CN112772676A - Preparation method and application of Cu-rGO nano composite antibacterial material - Google Patents
Preparation method and application of Cu-rGO nano composite antibacterial material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a preparation method of a Cu-rGO nano composite antibacterial material, which comprises the following steps: s1, dissolving water-soluble copper salt and hexamethylenetetramine in deionized water to obtain a solution A; s2, dropwise adding the water dispersion liquid of the graphene oxide into the solution A, and uniformly stirring to obtain a mixed solution B; s3, dropwise adding an ascorbic acid water solution into the mixed solution B, and uniformly stirring to obtain a mixed solution C; and S4, carrying out microwave heating reaction on the mixed solution C, cooling and centrifuging after the reaction is finished, and washing and drying the obtained precipitate to obtain the compound. The Cu-rGO composite material prepared by the invention has good antibacterial effect and antibacterial broad spectrum, has wide application range, can be used for preparing antibacterial coatings, antibacterial plates and other fields, and can be used in medical places, pharmaceutical factories and the like.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a preparation method and application of a Cu-rGO nano composite antibacterial material.
Background
With the standardized, intelligent and humanized development of green building materials, the design, construction and acceptance of clean workshops and medical places have higher industrial standards and requirements, wherein higher antibacterial requirements are provided for the building materials of the clean workshops and the medical places, particularly for the plates used on inner wall surfaces, roof surfaces, suspended ceilings and the like. The key point of the antibacterial board is that an antibacterial material with excellent antibacterial performance is compounded on the surface of the antibacterial board. The inorganic antibacterial coating is mainly an antibacterial material which takes metals such as silver, copper, zinc, titanium and the like with stronger sterilization or bacteriostatic ability and ions thereof as effective components, and the action mechanism is mainly that the cation effect is utilized, and the function of cell membranes is prevented by utilizing the reaction of cations and proteins on the cell membranes of bacteria. The inorganic antibacterial material has the characteristics of broad-spectrum antibacterial property, high-efficiency sterilization, long effect, no drug resistance and the like, and effectively makes up for the defects of the organic antibacterial material. The development of inorganic antibacterial materials with excellent antibacterial effect, broad antibacterial spectrum and capability of efficiently killing various bacteria is the direction of the current key research.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method and application of a Cu-rGO (reduced graphene oxide) nano composite antibacterial material.
The invention provides a preparation method of a Cu-rGO nano composite antibacterial material, which comprises the following steps:
s1, dissolving water-soluble copper salt and hexamethylenetetramine in deionized water to obtain a solution A;
s2, dropwise adding the water dispersion liquid of the graphene oxide into the solution A, and uniformly stirring to obtain a mixed solution B;
s3, dropwise adding an ascorbic acid water solution into the mixed solution B, and uniformly stirring to obtain a mixed solution C;
and S4, carrying out microwave heating reaction on the mixed solution C, cooling and centrifuging after the reaction is finished, and washing and drying the obtained precipitate to obtain the compound.
Preferably, in the step S4, the reaction temperature of the microwave heating reaction is 50-180 ℃, the microwave power is 300-1000W, and the reaction time is 20-40 min.
Preferably, the mass ratio of the water-soluble copper salt to the graphene oxide is (60-90): 1.
preferably, the molar ratio of the water-soluble copper salt, the hexamethylenetetramine and the ascorbic acid is 1: (30-35): (2-3).
Preferably, the water soluble copper salt is copper sulfate, copper nitrate or a combination thereof.
Preferably, the graphene oxide is prepared by adopting an improved Hummers method, and the specific method is as follows:
uniformly mixing 300-mesh 400-mesh natural crystalline flake graphite with concentrated sulfuric acid and phosphoric acid, slowly adding potassium permanganate under stirring at 2-4 ℃, keeping the temperature and stirring at 2-4 ℃ for reaction for 3-4h, then heating to 38-42 ℃, keeping the temperature and stirring for reaction for 50-80min, then heating to 46-48 ℃, keeping the temperature and stirring for reaction for 8-15h, cooling a product to room temperature after the reaction is finished, adding water for dilution, slowly dropwise adding hydrogen peroxide until no bubble is generated, sequentially carrying out acid pickling and water washing to neutrality, and drying to obtain the product;
the proportion of the natural crystalline flake graphite, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 1 g: (40-50) mL: (4-6) mL: (6-8) g.
