CN113307300A - Nano cuprous oxide and preparation method and application thereof - Google Patents
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Abstract
The invention provides nano cuprous oxide and a preparation method and application thereof. The preparation method of the nano cuprous oxide comprises the following steps: carrying out double decomposition reaction on a divalent copper salt and a basic substance in a solvent to obtain a precipitate; dispersing the precipitate in a dispersant, adding a reducing agent for reduction reaction, taking the solid, and drying to obtain nano cuprous oxide; wherein the double decomposition reaction and the reduction reaction are carried out for 0.5 to 4 hours at the temperature of between 10 and 37 ℃; the ratio of the amount of copper ions, alkaline substances and reducing agents in the cupric salt is 1 (1.5-3.5) to 0.01-1.0; the alkaline substance is at least one of ammonia water and alkali metal hydroxide. The preparation method of the nano cuprous oxide can prepare the cuprous oxide with nano size and antibacterial and antiviral performance by regulating the raw materials in a specific proportion range and simultaneously controlling the double decomposition reaction and the reduction reaction to be carried out under specific conditions through a two-step method.
Description
Technical Field
The invention relates to the technical field of antibacterial material synthesis, in particular to nano cuprous oxide and a preparation method and application thereof.
Background
The antibacterial material is a novel functional material with the function of killing or inhibiting microorganisms. Cuprous oxide is an oxide of monovalent copper and is also a p-type semiconductor with a forbidden band width of 2.17 eV. The cuprous oxide has high cost performance, acceptable cost and unique physical and chemical properties, and can be widely applied to the fields of ship antifouling paint, textiles, building materials, plastics, air conditioner filter screens, animal feeds, agricultural bactericides, ceramics, glass, photocatalysis and the like. Cuprous oxide also has certain antibacterial performance, but the antibacterial performance of the cuprous oxide is greatly related to the existing state of the cuprous oxide. Generally, cuprous oxide in micron or submicron level has only weak antibacterial activity, while cuprous oxide in nanometer size has higher antibacterial activity due to its unique size effect and morphology structure.
Micron-sized or submicron-sized cuprous oxide is already industrially produced, the powder appearance color usually presents brick red or bright red, the powder is not easy to dissolve in water, the powder can be slowly oxidized into black copper oxide in humid air, the dispersibility of the powder in water is poor, the powder can be precipitated after standing for one night, and the application scene is limited due to the micron-sized or submicron-sized copper oxide. The nano-sized cuprous oxide, although having better antibacterial activity, is easily oxidized by air, and the instability and the complexity of the scale-up production process limit the industrial mass production application.
At present, a plurality of related patent applications are available for the preparation and the bacteriostatic application of the nano-scale cuprous oxide. A technology discloses that a bacterial cellulose hydrogel containing a glucose solution is soaked in an aqueous solution of NaOH and copper ions, heating and pressurizing are carried out to react to obtain a bacterial cellulose composite cuprous oxide antibacterial dressing, and the obtained brick red cuprous oxide with a micron-sized octahedral crystal form is actually not nano-scale, while the antibacterial effect of large-size cuprous oxide depends on a larger addition amount. The other technology discloses a preparation method of a visible light excitation antibacterial coating containing nano cuprous oxide, the obtained 600nm large-size cubic cuprous oxide still has the actual size which is not the nano size, and nano Ag or ZnO nano particles are required to be doped to play a good antibacterial activity.
In conclusion, currently, the cuprous oxide which is industrially produced and applied is basically more than micron scale, the antibacterial performance of the cuprous oxide is generally poor, and other antibacterial active ingredients are required to be added to realize a better antibacterial function.
Disclosure of Invention
Based on the problem that the traditional micron-sized cuprous oxide is poor in antibacterial performance, the nano cuprous oxide with good antibacterial performance and the preparation method and application thereof are needed to be provided.
The invention is realized by the following technical scheme.
One aspect of the invention provides a preparation method of nano cuprous oxide, which comprises the following steps:
carrying out double decomposition reaction on a divalent copper salt and a basic substance in a solvent to obtain a precipitate;
dispersing the precipitate in a dispersing agent, adding a reducing agent for reduction reaction, taking a solid, and drying to obtain the nano cuprous oxide;
wherein the double decomposition reaction and the reduction reaction are carried out under the conditions of 10-37 ℃ for 0.5-4 h; the ratio of the amounts of the copper ions, the alkaline substance and the reducing agent in the cupric salt is 1 (1.5-3.5) to 0.01-1.0; the alkaline substance is at least one of ammonia water and alkali metal hydroxide.
In all embodiments, the ratio of the amounts of the copper ions, the alkaline substance and the reducing agent in the cupric salt is 1 (1.5-3.5) to 0.04-1.0.
In some of these embodiments, the cupric salt is at least one of copper sulfate, copper nitrate, copper chloride, and copper acetate.
In some of these embodiments, the solvent is water.
