CN112499664B - 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 preparation of metal nano materials. In the preparation process of the composite material, copper salt with cupric ions is used for providing a copper source, ascorbic acid is used as a reducing agent, and the copper source is stirred and prepared under the simple normal temperature and normal pressure condition under the action of a complexing agent, so that the cuprous oxide-doped nano zinc oxide composite material powder, namely the 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 property and the like, and can obviously improve the antibacterial activity under the illumination condition.
Description
Technical Field
The invention belongs to the technical field of preparation of metal nano materials.
Background
Along with the continuous improvement of social development and health consciousness of people, the requirements of people on living environments are also higher and higher. The development of a new antibacterial agent with environmental protection, good biocompatibility and high functionality is now a critical period of development, because the development of drug resistance by bacteria caused by abuse of antibiotics is an increasingly serious crisis worldwide.
Among the currently commonly used antibacterial agents are organic synthetic antibacterial agents, natural antibacterial agents and physical antibacterial agents, wherein the organic synthetic antibacterial agents have larger toxicity and are rarely used in antibacterial dressings, the natural antibacterial agents are also rarely used in wound dressings due to shorter antibacterial aging, and the physical antibacterial agents are widely paid attention to due to wider antibacterial spectrum and stronger antibacterial property. The most used nano silver is the physical antibacterial agent, which has excellent performance in the aspects of electricity, optics, catalysis and the like, and has good antibacterial activity in the aspect of antibacterial. However, the use of nano silver has been clearly prohibited by the FDA in the united states because nano silver can have a certain toxic and side effect on the human body.
The nano zinc oxide is a novel environment-friendly multifunctional material, and has a small-size effect, a surface effect and a 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, electricity, catalysis and antibiosis. However, since the research on the antibacterial mechanism of nano zinc oxide is not mature and a unified theory is not obtained, further research and discussion are required. However, many studies prove that the antibacterial activity of nano zinc oxide can be effectively improved by selecting proper doping elements or modification methods, but ideal performance indexes are not obtained all the time.
Disclosure of Invention
Aiming at the defects of the prior art, the first aim 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 composite material has no cytotoxicity in a certain concentration range, can be well applied to the field of antibacterial dressing, and has the advantages of high biocompatibility, low cytotoxicity, good antibacterial property and the like. In addition, the antibacterial activity of the composite material can be obviously improved under the illumination condition.
The doping mole amount of the cuprous oxide is 5.0-7.5% of the nano zinc oxide.
The repeated test proves that: although the antibacterial performance of the composite material is increased along with the increase of the doping amount of the cuprous oxide, the antibacterial effect is not obviously increased by increasing the doping amount of the cuprous oxide when the doping amount is 5%, so that the optimal choice is that the doping amount of the cuprous oxide is 5.0-7.5% of the molar amount of the nano zinc oxide, the sterilization effect is better than that of the nano zinc oxide without the cuprous oxide, and the antibacterial effect is obviously enhanced.
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) Under the condition of normal temperature and normal pressure, the stirring rotating speed is 50-1000 rpm, nano zinc oxide with the particle size of 10-100 nm is dispersed in deionized water, after stirring for 10-20 minutes, complexing agent is added, and under the condition of normal pressure, the mixture of complex and nano zinc oxide is obtained after stirring for 1.0-4.0 h at normal temperature;
2) Preparing copper ion complexed nano zinc oxide: mixing cupric salt with bivalent copper ions with a mixture of the complex and nano zinc oxide, stirring and stirring for 0.5-4.0 h under normal temperature and normal pressure to obtain a copper ion nano zinc oxide complex, and regulating 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 the 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 nano zinc oxide complex with deionized water, centrifuging, vacuum drying at 50-70 ℃ for 10-14 hours, and finally grinding into powder to obtain the cuprous oxide doped nano zinc oxide composite material.
The grain size of the nano zinc oxide adopted in the process is 10-100 nm.
The nano zinc oxide is a multifunctional novel photocatalytic inorganic material of direct band gap II-VI, and 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 the antibacterial performance is inferior to that of silver antibacterial agents. The antibacterial effect of the ZnO nano particles is closely related to the selected concentration and size, and the size of the zinc oxide particles shows that the antibacterial effect of the nano particles is increased along with the decrease of the particle size of the zinc oxide particles on 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 and h under the condition of normal temperature and normal pressure.
