Preparation method of silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial, its product and application

Abstract

The present invention discloses a preparation method of a silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial, and its products and applications are prepared by a supercritical-solvent thermal combined preparation system. Supercritical fluid has extremely low surface tension, and silver and copper ions can be introduced into the interlayer of two-dimensional nanosheets; the supercritical fluid rapid expansion method can increase the interlayer spacing of two-dimensional nanosheets and reduce the difficulty of metastable silver and copper ions entering the interlayer. The silver-copper zirconium phosphate composite nanomaterial prepared by the present invention has a dendritic or mesh morphology formed by nanowires, has a large specific surface area and a high silver ion loading rate, has good and stable antibacterial and antiviral effects, can be used to prepare antibacterial and antiviral polyester, nylon and other fibers, can be blended with Tencel, combed cotton, etc., can be widely used in underwear, sports jackets, home textiles and other fields, and the nanomaterial prepared by the present invention has good application prospects.

Description

Technical Field

[0001] The invention relates to a preparation method of a silver-copper layered zirconium phosphate composite antibacterial and antiviral nano material, a product and an application thereof, and belongs to the technical field of inorganic nano materials. Background Art

[0002] Antimicrobial agents such as silver, zinc, and copper have broad-spectrum antibacterial and disinfection effects, and can give various antimicrobial products excellent antimicrobial effects. The reason why silver-based antimicrobial agents have excellent antimicrobial properties is that the trace amount of silver ions released from the material have antimicrobial and sterilization effects. However, the current silver-based antimicrobial nanopowders have the following problems in industrial applications: 1. The release rate of the effective ingredient silver ions is too fast, and its long-term efficacy cannot be guaranteed; 2. Silver-based antimicrobial nanopowders are not stable enough and are easy to deteriorate; 3. The excessive migration of the effective ingredients from the inside of the material particles to the surface causes the antimicrobial products to have problems such as discoloration and odor.

[0003] Therefore, to solve the above problems, a new antibacterial material or a new structural design is needed to ensure that the antibacterial material can release its active ingredients at a slow and stable rate, and has high stability and can significantly delay the excessive migration of the active ingredients.

[0004] The two-dimensional nanosheets are bonded by van der Waals forces, and the adsorption of metal ions such as silver, zinc, and copper can improve the stability of the antibacterial agent. However, due to the small interlayer spacing and the surface tension of the solution, it is usually difficult for silver, zinc, and copper ions to enter the interlayer of the two-dimensional nanosheets, which affects the loading rate and causes the antibacterial effect of the material to fail to meet the requirements. Summary of the invention

[0005] In view of the problems and defects of existing silver-based antibacterial nanomaterials, the purpose of the present invention is to provide a method for preparing a silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial.

[0006] Another object of the present invention is to provide a silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial product prepared by the above method.

[0007] Another object of the present invention is to provide an application of the above product.

[0008] The object of the present invention is achieved by the following scheme: a preparation method of a silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial, which is prepared by a supercritical-solvent thermal combination preparation system, wherein the supercritical-solvent thermal combination preparation system comprises: a container CS for preparing a silver ammonia solution, a pressure pump U connected to the container CS, a carbon dioxide cylinder C, a cooler H connected to the cylinder C, a pressure pump B connected to the cooler H, a reactor A1 for preparing a copper sulfate-zirconium phosphate mixed solution, a main reactor A2, a separator S and valves K1-K5, wherein a metal basket is provided in the main reactor A2, a sintered disk is provided at the bottom of the metal basket, and the separator S is provided with outlets E1 and E2; and the following preparation steps are included:

[0009] Step 1: Add silver nitrate solution and ammonia water into container CS to prepare silver ammonia solution;

[0010] Step 2: Adding a copper sulfate solution, phosphoric acid and a zirconium salt into the reaction kettle A1 to prepare a copper sulfate-zirconium phosphate mixed solution;

[0011] Step 3: Close valves K1-K5, the high-purity CO2 in cylinder C passes through cooler H to reach the supercritical temperature, is pressurized by pump B to reach the supercritical state, and passes through valve K1; at the same time, the silver ammonia solution in container CS is pressurized by pump U to produce high-pressure fluid, which enters the subsequent reaction process together with the high-purity CO2;

