Rare earth-copper antibacterial material, preparation method and application

Abstract

The invention 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 preparation method of the rare earth-copper antibacterial material is good in antibacterial effect and low in cost, the problems that in the prior art, an antibacterial material prepared through a simple physical mixing method is uneven in component and poor in antibacterial performance can be solved, and the problems that when an antibacterial material is synthesized through a common liquid phase method, the reaction temperature is high, and the reaction time is long can be solved. The antibacterial material obtained by the invention has the advantages of higher specific surface area, better binding capacity of copper ions and a matrix and longer antibacterial effect, and is suitable for popularization and application.

Description

Technical Field

[0001] The present invention belongs to the field of rare earth material preparation, and in particular relates to a rare earth-copper antibacterial material, a preparation method and an application thereof. Background Art

[0002] Inorganic ion antimicrobial agents are the most widely used of several types of antimicrobial agents. Inorganic antimicrobial materials have broad-spectrum antimicrobial properties, long-lasting antimicrobial properties, and heat resistance. However, the inorganic ion antimicrobial agents commonly used on the market currently have the following problems: high cost, poor high-temperature resistance, easy discoloration, small specific surface area, easy loss of active ingredients in the antimicrobial agents, short antimicrobial durability, and uneven composition of antimicrobial agents prepared by solid-phase mixing method.

[0003] Rare earth elements also play a crucial role in antimicrobial applications. Rare earth ions interact with bacteria, damaging their cell walls, membranes, and intracellular DNA, proteins, and enzymes, hindering their vital functions and inhibiting their growth and reproduction. The unpaired electrons in the 4f sublayer of rare earth elements interact with the outer electrons of other elements, giving them active coordination properties, enabling the synthesis of rare earth complexes with antimicrobial properties. Rare earth elements doped into antimicrobial materials can produce synergistic antimicrobial effects with other antimicrobial agents, reducing the amount of other agents used and resulting in composite antimicrobial materials with enhanced antimicrobial properties. Copper-based antimicrobial materials, which use copper and its oxides (CuO, Cu2O) as antimicrobial agents, possess antimicrobial properties that are intermediate between those of silver and zinc. Due to their high antimicrobial efficacy and low cost, research on copper-based antimicrobial materials has intensified in recent years.

[0004] CN 117226105A discloses a method for preparing an 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 vessel. The gas in the reaction vessel is then evacuated and replaced with nitrogen or an inert gas. The reaction product is cooled, solid-liquid separated, and the solid matter is collected and subjected to vacuum rotary evaporation to obtain the 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 method for preparing a cubic zirconium phosphate carrier and its silver- or copper-silver dual-ion inorganic antibacterial powder. The method uses zirconium oxychloride, sodium fluoride, a soluble phosphate, and silicon dioxide as raw materials, prepares the zirconium phosphate carrier through a high-pressure hydrothermal reaction, and then loads the zirconium phosphate with copper or silver to produce the antibacterial material. This method has high reaction temperatures, high energy consumption, and requires high-pressure reactions, posing safety risks during the production process.

[0006] CN 115517268 A discloses a silver-zinc-copper-loaded 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. An amphoteric surfactant such as betaine is then added to exfoliate the layered zirconium phosphate to prepare the single-layer zirconium phosphate nanosheet. The zirconium phosphate prepared by this method of directly adding phosphoric acid and hydrofluoric acid to the soluble zirconium salt is difficult to filter and difficult to operate.

[0007] 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, drying and then calcining. 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.

[0008] 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. In addition, the obtained antibacterial powder is cubic and has a small specific surface area, which affects the antibacterial effect.

[0009] 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 reaction temperature reaches a maximum of 180°C, and the reaction pressure reaches a maximum of 1 MPa, resulting in high energy consumption. Furthermore, the resulting antibacterial powder is cubic and has a small specific surface area, which affects its antibacterial effect.

[0010] CN 115849325 A discloses a method for preparing a cubic sodium zirconium phosphate carrier and its silver-zinc-loaded antibacterial powder. While 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, the antibacterial powder produced by this method has a high viscosity and tends to agglomerate during the drying process, requiring pulverization before use. Furthermore, the powder still has a cubic morphology and a small specific surface area, which can affect its antibacterial effectiveness during subsequent use.

[0011] Therefore, how to provide a method for preparing a rare earth-copper antibacterial material with good antibacterial effect and low cost is a technical problem that needs to be solved urgently by those skilled in the art. Summary of the Invention

[0012] In view of this, the present invention discloses a rare earth-copper antibacterial material, a preparation method and an application thereof.

[0013] The present invention provides a method for preparing a rare earth-copper antimicrobial material with excellent antimicrobial efficacy and low cost. This method overcomes the uneven composition and poor antimicrobial performance of antimicrobial materials prepared using simple physical mixing methods in the prior art. It also overcomes the high reaction temperatures and long reaction times associated with conventional liquid-phase methods for synthesizing antimicrobial materials. The antimicrobial material obtained by the present invention exhibits a higher specific surface area, better copper ion-matrix binding, and a more durable antimicrobial effect.