In some of these embodiments, the reducing agent is at least one of sodium borohydride, sodium hypophosphite, and ascorbic acid; and/or
The dispersant is water.
In some embodiments, the ratio of the amounts of the copper ions, the alkaline substance and the reducing agent in the cupric salt is 1 (1.5-3.5) to 0.01-1.0.
When the amount ratio of the copper ions, the alkaline substance and the reducing agent in the cupric salt is controlled to be 1 (1.5-3.5) to 0.04-0.5, the yellow-green nano cuprous oxide with the shape of the coexistence of the nano rod and the round cake is prepared;
when the amount ratio of the copper ions, the alkaline substance and the reducing agent in the cupric salt is controlled to be 1 (1.5-3.5) to 0.55-1.0, the orange-yellow round cake-shaped nano cuprous oxide is prepared.
The invention also provides nano cuprous oxide prepared by the preparation method.
In some of these embodiments, the nano-cuprous oxide is yellow-green or orange-yellow; the minimum inhibitory concentration of the nano cuprous oxide to staphylococcus aureus and escherichia coli is 8 ppm-16 ppm.
In some embodiments, the nano cuprous oxide is yellow green, and has a shape of a nano rod and a round cake.
In some of the embodiments, the nano cuprous oxide is orange yellow and is cake-shaped.
The invention further provides application of the nano cuprous oxide in preparing antibacterial materials.
In another aspect, the invention provides an antibacterial material, which contains the nano cuprous oxide described in any one of the above.
The preparation method of the nano cuprous oxide can prepare the nano cuprous oxide by controlling the amount of copper ions, alkaline substances and reducing agents in the cupric salt in a specific ratio range through a two-step method and controlling the double decomposition reaction and the reduction reaction to be carried out under specific conditions. The preparation method of the nano cuprous oxide has the advantages of simple process, no need of special high-temperature and high-pressure conditions and equipment, simple and easily-controlled preparation flow, strong operability, safety, environmental protection and convenience for industrial production; in addition, a surfactant or a dispersing agent is not required to be added, the prepared nano cuprous oxide is not required to be doped with other metals such as noble metal nano silver and the like which have high toxicity and are easy to discolor, is not required to be compounded with other semiconductors such as zinc oxide, titanium dioxide, silicon dioxide, aluminum oxide, iron oxide, nickel oxide and the like, is not required to be compounded with high molecular substances such as chitosan nano fiber and the like, is not required to be used together with other antibacterial active ingredients, and has very excellent antibacterial and influenza virus killing performances.
Drawings
FIG. 1 is a diagram showing the nano cuprous oxide obtained in example 5 and example 23 of the present invention and the micro cuprous oxide obtained in comparative example 1;
FIG. 2 is an SEM image of yellowish green nano-cuprous oxide prepared in example 5 of the present invention;
FIG. 3 is an SEM picture of orange-yellow nano-cuprous oxide prepared by example 23 of the present invention;
FIG. 4 is an SEM image of brick red micron cuprous oxide prepared by comparative example 1 of the present invention;
FIG. 5 is an XRD pattern of nano-cuprous oxide prepared by the method of example 5 and example 23;
FIG. 6 is a comparison graph of the bacteriostatic effect of the blank control and the nano-cuprous oxide added with 16ppm in example 5 and example 23 on Staphylococcus aureus;
FIG. 7 is a comparison graph of the bacteriostatic effect of the blank control and the bacteriostatic effect of the addition of 16ppm nano-cuprous oxide on Escherichia coli in example 5 and example 23.
Fig. 8 is a dispersion diagram of nano cuprous oxide in water prepared in example 5 and example 23.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The nano cuprous oxide of the present invention will be described in detail below with reference to the method for preparing nano cuprous oxide of the present invention.
An embodiment of the invention provides a preparation method of nano cuprous oxide, which comprises the following steps of S10-S20:
s10: carrying out double decomposition reaction on a divalent copper salt and a basic substance in a solvent to obtain a precipitate. Wherein the double decomposition reaction is carried out for 0.5-4 h at the temperature of 10-37 ℃.
Step S10 is performed under mild conditions by controlling the metathesis reaction of the cupric salt and the basic substance in the solvent, which is favorable for obtaining a precipitate with a smaller particle size, so as to obtain cuprous oxide with a nano size.
In some of these embodiments, the metathesis reaction conditions are preferably from 10 ℃ to 37 ℃ for from 0.5h to 4 h. In this preferred range, it is more advantageous to obtain cuprous oxide of nanometer size. Specifically, the temperature of the double decomposition reaction can be 10 ℃, 25 ℃ and 37 ℃, and the reaction time can be 0.5h, 1h and 4 h.
In some of these embodiments, the cupric salt is at least one of copper sulfate, copper nitrate, copper chloride, and copper acetate. It is understood that the divalent copper salt is not limited thereto, and it may be all water-soluble divalent copper salts.
