Layered zirconium phosphate metal complex antimicrobial material and method of making

Abstract

The present application relates to a layered zirconium phosphate supported metal complex antibacterial agent material and a preparation method thereof, wherein the layered zirconium phosphate supported metal complex antibacterial agent material comprises a layered zirconium phosphate carrier, an inorganic salt containing antibacterial metal ions and a nitrogen-containing organic ligand. The present application prepares an antibacterial agent material with excellent stability, antibacterial property and dispersibility by loading the metal complex generated by the reaction of the inorganic salt containing antibacterial metal ions and the nitrogen-containing organic ligand on the layered zirconium phosphate carrier. The present application introduces the nitrogen-containing organic ligand to complex with the antibacterial metal ions to form a metal coordination polymer, which is different from the general form of the antibacterial metal ions. The combination mode of the complex state reduces the probability of metal ion precipitation, further avoids the occurrence of yellowing phenomenon, improves the dispersibility of the antibacterial metal ions, reduces the metal aggregation phenomenon, increases the contact area and probability of the metal with the bacteria, and thus improves the antibacterial efficiency.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of antibacterial materials, and particularly relates to a layered zirconium phosphate metal complex antibacterial agent material and a preparation method thereof. BACKGROUND

[0002] Inorganic antibacterial agents refer to antibacterial agents prepared by mainly utilizing the antibacterial properties of silver, copper, zinc and other metals, metal ions or metal oxides, and can be generally divided into two categories of photocatalytic type and dissolution type. The dissolution type antibacterial agent is usually prepared by fixing metals or metal ions on inorganic carriers in a physical adsorption or ion exchange manner, and common inorganic carriers include zeolite, silica gel, activated carbon and phosphate, etc. The inorganic antibacterial agent has the advantages of broad-spectrum antibacterial, good antibacterial durability, high safety and good stability, and is therefore widely applied in the fields of ceramics, glass, plastics, fibers and the like.

[0003] Zirconium phosphate is a functional material with strong catalytic, adsorptive and ion exchange properties, and has high loading capacity and low cytotoxicity, and can therefore be added to various resins to play an antibacterial role. The layered zirconium phosphate has attracted wide attention due to the chemical reactivity of the layered material, and can load and stabilize a large amount of metals with antibacterial activity in the form of cations and metal nanoparticles on the sites on the surface of the layered zirconium phosphate, and therefore exhibits better antibacterial effect.

[0004] However, the antibacterial agents prepared by using zirconium phosphate as an antibacterial metal ion carrier in the prior art still have certain limitations, such as deep color of copper-based antibacterial agents, easy oxidation and discoloration of silver-based antibacterial agents, relatively poor antibacterial effect of zinc and other metals, poor dispersibility and easy agglomeration of antibacterial metal ions, etc. Some patents have disclosed certain preparation methods of zirconium phosphate metal ion antibacterial agents, as follows:

[0005] Chinese patent CN102763678A discloses a preparation method of a cubic zirconium phosphate silver antibacterial powder, which adopts zirconium oxychloride, sodium dihydrogen phosphate and sodium oxalate to first react to prepare cubic zirconium phosphate, and then exchanges silver ions by a zinc ion transition method to prepare an antibacterial agent with excellent antibacterial property and safety, which has a broad application prospect in the fields of textiles, household appliances, ceramics and foamed shoe materials. However, the product prepared by the method has the problem that when the addition amount is relatively large, silver ions are easy to precipitate, and the product is prone to yellowing on some plastic substrates, thereby reducing the antibacterial efficiency.

[0006] Chinese patent CN110934153A discloses a kind of zirconium phosphate carrier, zirconium phosphate carrier copper antibacterial agent, zirconium phosphate antibacterial agent and its preparation method and application, after the aqueous solution containing alkali metal ion and phosphate is dropped into the acidic solution containing zirconium oxychloride and buffer pair, the pH value of mixed liquor is adjusted, then fully mixed with template agent, a smaller side length zirconium phosphate carrier is prepared, therefore, the zirconium phosphate antibacterial agent obtained after loading antibacterial ions has larger specific surface area and higher surface activity. But the product prepared by the method is yellow more obvious due to smaller particles, and the zirconium phosphate carrier copper antibacterial agent has color, cannot be used in light color products.

