Antibacterial and flame-retardant multifunctional cuprous oxide / santimony trioxide nanomaterial and preparation method thereof

Abstract

The present application relates to the technical field of nano new material preparation, in particular to a kind of antibacterial flame-retardant multifunctional cuprous oxide / sb2o3 nano material and its preparation method.The method of the present application is characterized by using electrostatic adsorption principle, copper oxide is loaded to the surface of sb2o3, and copper atom will partially replace antimony atom, and Cu-O-Sb binding bond is formed by electron transfer, to prepare cuprous oxide / sb2o3 nano material.The cuprous oxide / sb2o3 nano material prepared by the method of the present application has high purity, good dispersibility, stable structure and excellent antibacterial performance, and the detection of escherichia coli and staphylococcus aureus antibacterial rate is all >99%, the flame-retardant effect is remarkable, and the combustion limited oxygen index is increased by about 25%, which can be applied to the fields of textiles, plastic products and coatings, and is suitable for large-scale industrial production and popularization.

Description

Technical Field

[0001] This invention relates to the field of nanomaterial preparation technology, specifically to an antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterial and its preparation method. Background Technology

[0002] The rapid proliferation of harmful microorganisms not only affects human health and safety but also accelerates material corrosion, leading to material aging and failure, fires, and personal injury and property damage. For example, in the field of marine infrastructure construction, marine equipment and facilities typically operate in "four-high" environments: high salinity, high temperature, high humidity, and high radiation. These harsh environments easily cause severe corrosion on material surfaces. Simultaneously, the high temperature and humidity also easily lead to the growth and rapid reproduction of bacteria and mold on material surfaces. The rapid growth and reproduction of bacteria and mold not only accelerates material corrosion and failure but also easily leads to equipment aging, short circuits, fires, and economic losses. To address these problems, researchers currently mainly add functional fillers to the matrix material or coat the material surface with functional coatings. However, these functional materials suffer from limited functionality; in practical applications, multiple functional materials need to be used in combination to achieve comprehensive protection. The use of mixed functional materials significantly reduces their individual protective effects, failing to provide long-term effective protection for the matrix material. Therefore, developing a new multifunctional material has significant research value and potential commercial potential.

[0003] Antimony trioxide (ST) is an additive flame retardant characterized by its small particle size, high surface activity, and strong endothermic capacity. During combustion, the nanoparticles cover the surface of the polymeric condensed phase, effectively promoting the formation of a char layer and creating a flame-retardant barrier between the combustion source and the material, thus achieving a flame-retardant effect. Cuprous oxide, as an emerging green antibacterial material, can activate oxygen in water and air under light conditions, generating highly active and strongly oxidizing hydroxyl radicals (·OH) and reactive oxygen ions (O2-). These directly or indirectly damage the structure and function of cell membranes, leading to cell membrane rupture and leakage of contents, ultimately inhibiting and killing bacteria. The preparation of cuprous oxide / antimony trioxide nanocomposites by combining these two functional materials has significant application value due to its combined antibacterial, photocatalytic, and flame-retardant functions. However, no reports or disclosures of such materials or their preparation methods have been found in the existing technology. Summary of the Invention

[0004] Based on the above, this invention provides a halogen-free antibacterial and flame-retardant multifunctional nanomaterial and its preparation method. The material is a cuprous oxide / antimony trioxide nanomaterial, characterized by high purity, good dispersibility, structural stability, and excellent antibacterial properties. Furthermore, the invention provides a preparation method for this material that eliminates the need for surfactants and secondary calcination, making it safe, environmentally friendly, and easily scalable for industrial production. The specific technical solution is as follows:

[0005] A method for preparing antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials includes the following steps:

[0006] (1) Add copper acetate powder to deionized water, heat in a water bath, and then add a certain amount of sodium hydroxide to allow the reaction to proceed fully;

[0007] (2) After the reaction is complete, add ascorbic acid to the solution, stir well, and allow it to react fully. Keep the reaction temperature constant to obtain solution A.

