CN112723500A - Environment-friendly efficient nano copper ion compound and preparation method and application thereof - Google Patents

Environment-friendly efficient nano copper ion compound and preparation method and application thereof Download PDF

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CN112723500A
CN112723500A CN201911027777.6A CN201911027777A CN112723500A CN 112723500 A CN112723500 A CN 112723500A CN 201911027777 A CN201911027777 A CN 201911027777A CN 112723500 A CN112723500 A CN 112723500A
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copper ion
solution
environment
copper
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CN112723500B (en
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方海平
涂育松
谭砚文
李培
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East China University of Science and Technology
Fudan University
Yangzhou University
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Fudan University
Yangzhou University
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment

Abstract

The invention discloses an environment-friendly efficient nano copper ion compound which is composed of a copper ion solution with the concentration of 5-200 mu mol/L and a graphene solution with the concentration of 40-100 mg/L, wherein the volume ratio of the copper ion solution to the graphene solution is (0.5-2): 1. The invention provides an environment-friendly high-efficiency nano copper ion compound, which aims to solve the technical problem of utilizing the broad-spectrum sterilization characteristic of copper ions and simultaneously overcoming the biotoxicity caused by the high ion concentration of the existing copper ion bactericide so as to enable the copper ion compound to become a bactericide with high efficiency, rapidness and low toxicity.

Description

Environment-friendly efficient nano copper ion compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of bactericide preparation, and particularly relates to an environment-friendly efficient nano copper ion compound and a preparation method and application thereof.
Background
Copper ions are one of the long-acting broad-spectrum antibacterial materials of inorganic type known from ancient times and applied very early. Studies have shown that copper ions have the effect of inhibiting the growth of various unhealthy bacteria, viruses and aquatic microorganisms such as algae, such as escherichia coli, staphylococcus aureus, salmonella, campylobacter jejuni, clostridium, mycobacterium tuberculosis, blue algae, green algae, etc. (curr. med. chem.2005,12, 2163-. The copper ion bactericide has great application potential as an antibacterial product for daily use in health care facilities, food industry, agriculture and other places needing cleaning or disinfection. However, when the concentration of copper exceeds a certain range, it has high toxicity, which in turn threatens environmental safety (chem. res. toxicol.2015,28, 1815-. For example, more than half of Chinese weever can die when the concentration of copper ions reaches 14 mu mol/L (Fish physiology. academic Press,2011,31: 417-; the fatal threshold of the copper ion concentration of some fishes in the juvenile period is 1 mu mol/L; when the concentration of copper ions exceeds 16 μmol/L, it will cause toxicity to various human Cell lines such as human lung epithelial cells, human heart microvascular endothelial cells, kidney cells and nerve cells (Cell biol. toxicol.2011,27(5): 333-). 342). In fact, a series of copper content standards are established by various national health departments, the world health organization and the like. The sanitary Standard for Drinking Water (GB5749-2006) issued by the Ministry of health in China in 2006 requires that the copper content is lower than 16 mu mol/L, the Water quality criteria of the World Health Organization (WHO) requires that the copper content is lower than 32 mu mol/L, the Water Commission of the European Union (1998) requires that the copper content is lower than 32 mu mol/L, the national Standard for Drinking Water quality (2012) of the United states EPA requires that the copper content is lower than 20 mu mol/L and the Water quality Standard for Drinking Water in Japan requires that the copper content is lower than 16 mu mol/L. In view of the toxicity of copper to aquatic organisms and the water quality standard requirement of copper in China, the long-term dangerous concentration of copper when 95% of species are protected is lower than 0.15umol/L, the final acute value in the fresh water quality standard of copper newly revised by the U.S. environmental protection agency in 2007 is 0.074 mu mol/L, and the final chronic value is 0.023 mu mol/L (EPA-822-R-07-001). In the surface water environmental quality standards of copper promulgated by China and the world health organization, the standard of I-class water quality copper is 0.16 mu mol/L, and the standard of II-class water quality copper is 16 mu mol/L; the standard of fishery water issued by many countries is strictly higher than the human health standard, and the standard of fishery water copper is 0.16 mu mol/L. In addition, when the copper ion bactericide is used for preventing and treating agricultural product diseases, excess copper ions are destructive to soil (environmental International 36(2010) 138-151), and corresponding soil quality standards are established in various countries aiming at soil pollution. China issued soil environmental quality standards (GB15618-1995) in 1995 required the copper ion content in agricultural soil of farmlands and the like, wherein the first-level standard is lower than 35mg/kg, and the second-level standard is lower than 50 mg/kg. Therefore, in order to apply the copper ion bactericide more widely and simultaneously require to prevent harm to the environment, animals, plants and human bodies in the application process, the development of how to improve the efficiency and the sterilization speed of the copper ion bactericide and reduce the toxic side effect of the bactericide becomes an urgent task, and the realization of a novel environment-friendly, efficient, mass-producible and cheap bactericide reagent or material is still a major problem in the current sterilization application aspect.