[0007] Chinese patent CN105332078A discloses a kind of antibacterial polyester fiber based on silver-loaded zirconium phosphate and its preparation method, by first reacting zirconium phosphate powder, polythiol compound and silver nitrate to obtain silver-loaded zirconium phosphate nano powder, then combining terephthalic acid, dihydric alcohol and antimony catalyst with polyester reaction kettle to prepare silver-loaded zirconium phosphate antibacterial polyester in situ. The method forms zirconium phosphate particles with high silver content, but the antibacterial effect on Candida albicans is poor.

[0008] Therefore, the prior art still needs to be further improved and promoted. SUMMARY

[0009] The technical problem to be solved by the present application is to provide a layered zirconium phosphate metal complex antibacterial agent material and its preparation method, which solves the problems of poor dispersibility and easy precipitation of antibacterial metal ions, and effectively improves the antibacterial rate.

[0010] To solve the above technical problems, the technical scheme adopted by the present application is:

[0011] In a first aspect, the present application provides a layered zirconium phosphate metal complex antibacterial agent material, which comprises a layered zirconium phosphate carrier, an inorganic salt containing antibacterial metal ions and a nitrogen-containing organic ligand.

[0012] The layered zirconium phosphate metal complex antibacterial agent material proposed by the present application loads the metal complex generated by the reaction of the inorganic salt containing antibacterial metal ions and the nitrogen-containing organic ligand on the layered zirconium phosphate carrier, and prepares an antibacterial agent material with excellent stability, antibacterial property and dispersibility. The present application introduces the nitrogen-containing organic ligand to complex with the antibacterial metal ions to form a metal coordination polymer, which is different from the general form of antibacterial metal ions. The complexation mode not only reduces the precipitation probability of metal ions and further avoids the occurrence of yellowing phenomenon, but also improves the dispersibility of antibacterial metal ions, reduces the metal aggregation phenomenon, increases the contact area and probability with bacteria, and thus improves the antibacterial efficiency.

[0013] Preferably, the inorganic salt containing antibacterial metal ions is zinc salt.

[0014] Preferably, the inorganic salt containing antibacterial metal ions is silver salt.

[0015] Preferably, the layered zirconium phosphate carrier is used in an amount of 50-70 g;

[0016] The nitrogen-containing organic ligand is used in an amount of 1.7 x 10 -6 -5.0 x 10 -5 bbl, with a nitrogen content of 65-70%;

[0017] The nitrogen-containing organic ligand is at least one of azide ion, isothiocyanate ion, acetonitrile, pyridine, ammonia, melamine, ethylenediamine, triethylamine, 2,2'-bipyridine and 1,10-phenanthroline.

[0018] Preferably, the zinc salt is used in an amount of 6-7 g, with a zinc content of 66-68%;

[0019] The zinc salt is at least one of zinc oxide, nano-zinc oxide, zinc chloride, zinc sulfide, zinc selenide, zinc telluride, zinc sulfate, zinc cyanide, zinc nitrate and zinc acetate.

[0020] Preferably, the silver salt is used in an amount of 1.2-1.8 g, with a silver content of 65-70%;

[0021] The silver salt is at least one of silver halide, silver nitrate, silver sulfate and silver acetate.

[0022] Preferably, the antibacterial material has a space group of Cc, with cell parameters of a= 10. 0±0. 5A, b= 10. 0±0. 5A, c= 20. 0±0. 5A, α= 90±0. 5°, β= 125. 7±0. 5°, γ= 90±0. 5°. α= 90±0. 5°, β= 90±0. 5°, γ= 120±0. 5°; it has main diffraction peaks at diffraction angles 2θ of 14. 0, 19. 5, 23. 3, 28. 1, 33. 6, 34. 9, 39. 5, 41. 0, 42. 7, 44. 7, 45. 7, 46. 3, 47. 7, 51. 0 degrees, with a 2θ error range of ±0. 25°.