Preferably, in the solution A, the concentration of the water-soluble copper salt is 0.02-0.03mol/L, and the concentration of the hexamethylene tetramine is 0.6-1 mol/L; the concentration of the graphene oxide aqueous dispersion is 0.3-0.8 mg/mL; the concentration of the ascorbic acid aqueous solution is 0.1-0.15 mol/L.
A Cu-rGO nano composite antibacterial material is prepared by the preparation method.
An antibacterial coating comprises the Cu-rGO nano-composite antibacterial material.
Preferably, the Cu-rGO nano composite antibacterial material accounts for 25-30% of the total mass of the coating.
Preferably, the antibacterial coating comprises the following raw materials in parts by mass: 25-30% of Cu-rGO nano composite antibacterial material, 5-8% of triglycidyl isocyanurate, 2-3% of organic silicon flatting agent, 1-2% of benzoin, 3-5% of titanium dioxide, 0-1% of pigment and the balance of polyester resin.
An antibacterial plate comprises a substrate and a coating compounded on the surface of the substrate, wherein the coating is formed by the antibacterial coating.
Preferably, the preparation method of the antibacterial plate comprises the following steps:
and spraying the antibacterial coating to the surface of the base material by adopting an electrostatic spraying method under the condition that the spraying voltage is 45kV, and then curing for 10min at 180 ℃ to form a coating with the thickness of 40-60 mu m on the surface of the base material, thus obtaining the antibacterial coating.
The invention has the following beneficial effects:
the Cu-rGO composite material prepared by the invention has good antibacterial effect and antibacterial broad spectrum, has wide application range, can be used for preparing antibacterial coatings, antibacterial plates and other fields, and can be used in medical places, pharmaceutical factories and the like.
Drawings
FIG. 1 is an XRD spectrum of pure Cu and Cu-rGO composite material prepared in example 1 of the present invention.
Fig. 2 is an XRD spectrum of graphene oxide.
Fig. 3 is an SEM image of pure Cu.
FIG. 4 is an SEM image of a Cu-rGO composite material prepared in example 1 of the present invention.
FIG. 5 is an FT-IR spectrum of graphene oxide and Cu-rGO composite prepared in example 1 of the invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Preparing graphene oxide:
uniformly mixing 0.5g of 325-mesh natural crystalline flake graphite, 22.5mL of concentrated sulfuric acid and 2.5mL of phosphoric acid, slowly adding 3.5g of potassium permanganate under stirring at 3 ℃, keeping the temperature and stirring for reaction for 3.5h at 3 ℃, then heating to 40 ℃, keeping the temperature and stirring for reaction for 60min, then heating to 47 ℃, keeping the temperature and stirring for reaction for 10h, cooling a product to room temperature after the reaction is finished, adding water for dilution, slowly dropwise adding hydrogen peroxide until no bubble is generated, sequentially carrying out acid washing by using 5% HCl, washing by using distilled water to be neutral, and drying to obtain the graphite.
The preparation method for preparing the Cu-rGO nano composite antibacterial material comprises the following steps:
s1, dissolving 1mmol of anhydrous copper sulfate (0.1596g) and 32mmol of hexamethylenetetramine in 40mL of deionized water to obtain a solution A;
s2, dropwise adding 4mL of graphene oxide aqueous dispersion with the concentration of 0.5mg/mL into the solution A, and uniformly stirring to obtain a mixed solution B;
s3, dripping 20mL of ascorbic acid water solution with the concentration of 0.125mol/L into the mixed solution B, and uniformly stirring to obtain a mixed solution C;
s4, carrying out microwave heating reaction on the mixed solution C for 30min under the conditions that the power is 800W and the reaction temperature is 120 ℃, cooling and centrifuging after the reaction is finished, washing the obtained precipitate, and carrying out vacuum drying for 10h at 55 ℃ to obtain the compound.
Wherein the aqueous dispersion of graphene oxide is obtained by dispersing graphene oxide in water.
Preparing an antibacterial coating: weighing the following raw materials in percentage by mass: 27% of Cu-rGO nano composite antibacterial material, 6% of triglycidyl isocyanurate, 2.5% of organic silicon flatting agent, 1.5% of benzoin, 4% of titanium dioxide, 0.5% of pigment and the balance of polyester resin, and the Cu-rGO nano composite antibacterial material is obtained by uniformly mixing the raw materials.
Preparing an antibacterial plate: spraying the prepared antibacterial coating on the surface of a base material by adopting an electrostatic spraying method under the condition that the spraying voltage is 45kV, and then curing for 10min at 180 ℃ to form a coating with the thickness of 40-60 mu m on the surface of the base material.