[0012] Step 4: Open valve K2 to allow the silver ammonia solution to enter reactor A1 and adjust to the target temperature and pressure; open valves K1, K3 and K4, close pump U, and allow the supercritical carbon dioxide fluid flowing into A1 to push the mixed solution into reactor A2; in reactor A2, the mixed solution is mixed with supercritical carbon dioxide and reacted at a temperature and pressure under the combined supercritical-solvent thermal conditions;

[0013] Step 5: After the reaction is completed, open valve K5, and the mixed fluid flows into the separator S for separation. CO2 is discharged or recycled through outlet E1, and other components in the raw material except the target product are discharged and collected through outlet E2. After the operation is completed, close the CO2 pump B, open the upper cover of the reactor A2, and take out the target product precipitated in the metal basket to obtain the silver-copper layered zirconium phosphate composite antibacterial and antiviral material.

[0014] Preferably, in step 2, the molar ratio of copper sulfate solution, phosphoric acid and zirconium salt is 0.01:3:10.

[0015] Preferably, in step 1, the molar ratio of the silver nitrate solution to the copper sulfate solution in step 2 is 1:1.

[0016] Preferably, in step 4, the conditions for the heat and pressure maintenance reaction are: temperature 50-100° C., pressure 10-60 MPa, and time 1-5 h.

[0017] The present invention also provides a silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial, which is prepared according to any of the above methods. The prepared silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial is a dendritic or mesh morphology formed by nanowires. The diameter of the nanowires is about 3 to 10 nm, the length is between 80 and 500 nm, and they overlap each other. Silver particles with a particle size of about 1 to 4 nm are scattered on the surface of the nanowires.

[0018] The present invention also provides an application of a silver-copper-loaded layered zirconium phosphate composite antibacterial and antiviral nanomaterial in the preparation of antibacterial and antiviral yarns, fabrics or protective products.

[0019] A method combining supercritical and solvent thermal is used to prepare silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterials: on the one hand, the supercritical fluid has an extremely low surface tension and can introduce silver and copper ions into the interlayers of two-dimensional nanosheets; on the other hand, the supercritical fluid rapid expansion method can increase the interlayer spacing of the two-dimensional nanosheets and reduce the difficulty of metastable silver and copper ions entering the interlayers, thereby preparing a nanomaterial with a large specific surface area and a high silver ion loading rate.

[0020] The silver-loaded copper zirconium phosphate composite nanomaterial obtained by the preparation method of the present invention has high stability and is not prone to color change. It can be used to prepare antibacterial and antiviral polyester, nylon and other fibers, can be blended with Tencel, combed cotton and the like, and can be widely used in underwear, sports jackets, home textiles and other fields. The fabric has a comfortable feel and strong antibacterial and antiviral functions.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The present invention utilizes a supercritical-solvothermal combination method: on the one hand, the supercritical fluid has an extremely low surface tension, and silver-copper ions can be introduced into the interlayer of the two-dimensional nanosheets; on the other hand, the supercritical fluid rapid expansion method can increase the interlayer spacing of the two-dimensional nanosheets, reducing the difficulty of metastable silver-copper ions entering the interlayers; therefore, the layered material loaded with silver-copper ions composite antibacterial and antiviral material prepared by the method of the present invention has a large specific surface area and silver ion loading rate. On the one hand, it can quickly adsorb bacteria and viruses into the interlayers during use, and then use the complexed silver-copper ions to kill bacteria and viruses; on the other hand, it can solve the problem that ordinary silver ion antibacterial materials are easily oxidized and discolored to produce black spots, and the formed stable composite system significantly controls the release rate of the effective ingredients, and can delay or prevent the excessive migration of the silver effective ingredients to the particle surface, thereby ensuring the stability of the material, giving the material other excellent properties besides the antibacterial property, and greatly improving the material's anti-color change property and applicable range;

[0023] (2) The layered composite antibacterial and antiviral material prepared by the present invention can further enhance the broad spectrum of antibacterial and antiviral properties, and the composite antibacterial and antiviral material has the advantages of good heat resistance and high safety. It can be used to prepare antibacterial polyester, Nylon, Rayon fibers, and blended yarns and fabrics with Tencel, combed cotton, long-staple cotton, polyester, viscose, modal, etc., and can be widely used in underwear, sports and leisure jackets, shirts, home textiles and other fields. The fabric has a comfortable feel, strong antibacterial and antiviral functions, and health care functions. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the supercritical-solvothermal combined preparation system used in Examples 1-5;

[0025] Figure 2 This is a transmission electron microscope photograph of the silver-loaded copper zirconium phosphate composite nanomaterial prepared in Example 2. DETAILED DESCRIPTION

[0026] In order to make the present invention more clearly understood, preferred embodiments are described in detail below with reference to the accompanying drawings.