Meanwhile, with the vigorous development of current nanotechnology, the application of nanomaterials in biology and medical science and technology, the interaction between nanomaterials and cells has attracted attention, including the transmembrane effect of 0-dimensional fullerene, the cell-penetrating effect of 1-dimensional carbon nanotubes, the cutting of 2-dimensional graphene on cells, the large-scale extraction effect of phospholipid molecules of cell membranes, and the like. These studies and discoveries have stimulated extensive and ever-increasing research interest in the sterilization of nanomaterials, even though they are controversial.
Disclosure of Invention
The first purpose of the invention is to provide an environment-friendly efficient nano copper ion compound.
The second purpose of the invention is to provide a preparation method of the environment-friendly and efficient nano copper ion composite.
The third purpose of the invention is to provide the application of the environment-friendly efficient nano copper ion compound in preparing bactericide drugs.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an environment-friendly efficient nano copper ion compound, which consists of a copper ion solution with the concentration of 5-200 mu mol/L and a graphene solution with the concentration of 40-100 mg/L, wherein the volume ratio of the copper ion solution to the graphene solution is (0.5-2): 1.
The volume ratio of the copper ion solution to the graphene solution is 1: 1.
The copper ion solution is Cu2+The ionic solution is prepared by dissolving one of cupric chloride, cupric fluoride, cupric bromide, cupric sulfate, cupric nitrate, etc. in water to produce Cu2+Ionic solutions, with copper sulfate solution being the most preferred.
The graphene solution refers to a graphene oxide solution prepared by an oxidation exfoliation graphite method (i.e. Hummers method) and a reduced graphene oxide solution prepared by further reducing the graphene oxide solution, wherein the suspended graphene sheet layer is a monoatomic layer (about 0.5-1.0 nm) thick, and the sheet size diameter is 5-50 μm.
The second aspect of the invention provides a preparation method of the environment-friendly high-efficiency nano copper ion compound, which comprises the following steps: and mixing the copper ion solution with the concentration of 5-200 mu mol/L and the graphene solution with the concentration of 40-100 mg/L according to the volume ratio of (0.5-2) to 1 to obtain the environment-friendly efficient nano copper ion composite.
The third aspect of the invention provides application of the environment-friendly efficient nano copper ion compound in preparing bactericide medicaments in agriculture or other fields.
Other fields refer to the fields of daily necessities, washing products and the like.
The invention provides a bactericide composition, which contains the environment-friendly high-efficiency nano copper ion compound as an active component; wherein, the weight percentage of the active components in the bactericide composition is 0.1 to 99 percent.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the invention provides an environment-friendly high-efficiency nano copper ion compound, which aims to solve the technical problem that the biological toxicity (harm to animals, plants and human bodies) caused by high ion concentration of the existing copper ion bactericide is overcome by utilizing the broad-spectrum bactericidal characteristic of copper ions, so that the copper ion compound becomes a high-efficiency, quick and low-toxicity bactericide. The invention can ensure that the traditional copper ion bactericide can keep the extremely low environmental copper ion concentration level (less than 0.2 mu mol/L), basically meets the quality standard requirement of freshwater biological water of copper in China, ensures that the long-term dangerous concentration of copper is less than 0.15 mu mol/L when 95 percent of species are protected, realizes that the sterilization effect is improved by two orders of magnitude, namely, the novel sterilization reagent has the advantages of environmental protection, high efficiency, mass production and low cost, and has good application prospect.
