CN112499664A - Cuprous oxide-doped nano zinc oxide composite material and preparation method thereof - Google Patents
Cuprous oxide-doped nano zinc oxide composite material and preparation method thereof Download PDFInfo
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Abstract
A cuprous oxide doped nano zinc oxide composite material and a preparation method thereof belong to the technical field of metal nano material preparation. In the preparation process of the composite material, copper salt with divalent copper ions is used as a copper source, ascorbic acid is used as a reducing agent, and the composite material is prepared by simply stirring under normal temperature and normal pressure conditions under the action of a complexing agent, so that cuprous oxide-doped nano zinc oxide composite material powder, namely cuprous oxide-doped nano zinc oxide, is finally obtained, wherein the particle size of the nano zinc oxide is 10-100 nm. The composite material has the advantages of high biocompatibility, low cytotoxicity, good antibacterial performance and the like, and the antibacterial activity of the composite material can be obviously improved under the condition of illumination.
Description
Technical Field
The invention belongs to the technical field of preparation of metal nano materials.
Background
With the development of society and the increasing health consciousness of people, the requirements of people on the living environment are higher and higher. The development of a novel antibacterial agent which is environmentally friendly, has good biocompatibility and high functionality is in the critical period of development.
The commonly used antibacterial agents at present comprise organic synthetic antibacterial agents, natural antibacterial agents and physical antibacterial agents, wherein the organic synthetic antibacterial agents are high in toxicity and are rarely used in antibacterial dressings, the natural antibacterial agents are also low in usage in wound dressings due to short antibacterial aging, and the physical antibacterial agents are widely concerned due to wide antibacterial spectrum and strong antibacterial property. The most used physical antibacterial agent is nano silver, which has excellent performances in the aspects of electricity, optics, catalysis and the like and has good antibacterial activity in the aspect of antibiosis. However, the FDA in the united states has definitely prohibited the use of nano silver because nano silver may generate certain toxic and side effects to human body.
The nano zinc oxide is a novel environment-friendly multifunctional material, and has small size effect, surface effect and quantum size effect, so that a series of excellent physical, chemical, surface and interface properties are obtained, and the nano zinc oxide is widely applied to the aspects of optics, electrics, catalysis and antibiosis. However, the antibacterial mechanism of nano zinc oxide is not well studied, and no uniform theory is obtained, so further research and study are needed. However, many studies prove that the antibacterial activity of the nano zinc oxide can be effectively improved by selecting a proper doping element or modification method, but ideal performance indexes are not obtained all the time.
Disclosure of Invention
Aiming at the defects of the prior art, the first purpose of the invention is to provide the cuprous oxide doped nano zinc oxide composite material for the antibacterial dressing with good antibacterial performance.
The composite material is cuprous oxide-doped nano zinc oxide, and the particle size of the nano zinc oxide is 10-100 nm.
Compared with other nano silver particles, the cuprous oxide nano silver-doped composite material has no cytotoxicity in a certain concentration range, can be better applied to the field of antibacterial dressings, and has the advantages of high biocompatibility, low cytotoxicity, good antibacterial performance and the like. In addition, the composite material can obviously improve the antibacterial activity under the condition of illumination.
The doping molar weight of the cuprous oxide is 5.0-7.5% of that of the nano zinc oxide.
Repeated tests prove that: although the antibacterial performance of the composite material is improved along with the increase of the doping amount of the cuprous oxide, when the doping amount is 5%, the doping amount of the cuprous oxide is increased, so that the antibacterial effect is not obviously improved, the doping amount of the cuprous oxide is 5.0-7.5% of the molar amount of the nano zinc oxide, the optimal selection is adopted, the antibacterial effect of the composite material is better than that of the nano zinc oxide which is not doped with the cuprous oxide, and the composite material has a remarkable enhancing effect.
A second object of the present invention is to provide a method for preparing the above composite material.