In some of these embodiments, the alkaline material is at least one of ammonia and an alkali metal hydroxide. Further, the alkaline substance is at least one of ammonia water, sodium hydroxide and potassium hydroxide. It is understood that the alkaline substance is not limited thereto, and may be all water-soluble alkaline substances.
In some of these embodiments, the solvent is water. Thus, the preparation method does not use organic solvent, can reduce cost and reduce environmental pollution.
In some embodiments, after the metathesis reaction is completed, the precipitate can be obtained by solid-liquid separation such as centrifugation.
S20: dispersing the precipitate in a dispersant, adding a reducing agent for reduction reaction, taking the solid, and drying to obtain the nano cuprous oxide. Wherein the reduction reaction is carried out for 0.5 to 4 hours at the temperature of between 10 and 37 ℃; the ratio of the amounts of the copper ions, the alkaline substance and the reducing agent in the cupric salt is 1 (1.5-3.5) to 0.01-1.0.
The step S20 is advantageous to obtain the precipitate with smaller particle size by controlling the precipitate and the reducing agent to be performed under milder conditions, so as to obtain the cuprous oxide with nanometer size.
In some embodiments, the reduction reaction is preferably carried out at 10 ℃ to 37 ℃ for 0.5h to 4 h. In this preferred range, it is more advantageous to obtain cuprous oxide of nanometer size. Specifically, the temperature of the reduction reaction can be 10 ℃, 25 ℃ and 37 ℃, and the reaction time can be 0.5h, 1h and 4 h.
Wherein the ratio of the amounts of the copper ions, the basic substance and the reducing agent in the cupric salt is the ratio of the amount of the copper ions and the basic substance in the cupric salt to the amount of the reducing agent in step S20, which is required for the precipitate used in step S20.
Furthermore, the ratio of the amounts of the copper ions, the alkaline substance and the reducing agent in the cupric salt is preferably 1 (1.5-3.5) to 0.04-0.5, so as to obtain yellowish green cuprous oxide particles.
Furthermore, when the ratio of the amount of the copper ions, the alkaline substance and the reducing agent in the cupric salt is preferably 1 (1.5-3.5) to 0.55-1.0, the orange-yellow nano cuprous oxide is prepared.
It is understood that both step S10 and step S20 are performed under normal pressure.
In some of these embodiments, the reducing agent is at least one of sodium borohydride, sodium hypophosphite, and ascorbic acid. In some of these embodiments, the dispersant is water.
In some embodiments, the solid extraction can be achieved by solid-liquid separation such as centrifugation. The method also comprises a step of water washing before drying. The drying can be carried out in a vacuum manner.
The preparation method of the nano cuprous oxide can prepare the nano cuprous oxide by controlling the amount of copper ions, alkaline substances and reducing agents in the cupric salt in a specific ratio range through a two-step method and controlling the double decomposition reaction and the reduction reaction to be carried out under specific conditions. The preparation method of the nano cuprous oxide has the advantages of simple process, no need of special high-temperature and high-pressure conditions and equipment, simple and easily-controlled preparation flow, strong operability, safety, environmental protection and convenience for industrial production; in addition, a surfactant or a dispersing agent is not required to be added, the prepared nano cuprous oxide is not required to be doped with other metals such as noble metal nano silver with high toxicity and easy discoloration, is not required to be compounded with other semiconductors such as zinc oxide, titanium dioxide, silicon dioxide, aluminum oxide, iron oxide, nickel oxide and the like, is not required to be compounded with high molecular substances such as chitosan nano fiber and the like, is not required to be used together with other antibacterial active ingredients, and has very excellent antibacterial and antiviral properties.
An embodiment of the present invention further provides cuprous oxide nanoparticles prepared by the preparation method of cuprous oxide nanoparticles, wherein the cuprous oxide nanoparticles have a single component, a low dose, an excellent antibacterial effect, an excellent antibacterial property against escherichia coli and staphylococcus aureus, a broad-spectrum antibacterial property, and excellent antiviral properties, and can simultaneously resist gram-negative bacteria and gram-positive bacteria.
Specifically, the Minimum Inhibitory Concentration (MIC) of the nano cuprous oxide to staphylococcus aureus and escherichia coli is 8ppm to 16 ppm. Furthermore, the minimum inhibitory concentration of the nano cuprous oxide to staphylococcus aureus and escherichia coli is 12 ppm-16 ppm. The killing rate of the suspension containing 1000ppm of nano cuprous oxide to influenza virus H1N1 reaches 99.9997%.
According to test results, the nano cuprous oxide can reach 99.9% of bacteriostasis rate at the minimum bacteriostasis concentration of staphylococcus aureus and escherichia coli, such as 16 ppm. The killing rate of the nano cuprous oxide suspension with the concentration of 1000ppm to influenza virus H1N1 reaches 99.9997%.