[0023] Preferably, the antibacterial material has a space group of R-3c, with cell parameters of a= 10. 0±0. 5A, b= 10. 0±0. 5A, c= 20. 0±0. 5A, α= 90±0. 5°, β= 90±0. 5°, γ= 120±0. 5°. α= 90±0. 5°, β= 90±0. 5°, γ= 120±0. 5°; it has main diffraction peaks at diffraction angles 2θ of 14. 0, 19. 5, 23. 3, 28. 1, 33. 6, 34. 9, 39. 5, 41. 0, 42. 7, 44. 7, 45. 7, 46. 3, 47. 7, 51. 0 degrees, with a 2θ error range of ±0. 25°.

[0024] In a second aspect, the present application provides a preparation method of layered zirconium phosphate carrier metal complex antibacterial agent material, comprising the following steps:

[0025] S1. Add an inorganic salt containing antibacterial metal ions and a nitrogen-containing organic ligand to water to obtain a mixed solution;

[0026] S2. Add the layered zirconium phosphate support to water and stir. After mixing with the above mixture, heat in a constant temperature water bath to 100-150 degrees Fahrenheit and stir at 500-1000 rpm for 3-5 hours. Then filter the solution obtained from the reaction, dry it at 100 degrees Celsius, and finally calcine it at 1000-1050 Kelvin for 4 hours. Grind it into powder.

[0027] Preferably, when the inorganic salt containing antibacterial metal ions is a zinc salt, step S1 specifically involves: adding the zinc salt and a nitrogen-containing organic ligand to water to obtain an initial mixture, placing it in a three-necked flask, heating it in an oil bath to 200-250 degrees Fahrenheit, refluxing it for 1000-1500 minutes, and then filtering it to obtain the filtered mixture.

[0028] The technical effects of the preparation method of the layered zirconium phosphate metal complex antibacterial agent material provided in the second aspect are the same as those described in the first aspect. Attached Figure Description

[0029] Figure 1 The image shows the X-ray powder diffraction pattern of the layered zirconium phosphate zinc-supported complex antibacterial agent material obtained in Example 1.

[0030] Figure 2 The image shows the X-ray powder diffraction pattern of the layered zirconium phosphate silver-loaded antibacterial agent material obtained in Example 2. Detailed Implementation

[0031] To better understand the above technical solutions, exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the present invention can be understood more clearly and thoroughly, and that the scope of the present invention can be fully conveyed to those skilled in the art.

[0032] This invention provides a layered zirconium phosphate-supported metal complex antibacterial agent material, comprising a layered zirconium phosphate carrier, an inorganic salt containing antibacterial metal ions, and a nitrogen-containing organic ligand.

[0033] In a preferred embodiment of the present invention, the inorganic salt containing antibacterial metal ions is a zinc salt.

[0034] In a preferred embodiment of the present invention, the inorganic salt containing antibacterial metal ions is a silver salt.

[0035] In a preferred embodiment of the present invention, the amount of the layered zirconium phosphate support is 50-70g;

[0036] The amount of the nitrogen-containing organic ligand used is 1.7 × 10⁻⁶. -6 -5.0×10 -5 bbl, its nitrogen content is 65-70%;

[0037] The nitrogen-containing organic ligand is at least one selected from azide ion, isothiocyanate ion, acetonitrile, pyridine, ammonia, melamine, ethylenediamine, triethylamine, 2,2'-bipyridine, and 1,10-o-phenanthroline.

[0038] More preferably, when the inorganic salt containing antibacterial metal ions is a zinc salt, the amount of the nitrogen-containing organic ligand is 4.0 × 10⁻⁶. -5 -5.0×10 -5 bbl; When the inorganic salt containing antibacterial metal ions is a silver salt, the amount of the nitrogen-containing organic ligand is 1.7 × 10⁻⁶. -6 -1.9×10 -6 bbl.