The method comprises the following steps:
1) dispersing nano zinc oxide with the particle size of 10-100 nm in deionized water at the stirring speed of 50-1000 rpm under the conditions of normal temperature and normal pressure, stirring for 10-20 minutes, adding a complexing agent, and stirring for 1.0-4.0 hours at the normal temperature under the conditions of normal pressure to obtain a mixture of the complex and the nano zinc oxide;
2) preparing copper ion complexed nano zinc oxide: mixing copper salt with divalent copper ions and a mixture of a complex and nano zinc oxide, stirring and stirring for 0.5-4.0 h under the conditions of normal temperature and normal pressure to obtain a copper ion nano zinc oxide complex, and adjusting the pH value of the copper ion nano zinc oxide complex to 10-13;
3) preparing a cuprous oxide-doped nano zinc oxide composite material: adding an ascorbic acid solution into a copper ion nano zinc oxide complex with the pH value of 10-13, and stirring for 0.5-4 h under the conditions of normal temperature and normal pressure to obtain a cuprous ion nano zinc oxide complex; and washing the cuprous ion-doped nano zinc oxide complex with deionized water, centrifuging, drying in vacuum at 50-70 ℃ for 10-14 hours, and finally grinding into powder to obtain the cuprous oxide-doped nano zinc oxide composite material.
The particle size of the nano zinc oxide adopted in the process is 10-100 nm.
The nano zinc oxide is a novel multifunctional photocatalytic inorganic material with direct band gap II-VI family, has the characteristics of good antibacterial broad spectrum, high specific surface area, high photocatalytic activity, small particle size, no toxicity, low preparation cost, stable mechanical property, high ultraviolet emissivity and the like, and has the antibacterial property which is second to that of a silver antibacterial agent. The antibacterial effect of the ZnO nanoparticles is closely related to the concentration and the size of the ZnO nanoparticles, and the size of the zinc oxide particles shows that the antibacterial effect of the nanoparticles is increased along with the reduction of the particle size of bacterial strains such as escherichia coli, staphylococcus aureus, bacillus subtilis and the like.
In the step 1), the complex and the nano zinc oxide can be fully mixed by stirring for 1.0 to 4.0 hours under the conditions of normal temperature and normal pressure.
And 2) stirring at normal temperature and normal pressure for 0.5-4.0 h in the step 2), so that the complex can well complex the nano zinc oxide and the copper ions together.
The stirring under the conditions of normal pressure and normal temperature achieves the effects of low energy consumption, cost saving and high yield.
In the step 2), the pH value of the copper ion complexed nano zinc oxide is adjusted, so that the environment required by the reaction can be ensured to be an alkaline environment, and the formation of cuprous oxide is facilitated.
In the step 3), ascorbic acid is used as a reducing agent, is a mild reducing agent, is beneficial to the generation of cuprous oxide, and has good biocompatibility.
To ensure Cu during drying2O is not oxidized, and vacuum drying is selected in the step 3) of the invention.
In conclusion, in the preparation process of the composite material, the copper salt with the divalent copper ions is used as a copper source, the ascorbic acid is used as a reducing agent, and the nano zinc oxide composite material powder doped with cuprous oxide is finally obtained by stirring and preparing under the simple conditions of normal temperature and normal pressure under the action of a complexing agent.
Further, in the step 1), the complexing agent is at least any one of sodium aminotriacetate (NTA), disodium ethylenediaminetetraacetate (EDTA-2 Na), tetrasodium ethylenediaminetetraacetate (EDTA-4 Na) and Diethylenetriaminepentacarboxylate (DTPA). The complexing agents are not easy to dissociate after being complexed with copper ions, have good chemical stability and are easy to biodegrade.
Furthermore, the feeding ratio of the complexing agent to the nano zinc oxide is 1.8-7.2 mmol: 1 g.
The complexing agent can well react Cu2+Combined with nano-zinc oxide, according to Cu2+The addition amount of the copper-based copper alloy is adopted, and the Cu can be better tested by the feeding ratio through an inductively coupled plasma spectrometer (ICP) test2O is doped on the nano zinc oxide.