In the step 2), the stirring time at normal temperature and normal pressure is 0.5-4.0. 4.0h, so that the complex can better complex the nano zinc oxide and copper ions together.
The stirring under the normal pressure and normal temperature conditions has the effects of low energy consumption, cost saving and high yield.
In the step 2), the pH value of the nano zinc oxide complexed by copper ions 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 adopted as a reducing agent, so that the method is a mild reducing agent, is favorable for generating cuprous oxide and has good biocompatibility.
To ensure Cu during drying 2 O is not oxidized, and vacuum drying is selected in the step 3) of the invention.
In summary, in the preparation process of the composite material, copper salt with bivalent copper ions is used for providing a copper source, ascorbic acid is used as a reducing agent, and the copper source is prepared by stirring under the simple condition of normal temperature and normal pressure under the action of a complexing agent, so that the cuprous oxide doped nano zinc oxide composite material powder is finally obtained.
Further, the complexing agent in the step 1) of the invention is at least any one of sodium Nitrilotriacetate (NTA), disodium ethylenediamine tetraacetate (EDTA-2 Na), tetrasodium ethylenediamine tetraacetate (EDTA-4 Na) and diethylenetriamine pentacarboxylate (DTPA). The complexing agents are not easy to dissociate after being complexed with copper ions, have good chemical stability and are easy to biodegrade.
Further, the feeding ratio of the complexing agent to the nano zinc oxide is 1.8-7.2 mmol:1 g.
Complexing agent can better make Cu 2+ Combined with nano zinc oxide according to Cu 2+ Adopts the feeding ratio, and verifies that the feeding ratio can better lead Cu by inductively coupled plasma spectroscope (ICP) test 2 O is doped on the nano zinc oxide.
Experimental results show that when the complexing agent is disodium ethylenediamine tetraacetate, and the optimal feeding ratio of disodium ethylenediamine tetraacetate (EDTA-2 Na) to nano zinc oxide is 3.6 mmol/1 g.
The cupric salt with cupric ion is at least one of cupric sulfate, cupric chloride or cupric nitrate, and the selected cupric salt can provide Cu in water medium 2+ 。
When the copper salt is copper sulfate, the feeding mole ratio of the copper sulfate to the nano zinc oxide is 5-7.5:100. The invention is based on the idea of doping Cu in small amounts 2 O can obviously improve the content of nano ZnO, cu 2 The less doping amount of O is not obvious for improving the antibacterial effect of the nano zinc oxide, and the more doping amount can mask the active sites of the nano zinc oxide and can not play a synergistic effect, so that the good antibacterial effect can be obtained when the above feeding ratio is selected.
And 2) when the pH value of the copper ion nano zinc oxide complex is regulated in the step 2), ammonia water, sodium hydroxide, potassium hydroxide or triethanolamine is adopted.
The molar ratio of the ascorbic acid to the nano zinc oxide is 7-29:100, and Cu can be completely added 2+ Reduction to Cu + Making all doped on nano zinc oxide be Cu 2 O。
In summary, the invention has the following beneficial effects:
(1) The preparation method is simple and controllable, green, pollution-free, low in energy consumption and low in 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 a certain industrial prospect.
(3) Through repeated experiments, the dosage and the type of copper salt, complexing agent, reducing agent and the like are defined, 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 showing the comparison of the antibacterial effect of the doping amount of cuprous oxide on the composite material.
FIG. 2 is a graph showing the comparison of the antibacterial effect of EDTA addition on the composite material.
Fig. 3 is a graph comparing the antimicrobial properties of composite materials obtained by doping different metal oxides with nano zinc oxide.
Fig. 4 is a graph showing comparison of antibacterial effect of the nano zinc oxide composite material doped with cuprous oxide under illumination and light-shielding conditions.
FIG. 5 is a Transmission Electron Microscope (TEM) of the selected nano-zinc oxide of the present invention.
Fig. 6 is a Transmission Electron Microscope (TEM) image of a 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 of the present invention.