Example 2
Preparing graphene oxide:
uniformly mixing 0.5g of 300-mesh natural crystalline flake graphite with 20mL of concentrated sulfuric acid and 2mL of phosphoric acid, slowly adding 3g of potassium permanganate under stirring at 2 ℃, keeping the temperature and stirring for reaction for 4 hours at 2 ℃, then heating to 38 ℃, keeping the temperature and stirring for reaction for 80min, then heating to 46 ℃, keeping the temperature and stirring for reaction for 15 hours, cooling the product to room temperature after the reaction is finished, adding water for dilution, slowly dropwise adding hydrogen peroxide until no bubbles are generated, then washing with 5% HCl and distilled water in sequence until the product is neutral, and drying to obtain the graphite.
The preparation method for preparing the Cu-rGO nano composite antibacterial material comprises the following steps:
s1, dissolving 1mmol of anhydrous copper sulfate (0.1596g) and 30mmol of hexamethylenetetramine in 40mL of deionized water to obtain a solution A;
s2, dropwise adding 4mL of graphene oxide aqueous dispersion with the concentration of 0.625mg/mL into the solution A, and uniformly stirring to obtain a mixed solution B;
s3, dripping 20mL of ascorbic acid water solution with the concentration of 0.1mol/L into the mixed solution B, and uniformly stirring to obtain a mixed solution C;
s4, carrying out microwave heating reaction on the mixed solution C for 20min under the conditions that the power is 1000W and the reaction temperature is 180 ℃, cooling and centrifuging after the reaction is finished, washing the obtained precipitate, and carrying out vacuum drying for 10h at 55 ℃ to obtain the compound.
Wherein the aqueous dispersion of graphene oxide is obtained by dispersing graphene oxide in water.
Preparing an antibacterial coating: weighing the following raw materials in percentage by mass: 25% of Cu-rGO nano composite antibacterial material, 8% of triglycidyl isocyanurate, 2% of organic silicon flatting agent, 1% of benzoin, 3% of titanium dioxide and the balance of polyester resin, and uniformly mixing the raw materials to obtain the antibacterial copper-oxide-copper alloy material.
Preparing an antibacterial plate: spraying the prepared antibacterial coating on the surface of a base material by adopting an electrostatic spraying method under the condition that the spraying voltage is 45kV, and then curing for 10min at 180 ℃ to form a coating with the thickness of 40-60 mu m on the surface of the base material.
Example 3
Preparing graphene oxide:
uniformly mixing 0.5g of 400-mesh natural crystalline flake graphite with 25mL of concentrated sulfuric acid and 3mL of phosphoric acid, slowly adding 4g of potassium permanganate under stirring at 3 ℃, keeping the temperature and stirring for reaction for 3h at 4 ℃, then heating to 42 ℃, keeping the temperature and stirring for reaction for 50min, then heating to 48 ℃, keeping the temperature and stirring for reaction for 8h, cooling the product to room temperature after the reaction is finished, adding water for diluting, slowly dropwise adding hydrogen peroxide until no bubbles are generated, then sequentially carrying out acid washing with 5% HCl, washing with distilled water until the product is neutral, and drying to obtain the product.
The preparation method for preparing the Cu-rGO nano composite antibacterial material comprises the following steps:
s1, dissolving 1mmol of anhydrous copper sulfate (0.1596g) and 35mmol of hexamethylenetetramine in 40mL of deionized water to obtain a solution A;
s2, dropwise adding 4mL of graphene oxide aqueous dispersion with the concentration of 0.45mg/mL into the solution A, and uniformly stirring to obtain a mixed solution B;
s3, dripping 20mL of ascorbic acid water solution with the concentration of 0.15mol/L into the mixed solution B, and uniformly stirring to obtain a mixed solution C;
s4, carrying out microwave heating reaction on the mixed solution C for 40min under the conditions that the power is 300W and the reaction temperature is 50 ℃, cooling and centrifuging after the reaction is finished, washing the obtained precipitate, and carrying out vacuum drying for 10h at 55 ℃ to obtain the compound.
Wherein the aqueous dispersion of graphene oxide is obtained by dispersing graphene oxide in water.