[0008] (3) Add the dry antimony glycolate powder to the anhydrous ethanol solution and disperse it by ultrasonication to obtain solution B;

[0009] (4) Quickly pour solution B into solution A, and adjust the pH of the solution to weakly alkaline using an acidic or alkaline medium, stir well, and obtain solution C;

[0010] (5) Transfer all of solution C to a high-pressure reactor for reaction;

[0011] (6) After the reaction is complete, let it stand to precipitate, pour off the supernatant, wash by centrifugation, dry, grind, and finally obtain antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials.

[0012] Furthermore, in step (1), the water bath heating temperature is 60-80℃; the reaction time is 20-30 min; and the molar ratio of copper acetate to sodium hydroxide is: n 乙酸铜 :n 氢氧化钠 =1:5-10, preferably 1:6-8.

[0013] Furthermore, in step (2), the reaction temperature is 60-80℃; the reaction time is 40-60 min; and the molar ratio of ascorbic acid to copper acetate is: n 抗坏血酸 :n 乙酸铜 =1:2-6, preferably 1:3-4.

[0014] Furthermore, in step (3), the molar ratio of antimony glycolate powder to copper acetate is: n 乙二醇锑 :n 乙酸铜 =1:3-50, preferably 1:5-10; the mass ratio of the added antimony glycolate powder to anhydrous ethanol is: m 乙二醇锑 :m 无水乙醇 =1:4-10, preferably 1:5-7.

[0015] Furthermore, in step (4), the acidic medium is selected from one or more of phosphoric acid, sulfuric acid, hydrochloric acid, and acetic acid; the alkaline medium is selected from one or more of sodium hydroxide, potassium hydroxide, and ammonia water; the weak alkalinity is pH=8-9.

[0016] Furthermore, in step (5), the reaction temperature is 120-140℃ and the reaction time is 10-12h.

[0017] Furthermore, step (6) involves washing 2-5 times; the drying temperature is 70-90℃.

[0018] Furthermore, the stirring method in steps (2) and (4) is one of manual stirring, mechanical stirring or magnetic stirring.

[0019] Furthermore, mechanical stirring can be one of the following: inclined blade paddle stirring, frame stirring, flat blade disc turbine stirring, or propeller stirring.

[0020] The present invention also provides a cuprous oxide / antimony trioxide nanomaterial prepared according to the aforementioned preparation method. The material is cuprous oxide / antimony trioxide nanoparticles with a particle size of 80-120 nm.

[0021] The mechanism by which this invention produces excellent antibacterial effects is mainly due to the synergistic effect of cuprous oxide and antimony trioxide: On the one hand, the cuprous oxide / antimony trioxide nanomaterials prepared by the method of this invention form Cu-O-Sb bonds through electron transfer. Since the band gap of cuprous oxide is 2.14 eV and that of antimony trioxide is 3.00 eV, the conduction band and valence band energy levels of cuprous oxide are both lower than those of antimony trioxide. Electrons in the conduction band of antimony trioxide easily migrate to the conduction band of cuprous oxide, and holes in the valence band of cuprous oxide easily migrate to the valence band of antimony trioxide, thus hindering the recombination of free electrons and holes. The unrecombined electrons and holes react with oxygen and water molecules in the water to generate highly oxidizing free radicals, which interact with bacteria and kill them. On the other hand, Cu and Sb ions released from the cuprous oxide / antimony trioxide nanomaterials can bind to the bacterial membrane and proteins, destroying the bacterial structure and thus killing the bacteria. Furthermore, the mechanism by which the present invention produces excellent flame retardant effect is mainly due to the small particle size of cuprous oxide / antimony trioxide nanomaterials, which are at the nanoscale (80-120 nm). Nanoscale cuprous oxide can catalyze dehydroxylation and decarbonylation, increase the residual carbon rate, reduce the generation of combustible small organic molecules, and at the same time synergize with the flame retardant effect of antimony trioxide, thereby effectively improving the flame retardant performance of the material.