[0039] In a preferred embodiment of the present invention, the amount of zinc salt used is 6-7g, and its zinc content is 66-68%;

[0040] The zinc salt is at least one of zinc oxide, nano zinc oxide, zinc chloride, zinc sulfide, zinc selenide, zinc telluride, zinc sulfate, zinc cyanide, zinc nitrate, and zinc acetate.

[0041] In a preferred embodiment of the present invention, the amount of silver salt used is 1.2-1.8g, and its silver content is 65-70%;

[0042] The silver salt is at least one of silver halide, silver nitrate, silver sulfate, and silver acetate.

[0043] In a preferred embodiment of the present invention, the space group of the antibacterial material is Cc, and the unit cell parameters are: α = 90 ± 0.5°, β = 125.7 ± 0.5°, γ = 90 ± 0.5°; it has main diffraction peaks at diffraction angles 2θ of 18.6, 20.1, 21.6, 23.8, 24.1, 26.5, 29.3, 30.6, 35.0, 36.1, 48.0, and 49.4 degrees, with an error range of ±0.25° for 2θ.

[0044] In a preferred embodiment of the present invention, the space group of the antibacterial material is R-3c, and the cell parameters are: α = 90 ± 0.5°, β = 90 ± 0.5°, γ = 120 ± 0.5°; it has major diffraction peaks at diffraction angles 2θ of 14.0, 19.5, 23.3, 28.1, 33.6, 34.9, 39.5, 41.0, 42.7, 44.7, 45.7, 46.3, 47.7, and 51.0 degrees, with an error range of ±0.25° for 2θ.

[0045] It is prepared by the following method:

[0046] S1. Add an inorganic salt containing antibacterial metal ions and a nitrogen-containing organic ligand to water to obtain a mixed solution;

[0047] S2. Add the layered zirconium phosphate support to water and stir. After mixing with the above mixture, heat in a constant temperature water bath to 100-150 degrees Fahrenheit and stir at 500-1000 rpm for 3-5 hours. Then filter the solution obtained from the reaction, dry it at 100 degrees Celsius, and finally calcine it at 1000-1050 Kelvin for 4 hours. Grind it into powder.

[0048] In a preferred embodiment of the present invention, when the inorganic salt containing antibacterial metal ions is a zinc salt, step S1 specifically involves: adding zinc salt and nitrogen-containing organic ligand to water to obtain an initial mixture, placing it in a three-necked flask, heating it in a stirring oil bath to 200-250 degrees Fahrenheit, refluxing it for 1000-1500 minutes, and then filtering it to obtain the filtered mixture.

[0049] Example 1

[0050] A layered zirconium phosphate-supported metal complex antibacterial agent material includes a layered zirconium phosphate carrier, an inorganic salt containing antibacterial metal ions, and a nitrogen-containing organic ligand.

[0051] The inorganic salt containing antibacterial metal ions is a zinc salt.

[0052] The amount of the layered zirconium phosphate carrier used is 50g;

[0053] The amount of the nitrogen-containing organic ligand used is 4.03 × 10⁻⁶. -5 bbl has a nitrogen content of 66.67%;

[0054] The nitrogen-containing organic ligand is at least one selected from azide ion, isothiocyanate ion, acetonitrile, pyridine, ammonia, melamine, ethylenediamine, triethylamine, 2,2'-bipyridine, and 1,10-o-phenanthroline.

[0055] The amount of zinc salt used is 6.85g, and its zinc content is 67.14%.

[0056] The zinc salt is at least one of zinc oxide, nano zinc oxide, zinc chloride, zinc sulfide, zinc selenide, zinc telluride, zinc sulfate, zinc cyanide, zinc nitrate, and zinc acetate.

[0057] The space group of the antibacterial material is Cc, and its unit cell parameters are: α = 90 ± 0.5°, β = 125.7 ± 0.5°, γ = 90 ± 0.5°; it has main diffraction peaks at diffraction angles 2θ of 18.6, 20.1, 21.6, 23.8, 24.1, 26.5, 29.3, 30.6, 35.0, 36.1, 48.0, and 49.4 degrees, with an error range of ±0.25° for 2θ.