Detailed Description
1. Preparing a nano zinc oxide composite material doped with different amounts of cuprous oxide:
example 1:
(1) Mixing of complex with nano zinc oxide:
under the condition of normal temperature and normal pressure and with the stirring rotation speed of 200 rpm, adding 1g of nano zinc oxide with the particle size of 30 nm into 40 mL deionized water, stirring for 15 minutes, then adding 3.6 mmol of disodium ethylenediamine tetraacetate (EDTA-2 Na), and stirring for 3.0 h under the condition of normal temperature and normal pressure to obtain the mixture of disodium ethylenediamine tetraacetate (EDTA-2 Na) and nano zinc oxide.
(2) Preparing copper ion complexed nano zinc oxide:
to the above mixture, 0.6 mmol of copper sulfate was added, and stirring was continued at room temperature and normal pressure for 1.0. 1.0 h, followed by adjusting the pH to 12.0 with 0.036 mol (1.5 mol/L) of an aqueous sodium hydroxide solution, whereby copper ion-complexed nano zinc oxide was obtained.
(3) Preparing a cuprous oxide doped nano zinc oxide composite material:
adding 1.8 mmol (0.1 mol/L) of ascorbic acid solution into the copper ion complexed nano zinc oxide, stirring for 1h at normal temperature and normal pressure to obtain copper ion complexed nano zinc oxide, washing with deionized water, and centrifuging to obtain a solid phase. And then drying the solid phase in a vacuum drying oven at 60 ℃ for 12 hours, and grinding the solid phase into powder to obtain the cuprous oxide doped nano zinc oxide composite material.
Example 2:
(1) Mixing of complex with nano zinc oxide:
under the condition of normal temperature and normal pressure and with the stirring rotation speed of 100 rpm, adding 1g of nano zinc oxide with the particle size of 10 nm into 40 mL deionized water, stirring for 10 minutes, then adding 1.8 mmol of sodium nitrilotriacetate (N TA), and stirring for 1.0 h under the condition of normal temperature and normal pressure to obtain the mixture of sodium Nitrilotriacetate (NTA) and nano zinc oxide.
(2) Preparing copper ion complexed nano zinc oxide:
to the above mixture, 0.3 mmol of copper nitrate was added, and stirring was continued at room temperature and normal pressure for 0.5. 0.5 h, followed by adjusting the pH to 10.0 with 0.018 mol (1.5 mol/L) of an aqueous triethanolamine solution to obtain copper ion-complexed nano zinc oxide.
(3) Preparing a cuprous oxide doped nano zinc oxide composite material:
adding 0.9 mmol (0.1 mol/L) of ascorbic acid solution into the copper ion complexed nano zinc oxide, stirring at normal temperature and normal pressure for 0.5. 0.5 h to obtain cuprous ion complexed nano zinc oxide, washing with 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 of complex with nano zinc oxide:
under the condition of normal temperature and pressure and the stirring rotation speed of 300 rpm, adding 1g of nano zinc oxide with the particle size of 100nm into 40 mL deionized water, stirring for 30 minutes, then adding 7.2mmol of diethylenetriamine pentacarboxylate (DTPA), and refluxing for 4.0h in a stirring state to obtain the mixture of the diethylenetriamine pentacarboxylate (DTPA) and the nano zinc oxide.
(2) Preparing copper ion complexed nano zinc oxide:
1.2 mmol of copper chloride was added to the above mixture, stirring was continued at normal temperature and normal pressure for 2.0. 2.0 h, and then the pH was adjusted to 13.0 with 0.072 mol (1.5 mol/L) of an aqueous potassium hydroxide solution (or aqueous ammonia), to obtain copper ion-complexed nano zinc oxide.
(3) Preparing a cuprous oxide doped nano zinc oxide composite material:
adding 3.6 mmol (0.1 mol/L) of ascorbic acid solution into the copper ion complexed nano zinc oxide, stirring at normal temperature and normal pressure for 4.0h to obtain cuprous ion complexed nano zinc oxide, washing with 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.
The particle size of the nano zinc oxide in each example is 10 to 100. 100nm.