The graphene does not have a bactericidal effect, and the environment-friendly efficient nano copper ion compound provided by the invention is based on the ion pi interaction between copper ions and graphene from the functional angle of the graphene, utilizes the high adsorbability of the graphene oxide to the copper ions, and realizes the transfer of the copper ions to the surface of bacteria at low concentration through the electrostatic interaction between the graphene with positively charged ions and the bacterial cell membrane with negatively charged ions after adsorption, so as to realize the enrichment of the surface of the bacteria with the copper ions at high concentration locally, and finally realize the two-order enhancement of the bactericidal effect of the copper ions under the condition of keeping the extremely low environmental copper ion concentration.
Drawings
FIG. 1 is a graph showing the comparison of the bactericidal effect of the environmentally-friendly and highly effective nano copper ion complex and the conventional copper ion bactericide on Escherichia coli in example 1.
FIG. 2 is a graph comparing the bactericidal effect of the environmentally-friendly and highly effective nano-copper ion complex of example 2 and the conventional copper ion bactericide on Staphylococcus aureus.
FIG. 3 is a graph comparing the killing effect of the environmentally-friendly and highly effective nano-copper ion complex of example 3 and the conventional copper ion bactericide on Chlamydomonas reinhardtii.
FIG. 4 is a graph comparing the killing effect of the environmentally-friendly and highly effective nano-copper ion complex and the traditional copper ion bactericide on blue algae in example 4.
Fig. 5 is a schematic process flow diagram of the environment-friendly efficient nano copper ion composite.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The reagents used in the present invention are shown in table 1:
table 1 preparation of graphene oxide materials as main raw materials
Name of raw materials Specification of Manufacturer of the product
Natural graphite (C) Analytically pure (A.R.)325 mesh Shanghai colloid chemical plant
Hydrochloric acid (HCl) Analytically pure (A.R.) SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Phosphorus pentoxide (P)2O5) Analytically pure (A.R.) SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Potassium persulfate (K)2S2O8) Analytically pure (A.R.) SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Potassium permanganate (KMnO)4) Analytically pure (A.R.) SHANGHAI HAOSHEN CHEMICAL REAGENT Co.,Ltd.
Hydrogen peroxide (H)2O2) Analytically pure (A.R.) SHANGHAI HAOSHEN CHEMICAL REAGENT Co.,Ltd.
Concentrated sulfuric acid (H)2SO4) Analytically pure (A.R.) SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Copper sulfate (CuSO)4·5H2O) Analytically pure (A.R.) SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Cupric chloride (CuCl)2·2H2O) Analytically pure (A.R.) SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Copper fluoride (CuF)2·2H2O) Analytically pure (A.R.) SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Copper nitrate (Cu (NO)3)2·2.5H2O) Analytically pure (A.R.) SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Deionized water Ultrapure water purifier from Sartorius Arium611 of germany
Example 1
As shown in fig. 5, fig. 5 is a schematic process flow diagram of the environment-friendly and efficient nano copper ion composite.
A preparation method of an environment-friendly high-efficiency nano copper ion compound comprises the following steps: mixing a copper ion solution with the concentration of 100 mu mol/L and a graphene solution with the concentration of 80mg/L according to the volume ratio of 1:1 to obtain the environment-friendly efficient nano copper ion compound.
The copper ion solution: with copper sulphate (CuSO)4·5H2O) preparing 100 mu mol/L aqueous solution of crystals, and then filtering the solution by using a 0.22 mu m filter membrane, wherein the mother solution can be stored at room temperature.
The graphene solution is prepared by an oxidation exfoliation graphite method (Hummers method), wherein the suspended graphene sheets are about 0.5nm thick in terms of a monoatomic layer thickness, and the sheet size diameter is 5-50 μm.
And mixing the environment-friendly efficient nano copper ion compound with a solution containing bacteria or algae and needing to be treated according to an equal volume ratio, and reacting at room temperature for 2 hours, wherein the concentration of graphene oxide in the system is 40mg/L, the concentration of the mixed copper ions is 50 mu mol/L, and the concentration level of environmental copper ions (free copper ions) is less than 0.2 mu mol/L. (the mixed solution was passed through a microfiltration filter having a pore size of 0.22 μm, vacuum-filtered to remove graphene oxide, and then the results were measured using a plasma emission spectrometer (ICP-OES) experiment.)