[0058] It is prepared by the following method:

[0059] S1. Add 6.85g of zinc salt with a zinc content of 67.14% and 4.03×10 to 0.3L of water. -5 Nitrogen-containing organic ligands with a nitrogen content of 66.67% were used to obtain an initial mixture, which was placed in a three-necked flask, heated to 212 degrees Fahrenheit by stirring in an oil bath, refluxed for 1440 min, and then filtered to obtain the filtered mixture.

[0060] S2. Add 50g of layered zirconium phosphate carrier to 0.3L of water and stir. After mixing with the above mixture, heat to 104°F in a constant temperature water bath and stir at 900rpm for 4h. Then filter the solution obtained from the reaction, dry at 100°C, and finally calcine at 1023.15K°C for 4h. Grind into powder to obtain the layered zirconium phosphate zinc-supported complex antibacterial agent material.

[0061] After X-ray diffraction testing (such as...) Figure 1 As shown in the figure, the structural information of the obtained layered zirconium phosphate zinc-supported complex antibacterial material is as follows: space group is Cc, and cell parameters are... α = 90 ± 0.5°, β = 125.7 ± 0.5°, γ = 90 ± 0.5°; it has major diffraction peaks at diffraction angles 2θ of 18.6, 20.1, 21.6, 23.8, 24.1, 26.5, 29.3, 30.6, 35.0, 36.1, 48.0, and 49.4 degrees, with an error range of ±0.25°, corresponding to crystal planes (0,2,0), (1,1,1), (-3,1,1), (-3,1,2), (0,0,2), (-4,0,2), (1,3,0), (0,2,2), (-1,3,2), (2,0,2), (-7,1,2), and (-3,3,4); its main constituent chemical formula is ZrP₂O₇ (72.3 wt%), Zn 0.5Zr2(PO4)3(14.6wt%), ZnZr3P8O 28.5 (13.1 wt%). This result indicates that the layered zirconium phosphate zinc-loaded antibacterial material has high dispersibility, with most zinc ions located on the surface of the layered zirconium phosphate, thus increasing its antibacterial activity.

[0062] Example 2

[0063] A layered zirconium phosphate-supported metal complex antibacterial agent material includes a layered zirconium phosphate carrier, an inorganic salt containing antibacterial metal ions, and a nitrogen-containing organic ligand.

[0064] The inorganic salt containing antibacterial metal ions is a silver salt.

[0065] The amount of the layered zirconium phosphate carrier used is 50g;

[0066] The amount of the nitrogen-containing organic ligand used is 1.7 × 10⁻⁶. -6 bbl has a nitrogen content of 66.67%;

[0067] The nitrogen-containing organic ligand is at least one selected from azide ion, isothiocyanate ion, acetonitrile, pyridine, ammonia, melamine, ethylenediamine, triethylamine, 2,2'-bipyridine, and 1,10-o-phenanthroline.

[0068] The amount of silver salt used is 1.57g, and its silver content is 65.5%;

[0069] The silver salt is at least one of silver halide, silver nitrate, silver sulfate, and silver acetate.

[0070] The antibacterial material has space group R-3c and cell parameters: α = 90 ± 0.5°, β = 90 ± 0.5°, γ = 120 ± 0.5°; it has major diffraction peaks at diffraction angles 2θ of 14.0, 19.5, 23.3, 28.1, 33.6, 34.9, 39.5, 41.0, 42.7, 44.7, 45.7, 46.3, 47.7, and 51.0 degrees, with an error range of ±0.25° for 2θ.

[0071] It is prepared by the following method:

[0072] S1. Add 1.57g of silver salt with a silver content of 65.5% and 1.7×10 to 0.05L of water. -6 A nitrogen-containing organic ligand with a nitrogen content of 66.67% was used to obtain a mixed solution;

[0073] S2. Add 50g of layered zirconium phosphate carrier to 0.3L of water and stir. After mixing with the above mixture, heat to 104°F in a constant temperature water bath and stir at 900rpm for 4h. Then filter the solution obtained from the reaction, dry at 100°C, and finally calcine at 1023.15K°C for 4h. Grind into powder to obtain the layered zirconium phosphate silver complex antibacterial agent material.