[0014] In order to achieve the above object, the present invention adopts the following technical solutions:

[0015] The first technical purpose of the present invention is to provide a method for preparing a rare earth-copper antibacterial material, the method specifically comprising the following steps:

[0016] A mixed solution is prepared by mixing rare earth chloride (preferably lanthanum cerium), zinc chloride, and zirconium oxychloride, and the mixed solution is heated to 40-80° C., and PEG and glacial acetic acid are added; after the addition is complete, an ammonium bicarbonate solution is added to the mixed solution, and the mixture is reacted until the pH value of the system is 6.7-7, and the mixture is filtered and dried to obtain a first reactant;

[0017] The first reactant is slurried with deionized water, concentrated phosphoric acid is added, and then 1-butyl-3-methylimidazole dibutyl phosphate is added for reaction, filtered, and dried to obtain a second reactant;

[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. Glacial acetic acid is added for dispersion, reaction, filtration, washing, drying and calcination are performed to obtain the rare earth-copper antibacterial material.

[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 0.3-0.9 mol / L, preferably 0.6 mol / L.

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

[0021] Furthermore, the concentration of the ammonium bicarbonate solution is 1.5-2.8 mol / L, preferably 2.53 mol / L, and citric acid or tartaric acid is added to the ammonium bicarbonate solution to form an organic rare earth salt such as citric acid or tartaric acid, thereby reducing the agglomeration of the powder during the calcination process; 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-methylimidazole dibutyl phosphate to the first reactant is 0.001-0.01:1.

[0023] Furthermore, the reaction time is 0.5-2h, and the reaction temperature is 60°C.

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

[0025] Furthermore, the reaction time is 4 hours, the calcination temperature is 400-600°C, the heating rate is 10°C / min, and the temperature is kept at 150°C for 30 minutes and then raised to the required temperature.

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

[0027] The rare earth-copper antibacterial material prepared by the present invention has a copper adsorption capacity of 1.5-8g / 100g, an agglomerated particle size of 500nm-2000nm, and a specific surface area of 25-150m 2 / g, with an antibacterial rate of 99.9% against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae, and over 99% against Candida albicans and Pseudomonas aeruginosa. After 2000 hours of UV light irradiation, the antibacterial rate against Staphylococcus aureus reached 99.9%, the antibacterial rate against Escherichia coli was greater than 99.5%, the antibacterial rate against Pseudomonas aeruginosa was greater than 99%, the antibacterial rate against Klebsiella pneumoniae was greater than 98%, and the antibacterial rate against Candida albicans was greater than 97%.

[0028] The third technical purpose of the present invention is to provide a rare earth-copper antibacterial material prepared by the method as described above for use in the fields of fibers, ceramics, coatings, plastics, etc.

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

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

[0031] 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.

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

[0033] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all 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.

[0034] The term "embodiment" is used herein specifically to describe any embodiment as "exemplary," and should not be construed as superior or preferable to other embodiments. Performance indicators in the embodiments of this application were tested using conventional testing methods in the art, unless otherwise specified. It should be understood that the terms used in this application are intended solely to describe specific implementations and are not intended to limit the disclosure herein.

[0035] Unless otherwise specified, the technical and scientific terms used herein have the same meanings as commonly understood by ordinary technicians in the technical field to which this application belongs; other experimental methods and technical means not specifically specified in this application refer to experimental methods and technical means commonly used by ordinary technicians in this field.

[0036] In order to better illustrate the content of this application, numerous specific details are provided in the specific examples below. It should be understood by those skilled in the art that this application can be implemented without certain specific details. In the examples, some methods, means, instruments, equipment, etc. well known to those skilled in the art are not described in detail in order to highlight the main purpose of this application.

[0037] Under the premise of no conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solutions belong to the contents disclosed in the embodiments of this application.

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

[0039] For a better understanding of the present invention, the present invention is further specifically described below through the following examples, but it should not be understood as limiting the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above invention content are also considered to fall within the scope of protection of the present invention.

[0040] Example 1

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

[0042] 100 g of the first reactant was slurried with 450 g of water, 30 g of concentrated phosphoric acid was added, and then 0.2 g of 1-butyl-3-methylimidazole dibutyl phosphate was added. The mixture was reacted at 60° C. for 1.5 h, filtered, washed, and dried to obtain the second reactant.

[0043] A 12% copper acetate solution was added to the second reactant, reacted for 4 hours, filtered, washed, dried, and then calcined at 400° C. for 4 hours to obtain a 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. Its antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae exceeds 99.97%, and its antibacterial rate against Candida albicans and Pseudomonas aeruginosa exceeds 99.8%. After 2000 hours of UV light irradiation, the antibacterial rate against Staphylococcus aureus reached 99.99%, against Escherichia coli reached 99.96%, against Pseudomonas aeruginosa reached 99.1%, against Klebsiella pneumoniae reached 98.12%, and against Candida albicans reached 97.56%.