The bactericidal activity is detected by adopting a clone counting method: the concentration of Escherichia coli is 108mL-1And performing a bactericidal activity experiment by using the deionized water solution, the 3 mu mol/L pure copper ion solution and the environment-friendly high-efficiency nano copper ion compound. Wherein the aqueous solution is used as controlExperiment, 3 mu mol/L pure copper ion solution is used as a reference control experiment for the sterilizing effect of the traditional copper ion bactericide. The test samples were subjected to the antibacterial test by shaking continuously at 200rpm for 2 hours at room temperature. Each sample was diluted 10 with a standard series of dilutions4Double, and from each sample 500 u L suspension evenly spread on LB agar plate, at 37 degrees C were incubated for 24 hours, counting the number of live bacterial colonies. The ratio of the number of the bacterial colonies in the aqueous solution contrast experiment to the number of the bacterial colonies in the environment-friendly high-efficiency nano copper ion composite sterilization experiment is taken as the antibacterial activity of the environment-friendly high-efficiency nano copper ion composite.
As shown in fig. 1, fig. 1 is a comparison graph of the bactericidal effect of the environmentally-friendly and efficient nano copper ion composite in example 1 and the bactericidal effect of the traditional copper ion bactericide on escherichia coli, and the bactericidal ability of the environmentally-friendly and efficient nano copper ion composite is improved by two orders of magnitude (225 times) compared with that of the traditional copper ion bactericide under the condition that the extremely low environmental copper ion concentration level (less than 0.2 μmol/L, which basically meets the water quality standard requirement of freshwater organisms of copper in China and the long-term dangerous concentration of copper should be less than 0.15 μmol/L when 95% of species are protected) is maintained.
Example 2
A preparation method of an environment-friendly high-efficiency nano copper ion compound comprises the following steps: mixing a copper ion solution with the concentration of 100 mu mol/L and a graphene solution with the concentration of 80mg/L according to the volume ratio of 1:1 to obtain the environment-friendly efficient nano copper ion compound.
The copper ion solution: with copper chloride (CuCl)2·2H2O) preparing 100 mu mol/L aqueous solution of crystals, and then filtering the solution by using a 0.22 mu m filter membrane, wherein the mother solution can be stored at room temperature.
The graphene solution is prepared by an oxidation exfoliation graphite method (Hummers method), wherein the suspended graphene sheets are about 0.5nm thick in terms of a monoatomic layer thickness, and the sheet size diameter is 5-50 μm.
And mixing the environment-friendly efficient nano copper ion compound with a solution containing bacteria or algae and needing to be treated according to an equal volume ratio, and reacting at room temperature for 2 hours, wherein the concentration of graphene oxide in the system is 40mg/L, the concentration of the mixed copper ions is 50 mu mol/L, and the concentration level of environmental copper ions (free copper ions) is less than 0.2 mu mol/L.
And (3) detecting the bactericidal activity by adopting a clone counting method. Staphylococcus aureus concentration of 1010mL-1And performing a bactericidal activity experiment by using the deionized water solution, the 3 mu mol/L pure copper ion solution and the environment-friendly high-efficiency nano copper ion compound. The water solution is used as a control experiment, and the 3 mu mol/L pure copper ion solution is used as a reference control experiment for the sterilizing effect of the traditional copper ion bactericide. The test samples were subjected to the antibacterial test by shaking continuously at 200rpm for 2 hours at room temperature. Each sample was diluted 10 with a standard series of dilutions4Double, and from each sample 500 u L suspension evenly spread on LB agar plate, at 37 degrees C were incubated for 24 hours, counting the number of live bacterial colonies. The ratio of the number of the bacterial colonies in the aqueous solution contrast experiment to the number of the bacterial colonies in the environment-friendly high-efficiency nano copper ion composite sterilization experiment is taken as the antibacterial activity of the environment-friendly high-efficiency nano copper ion composite.
As shown in FIG. 2, FIG. 2 is a graph comparing the bactericidal effect of the environmentally-friendly and highly effective nano-copper ion complex on Staphylococcus aureus in example 2 with that of the conventional copper ion bactericide. Under the condition of keeping an extremely low environmental copper ion concentration level (less than 0.2 mu mol/L, basically meeting the water quality standard requirement of freshwater organisms of copper in China and protecting the long-term dangerous concentration of copper to be less than 0.15 mu mol/L when 95 percent of species are protected), the sterilizing capability of the environment-friendly high-efficiency nano copper ion compound is improved by one order of magnitude (23 times) compared with the sterilizing effect of the traditional copper ion bactericide.