Preparing an antibacterial coating: weighing the following raw materials in percentage by mass: 30% of Cu-rGO nano composite antibacterial material, 5% of triglycidyl isocyanurate, 3% of organic silicon flatting agent, 2% of benzoin, 5% of titanium dioxide, 1% of pigment and the balance of polyester resin, and the Cu-rGO nano composite antibacterial material is obtained by uniformly mixing the raw materials.
Preparing an antibacterial plate: spraying the prepared antibacterial coating on the surface of a base material by adopting an electrostatic spraying method under the condition that the spraying voltage is 45kV, and then curing for 10min at 180 ℃ to form a coating with the thickness of 40-60 mu m on the surface of the base material.
Comparative example 1
Preparing a Cu-G (graphene) nanocomposite material by referring to a traditional impregnation method:
weighing 200mg of graphene material, adding 10mL of deionized water and 10mL of absolute ethyl alcohol, uniformly dispersing to obtain graphene dispersion liquid, then weighing 0.161g of copper nitrate trihydrate, dissolving in a small amount of water, adding into the graphene dispersion liquid, and stirring at a constant temperature of 25 ℃ until the solvent is completely volatilized, thus obtaining the graphene.
Preparing a coating containing the Cu-G nano composite material: weighing the following raw materials in percentage by mass: 27% of Cu-rGO nano composite antibacterial material, 6% of triglycidyl isocyanurate, 2.5% of organic silicon flatting agent, 1.5% of benzoin, 4% of titanium dioxide, 0.5% of pigment and the balance of polyester resin, and the Cu-rGO nano composite antibacterial material is obtained by uniformly mixing the raw materials.
Preparing a plate containing the Cu-G nano composite material: spraying the prepared coating to the surface of a base material by adopting an electrostatic spraying method under the condition that the spraying voltage is 45kV, and then curing for 10min at 180 ℃ to form a coating with the thickness of 40-60 mu m on the surface of the base material, thus obtaining the coating.
The plates prepared in example 1 and comparative example 1 were tested for antibacterial performance, the test method is referred to GB/T21866-2008, and the test results are shown in Table 1:
FIG. 1 is an XRD spectrum of pure Cu and Cu-rGO composite material prepared in example 1 of the present invention. In fig. 1, from bottom to top, the XRD spectrum of pure Cu and the XRD spectrum of Cu-rGO composite material are shown. Analysis confirms that the three strong peaks are consistent with face-centered cubic copper (Cu-PDF #04-0836), diffraction peaks with 2 theta equal to 43.3 degrees and 50.4 degrees and 74.1 degrees respectively correspond to crystal faces of (111), (200) and (220), no miscellaneous peak is generated, and meanwhile, the sharp diffraction peaks of copper indicate that the crystal structure of copper with higher purity is complete.
Fig. 2 is an XRD spectrum of graphene oxide. From fig. 2, it can be seen that the characteristic diffraction peak of GO is less than 10 ° and is the characteristic peak of the (001) crystal plane of graphene oxide, and according to the scherrer equation, the distance between the crystal planes of graphene oxide is greater than 0.79nm, which is significantly increased compared with the 0.34nm crystal plane of graphite.
As can be seen by combining the figures 1 and 2, the (001) characteristic peak of GO does not appear in the XRD spectrum of the Cu-rGO composite material, which indicates that GO is reduced into rGO in the preparation of the material. And the characteristic diffraction peak of the rGO is about 24 degrees, and the diffraction peak of the rGO is not observed in the XRD spectrum of the Cu-rGO composite material, which is probably because the content of the rGO introduced into the composite material is low on one hand, and the ordered stacking of rGO lamella is effectively inhibited due to the existence of Cu particles on the other hand, so the characteristic diffraction peak of the rGO does not appear in the XRD spectrum of the Cu-rGO composite material.
Fig. 3 is an SEM image of pure Cu. It can be seen that pure Cu is in the form of small irregularly shaped particles and the more agglomerated particles are not of the same size.
FIG. 4 is an SEM image of a Cu-rGO composite material prepared in example 1 of the present invention. It can be seen that the Cu particle morphology in the Cu-rGO composite material is spherical-like, and the particle size morphology tends to be uniform, which may be that oxygen-containing functional groups of GO participate in the nucleation and growth of Cu particles, and simultaneously provide nucleation sites for Cu ions, thereby playing a role in modifying the particle morphology. It can be seen that rGO wraps the Cu particles as a transparent and wrinkled film, with tighter bonding. When GO is reduced into rGO, certain structural defects can be generated on the surface of the rGO, and the nucleation and dispersion of Cu particles on the carrier are governed by defect sites, so that the dispersion of the Cu particles is promoted. The Cu-rGO composite material particles are concentrated between 100nm and 200 nm. The rGO film and Cu particles in the Cu-rGO nano composite material are tightly compounded together, and the stacking and agglomeration phenomena are avoided.