The preparation method of the nano cuprous oxide can be used for preparing the nano cuprous oxide which has controllable size, shape and color and can be used as an antibacterial nano material by regulating and controlling the quantity ratio of the copper ions, the alkaline substances and the reducing agent in the cupric salt.
The nano cuprous oxide synthesized by the preparation method of the nano cuprous oxide has yellowish green and orange yellow macroscopically, and the nano cuprous oxide has excellent antibacterial and antiviral effects.
When the ratio of the amount of the copper ions, the alkaline substance and the reducing agent in the cupric salt is 1 (1.5-3.5) to 0.04-0.5, the prepared nano cuprous oxide is yellow green.
In some embodiments, the nano cuprous oxide is yellow green, and has a shape of a nano rod and a round cake. Furthermore, the diameter of the nano rod is 20 nm-40 nm, the length of the nano rod is 200 nm-400 nm, and the grain diameter of the round cake-shaped grains is 30 nm-110 nm.
When the ratio of the amount of the copper ions, the alkaline substance and the reducing agent in the cupric salt is 1 (1.5-3.5) to 0.55-1.0, the prepared nano cuprous oxide is orange yellow.
In some of these embodiments, the nano-cuprous oxide is orange yellow and is a cake-like particle. Further, the particle diameter of the cake-shaped particles is 50nm to 120 nm.
Further research shows that the prepared yellowish green and orange-yellow nano cuprous oxide water, ethanol, methanol, isopropanol, DMF and DMSO can be uniformly dispersed in a solution or in a molten state of high molecular polymer materials such as Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), Polystyrene (PS) and modified polystyrene (ABS), and the powder is not discolored after being placed in the air for a long time, is stable and not easily oxidized and is convenient to store in the air for a long time.
The nano cuprous oxide has excellent antibacterial and antiviral effects, and can be used as an antibacterial nano material or an antiviral material.
An embodiment of the invention also provides application of any one of the nano cuprous oxides in preparation of antibacterial materials or antiviral materials.
An embodiment of the invention also provides an antibacterial and antiviral material, which comprises any one of the nano cuprous oxide.
It is understood that the antibacterial and antiviral material can also contain other antibacterial active ingredients besides the nano cuprous oxide of any one of the above.
The technical solution of the present invention is further explained and illustrated below in the form of specific examples, which are intended to help the understanding of the present invention without limiting the same. It should also be emphasized that various modifications of the invention, which are obvious to those skilled in the art after reading the description herein, may be made, and such equivalent changes fall within the scope of the claims appended hereto.
Unless otherwise specified, the experimental procedures in the following examples are conventional, and the reagents and materials used are conventional biochemical reagents and materials.
Firstly, preparing a cupric salt:
(1) 2.5000g of CuSO4·5H2Adding O powder into 100mL of water, stirring and dissolving at room temperature to obtain a blue solution, namely a copper sulfate solution with the substance quantity concentration of 0.1 mol/L;
(2) 2.4160g of Cu (NO)3)2·3H2Adding O powder into 100mL of water, stirring and dissolving at room temperature to obtain a blue solution, namely a copper nitrate solution with the mass concentration of 0.1 mol/L;
(3) 1.7048g of CuCl2·2H2Adding O powder into 100mL of water, stirring and dissolving at room temperature to obtain a blue solution, namely a copper chloride solution with the mass concentration of 0.1 mol/L;
(4) 1.9965g of Cu (CH)3COO)2·H2Adding O powder into 100mL of water, stirring and dissolving at room temperature to obtain a blue solution, namely a copper acetate solution with the mass concentration of 0.1 mol/L;
preparation of di, alkali solution
(1) Adding 5.61g of potassium hydroxide powder into 100mL of water, stirring at room temperature to dissolve a colorless solution, namely a potassium hydroxide solution with the amount of a substance being 1 mol/L;
(2) adding 4.00g of sodium hydroxide powder into 100mL of water, stirring at room temperature to dissolve a colorless solution, namely a sodium hydroxide solution with the amount of a substance being 1 mol/L;
(3) 153.8mL of concentrated ammonia water (25%, density 0.91 g/cm)3) Diluting to 1L, namely obtaining the ammonia water solution with the substance amount of 1 mol/L.
Preparation of nano cuprous oxide
Examples 1 to 9
Step one, taking 9 parts of 100mL of 0.1mol/L copper sulfate solution, respectively adding 15mL of 1mol/L potassium hydroxide solution, and respectively stirring at 10 ℃ and normal pressure for reaction for 0.5h, 1h and 4 h; or stirring at 25 ℃ under normal pressure, wherein the reaction duration is 0.5h, 1h and 4h respectively; or stirring at 37 deg.C under normal pressure for 0.5h, 1h and 4h to obtain blue flocculent precipitate, centrifuging at 7500r/min to obtain substrate, and washing with deionized water for three times to obtain blue precipitate.