Example 3
A preparation method of an environment-friendly high-efficiency nano copper ion compound comprises the following steps: mixing a copper ion solution with the concentration of 100 mu mol/L and a graphene solution with the concentration of 80mg/L according to the volume ratio of 1:1 to obtain the environment-friendly efficient nano copper ion compound.
The copper ion solution: with copper fluoride (CuF)2·2H2O) preparing 100 mu mol/L aqueous solution of crystals, and then filtering the solution by using a 0.22 mu m filter membrane, wherein the mother solution can be stored at room temperature.
The graphene solution is prepared by an oxidation exfoliation graphite method (Hummers method), wherein the suspended graphene sheets are about 0.5nm thick in terms of a monoatomic layer thickness, and the sheet size diameter is 5-50 μm:
and mixing the environment-friendly efficient nano copper ion compound with a solution containing bacteria or algae and needing to be treated according to an equal volume ratio, and reacting at room temperature for 2 hours, wherein the concentration of graphene oxide in the system is 40mg/L, the concentration of the mixed copper ions is 50 mu mol/L, and the concentration level of environmental copper ions (free copper ions) is less than 0.2 mu mol/L.
Chlamydomonas reinhardtii activity was determined by Fluorescein Diacetate (FDA) staining imaging. Chlamydomonas reinhardtii concentration is 106mL-1The algae killing activity experiment is carried out by using deionized water solution, 3 mu mol/L pure copper ion solution and environment-friendly high-efficiency nano copper ion compound. The water solution is used as a control experiment, and a 3 mu mol/L pure copper ion solution is used as a reference control experiment for the algae killing effect of the traditional copper ion algicide. The experimental samples were incubated at room temperature for 30 minutes for Chlamydomonas reinhardtii testing, followed by FDA staining of the cells for 5 minutes and identification of viable cells by green fluorescence of fluorescein. 20 μ L of cell suspension from each sample was spread evenly over a siliconized glass cover slip. Fluorescence pictures were taken using an inverted confocal microscope system and viable cell counts were calculated. The ratio of the number of cells in the aqueous solution control experiment to the number of cells in the environment-friendly high-efficiency nano copper ion composite algae killing experiment is used as the algae killing activity of the environment-friendly high-efficiency nano copper ion composite.
As shown in FIG. 3, FIG. 3 is a graph comparing the killing effect of the environmentally-friendly and highly effective nano-copper ion complex of example 3 and the conventional copper ion bactericide on Chlamydomonas reinhardtii. Under the condition of keeping an extremely low environmental copper ion concentration level (less than 0.2 mu mol/L, basically meeting the water quality standard requirement of freshwater organisms of copper in China and ensuring that the long-term dangerous concentration of copper is lower than 0.15 mu mol/L when 95 percent of species are protected), the algae killing capability of the environment-friendly high-efficiency nano copper ion compound is improved by one order of magnitude (about 27 times) compared with the algae killing effect of the traditional copper ion algicide.
Example 4
A preparation method of an environment-friendly high-efficiency nano copper ion compound comprises the following steps: mixing a copper ion solution with the concentration of 100 mu mol/L and a graphene solution with the concentration of 80mg/L according to the volume ratio of 1:1 to obtain the environment-friendly efficient nano copper ion compound.
The copper ion solution: with copper nitrate (Cu (NO)3)2·2.5H2O) preparing 100 mu mol/L aqueous solution of crystals, and then filtering the solution by using a 0.22 mu m filter membrane, wherein the mother solution can be stored at room temperature.
The graphene solution is prepared by an oxidation exfoliation graphite method (Hummers method), wherein the suspended graphene sheets are about 0.5nm thick in terms of a monoatomic layer thickness, and the sheet size diameter is 5-50 μm:
and mixing the environment-friendly efficient nano copper ion compound with a solution containing bacteria or algae and needing to be treated according to an equal volume ratio, and reacting at room temperature for 2 hours, wherein the concentration of graphene oxide in the system is 40mg/L, the concentration of the mixed copper ions is 50 mu mol/L, and the concentration level of environmental copper ions (free copper ions) is less than 0.2 mu mol/L.