[0074] After X-ray diffraction testing (such as...) Figure 2 As shown in the figure, the structural information of the obtained layered zirconium phosphate silver-supported antibacterial material is as follows: it belongs to the hexagonal crystal system, space group R-3c, and cell parameters are as follows. α = 90 ± 0.5°, β = 90 ± 0.5°, γ = 120 ± 0.5°; it has major diffraction peaks at diffraction angles 2θ of 14.0, 19.5, 23.3, 28.1, 33.6, 34.9, 39.5, 41.0, 42.7, 44.7, 45.7, 46.3, 47.7, and 51.0 degrees, with an error range of ±0.25°, corresponding to ( The crystal planes are 0,1,2), (1,0,4), (1,1,3), (0,2,4), (0,1,8), (2,1,4), (2,0,8), (2,2,0), (2,2,3), (1,2,8), (1,3,4), (0,2,10), (2,2,6), and (2,1,10). The main chemical formula of this material is AgZr2(PO4)3. This result indicates that in the layered zirconium phosphate silver complex antibacterial material, most silver ions exist in the layered structure, forming zirconium silver phosphate, and only the surface protrusions possess high antibacterial activity.

[0075] Comparative Example 1

[0076] The main difference between this comparative example and Example 1 is that no nitrogen-containing organic ligands are added.

[0077] Comparative Example 2

[0078] The main difference between this comparative example and Example 2 is that no nitrogen-containing organic ligands are added.

[0079] The antibacterial agent materials obtained in Examples 1-2 and Comparative Examples 1-2 with different weight percentage additions were subjected to plate tests to determine their antibacterial rate and UV color difference value. Specifically, the layered zirconium phosphate zinc-loaded complex antibacterial agent material obtained in Example 1 was designated as Sample 1…Sample 5, and the layered zirconium phosphate silver-loaded complex antibacterial agent material obtained in Example 2 was designated as Sample 6…Sample 10. The test results are recorded in Table 1. The traditional layered zirconium phosphate zinc-loaded antibacterial agent material obtained in Comparative Example 1 was designated as Comparative Sample 1…Comparative Sample 5, and the traditional layered zirconium phosphate silver-loaded antibacterial agent material obtained in Comparative Example 2 was designated as Comparative Sample 6…Comparative Sample 10. The test results are recorded in Table 2.

[0080] Test method: Antibacterial agent powder of different weight percentages was added to PP (9025) for extrusion granulation. The temperature was set at 180-190℃, the screw speed was 10r / min, the pelletizer speed was 10r / min, and the main machine speed was 260r / min. After granulation, a plate test was conducted with a thickness of 3.2mm. The injection molding machine temperature was set at 190-200℃ and the pressure was 30-50MPa.

[0081] Table 1. Test results of antibacterial rate and color difference value of the antibacterial agent materials obtained in Examples 1 and 2.

[0082]

[0083] Table 2 shows the test results of antibacterial rate and color difference value of the antibacterial agent materials obtained in Comparative Examples 1 and 2.

[0084]

[0085]

[0086] The data above shows that, compared to the test results of the traditional layered zirconium phosphate antibacterial agent without nitrogen-containing organic ligands, the color difference values ​​of the samples obtained in Examples 1 and 2 were not significantly improved, but the antibacterial efficiency was significantly improved. For example, in the layered zirconium phosphate zinc-loaded complex antibacterial agent materials of samples 1-5, the antibacterial rate against Staphylococcus aureus can reach more than 95% when the addition amount is 0.5% (i.e., sample 3). In contrast, to achieve the same effect in the control sample, the addition amount of both traditional layered zirconium phosphate zinc-loaded and silver antibacterial agents needs to be higher than 0.5%. This also confirms that the introduction of nitrogen-containing ligands plays an important role in improving the dispersibility and antibacterial properties of metal ions.