[0022] Based on the above, compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] 1. The cuprous oxide / antimony trioxide nanomaterial of this invention possesses both excellent antibacterial and flame-retardant properties. Testing showed that its antibacterial rate against both *Escherichia coli* and *Staphylococcus aureus* was >99%, and its flame-retardant effect was significant, increasing the limiting oxygen index by ~25%.

[0024] 2. Since antimony trioxide has a negative surface charge and cuprous oxide has a positive surface charge, cuprous oxide was successfully loaded onto the antimony trioxide surface using the principle of electrostatic adsorption. At the same time, copper atoms partially replaced antimony atoms, forming Cu-O-Sb bonds through electron transfer, which improved its stability from the nanostructure perspective.

[0025] 3. In a weakly alkaline environment, the presence of trace amounts of hydroxide ions (OH-) inhibits the disproportionation reaction of copper, hinders the formation of divalent copper and elemental copper, and improves the purity of cuprous oxide / antimony trioxide nanomaterials.

[0026] 4. The product has good dispersibility, uniform size, and a particle size of 80-120nm, and also has a certain photocatalytic effect.

[0027] 5. The method of the present invention is simple in process, requires no surfactants or secondary calcination, the equipment is simple, safe and environmentally friendly, easy to carry out large-scale industrial production, and has broad market prospects. Attached Figure Description

[0028] Figure 1 The image shows the SEM morphology of the antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials prepared in Example 1.

[0029] Figure 2 TEM image and elemental distribution map of the antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials prepared in Example 1.

[0030] Figure 3 The image shows the XRD pattern of the antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials prepared in Example 1.

[0031] Figure 4 The image shows the FTIR analysis of the antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials prepared in Example 1.

[0032] Figure 5 A digital camera image showing the antibacterial effect of the antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials prepared in Example 1. Detailed Implementation

[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example 1

[0034] The cuprous oxide / antimony trioxide nanoparticles in this embodiment were prepared according to the following steps:

[0035] 1) Add 0.003 mol copper acetate powder to 50 ml of deionized water, heat in an 80°C water bath, then add 0.024 mol sodium hydroxide and react for 30 min.

[0036] 2) After the reaction is complete, add 0.001 mol of ascorbic acid to the solution, stir well, and let it react for 60 min. Keep the reaction temperature constant at 80℃ to obtain solution A.

[0037] 3) Add 0.015 mol of dry antimony glycolate powder to 50 ml of anhydrous ethanol solution and sonicate for 20 min to obtain solution B;

[0038] 4) Quickly pour solution B into solution A, and adjust the pH of the solution to 8 using hydrochloric acid medium. Stir well for 20 minutes to obtain solution C.

[0039] 5) Transfer all of solution C to a high-pressure reactor and react at 120°C for 12 hours;

[0040] 6) After the reaction is complete, let it stand for 2 hours to precipitate, discard the supernatant, wash it 3 times with deionized water, centrifuge, dry it at 90℃, grind it, and finally obtain antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials.

[0041] For the nanomaterials prepared by the above method, the surface morphology, elemental distribution, phase composition, and antibacterial properties of the antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials prepared in this embodiment were detected by SEM, TEM, XRD, FTIS, and agar plate counting (see details). Figures 1-5 ).

[0042] from Figure 1 The results show that the prepared antibacterial and flame-retardant nanomaterials exhibit a polygonal shape, good dispersibility, and a particle size of 80-120 nm. According to... Figure 2 It can be seen that the elements (Cu, Sb, and O) in the prepared nanomaterials are uniformly distributed on the sample surface, indicating that the prepared nanomaterials have good consistency. From Figure 3 and Figure 4 The results show that the prepared nanomaterials are composed of cuprous oxide and antimony trioxide, with no other impurities, indicating high product purity. Figure 5 The results show that the prepared nanomaterials have excellent antibacterial effects, with antibacterial rates of >99.9% against both Escherichia coli and Staphylococcus aureus. Example 2

[0043] The cuprous oxide / antimony trioxide nanoparticles in this embodiment were prepared according to the following steps:

[0044] 1) Add 0.003 mol copper acetate powder to 50 ml of deionized water, heat in a 70°C water bath, then add 0.024 mol sodium hydroxide and react for 30 min.