Experimental results show that when the complexing agent is disodium ethylene diamine tetraacetate, the optimal feeding ratio of the disodium ethylene diamine tetraacetate (EDTA-2 Na) to the nano zinc oxide is 3.6 mmol: 1 g.
The copper salt with divalent copper ions is at least one of copper sulfate, copper chloride or copper nitrate, and the selected copper salt can provide Cu in an aqueous medium2+。
When the copper salt is copper sulfate, the feeding molar ratio of the copper sulfate to the nano zinc oxide is 5-7.5: 100. The starting point of the invention is that a small amount of Cu is doped2O can obviously increase the content of nano ZnO and Cu2The small doping amount of O has no obvious effect on improving the bacteriostatic effect of the nano zinc oxide, and the large doping amount can cover the active sites of the nano zinc oxide and can not play a synergistic effect, so that the good bacteriostatic effect can be obtained when the material ratio is selected.
And 2) adjusting the pH value of the copper ion nano zinc oxide complex in the step 2), wherein ammonia water, sodium hydroxide, potassium hydroxide or triethanolamine is adopted.
The feeding molar ratio of the ascorbic acid to the nano zinc oxide is 7-29: 100, and Cu can be completely mixed2+Reduction to Cu+Making all doped to the nano zinc oxide be Cu2O。
In summary, the present invention has the following beneficial effects:
(1) the preparation method is simple and controllable, green and pollution-free, has low energy consumption, and has low cost compared with other antibacterial dressings.
(2) The ascorbic acid used in the invention is a mild reducing agent, does not pollute the environment and has no toxicity, thus having certain industrial prospect.
(3) Repeated tests show that the dosage and the type of the copper salt, the complexing agent, the reducing agent and the like are determined, the cuprous oxide-doped nano zinc oxide composite material and the preparation method thereof are provided, and finally the antibacterial effect of the nano zinc oxide material is obviously improved.
Drawings
Fig. 1 is a graph comparing the antibacterial effect of the doping amount of cuprous oxide on the composite material.
FIG. 2 is a graph showing the antibacterial effect of EDTA added in the composite material.
Fig. 3 is a comparison graph of antibacterial properties of the composite material obtained by doping different metal oxides with nano zinc oxide.
Fig. 4 is a comparison graph for testing the antibacterial effect of the cuprous oxide-doped nano zinc oxide composite material under the conditions of illumination and dark.
FIG. 5 is a Transmission Electron Microscope (TEM) image of the nano zinc oxide selected by the present invention.
Fig. 6 is a Transmission Electron Micrograph (TEM) of cuprous oxide doped nano zinc oxide composite according to the experimental procedure of example one.
Fig. 7 is an XRD pattern of the cuprous oxide doped nano zinc oxide composite material of the present invention.
Detailed Description
Firstly, preparing nano zinc oxide composite materials doped with cuprous oxide with different amounts:
example 1:
(1) mixing the complex with nano zinc oxide:
under the conditions of normal temperature and normal pressure and the stirring speed of 200 rpm, 1g of nano zinc oxide with the particle size of 30 nm is added into 40 mL of deionized water, stirred for 15 minutes, then 3.6 mmol of disodium ethylene diamine tetraacetate (EDTA-2 Na) is added, and the mixture of the disodium ethylene diamine tetraacetate (EDTA-2 Na) and the nano zinc oxide is obtained after stirring for 3.0 hours under the conditions of normal temperature and normal pressure.
(2) Preparing copper ion complexed nano zinc oxide:
adding 0.6 mmol copper sulfate into the mixture, continuing stirring for 1.0 h under the conditions of normal temperature and normal pressure, and then adjusting the pH value to 12.0 by using 0.036 mol (1.5mol/L) sodium hydroxide aqueous solution to obtain the nano zinc oxide complexed by copper ions.