2. And verifying the antibacterial performance of the composite material:
and (3) effect measurement: staphylococcus aureus is tested and selected as a sterilization object according to a bacteriostasis efficacy examination method (general rule 1121) in the 2015 edition of Chinese pharmacopoeia, and the antibacterial performance of the staphylococcus aureus is researched by a dilution coating method. The number of colonies in the dish showed the antibacterial property of the material, and the smaller the number of colonies, the stronger the antibacterial property thereof, compared with the control group. The antibacterial effect is represented by the Log value of the colony count, and the smaller the Log value is, the smaller the colony count is, and the better the antibacterial effect is. To ensure data accuracy, several plates were applied per dilution gradient, reducing the error between them and doing three passes per sample.
The particle size of the nano zinc oxide is 10-100 nm, the doping amount of the cuprous oxide is respectively adjusted to 5%, 7.5% and 10% of the molar amount of the nano zinc oxide, and the rest of the process parameters, the process steps and the measuring method are completely the same as those of the example 1.
The results of fig. 1 show that: the cuprous oxide doping can effectively enhance the antibacterial performance of the nano zinc oxide. In addition, with the increase of the doping amount of the cuprous oxide, the antibacterial performance of the composite material is obviously increased, and when the doping amount of the cuprous oxide is more than 7.5%, the antibacterial performance of the composite material is smooth, so that the doping molar amount of the cuprous oxide is preferably 5.0-7.5% of the nano zinc oxide.
(1) Comparing the antibacterial effect of EDTA-2Na addition on the composite material: the addition amounts of EDTA-2Na were selected to be 1.8, 3.6, 5.4, 7.2mmol, marked Cu, respectively 2 The O/ZnO 1-4, the other process parameters, process steps and measurement methods are identical to those of the example 1, and the comparison result is shown in figure 2.
The results of fig. 2 show that: the addition amount of EDTA-2Na is too large, which may adversely decrease the antibacterial property of the composite material, so that the addition amount of EDTA-2Na is preferably 3.6 mmol.
(2) Comparison of Cu with different Metal oxides 2 O、CuO、Fe 2 O 3 、CeO 2 、Bi 2 O 3 The doping was performed, and the other process parameters, process steps and measurement methods were exactly the same as those of example 1, and the comparison results are shown in fig. 3.
The results of fig. 3 show that: compared with other metal oxides, the nano zinc oxide doped with cuprous oxide has obviously improved antibacterial property.
(3) In order to compare the antibacterial effect of the composite material under the illumination and light-shielding conditions, antibacterial tests are respectively carried out under the illumination and light-shielding conditions, and the test results are shown in fig. 4.
From the antibacterial results of fig. 4, the antibacterial effect of the pure nano zinc oxide or the cuprous oxide doped nano zinc oxide is significantly higher than that of the light-shielding condition. 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 used in the invention, the size of the nano zinc oxide is 10-100 nm.
Fig. 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 microscope 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 morphology 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 prepared by the method of the present invention.
As can be seen from the XRD pattern of fig. 7: stronger diffraction peaks appear at 31.76 °, 31.42 °, 36.25 °, 47.53 °, 56.59, 62.85 °, 66.37 °, 67.94 ° and 69.08 ° respectively, corresponding in sequence to the (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal planes of the hexagonal single-phase wurtzite nano ZnO structure (JCPDS No. 99-0111); on the other hand, diffraction peaks at 29.57 °, 36.42 °, 42.31 °, 61.37 °, and 73.52 ° correspond to Cu, respectively 2 The (110), (111), (200), (220) and (311) crystal faces of O (JCPDS No. 99-0041) show that the method can successfully prepare the cuprous oxide doped nano zinc oxide composite material.
Claims (5)
1. The cuprous oxide-doped nano zinc oxide composite material is characterized in that the composite material is cuprous oxide-doped nano zinc oxide, and the particle size of the nano zinc oxide is 10-100 nm; the doping mole amount of the cuprous oxide is 5.0-7.5% of the nano zinc oxide.