[0045] 2) After the reaction is complete, add 0.001 mol of ascorbic acid to the solution, stir well, and let it react for 60 min. Keep the reaction temperature constant at 70℃ to obtain solution A.

[0046] 3) Add 0.015 mol of dry antimony glycolate powder to 50 ml of anhydrous ethanol solution and sonicate for 20 min to obtain solution B;

[0047] 4) Quickly pour solution B into solution A, and adjust the pH of the solution to 9 using hydrochloric acid medium. Stir well for 10 minutes to obtain solution C.

[0048] 5) Transfer all of solution C to a high-pressure reactor and react at 130°C for 11 h;

[0049] 6) After the reaction is complete, let it stand for 2 hours to precipitate, discard the supernatant, wash it 3 times with deionized water, centrifuge, dry it at 90℃, grind it, and finally obtain antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials. Example 3

[0050] The cuprous oxide / antimony trioxide nanoparticles in this embodiment were prepared according to the following steps:

[0051] 1) Add 0.003 mol copper acetate powder to 50 ml of deionized water, heat in a 60°C water bath, then add 0.024 mol sodium hydroxide and react for 30 min.

[0052] 2) After the reaction is complete, add 0.001 mol of ascorbic acid to the solution, stir well, and let it react for 60 min. Keep the reaction temperature constant at 60℃ to obtain solution A.

[0053] 3) Add 0.015 mol of dry antimony glycolate powder to 50 ml of anhydrous ethanol solution and sonicate for 10 min to obtain solution B;

[0054] 4) Quickly pour solution B into solution A, and adjust the pH of the solution to 8 using hydrochloric acid medium. Stir well for 20 minutes to obtain solution C.

[0055] 5) Transfer all of solution C to a high-pressure reactor and react at 140°C for 10 h;

[0056] 6) After the reaction is complete, let it stand for 2 hours to precipitate, discard the supernatant, wash it 5 times with deionized water, centrifuge, dry it at 90℃, grind it, and finally obtain antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials. Comparative Example 1

[0057] The difference between Comparative Example 1 and Example 1 is that the antibacterial and flame-retardant multifunctional nanomaterial described in Comparative Example 1 does not contain cuprous oxide, but all other aspects are the same. Comparative Example 2

[0058] The difference between Comparative Example 2 and Example 1 is that the antibacterial and flame-retardant multifunctional nanomaterial described in Comparative Example 2 does not contain antimony trioxide, but all other aspects are the same. Comparative Example 3

[0059] The difference between Comparative Example 3 and Example 1 is that the antibacterial and flame-retardant multifunctional nanomaterial described in Comparative Example 3 is prepared by simply physically mixing two substances, cuprous oxide particles and antimony trioxide particles; all other aspects are the same.

[0060] To further demonstrate the effectiveness of the present invention, the following test methods are provided.

[0061] 1. The antibacterial properties of the antibacterial and flame-retardant multifunctional nanomaterials were tested according to Appendix A of the national standard GB / T 21510-2008. The test results are shown in Table 1.

[0062] Table 1. Antibacterial test results of antibacterial and flame-retardant multifunctional nanomaterials

[0063] E. coli Staphylococcus aureus Example 1 ＞99.9% ＞99.9% Example 2 ＞99.9% ＞99.9% Example 3 ＞99.9% ＞99.9% Comparative Example 1 27.4% 20.58% Comparative Example 2 ＞99% ＞99% Comparative Example 3 36.2% 28.5%

[0064] 2. The flame retardant properties of the antibacterial and flame retardant multifunctional nanomaterials were tested according to the national standard GB / T 5454-1997. The test results are shown in Table 2.