[0027] Example 1

[0028] A silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial is prepared by a supercritical-solvent thermal combination preparation system. The supercritical-solvent thermal combination preparation system is as follows Figure 1As shown, it includes: a container CS for preparing a silver ammonia solution, a pressure pump U connected to the container CS, a carbon dioxide cylinder C, a cooler H connected to the cylinder C, a pressure pump B connected to the cooler H, a reactor A1 for preparing a copper sulfate-zirconium phosphate mixed solution, a main reactor A2, a separator S and valves K1-K5, the main reactor A2 is provided with a metal basket, the bottom of the metal basket is provided with a sintered disk, and the separator S is provided with outlets E1 and E2; it is prepared according to the following steps:

[0029] Step 1: Weigh 0.01 mol of silver nitrate and dissolve it in 50 mL of 0.03 mol ammonia solution and put it into container CS;

[0030] Step 2: Add 30 ml of 0.01 mol copper sulfate solution to the reaction kettle A1, and add 3 mol phosphoric acid and 100 ml of 10 mol zirconium salt solution to the reaction kettle A2 to prepare a copper sulfate-zirconium phosphate mixed solution;

[0031] Step 3: Close valves K1-K5, the high-purity CO2 in cylinder C passes through cooler H to reach the supercritical temperature, is pressurized by pump B to reach the supercritical state, and passes through valve K1; at the same time, the mixed solution in container CS is pressurized by pump U to produce high-pressure fluid, which enters the subsequent reaction process together with the high-purity CO2;

[0032] Step 4: Open valve K2 to allow the silver ammonia solution to enter reactor A1 and adjust to the target temperature and pressure; open valves K1, K3 and K4, close pump U, and allow the supercritical carbon dioxide fluid flowing into A1 to push the mixed solution into reactor A2; in reactor A2, the mixed solution is mixed with supercritical carbon dioxide, and the temperature is adjusted to 60°C and 10MPa, and the temperature and pressure are maintained for 1 hour under the combined supercritical-solvent thermal conditions;

[0033] Step 5: After the reaction is completed, open valve K5, and the mixed fluid flows into the separator S for separation. CO2 is discharged or recycled through outlet E1, and other components in the raw material except the target product are discharged and collected through outlet E2. After the operation is completed, close the CO2 pump B, open the upper cover of the reactor A2, and take out the target product precipitated in the metal basket to obtain the silver-copper loaded layered zirconium phosphate composite antibacterial and antiviral material.

[0034] Example 2

[0035] A silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial is prepared by the following steps using the same equipment and similar reaction steps as in Example 1:

[0036] Step 1: Weigh 0.01 mol of silver nitrate and dissolve it in 50 ml of 0.05 mol ammonia solution and put it into container CS;

[0037] Step 2: Add 0.005 mol of copper sulfate to the reaction kettle A1, the solution volume is 30 ml, and add 2.5 mol of phosphoric acid and 10 mol of zirconium salt solution 100 ml to the reaction kettle A2;

[0038] Step 3: Close valves K1-K5, the high-purity CO2 in cylinder C passes through cooler H to reach the supercritical temperature, is pressurized by pump B to reach the supercritical state, and passes through valve K1; at the same time, the silver ammonia solution in container CS is pressurized by pump U to produce high-pressure fluid, which enters the subsequent reaction process together with the high-purity CO2;

[0039] Step 4: Open valve K2 to allow the silver ammonia solution to enter reactor A1 and adjust to the target temperature and pressure; open valves K1, K3 and K4, close pump U, and allow the supercritical carbon dioxide fluid flowing into A1 to push the mixed solution into reactor A2; in reactor A2, the mixed solution is mixed with supercritical carbon dioxide, and the temperature is adjusted to 100°C and 60MPa, and the temperature and pressure are maintained for 5 hours under the combined supercritical-solvent thermal conditions;

[0040] Step 5: After the reaction is completed, open valve K5, and the mixed fluid flows into the separator S for separation. CO2 is discharged or recycled through outlet E1, and other components in the raw material except the target product are discharged and collected through outlet E2. After the operation is completed, close the CO2 pump B, open the upper cover of the reactor A2, and take out the target product precipitated in the metal basket to obtain the loaded silver-copper composite antibacterial and antiviral material.