(3) Preparing a cuprous oxide-doped nano zinc oxide composite material:
adding 1.8 mmol (0.1mol/L) ascorbic acid solution into the nano zinc oxide complexed by the copper ions, stirring for 1h under the conditions of normal temperature and normal pressure to obtain the nano zinc oxide complexed by the cuprous ions, then washing by using deionized water, and centrifuging to obtain a solid phase. And then, drying the solid phase in a vacuum drying oven at 60 ℃ for 12h, and grinding the solid phase into powder to obtain the cuprous oxide-doped nano zinc oxide composite material.
Example 2:
(1) mixing the complex with nano zinc oxide:
under the conditions of normal temperature and normal pressure and the stirring speed of 100 rpm, 1g of nano zinc oxide with the particle size of 10 nm is added into 40 mL of deionized water, stirred for 10 minutes, then added with 1.8 mmol of sodium aminotriacetate (N TA), and stirred for 1.0 hour under the conditions of normal temperature and normal pressure to obtain a mixture of sodium aminotriacetate (NTA) and nano zinc oxide.
(2) Preparing copper ion complexed nano zinc oxide:
adding 0.3 mmol of copper nitrate into the mixture, continuing stirring for 0.5 h under the conditions of normal temperature and normal pressure, and then adjusting the pH value to 10.0 by using 0.018 mol (1.5mol/L) of triethanolamine aqueous solution to obtain the nano zinc oxide complexed by copper ions.
(3) Preparing a cuprous oxide doped nano zinc oxide composite material:
adding 0.9 mmol (0.1mol/L) ascorbic acid solution into the nano zinc oxide complexed by the copper ions, stirring for 0.5 h under the conditions of normal temperature and normal pressure to obtain the nano zinc oxide complexed by the cuprous ions, then washing by using deionized water, and centrifuging to obtain a solid phase. And then, drying the solid phase in a vacuum drying oven at 50 ℃ for 14 h, and grinding the solid phase into powder to obtain the cuprous oxide-doped nano zinc oxide composite material.
Example 3:
(1) mixing the complex with nano zinc oxide:
under the conditions of normal temperature and normal pressure and the condition of stirring rotation speed of 300 rpm, adding 1g of nano zinc oxide with the particle size of 100nm into 40 mL of deionized water, stirring for 30 minutes, then adding 7.2mmol of diethylenetriamine pentacarboxylate (DTPA), and refluxing for 4.0 hours under the stirring state to obtain a mixture of the diethylenetriamine pentacarboxylate (DTPA) and the nano zinc oxide.
(2) Preparing copper ion complexed nano zinc oxide:
adding 1.2 mmol of copper chloride into the mixture, continuing stirring for 2.0 h under normal temperature and pressure, and then adjusting the pH value to 13.0 by using 0.072 mol (1.5mol/L) of potassium hydroxide aqueous solution (or ammonia water) to obtain the nano zinc oxide complexed with copper ions.
(3) Preparing a cuprous oxide doped nano zinc oxide composite material:
adding 3.6 mmol (0.1mol/L) ascorbic acid solution into the nano zinc oxide complexed by the copper ions, stirring for 4.0h under the conditions of normal temperature and normal pressure to obtain the nano zinc oxide complexed by the cuprous ions, then washing by using deionized water, and centrifuging to obtain a solid phase. And then, drying the solid phase in a vacuum drying oven at 70 ℃ for 10 h, and grinding the solid phase into powder to obtain the cuprous oxide-doped nano zinc oxide composite material.
In each of the above examples, the particle size of the nano zinc oxide is 10 to 100 nm.
Secondly, verifying the antibacterial performance of the composite material:
and (3) effect measurement: according to the test of the bacteriostatic efficacy inspection method (general rule 1121) in 'Chinese pharmacopoeia' 2015 edition, staphylococcus aureus is selected as a sterilization object and the antibacterial performance of the staphylococcus aureus is researched by a dilution coating method. The number of colonies in the culture dish shows the antibacterial performance of the material, and compared with a control group, the lower the number of colonies represents the stronger the antibacterial performance. The antibacterial effect is represented by a Log value of the number of colonies, and the lower the Log value, the lower the number of colonies, the better the antibacterial effect. To ensure the accuracy of the data, several plates were coated for each dilution gradient, reducing the error between and three times for each sample.
