the agglomerated particle size is 2230nm, and the specific surface area is 113.6m 2 / g. The antibacterial rate against Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae is greater than 99.92%, and the antibacterial rate against Candida albicans and Pseudomonas aeruginosa is greater than 99.13%. After irradiation by the ultraviolet lamp for 2000h, the antibacterial rate against Staphylococcus aureus reaches 99.98%, the antibacterial rate against Escherichia coli reaches 99.98%, the antibacterial rate against Pseudomonas aeruginosa reaches 99.23%, the antibacterial rate against Klebsiella pneumoniae reaches 98.67%, and the antibacterial rate against Candida albicans reaches 97.88%.

[0060] Comparative Example 1

[0061] Compared with Example 1, other conditions remain unchanged, and no citric acid is added when preparing the first reactant. The specific surface area of the finally obtained rare earth-copper antibacterial material is 89.12m 2 / g. and the material dispersion performance is poor, the agglomerated particle size reaches 13 μm, the antibacterial rate against Staphylococcus aureus is 98.12%, the antibacterial rate against Escherichia coli is 97.56%, the antibacterial rate against Klebsiella pneumoniae is 95.36%, the antibacterial rate against Candida albicans is 88.6%, and the antibacterial rate against Pseudomonas aeruginosa is 91.25%.

[0062] Comparative Example 2

[0063] Compared with Example 1, other conditions are unchanged, and no 1-butyl-3-methyl imidazole dibutyl phosphate salt is added when preparing the second reactant, and finally the specific surface area of the rare earth-copper antibacterial material is 75.32 m 2 / g. and the material dispersion performance is poor, the agglomerated particle size reaches 13 μm, the antibacterial rate against Staphylococcus aureus is 98.12%, the antibacterial rate against Escherichia coli is 97.56%, the antibacterial rate against Klebsiella pneumoniae is 95.36%, the antibacterial rate against Candida albicans is 88.6%, and the antibacterial rate against Pseudomonas aeruginosa is 91.25%.

[0064] The above description of disclosed examples enables one skilled in the art to make or use the invention. Numerous modifications to these examples will be apparent to those skilled in the art, and the general principles defined herein can be applied to other examples without departing from the spirit or scope of the invention. Therefore, the present invention 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 preparing a rare earth-copper antibacterial material, characterized in that, The method specifically includes the following steps: rare earth chloride, zinc chloride, and zirconium oxychloride are prepared into a mixed solution, the mixed solution is heated to 40-80℃, and PEG and glacial acetic acid are added; after the addition is complete, ammonium bicarbonate solution is added to the mixed solution, and the reaction is carried out until the pH value of the system is 6.7-7, filtered, dried, and the first reactant is obtained. The first reactant was slurried with deionized water and then concentrated phosphoric acid was added. Subsequently, 1-butyl-3-methylimidazolium dibutyl phosphate was added and reacted for 0.5-2 hours at a temperature of 60°C. The mixture was then filtered, dried, and the second reactant was obtained. Copper nitrate or copper acetate solution is added to the second reactant, and the pH value is adjusted to 1-2 with nitric acid. Glacial acetic acid is added for dispersion and reaction. The mixture is then filtered, washed, dried, and calcined to obtain the rare earth-copper antibacterial material.

2. The preparation method of the rare earth-copper antibacterial material according to claim 1, characterized in that, The molar ratio of rare earth, zinc and zirconium in the mixed solution is (2-8):1:(2-8), and the concentration of rare earth ions in the mixed solution is 0.3-0.9 mol / L.

3. The method for preparing the rare earth-copper antibacterial material according to claim 1 or 2, characterized in that, 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. The amount of glacial acetic acid added is 1%-3% of the total mass of rare earth chloride, zinc chloride, and zirconium oxychloride.

4. The method for preparing the rare earth-copper antibacterial material according to claim 3, characterized in that, The concentration of the ammonium bicarbonate solution is 1.5-2.8 mol / L. 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.

5. The method for preparing the rare earth-copper antibacterial material according to claim 1, characterized in that, 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-methylimidazolium dibutyl phosphate to the first reactant is 0.001-0.01:

1.

6. The method for preparing the rare earth-copper antibacterial material according to claim 1, characterized in that, The concentration of copper nitrate or copper acetate solution is 8-20%, and the volume ratio of glacial acetic acid added to the mass ratio of copper nitrate solute is 0.01-0.02:1; and if copper acetate is used, glacial acetic acid is not required.

7. The method for preparing the rare earth-copper antibacterial material according to claim 1 or 6, characterized in that, The reaction time is 4 hours, the calcination temperature is 400-600℃, the heating rate is 10℃ / min, and the temperature is raised to the required temperature after holding at 150℃ for 30 minutes.

8. A rare earth-copper antibacterial material prepared by the method described in claim 1.

9. The application of a rare earth-copper antibacterial material prepared by the method described in claim 1 in fibers, ceramics, coatings, and plastics.

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