[0065] Table 2. Flame retardant test results of antibacterial and flame retardant multifunctional nanomaterials

[0066] Limiting Oxygen Index (LOI) / % textile 18.0 Example 1 22.7 Example 2 22.5 Example 3 22.6 Comparative Example 1 22.0 Comparative Example 2 19.2 Comparative Example 3 18.9

[0067] As shown in Tables 1 and 2, the antibacterial and flame-retardant tests of the nanoparticles prepared by the method of this invention exhibit higher antibacterial and flame-retardant effects than single-component nanoparticles and also higher than nanoparticles with simple mixed components. This invention's method achieves synergistic reinforcement between the two materials, enhancing their antibacterial and flame-retardant effects. The antibacterial rate against *Escherichia coli* and *Staphylococcus aureus* is >99%, and the limiting oxygen index for combustion is ~25% higher than that of textiles. This indicates that the antibacterial and flame-retardant multifunctional nanomaterials prepared by this invention can effectively endow materials with antibacterial and flame-retardant functions, and can be applied in textiles, plastic products, coatings, and other fields, possessing significant economic and social value.

[0068] The preferred embodiments of this patent have been described in detail above. However, this patent is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of this patent.

Claims

1. A method for preparing an antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterial, characterized in that: Includes the following steps: (1) Add copper acetate powder to deionized water, heat in a water bath at 60-80℃, then add a certain amount of sodium hydroxide and react fully for 20-30 minutes; (2) After the reaction is complete, add ascorbic acid to the solution, stir evenly, and allow it to react fully. Keep the reaction temperature constant at 60-80℃ and the reaction time at 40-60 min to obtain solution A. (3) Add the dry antimony glycolate powder to the anhydrous ethanol solution and disperse it by ultrasonication to obtain solution B; (4) Quickly pour solution B into solution A, and adjust the pH of the solution to 8-9 using an acidic or alkaline medium, stir well to obtain solution C; (5) Transfer all of solution C to a high-pressure reactor and react at 120-140℃ for 10-12 hours; (6) After the reaction is complete, let it stand to precipitate, pour off the supernatant, wash by centrifugation, dry, grind, and finally obtain antibacterial and flame-retardant multifunctional cuprous oxide / antimony trioxide nanomaterials.

2. The preparation method according to claim 1, characterized in that: In step (1), the molar ratio of copper acetate to sodium hydroxide is: n 乙酸铜 :n 氢氧化钠 =1:5-10.

3. The preparation method according to claim 2, characterized in that: In step (1), the molar ratio of copper acetate to sodium hydroxide is: n 乙酸铜 :n 氢氧化钠 =1:6-8.

4. The preparation method according to claim 1, characterized in that: In step (2), the molar ratio of ascorbic acid to copper acetate is: n 抗坏血酸 :n 乙酸铜 =1:2-6.

5. The preparation method according to claim 4, characterized in that: In step (2), the molar ratio of ascorbic acid to copper acetate is: n 抗坏血酸 :n 乙酸铜 =1:3-4.

6. The preparation method according to claim 1, characterized in that: The mass ratio of antimony glycolate powder to anhydrous ethanol added in step (3) is: m 乙二醇锑 :m 无水乙醇 =1:4-10.

7. The preparation method according to claim 6, characterized in that: The mass ratio of antimony glycolate powder to anhydrous ethanol added in step (3) is: m 乙二醇锑 :m 无水乙醇 =1:5-7.

8. The preparation method according to claim 1, characterized in that: In step (4), the acidic medium is selected from one or more of phosphoric acid, sulfuric acid, and hydrochloric acid; the alkaline medium is selected from one or more of sodium hydroxide and potassium hydroxide.

9. The preparation method according to claim 1, characterized in that: Step (6) involves washing 2-5 times; the drying temperature is 70-90℃.

10. The preparation method according to claim 1, characterized in that: The stirring method in steps (2) and (4) is manual stirring or mechanical stirring.

11. The preparation method according to claim 10, characterized in that: Mechanical mixing is one of the following: inclined blade paddle mixing, frame mixing, flat blade disc turbine mixing, or propeller mixing.

12. The preparation method according to claim 1, characterized in that: The stirring method in steps (2) and (4) is magnetic stirring.

13. The cuprous oxide / antimony trioxide nanomaterial prepared by any one of the preparation methods according to claims 1-12, characterized in that: The material consists of cuprous oxide / antimony trioxide nanoparticles with a particle size of 80-120 nm.

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