[0087] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A layered zirconium phosphate-supported metal complex antibacterial agent material, comprising a layered zirconium phosphate carrier, an inorganic salt containing antibacterial metal ions, and a nitrogen-containing organic ligand; The nitrogen-containing organic ligand is at least one selected from the following: azide ion, isothiocyanate ion, acetonitrile, pyridine, ammonia, melamine, ethylenediamine, triethylamine, 2,2'-bipyridine, and 1,10-o-phenanthroline. The amount of the layered zirconium phosphate support used is 50-70g; The amount of the nitrogen-containing organic ligand used is 1.7 × 10⁻⁶. -6 -5.0×10 -5 bbl has a nitrogen content of 65-70%; The preparation method of the layered zirconium phosphate-supported metal complex antibacterial agent material includes the following steps: S1. Add an inorganic salt containing antibacterial metal ions and a nitrogen-containing organic ligand to water to obtain a mixed solution; S2. Add the layered zirconium phosphate support to water and stir. After mixing with the above mixture, heat in a constant temperature water bath to 100-150 degrees Fahrenheit and stir at 500-1000 rpm for 3-5 hours. Then filter the solution obtained from the reaction, dry it at 100 degrees Celsius, and finally calcine it at 1000-1050 Kelvin for 4 hours. Grind it into powder.

2. The layered zirconium phosphate-supported metal complex antibacterial agent material as described in claim 1, characterized in that, The inorganic salt containing antibacterial metal ions is a zinc salt.

3. The layered zirconium phosphate-supported metal complex antibacterial agent material as described in claim 1, characterized in that, The inorganic salt containing antibacterial metal ions is a silver salt.

4. The layered zirconium phosphate-supported metal complex antibacterial agent material as described in claim 2, characterized in that, The zinc salt is used in an amount of 6-7g, and its zinc content is 66-68%. The zinc salt is at least one of zinc oxide, nano zinc oxide, zinc chloride, zinc sulfide, zinc selenide, zinc telluride, zinc sulfate, zinc cyanide, zinc nitrate, and zinc acetate.

5. The layered zirconium phosphate-supported metal complex antibacterial agent material as described in claim 3, characterized in that, The amount of silver salt used is 1.2-1.8g, and its silver content is 65-70%. The silver salt is at least one of silver halide, silver nitrate, silver sulfate, and silver acetate.

6. The layered zirconium phosphate-supported metal complex antibacterial agent material as described in claim 2, characterized in that, The antibacterial agent material has a space group of Cc and unit cell parameters of a = 13.8±0.3Å, b = 9.5±0.3Å, c = 9.1±0.3Å, α = 90±0.5°, β = 125.7±0.5°, and γ = 90±0.5°. It exhibits major diffraction peaks at diffraction angles 2θ of 18.6, 20.1, 21.6, 23.8, 24.1, 26.5, 29.3, 30.6, 35.0, 36.1, 48.0, and 49.4 degrees, with a 2θ error range of ±0.25°.

7. The layered zirconium phosphate-supported metal complex antibacterial agent material as described in claim 3, characterized in that, The antibacterial agent material has space group R-3c and cell parameters: a = 8.8±0.3Å, b = 8.8±0.3Å, c = 22.8±0.3Å, α = 90±0.5°, β = 90±0.5°, γ = 120±0.5°. It has main diffraction peaks at diffraction angles 2θ of 14.0, 19.5, 23.3, 28.1, 33.6, 34.9, 39.5, 41.0, 42.7, 44.7, 45.7, 46.3, 47.7, and 51.0 degrees, with a 2θ error range of ±0.25°.

8. The method for preparing the layered zirconium phosphate-supported metal complex antibacterial agent material as described in claim 1, characterized in that, When the inorganic salt containing antibacterial metal ions is zinc salt, step S1 is specifically as follows: add zinc salt and nitrogen-containing organic ligand to water to obtain an initial mixture, place it in a three-necked flask, heat it in an oil bath to 200-250 degrees Fahrenheit with stirring, reflux for 1000-1500 min, and then filter it to obtain the filtered mixture.

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