Step two, adding 100mL of water into 9 parts of the substrate obtained in the step one, stirring to uniformly disperse the substrate, respectively and gradually adding 20mL of 0.02mol/L sodium borohydride aqueous solution, stirring at 10 ℃ under normal pressure, and respectively reacting for 0.5h, 1h and 4 h; or stirring at 25 deg.C under normal pressure for 0.5h, 1h and 4 h; or stirring at 37 ℃ under normal pressure, keeping the reaction duration time of 0.5h, 1h and 4h respectively, centrifuging at 7500r/min to obtain 9 parts of product, washing with water for three times, and vacuum drying at 80 ℃ for 4h to obtain the product which is the yellow-green cuprous oxide nano-particles. The product obtained in example 5 is shown in FIG. 1 (a).
Some of the parameters of examples 1 to 9 are shown in Table 1 below
TABLE 1
| Group of | Step one | Step two |
| Example 1 | 10℃，0.5 |
10℃，0.5h |
| Example 2 | 10℃，1h | 10℃，1h |
| Example 3 | 10℃，4h | 10℃，4h |
| Example 4 | 25℃，0.5h | 25℃，0.5h |
| Example 5 | 25℃，1h | 25℃，1h |
| Example 6 | 25℃，4h | 25℃，4h |
| Example 7 | 37℃，0.5h | 37℃，0.5h |
| Example 8 | 37℃，1h | 37℃，1h |
| Example 9 | 37℃，4h | 37℃，4h |
From the above, it can be seen that, in the first double decomposition step, the reaction temperature is 10 ℃, 25 ℃ and 37 ℃, the stirring time is 0.5h, 1h and 4h, the obtained precipitate is blue, the obtained precipitate is taken as the precursor of the second copper step, the reduction reaction temperature is also 10 ℃, 25 ℃ and 37 ℃, the reaction stirring time is 0.5h, 1h and 4h, and after washing and drying, the obtained products are all yellow-green cuprous oxide nanoparticles, and no significant difference exists. The method shows that under the condition that other conditions are not changed, the temperature of the double decomposition reaction and the reduction reaction are controlled to be 10-37 ℃, the reaction time is 0.5-4 h, and the yellowish green cuprous oxide nano particles can be prepared under the mild condition.
Examples 10 to 12
The preparation processes of the embodiments 10 to 12 are basically the same as those of the embodiment 5, and the differences are that:
in the first step, the dosage of 1mol/L potassium hydroxide solution is respectively 20mL, 25mL and 35mL, the mixture is stirred for 1h at the temperature of 25 ℃ and under normal pressure, and all obtained precipitates are blue; and the products obtained in the second step are all yellow green cuprous oxide nano particles.
Examples 1 to 12 show that the products obtained by controlling the ratio of the amount of the copper salt, the amount of the alkali and the amount of the reducing agent substance to 1 (1.5 to 3.5) to 0.04 are all greenish yellow cuprous oxide nanoparticles.
Examples 13 to 14
Examples 13-14 are substantially the same as example 5 except that:
in the second step, the concentration of the 0.02mol/L sodium borohydride aqueous solution is 0.1mol/L and 0.25mol/L respectively, and the obtained products are all yellow green cuprous oxide nano particles.
Examples 5 and 10 to 14 show that the obtained products are all greenish yellow cuprous oxide nanoparticles by controlling the amount ratio of the copper salt, the alkali and the reducing agent substance to be 1 (1.5 to 3.5) and 0.04 to 0.5.
Examples 15 to 16
The preparation processes of the examples 15 to 16 are basically the same as those of the example 5, and the differences are that: and changing the 0.02mol/L sodium borohydride solution in the step two into a 0.02mol/L sodium hypophosphite solution and a 0.02mol/L ascorbic acid solution respectively to obtain the yellowish green cuprous oxide nano-particles.
Examples 5 and 15 to 16 show that sodium borohydride, sodium hypophosphite and ascorbic acid are used as reducing agents, and all obtained substances are yellow green cuprous oxide.
Examples 17 to 19 were substantially the same as example 5 except that: changing the 0.1mol/L copper sulfate solution in the first step into a 0.1mol/L copper nitrate solution, a 0.1mol/L copper chloride solution and a 0.1mol/L copper acetate solution respectively to obtain the yellowish green cuprous oxide nano-particles.
Examples 5 and 17 to 19 show that copper sulfate, copper nitrate, copper chloride and copper acetate are used as copper salts, and all the copper salts are yellow green cuprous oxide.
Examples 20 to 21
The preparation processes of the examples 20-21 are basically the same as those of the example 5, and the differences are only that: 1mol/L potassium hydroxide solution is changed into 1mol/L sodium hydroxide and 1mol/L ammonia water solution, and the obtained products are all yellow green cuprous oxide nano particles.
Examples 20 to 21 show that the alkaline substance is ammonia water and alkali metal hydroxide, and the obtained cuprous oxide is yellowish green.