The particle size of the nano zinc oxide is 10-100 nm, the doping amount of the cuprous oxide is respectively adjusted to be 5%, 7.5% and 10% of the molar amount of the nano zinc oxide, and the rest process parameters, process steps and measuring methods are completely the same as those in example 1.
The results of fig. 1 show that: the doping of cuprous oxide can effectively enhance the antibacterial performance of the nano zinc oxide. In addition, the antibacterial performance of the composite material is remarkably improved along with the increase of the doping amount of the cuprous oxide, and when the doping amount of the cuprous oxide is more than 7.5%, the antibacterial performance of the composite material tends to be stable, so that the doping molar amount of the cuprous oxide is preferably 5.0-7.5% of that of the nano zinc oxide.
(1) Comparing the antibacterial effect of the addition amount of EDTA-2 Na on the composite material: the amounts of EDTA-2 Na added were selected to be 1.8, 3.6, 5.4, and 7.2mmol, and the respective amounts are designated as Cu2O/ZnO 1-4, and the rest of process parameters, process steps and measurement methods are completely the same as those of example 1, and the comparison result is shown in figure 2.
The results of fig. 2 show that: since too much addition amount of EDTA-2 Na rather lowers the antibacterial property of the composite material, the addition amount of EDTA-2 Na is preferably 3.6 mmol.
(2) Comparison with different Metal oxides Cu2O、CuO、Fe2O3、CeO2、Bi2O3Doping was performed, and the remaining process parameters, process steps, and measurement methods were exactly the same as in example 1, and the comparison results are shown in fig. 3.
The results of fig. 3 show that: compared with other metal oxides, the antibacterial property of the cuprous oxide doped nano zinc oxide is obviously improved.
(3) In order to compare the antibacterial effect of the composite material under the conditions of illumination and dark, antibacterial tests were performed under the conditions of illumination and dark, respectively, and the test results are shown in fig. 4.
From the antibacterial result of fig. 4, the antibacterial effect of the nano zinc oxide is significantly higher than that of the light-shielding condition under the illumination condition, regardless of pure nano zinc oxide or nano zinc oxide doped with cuprous oxide. Therefore, the antibacterial effect of the composite material can be effectively improved by adopting illumination.
FIG. 5 is a transmission electron microscope image of the nano zinc oxide adopted in the present invention, the size of which is 10 to 100 nm.
Figure 6 shows a transmission electron microscope image of the nano zinc oxide doped cuprous oxide composite material prepared by the method of example 1.
As can be seen from the transmission electron micrograph of fig. 6: the size of the prepared nano zinc oxide doped cuprous oxide composite material is 10-100 nm, and the size and the shape of the nano zinc oxide are not obviously changed after the cuprous oxide is doped.
Figure 7 shows the XRD pattern of the nano zinc oxide doped cuprous oxide composite material prepared by the method of the invention.
As can be seen from the XRD pattern of fig. 7: stronger diffraction peaks appear at 31.76 degrees, 31.42 degrees, 36.25 degrees, 47.53 degrees, 56.59 degrees, 62.85 degrees, 66.37 degrees, 67.94 degrees and 69.08 degrees, and sequentially correspond to (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal faces of a hexagonal single-phase wurtzite nano ZnO structure (JCPDS number 99-0111); on the other hand, diffraction peaks at 29.57 °, 36.42 °, 42.31 °, 61.37 ° and 73.52 ° correspond to Cu, respectively2The (110), (111), (200), (220) and (311) crystal faces of O (JCPDS number 99-0041) show that the method can successfully prepare the nano zinc oxide composite material doped with cuprous oxide.