The blue algae killing activity is determined by a Fluorescein Diacetate (FDA) staining imaging method. The concentration of the blue algae is 106mL-1The blue algae killing activity experiment is carried out by using deionized water solution, 3 mu mol/L pure copper ion solution and an environment-friendly high-efficiency nano copper ion compound. The water solution is used as a control experiment, and a 3 mu mol/L pure copper ion solution is used as a reference control experiment for the algae killing effect of the traditional copper ion algicide. The experimental sample is incubated for 30 minutes at room temperature for blue algae killing test, then the cells are dyed and incubated for 5 minutes by FDA, and the living cells are identified by the green fluorescence of fluorescein. 20 μ L of cell suspension from each sample was spread evenly over a siliconized glass cover slip. The fluorescence intensity of fluorescein at 512nm was measured with a fluorescence spectrophotometer, and the number of living cells was calculated from the direct ratio of the fluorescence intensity to the number of living cells. The ratio of the number of cells in the aqueous solution contrast experiment to the number of cells in the experiment for killing the blue-green algae by the nano copper ion compound is used as the blue-green algae killing activity of the environment-friendly high-efficiency nano copper ion compound.
As shown in FIG. 4, FIG. 4 is a graph comparing the killing effect of the environmentally-friendly and highly effective nano-copper ion complex and the traditional copper ion bactericide on blue algae in example 4. The blue algae killing capability of the environment-friendly high-efficiency nano copper ion compound is improved by 6 times compared with the blue algae killing effect of the traditional copper ion algicide under the condition that the extremely low environmental copper ion concentration level (less than 0.2 mu mol/L) is kept, the freshwater biological water quality standard requirement of copper in China is basically met, and the long-term dangerous concentration of copper is lower than 0.15 mu mol/L when 95% of species are protected.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. The environment-friendly efficient nano copper ion compound is characterized by consisting of a copper ion solution with the concentration of 5-200 mu mol/L and a graphene solution with the concentration of 40-100 mg/L, wherein the volume ratio of the copper ion solution to the graphene solution is (0.5-2): 1.
2. The environment-friendly efficient nano copper ion composite according to claim 1, wherein the volume ratio of the copper ion solution to the graphene solution is 1: 1.
3. The environmentally friendly and efficient nano copper ion composite according to claim 1, wherein the copper ion solution is Cu2+An ionic solution.
4. The environment-friendly efficient nano copper ion composite as claimed in claim 3, wherein the copper ion solution is Cu generated by dissolving one of copper chloride, copper fluoride, copper bromide, copper sulfate and copper nitrate in water2+Of ionsAnd (3) solution.
5. The environment-friendly efficient nano copper ion composite according to claim 1, wherein the graphene solution is a graphene oxide solution prepared by an oxidation stripping graphite method and a reduced graphene oxide solution prepared by further reduction of the graphene oxide solution, wherein the suspended graphene sheets are about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet size diameter is 5-50 μm.
6. The preparation method of the environment-friendly high-efficiency nano copper ion composite as claimed in any one of claims 1 to 5, characterized by comprising the following steps: and mixing the copper ion solution with the concentration of 5-200 mu mol/L and the graphene solution with the concentration of 40-100 mg/L according to the volume ratio of (0.5-2) to 1 to obtain the environment-friendly efficient nano copper ion composite.
7. Use of the environment-friendly efficient nano copper ion complex as defined in any one of claims 1 to 5 in agriculture or other fields for preparing bactericide medicaments.
8. A bactericide composition, which is characterized by comprising the environment-friendly high-efficiency nano copper ion complex as claimed in any one of claims 1 to 5 as an active component; wherein, the weight percentage of the active components in the bactericide composition is 0.1 to 99 percent.
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CN107114407A (en) * 2017-05-26 2017-09-01 中国石油大学(华东) The preparation method and application of Nanometer Copper zinc composite antibacterial material
RU2698713C1 (en) * 2018-11-28 2019-08-29 федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный университет имени Г.Р. Державина" Method of producing composite material with antimicrobial properties based on graphene oxide and copper oxide nanoparticles

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CN114044992A (en) * 2021-11-29 2022-02-15 厦门福纳新材料科技有限公司 Copper-containing antibacterial polymer composite material and preparation method and application thereof

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