The conditions of the first double decomposition reaction and the second reduction reaction in the above examples 1 to 21 are 10 ℃ to 37 ℃ for 0.5h to 4h, the ratio of the amounts of the copper ions, the alkaline substance and the reducing agent in the cupric salt is controlled to 1 (1.5 to 3.5) to (0.04 to 0.5), the obtained cuprous oxide powder is yellow-green, as shown in (a) of fig. 1, the microstructure of the yellow-green cuprous oxide is the appearance of coexistence of nano-rod shape and round cake shape, as shown in fig. 2.
Examples 22 to 24
The preparation processes of the examples 22 to 24 are basically the same as those of the example 5, and the differences are that: and replacing the 0.02mol/L sodium borohydride solution with 0.275mol/L, 0.375mol/L and 0.5mol/L sodium borohydride solutions to obtain orange-yellow cuprous oxide nanoparticles. The product obtained in example 23 is shown in FIG. 1 (b).
Examples 22 to 24 show that the products obtained by controlling the amount ratio of the copper salt, the alkali and the reducing agent to 1:1.5 (0.55 to 1.0) are orange-yellow cuprous oxide nanoparticles.
Examples 25 to 27
The preparation processes of the examples 25 to 27 are basically the same as those of the example 23, and the differences are only that: in the first step, the dosage of 1mol/L potassium hydroxide solution is respectively 20mL, 25mL and 35mL, the mixture is stirred for 1h at the temperature of 25 ℃ and under normal pressure, and all obtained precipitates are blue; and the products obtained in the second step are all orange-yellow cuprous oxide nanoparticles.
Examples 22 to 27 show that the products obtained by controlling the ratio of the amounts of the copper salt, the alkali and the reducing agent to 1 (1.5 to 3.5) and (0.55 to 1.0) are orange-yellow cuprous oxide nanoparticles.
Examples 28 to 29
Examples 28 to 29 were substantially the same as example 23 except that: and D, changing the sodium borohydride solution in the step two into a sodium hypophosphite solution and an ascorbic acid solution with equal substance amounts respectively to obtain orange cuprous oxide nano-particles.
Examples 28 to 29 show that orange-yellow cuprous oxide is obtained by controlling the amount ratio of the copper salt, the alkali and the reducing agent to 1 (1.5 to 3.5) to (0.55 to 1.0), wherein the reducing agent is sodium borohydride, sodium hypophosphite and ascorbic acid.
Examples 30 to 32
The preparation processes of the examples 30 to 32 are basically the same as those of the example 23, and the differences are that: and D, changing the 0.1mol/L copper sulfate solution in the step I into a 0.1mol/L copper nitrate solution, a 0.1mol/L copper chloride solution and a 0.1mol/L copper acetate solution respectively to obtain orange-yellow cuprous oxide nanoparticles.
Examples 30-32 show that copper sulfate, copper nitrate, copper chloride and copper acetate are used as copper salts, and all obtained copper oxides are orange-yellow cuprous oxide.
Examples 33 to 34
The preparation processes of the examples 33 to 34 are basically the same as those of the example 23, and the differences are that: 1mol/L potassium hydroxide solution is changed into 1mol/L sodium hydroxide and 1mol/L ammonia water solution, and the obtained products are orange-yellow cuprous oxide nano particles.
Examples 33 to 34 show that the alkaline substance was ammonia water and alkali metal hydroxide, and all obtained were orange-yellow cuprous oxide.
In the above examples 22 to 34, when the ratio of the amounts of the copper ion, the alkaline substance and the reducing agent in the cupric salt is controlled to 1 (1.5 to 3.5) to 0.55 to 1.0, the obtained cuprous oxide powder is orange yellow, as shown in (b) of FIG. 1, and the orange-yellow cuprous oxide microstructure is a round cake shape as shown in FIG. 3.
Comparative example 1
Step one, adding 500mL of 0.1mol/L copper chloride solution into 85mL of 2mol/L sodium hydroxide solution, stirring at 25 ℃ under normal pressure, reacting for 0.5h, centrifuging at 7500r/min to obtain a substrate, and washing with deionized water for three times for later use.
And step two, adding 500mL of water into the substrate obtained in the step one, stirring to uniformly disperse the substrate, adding 100mL of 2mol/L ascorbic acid solution, stirring at 25 ℃ under normal pressure for 1h, centrifuging at 7500r/min to obtain a product, washing with water for three times, and drying at 80 ℃ in vacuum for 4h to obtain the micron-sized brick red cuprous oxide particles.
Comparative example 2
Comparative example 2 is substantially the same as the preparation process of comparative example 1 except that: 2mol/L ascorbic acid solution is replaced by 2mol/L sodium borohydride, and the obtained product is brick red cuprous oxide particles.