Claims (10)
1. The cuprous oxide-doped nano zinc oxide composite material is characterized by being nano zinc oxide doped with cuprous oxide, wherein the particle size of the nano zinc oxide is 10-100 nm.
2. The cuprous oxide-doped nano zinc oxide composite material according to claim 1, wherein the doping molar amount of the cuprous oxide is 5.0-7.5% of that of the nano zinc oxide.
3. The preparation method of the cuprous oxide doped nano zinc oxide composite material according to claim 1, characterized by comprising the following steps:
1) dispersing nano zinc oxide with the particle size of 10-100 nm in deionized water at the stirring speed of 50-1000 rpm under the conditions of normal temperature and normal pressure, stirring for 10-20 minutes, adding a complexing agent, and stirring for 1.0-4.0 hours under the conditions of normal temperature and normal pressure to obtain a mixture of the complex and the nano zinc oxide;
2) preparing copper ion complexed nano zinc oxide: mixing copper salt with divalent copper ions and a mixture of a complex and nano zinc oxide, stirring for 0.5-4.0 h at normal temperature and pressure to obtain a copper ion nano zinc oxide complex, and adjusting the pH value of the copper ion nano zinc oxide complex to 10-13;
3) preparing a cuprous oxide-doped nano zinc oxide composite material: adding an ascorbic acid solution into a copper ion nano zinc oxide complex with the pH value of 10-13, and stirring for 0.5-4 h under the conditions of normal temperature and normal pressure to obtain a cuprous ion nano zinc oxide complex; and washing the cuprous ion-doped nano zinc oxide complex with deionized water, centrifuging, drying in vacuum at 50-70 ℃ for 10-14 hours, and finally grinding into powder to obtain the cuprous oxide-doped nano zinc oxide composite material.
4. The preparation method of cuprous oxide doped nano zinc oxide composite material according to claim 3, wherein the complexing agent in step 1) is at least any one of sodium aminotriacetate, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, and diethylenetriaminepentacarboxylate.
5. The preparation method of cuprous oxide doped nano zinc oxide composite material according to claim 4, wherein the feeding ratio of complexing agent to nano zinc oxide is 1.8-7.2 mmol: 1 g.
6. The preparation method of cuprous oxide doped nano zinc oxide composite material according to claim 5, wherein the complexing agent is disodium ethylene diamine tetraacetate, and the optimal charge ratio of disodium ethylene diamine tetraacetate to nano zinc oxide is 3.6 mmol: 1 g.
7. The method for preparing cuprous oxide doped nano zinc oxide composite material according to claim 3, wherein said cupric salt having cupric ion in step 2) is at least any one of cupric sulfate, cupric chloride or cupric nitrate.
8. The preparation method of the cuprous oxide doped nano zinc oxide composite material according to claim 7, wherein the feeding molar ratio of the copper salt to the nano zinc oxide in the step 2) is 5-7.5: 100.
9. The method for preparing cuprous oxide doped nano zinc oxide composite material according to claim 3, wherein at least any one of ammonia water, sodium hydroxide, potassium hydroxide or triethanolamine is used to adjust the pH of copper ion nano zinc oxide complex in step 2).
10. The preparation method of cuprous oxide doped nano zinc oxide composite material according to claim 3, wherein the molar ratio of ascorbic acid to nano zinc oxide in step 3) is 7-29: 100.
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| CN112957520A (en) * | 2021-03-18 | 2021-06-15 | 扬州大学 | Photocatalytic antibacterial hydrogel dressing and preparation method thereof |
| CN113349220A (en) * | 2021-05-12 | 2021-09-07 | 昆明理工大学 | Preparation method of cuprous oxide-zinc oxide core-shell antibacterial material |
| CN114409398A (en) * | 2021-12-28 | 2022-04-29 | 福建省德化县益宝陶瓷有限公司 | Antibacterial high-strength white porcelain and processing technology thereof |
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