[0045] Example 2

[0046] Take 316 g of cerium chloride, 26 g of zinc chloride, and 230 g of zirconium oxychloride, add 1100 ml of water, heat to 60°C, add 4.0 g of PEG4000 and 5 ml 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 10:1.5) until the system pH is 6.7-7, filter, wash, and dry at 80°C to obtain the first reactant;

[0047] 100 g of the first reactant was slurried with 550 g of water, 32 g of concentrated phosphoric acid was added, and then 0.18 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.

[0048] A 15% copper nitrate solution (with 2 g of glacial acetic acid) was added to the second reactant, reacted for 4 h, filtered, washed, dried, and then calcined at 400° C. for 4 h to obtain a rare earth-copper antibacterial material.

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

[0050] Example 3

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

[0052] 100 g of the first reactant was slurried with 750 g of water, 36.5 ml of concentrated phosphoric acid was added, and then 0.25 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.

[0053] A 10% copper acetate solution was added to the second reactant, reacted for 4 hours, filtered, washed, dried, and then calcined at 400° C. for 4 hours to obtain a rare earth-copper antibacterial material.

[0054] The copper adsorption capacity of the prepared rare earth-copper antibacterial material is 3.7g / 100g, the agglomerated particle size is 650nm, and the specific surface area is 145.67m 2 / g. Its antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae exceeds 99.96%, and against Candida albicans and Pseudomonas aeruginosa exceeds 99.34%. After 2000 hours of UV irradiation, the antibacterial rate against Staphylococcus aureus reached 99.99%, against Escherichia coli reached 99.98%, against Pseudomonas aeruginosa reached 99.45%, against Klebsiella pneumoniae reached 98.53%, and against Candida albicans reached 98.79%.

[0055] Example 4

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

[0057] 100 g of the first reactant was slurried with 750 g of water, 36.5 ml of concentrated phosphoric acid was added, and then 0.25 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.

[0058] A 10% copper acetate solution was added to the second reactant, reacted for 4 hours, filtered, washed, dried, and then calcined at 400° C. for 4 hours to obtain a 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. Its antibacterial rate against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumoniae exceeds 99.92%, and its antibacterial rate against Candida albicans and Pseudomonas aeruginosa exceeds 99.13%. After 2000 hours of UV light irradiation, the antibacterial rate against Staphylococcus aureus reached 99.98%, against Escherichia coli reached 99.98%, against Pseudomonas aeruginosa reached 99.23%, against Klebsiella pneumoniae reached 98.67%, and against Candida albicans reached 97.88%.

[0060] Comparative Example 1

[0061] Compared with Example 1, other conditions remain unchanged, citric acid is not added when preparing the first reactant, and the rare earth-copper antibacterial material obtained has a specific surface area of 89.12 m 2 / g. The material has poor dispersion performance, with agglomerated particle size reaching 13μm. The antibacterial rates against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Candida albicans, and Pseudomonas aeruginosa are 98.12%, 97.56%, and 95.36%, respectively.

[0062] Comparative Example 2

[0063] Compared with Example 1, other conditions remain unchanged, and 1-butyl-3-methylimidazole dibutyl phosphate is not added when preparing the second reactant. The specific surface area of the rare earth-copper antibacterial material obtained is 75.32m 2 / g. The material has poor dispersion performance and the particle size reaches 15μm. The antibacterial rate against Staphylococcus aureus is 96.32%, the antibacterial rate against Escherichia coli is 95.41%, the antibacterial rate against Klebsiella pneumoniae is 92.67%, the antibacterial rate against Candida albicans is 89.65%, and the antibacterial rate against Pseudomonas aeruginosa is 92.31%.

[0064] 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-copper antibacterial material, characterized in that: The method specifically comprises 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° C., and PEG and glacial acetic acid are added; after the addition is complete, ammonium bicarbonate solution is added to the mixed solution, reacted until the system pH value is 6.7-7, filtered, and dried to obtain a first reactant; The first reactant is slurried with deionized water, concentrated phosphoric acid is added, and then 1-butyl-3-methylimidazole dibutyl phosphate is added for reaction, filtered, and dried to obtain a second reactant; 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, reaction, filtration, washing, drying and calcination are performed to obtain the rare earth-copper antibacterial material.

2. The method for preparing 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, and 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, and citric acid or tartaric acid is added to the ammonium bicarbonate solution, and the molar ratio of the citric acid or tartaric acid to the 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-methylimidazole 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 or 5, characterized in that: The reaction time is 0.5-2h, and the reaction temperature is 60°C.

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

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

9. A rare earth-copper antibacterial material prepared by the method according to claim 1.

10. Use of the rare earth-copper antibacterial material prepared by the method of claim 1 in fibers, ceramics, coatings, and plastics.

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