Comparative example 3
Comparative example 3 is substantially the same as the preparation process of comparative example 1 except that: 2mol/L ascorbic acid solution is replaced by 2mol/L sodium hypophosphite solution, and the obtained product is brick red cuprous oxide particles. The brick red cuprous oxide particles obtained in comparative examples 1 to 3 are all shown in fig. 1 (c).
SEM images of nano-cuprous oxide prepared in example 5, example 23 and comparative example 1 are shown in fig. 2 to 4, respectively.
As can be seen from FIG. 2, the yellowish green cuprous oxide nanoparticles obtained in example 5 have a morphology of both nanorod shapes with a diameter of 20nm to 40nm, a length of 200nm to 400nm, and a cake-shaped particle size of 30nm to 110 nm.
As can be seen from fig. 3, the yellowish green nano-cuprous oxide prepared in example 23 was a cake-like particle having a particle size of 50nm to 120 nm.
As can be seen from FIG. 4, the brick red micro cuprous oxide prepared in comparative example 1 is cubic, and has a particle size of about 1 to 3 μm.
XRD tests are carried out on the nano cuprous oxides prepared in the example 5 and the example 23, and the test results are shown in figure 5, the peak positions of 2 theta are respectively 29.6 degrees, 36.4 degrees, 42.3 degrees, 61.4 degrees, 73.5 degrees and 77.4 degrees, and the peak positions are consistent with the characteristic diffraction peaks of the JCPDS No.78-2076 cuprous oxide in a standard spectrogram, which indicates that the yellow-green cuprous oxide and the orange-yellow cuprous oxide are successfully synthesized. The micro structure of the yellowish green cuprous oxide is the coexistence appearance of a nano rod and a round cake, the rod diameter of the nano rod is 20 nm-40 nm, the rod length is 200 nm-400 nm, and the grain diameter of the round cake is 30 nm-110 nm. The microscopic structure of the orange-yellow nano cuprous oxide is in a round cake shape, and the particle size is 50 nm-120 nm. This difference in microstructure is responsible for the difference in macroscopic colour.
Test of antibacterial Property
According to GB/T21510-. In addition, according to the Minimum Inhibitory Concentration (MIC) test, the nano-cuprous oxide prepared in each example has a concentration of 16ppm at a bacteriostatic rate of 99.9%.
TABLE 2
Example 5, example 23, comparison of the photomicrographs of the bacteriostatic effect of the added 16ppm nano-cuprous oxide on staphylococcus aureus and escherichia coli, as shown in fig. 6 and 7, respectively, wherein the blank control group is the control group without the added nano-cuprous oxide. In FIG. 6, the reference group and examples 1 to 2 are denoted as C-1, 1# -1 and 2# -1, respectively; in FIG. 7, the reference group and examples 1 to 2 are denoted by C-2, 1# -2 and 2# -2, respectively.
As can be seen from the above table 2 and FIGS. 6 to 7, the 16ppm powder test and the shaking table oscillation for 4 hours in all the examples can respectively achieve 99.9% of the bacteriostasis rates of Escherichia coli and Staphylococcus aureus, and can achieve broad-spectrum antibiosis, i.e., the antibiosis against both gram-negative bacteria and gram-positive bacteria.
Test for antiviral Properties
Nano cuprous oxide (named Abm-101) prepared in example 5 and example 23 was used to test the inactivation ratio of influenza virus H1N 1/half virus infection amount (TCID)50). Weighing 1g of nano cuprous oxide powder, adding into 1L of water, stirring and ultrasonically dispersing to obtain a sample with the sample concentration of 1000ppm according to virus TCID50(tissue median infection) assay the standard procedure was tested.
Wherein: the neutralizer (PBS solution containing 3% of Tween-80, 0.5% of sodium thiosulfate, 0.5% of histidine, 0.85% of sodium chloride, 1.43% of lecithin and 0.1% of cysteine) can partially neutralize Abm-101 (sample stock solution to be checked, the action time is 24 hours), and the neutralizer and the neutralized product have no influence on the growth of influenza virus H1N 1; virus inactivation assay (stock sample, 24h exposure, assay repeat 3 times).
The results show that the average extinction logarithm of the nano-cuprous oxide prepared in example 5 and example 23 to influenza virus H1N1 is 5.54logs (corresponding to an extinction ratio of 99.9997%).
Stability, dispersibility Performance test
And (3) pouring a bag of 25kg of polypropylene (PP) into a stirrer container, adding 0.8g of orange-yellow nano cuprous oxide prepared in the example 5, and stirring for 10 minutes to ensure that pure white polypropylene particles become beige and have uniform and stable color.
And in addition, a bag of 25kg of polypropylene (PP) is poured into a container of a stirrer, 0.8g of the yellowish green nano cuprous oxide prepared in the example 23 is added, and the stirring is carried out for 10 minutes, so that the pure white polypropylene particles become yellowish green and have uniform and stable color.