2. The method for preparing the cuprous oxide-doped nano zinc oxide composite material as claimed in claim 1, which is characterized by comprising the following steps:
1) Under the condition of normal temperature and normal pressure, the stirring rotating speed is 50-1000 rpm, nano zinc oxide with the particle size of 10-100 nm is dispersed in deionized water, after stirring for 10-20 minutes, complexing agent is added, and stirring is carried out for 1.0-4.0 h under the condition of normal temperature and normal pressure, thus obtaining a mixture of complex and nano zinc oxide; the feeding ratio of the complexing agent to the nano zinc oxide is 1.8-7.2 mmol to 1 g; the complexing agent is at least any one of sodium nitrilotriacetate, disodium ethylenediamine tetraacetate, and diethylenetriamine pentacarboxylate;
2) Preparing copper ion complexed nano zinc oxide: mixing cupric salt with bivalent copper ions with a mixture of the complex and nano zinc oxide, stirring for 0.5-4.0 h under normal temperature and normal pressure to obtain a copper ion nano zinc oxide complex, and regulating the pH value of the copper ion nano zinc oxide complex to 10-13; the cupric salt with cupric ion is at least any one of cupric sulfate, cupric chloride or cupric nitrate, and the feeding mole ratio of the cupric salt to the nano zinc oxide is 5-7.5:100;
3) Preparing a cuprous oxide-doped nano zinc oxide composite material: adding the 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 nano zinc oxide complex with deionized water, centrifuging, vacuum drying at 50-70 ℃ for 10-14 hours, and finally grinding into powder to obtain the cuprous oxide doped nano zinc oxide composite material.
3. The method for preparing the cuprous oxide-doped nano zinc oxide composite material according to claim 2, wherein the complexing agent is disodium edetate, and the feeding ratio of disodium edetate to nano zinc oxide is 3.6 mmol/1 g.
4. The method for preparing the cuprous oxide-doped nano zinc oxide composite material according to claim 2, wherein at least one of ammonia water, sodium hydroxide, potassium hydroxide or triethanolamine is adopted when the pH value of the copper ion nano zinc oxide complex is regulated in the step 2).
5. The method for preparing the cuprous oxide-doped nano zinc oxide composite material according to claim 2, wherein the feeding mole ratio of the ascorbic acid to the nano zinc oxide in the step 3) is 7-29:100.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327574A (en) * | 2014-09-29 | 2015-02-04 | 中国海洋大学 | Micro/nano Cu2O/ZnO composite material, preparation method and application thereof |
| CN109820001A (en) * | 2019-02-18 | 2019-05-31 | 江苏理工学院 | A kind of Cu2The preparation method of O/ZnO composite nano materials and the application of the material |
| CN110102312A (en) * | 2019-05-14 | 2019-08-09 | 福州大学 | A kind of one-dimensional cuprous oxide/silver/zinc oxide nanometer rods optic catalytic composite material and the preparation method and application thereof |
| CN110479289A (en) * | 2019-08-29 | 2019-11-22 | 陕西科技大学 | A kind of composite nano cuprous oxide/zinc oxide material and its preparation method and application with photocatalysis performance |
| JP2020075833A (en) * | 2018-11-07 | 2020-05-21 | Ｊｘ金属株式会社 | Cuprous oxide particles and method for producing cuprous oxide particles |
-
2020
- 2020-12-07 CN CN202011414500.1A patent/CN112499664B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327574A (en) * | 2014-09-29 | 2015-02-04 | 中国海洋大学 | Micro/nano Cu2O/ZnO composite material, preparation method and application thereof |
| JP2020075833A (en) * | 2018-11-07 | 2020-05-21 | Ｊｘ金属株式会社 | Cuprous oxide particles and method for producing cuprous oxide particles |
| CN109820001A (en) * | 2019-02-18 | 2019-05-31 | 江苏理工学院 | A kind of Cu2The preparation method of O/ZnO composite nano materials and the application of the material |
| CN110102312A (en) * | 2019-05-14 | 2019-08-09 | 福州大学 | A kind of one-dimensional cuprous oxide/silver/zinc oxide nanometer rods optic catalytic composite material and the preparation method and application thereof |
| CN110479289A (en) * | 2019-08-29 | 2019-11-22 | 陕西科技大学 | A kind of composite nano cuprous oxide/zinc oxide material and its preparation method and application with photocatalysis performance |
Non-Patent Citations (2)
| Title |
|---|
| 氧化亚铜的复合改性及其光催化性质研究;宋继梅等;《中国钼业》;第36卷(第3期);第38-43页 * |
| 纳米晶氧化亚铜的可控合成;李军奇等;《陕西科技大学学报(自然科学版)》;第33卷(第1期);第57-61页 * |
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