[0041] The obtained materials were characterized by transmission electron microscopy. Figure 2 As shown, the nanowires are stacked into a dendrite or mesh-like morphology. The diameter of the nanowires is about 3 to 10 nm, the length is between 80 and 500 nm, and they are stacked together. Among them, silver particles with a particle size of about 1 to 4 nm are scattered on the surface of the nanowires.

[0042] Table 1 is an antiviral report of the silver-copper zirconium phosphate composite nanomaterial prepared in this example:

[0043] .

[0044] Example 3

[0045] A silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial is prepared by the following steps using the same equipment and similar reaction steps as in Example 1:

[0046] Step 1: Weigh 0.01 mol of silver nitrate and dissolve it in 50 ml of 0.04 mol ammonia solution and put it into container CS;

[0047] Step 2: Add 0.005 mol of copper sulfate to the reaction kettle A1, the solution volume is 30 ml, and add 3 mol of phosphoric acid and 15 mol of zirconium salt solution 100 ml to the reaction kettle A2;

[0048] Step 3: Close valves K1-K5, the high-purity CO2 in cylinder C passes through cooler H to reach the supercritical temperature, is pressurized by pump B to reach the supercritical state, and passes through valve K1; at the same time, the mixed solution in container CS is pressurized by pump U to produce high-pressure fluid, which enters the subsequent reaction process together with the high-purity CO2;

[0049] Step 4: Open valve K2 to allow the mixed solution to enter reactor A1 and adjust to the target temperature and pressure; open valves K1, K3 and K4, close pump U, and allow the supercritical carbon dioxide fluid flowing into A1 to push the mixed solution into reactor A2; in reactor A2, the mixed solution is mixed with supercritical carbon dioxide, and the temperature is adjusted to 80°C and 50MPa, and the temperature and pressure are maintained for 3 hours under the combined supercritical-solvent thermal conditions;

[0050] Step 5: After the reaction is completed, open valve K5, and the mixed fluid flows into the separator S for separation. CO2 is discharged or recycled through outlet E1, and other components in the raw material except the target product are discharged and collected through outlet E2. After the operation is completed, close the CO2 pump B, open the upper cover of the reactor A2, and take out the target product precipitated in the metal basket to obtain the loaded silver-copper composite antibacterial and antiviral material.

[0051] Example 4

[0052] A silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial is prepared by the following steps using the same equipment and similar reaction steps as in Example 1:

[0053] Step 1: Weigh 0.01 mol of silver nitrate and dissolve it in 50 ml of 0.05 mol ammonia solution and put it into container CS;

[0054] Step 2: Add 0.01 mol of copper sulfate to the reaction kettle A1, the solution volume is 30 ml, and add 2 mol of phosphoric acid and 10 mol of zirconium salt solution 100 ml to the reaction kettle A2;

[0055] Step 3: Close valves K1-K5, the high-purity CO2 in cylinder C passes through cooler H to reach the supercritical temperature, is pressurized by pump B to reach the supercritical state, and passes through valve K1; at the same time, the silver ammonia solution in container CS is pressurized by pump U to produce high-pressure fluid, which enters the subsequent reaction process together with the high-purity CO2;

[0056] Step 4: Open valve K2 to allow the silver ammonia solution to enter reactor A1 and adjust to the target temperature and pressure; open valves K1, K3 and K4, close pump U, and allow the supercritical carbon dioxide fluid flowing into A1 to push the mixed solution into reactor A2; in reactor A2, the mixed solution is mixed with supercritical carbon dioxide, and the temperature is adjusted to 50°C and 60MPa, and the temperature and pressure are maintained for 5 hours under the combined supercritical-solvent thermal conditions;

[0057] Step 5: After the reaction is completed, open valve K5, and the mixed fluid flows into the separator S for separation. CO2 is discharged or recycled through outlet E1, and other components in the raw material except the target product are discharged and collected through outlet E2. After the operation is completed, close the CO2 pump B, open the upper cover of the reactor A2, and take out the target product precipitated in the metal basket to obtain the loaded silver-copper composite antibacterial and antiviral material.