Other high molecular polymer materials with similar forms, such as Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), Polystyrene (PS) and modified polystyrene (ABS), can be uniformly mixed with orange-yellow and yellow-green nano cuprous oxide, and the mixture is not discolored after being placed in the air for a long time and is stable and not easily oxidized.
Uniformly dispersing the orange-yellow nano cuprous oxide prepared in the example 5 in water to obtain a nano cuprous oxide aqueous solution with the concentration of 355ppm, wherein the solution is uniformly and stably dispersed; as shown in the solution labeled "CanAbm-101355 ppm" in figure 8.
The orange-yellow nano cuprous oxide prepared in the example 23 is uniformly dispersed in water to respectively obtain nano cuprous oxide aqueous solutions with the concentrations of 126ppm and 63ppm, and the nano cuprous oxide aqueous solutions are uniformly and stably dispersed; as shown in the solutions labeled "CanAbm-101126 ppm" and labeled "CanAbm-10163 ppm" in figure 8.
Therefore, the nano cuprous oxide prepared by the embodiment of the invention is uniformly dispersed in water and has stable property, and can be stably dispersed in solvents such as ethanol, methanol, isopropanol, DMF (dimethyl formamide), DMSO (dimethyl sulfoxide) and the like.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the nano cuprous oxide is characterized by comprising the following steps of:
carrying out double decomposition reaction on a divalent copper salt and a basic substance in a solvent to obtain a precipitate;
dispersing the precipitate in a dispersing agent, adding a reducing agent for reduction reaction, taking a solid, and drying to obtain the nano cuprous oxide;
wherein the double decomposition reaction and the reduction reaction are carried out under the conditions of 10-37 ℃ for 0.5-4 h; the ratio of the amounts of the copper ions, the alkaline substance and the reducing agent in the cupric salt is 1 (1.5-3.5) to 0.01-1.0; the alkaline substance is at least one of ammonia water and alkali metal hydroxide.
2. The method for preparing nano cuprous oxide according to claim 1, wherein the ratio of the amount of copper ions in the cupric salt, the alkaline substance and the reducing agent is 1 (1.5-3.5) to 0.04-1.0.
3. The method for preparing nano cuprous oxide according to claim 1, wherein said cupric salt is at least one of cupric sulfate, cupric nitrate, cupric chloride and cupric acetate; and/or
The solvent is water.
4. The method for preparing nano cuprous oxide according to any of claims 1 to 3, wherein said reducing agent is at least one of sodium borohydride, sodium hypophosphite and ascorbic acid; and/or
The dispersant is water.
5. The method for producing cuprous oxide nanoparticles as claimed in any of claims 1 to 3, wherein the ratio of the amount of copper ions in the cupric salt, the alkaline substance and the reducing agent is 1 (1.5-3.5) to 0.01-1.0.
6. The method for preparing nano cuprous oxide according to any of claims 1 to 3, wherein,
when the amount ratio of the copper ions, the alkaline substance and the reducing agent in the cupric salt is controlled to be 1 (1.5-3.5) to 0.04-0.5, the yellow-green nano cuprous oxide with the shape of the coexistence of the nano rod and the round cake is prepared;
when the amount ratio of the copper ions, the alkaline substance and the reducing agent in the cupric salt is controlled to be 1 (1.5-3.5) to 0.55-1.0, the orange-yellow round cake-shaped nano cuprous oxide is prepared.
7. A nano cuprous oxide characterized by being produced by the method for producing nano cuprous oxide according to any one of claims 1 to 6.
8. The nano-cuprous oxide of claim 7, wherein said nano-cuprous oxide is yellowish green or orange yellow; the minimum inhibitory concentration of the nano cuprous oxide to staphylococcus aureus and escherichia coli is 8 ppm-16 ppm.
9. Application of nano cuprous oxide as claimed in any one of claims 7 to 8 in preparation of antibacterial material or antiviral material.
10. An antibacterial and antiviral material, characterized by comprising nano cuprous oxide as claimed in any one of claims 7 to 8.
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| CN113684611A (en) * | 2021-09-30 | 2021-11-23 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial and mildewproof melt-blown non-woven fabric |
| CN114232326A (en) * | 2021-11-17 | 2022-03-25 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial non-woven fabric and preparation method thereof |
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| CN107473257A (en) * | 2016-06-07 | 2017-12-15 | 中国科学院化学研究所 | Controllable cuprous nano crystalline substance of a kind of pattern, size and its preparation method and application |
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| CN107473257A (en) * | 2016-06-07 | 2017-12-15 | 中国科学院化学研究所 | Controllable cuprous nano crystalline substance of a kind of pattern, size and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113684611A (en) * | 2021-09-30 | 2021-11-23 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial and mildewproof melt-blown non-woven fabric |
| CN114232326A (en) * | 2021-11-17 | 2022-03-25 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial non-woven fabric and preparation method thereof |
| CN114232326B (en) * | 2021-11-17 | 2024-02-20 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial non-woven fabric and preparation method thereof |
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