FIG. 5 is an FT-IR spectrum of graphene oxide and Cu-rGO composite prepared in example 1 of the invention. It can be seen that, because GO contains a large number of oxygen-containing functional groups, the infrared spectrum is shown in3425cm-1Is marked by-OH stretching vibration peak, 3130cm-1Is a C-H telescopic absorption peak of 2923cm-1And 2846cm-1Are respectively CH21630cm of antisymmetric and symmetric telescopic vibration peak-1The peak is-O-H bending vibration peak 1380cm-1The sum of the C-O bending vibration peak in the C-OH functional group and 1085cm-1C-O stretching vibration peak in the epoxy group. In infrared spectrograms of Cu-rGO composite materials prepared by two different copper sources, the peak intensities of the oxygen-containing functional groups are greatly weakened or even partially disappeared, which shows that GO is reduced into rGO in the preparation process of the Cu-rGO composite material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a Cu-rGO nano composite antibacterial material is characterized by comprising the following steps:
s1, dissolving water-soluble copper salt and hexamethylenetetramine in deionized water to obtain a solution A;
s2, dropwise adding the water dispersion liquid of the graphene oxide into the solution A, and uniformly stirring to obtain a mixed solution B;
s3, dropwise adding an ascorbic acid water solution into the mixed solution B, and uniformly stirring to obtain a mixed solution C;
and S4, carrying out microwave heating reaction on the mixed solution C, cooling and centrifuging after the reaction is finished, and washing and drying the obtained precipitate to obtain the compound.
2. The method for preparing Cu-rGO nano-composite antibacterial material as claimed in claim 1, wherein in step S4, the reaction temperature of the microwave heating reaction is 50-180 ℃, the microwave power is 300-1000W, and the reaction time is 20-40 min.
3. The preparation method of the Cu-rGO nano-composite antibacterial material according to claim 1 or 2, wherein the mass ratio of the water-soluble copper salt to the graphene oxide is (60-90): 1.
4. the method for preparing a Cu-rGO nano-composite antibacterial material according to any one of claims 1 to 3, wherein the molar ratio of the water-soluble copper salt, hexamethylenetetramine and ascorbic acid is 1: (30-35): (2-3).
5. The preparation method of the Cu-rGO nano-composite antibacterial material according to any one of claims 1 to 4, wherein the graphene oxide is prepared by a modified Hummers method, and the specific method is as follows:
uniformly mixing 300-mesh 400-mesh natural crystalline flake graphite with concentrated sulfuric acid and phosphoric acid, slowly adding potassium permanganate under stirring at 2-4 ℃, keeping the temperature and stirring at 2-4 ℃ for reaction for 3-4h, then heating to 38-42 ℃, keeping the temperature and stirring for reaction for 50-80min, then heating to 46-48 ℃, keeping the temperature and stirring for reaction for 8-15h, cooling a product to room temperature after the reaction is finished, adding water for dilution, slowly dropwise adding hydrogen peroxide until no bubble is generated, sequentially carrying out acid pickling and water washing to neutrality, and drying to obtain the product;
the proportion of the natural crystalline flake graphite, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 1 g: (40-50) mL: (4-6) mL: (6-8) g.
6. The method for preparing a Cu-rGO nano composite antibacterial material according to any one of claims 1 to 5, wherein in the solution A, the concentration of water-soluble copper salt is 0.02-0.03mol/L, and the concentration of hexamethylenetetramine is 0.6-1 mol/L; the concentration of the graphene oxide aqueous dispersion is 0.3-0.8 mg/mL; the concentration of the ascorbic acid aqueous solution is 0.1-0.15 mol/L.
7. A Cu-rGO nano composite antibacterial material, which is characterized by being obtained by the preparation method of any one of claims 1 to 6.
8. An antimicrobial coating comprising the Cu-rGO nanocomposite antimicrobial material of claim 7.
9. The antimicrobial coating of claim 8, wherein the Cu-rGO nanocomposite antimicrobial material comprises 25-30% of the total mass of the coating.
10. An antibacterial sheet material, comprising a substrate and a coating layer compounded on the surface of the substrate, wherein the coating layer is formed by the antibacterial coating material according to claim 8 or 9.
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