[0058] Example 5

[0059] A silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial is prepared by the following steps using the same equipment and similar reaction steps as in Example 1:

[0060] Step 1: Weigh 0.1 mol of silver nitrate and dissolve it in 50 ml of 0.3 mol ammonia solution and put it into container CS;

[0061] Step 2: Add 0.08 mol of copper sulfate to the reaction kettle A1, the solution volume is 30 ml, and add 2.5 mol of phosphoric acid and 10 mol of zirconium salt solution 100 ml to the reaction kettle A2;

[0062] Step 3: Close valves K1-K5, the high-purity CO2 in cylinder C passes through cooler H to reach the supercritical temperature, is pressurized by pump B to reach the supercritical state, and passes through valve K1; at the same time, the mixed solution in container CS is pressurized by pump U to produce high-pressure fluid, which enters the subsequent reaction process together with the high-purity CO2;

[0063] Step 4: Open valve K2 to allow the mixed solution to enter reactor A1 and adjust to the target temperature and pressure; open valves K1, K3 and K4, close pump U, and allow the supercritical carbon dioxide fluid flowing into A1 to push the mixed solution into reactor A2; in reactor A2, the mixed solution is mixed with supercritical carbon dioxide, and the temperature is adjusted to 100°C and 60MPa, and the temperature and pressure are maintained for 3 hours under the combined supercritical-solvent thermal conditions;

[0064] Step 5: After the reaction is completed, open valve K5, and the mixed fluid flows into the separator S for separation. CO2 is discharged or recycled through outlet E1, and other components in the raw material except the target product are discharged through outlet E2. After the operation is completed, close the CO2 pump B, open the upper cover of the reactor A2, and take out the target product precipitated in the metal basket to obtain the loaded silver-copper composite antibacterial and antiviral material.

Claims

1. A method for preparing a silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial, characterized in that: The preparation is carried out by using a supercritical-solvent thermal combination preparation system, which comprises: a container (CS) for preparing a silver ammonia solution, a pressure pump (U) connected to the container (CS), a carbon dioxide cylinder (C), a cooler (H) connected to the cylinder (C), a pressure pump (B) connected to the cooler (H), a reaction kettle (A1) for preparing a copper sulfate-zirconium phosphate mixed solution, a main reaction kettle (A2), a separator (S) and valves (K1-K5), wherein a metal basket is provided in the main reaction kettle (A2), a sintering disk is provided at the bottom of the metal basket, and the separator (S) is provided with outlets (E1 and E2); the preparation is carried out according to the following steps: Step 1: Weigh 0.01 mol of silver nitrate and dissolve it in 50 mL of 0.03 mol ammonia solution and put it into a container (CS); Step 2: Add 0.01 mol of copper sulfate to the reaction kettle (A1) with a solution volume of 30 ml, and add 3 mol of phosphoric acid and 10 mol of zirconium salt solution (100 ml) to the main reaction kettle (A2) to prepare a copper sulfate-zirconium phosphate mixed solution; Step 3: Close valves (K1-K5), the high-purity CO2 in the cylinder (C) passes through the cooler (H) to reach the supercritical temperature, and is pressurized by the pressure pump (B) to reach the supercritical state, and passes through valve (K1); at the same time, the mixed solution in the container (CS) is pressurized by the pump (U) to generate a high-pressure fluid, which enters the subsequent reaction process together with the high-purity CO2; Step 4: Open valve (K2) to allow the silver ammonia solution to enter the reactor (A1) and adjust to the target temperature and pressure; open valves (K1, K3 and K4), close pump (U), and the supercritical carbon dioxide fluid flowing into the reactor (A1) pushes the mixed solution into the main reactor (A2); in the main reactor (A2), the mixed solution is mixed with supercritical carbon dioxide, and the temperature is adjusted to 60°C and 10MPa, and the temperature and pressure are maintained for 1 hour under the combined supercritical-solvent thermal conditions; Step 5: After the reaction is completed, open the valve (K5), the mixed fluid flows into the separator (S) for separation, CO2 is discharged or recycled through the outlet (E1), and the other components in the raw material except the target product are discharged and collected through the outlet (E2); after the operation is completed, turn off the CO2 booster pump (B), open the upper cover of the main reactor (A2), take out the target product precipitated in the metal basket, and obtain the silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial.

2. A silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial, characterized in that Prepared by the preparation method as described in claim 1; the prepared silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial is a dendritic or mesh morphology formed by nanowires, the diameter of the nanowires is 3~10nm, the length is between 80~500nm, they are overlapped with each other, and silver particles with a particle size of 1~4nm are scattered on the surface of the nanowires.

3. An application of the silver-copper layered zirconium phosphate composite antibacterial and antiviral nanomaterial according to claim 2 in the preparation of antibacterial and antiviral yarns, fabrics or protective products.

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