CN113349220A - Preparation method of cuprous oxide-zinc oxide core-shell antibacterial material - Google Patents
Preparation method of cuprous oxide-zinc oxide core-shell antibacterial material Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 125
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 91
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 85
- 239000011258 core-shell material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 49
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 83
- 239000000843 powder Substances 0.000 claims description 30
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 22
- 239000012279 sodium borohydride Substances 0.000 claims description 22
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000008103 glucose Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003242 anti bacterial agent Substances 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 32
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 230000002045 lasting effect Effects 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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Abstract
The invention discloses a preparation method of a cuprous oxide-zinc oxide core-shell antibacterial material. The material prepared by the invention combines the characteristics of N-type semiconductor zinc oxide and P-type semiconductor cuprous oxide, and the problems of sudden release, instability, short antibacterial timeliness and the like of the cuprous oxide are solved by wrapping the zinc oxide on the cuprous oxide, so that the cuprous oxide-zinc oxide core-shell antibacterial material prepared by the method has a good application prospect in the antibacterial field.
Description
Technical Field
The invention belongs to the technical field of antibacterial material preparation, and particularly relates to a preparation method of a cuprous oxide-zinc oxide core-shell antibacterial material.
Background
With the rapid development of Chinese economy and the continuous improvement of the living standard of people in China, people pay more and more attention to healthy living style. Since ancient times and to date, diseases induced by pathogenic microorganisms are threatening human health, and even today, the study of antibacterial materials for controlling and eliminating the growth and reproduction of harmful bacteria is still an important work closely related to human health.
Among the antibacterial materials, inorganic antibacterial materials have the advantages of stable property, broad antibacterial spectrum, difficult generation of drug resistance, high safety coefficient and the like, and become a hotspot of research and application in the field of the current antibacterial materials. With the continuous and deep research, zinc oxide becomes an antibacterial material for more research by virtue of the advantages of good stability, low toxicity, low price, broad antibacterial spectrum, difficult generation of drug resistance, good biocompatibility and the like, but the antibacterial effect is poor; cuprous oxide has better antibacterial property than zinc oxide, but is unstable, and the release rate of copper ions is high, so that the durable antibacterial property can not be achieved, thereby limiting the application range of the copper oxide.
Therefore, in order to solve the problems of short antibacterial period and unstable antibacterial effect of the antibacterial agent in the prior art, the invention aims to integrate cuprous oxide and zinc oxide antibacterial materials which are relatively low in price to construct a novel multifunctional antibacterial material, and solve the problem of slow release of the cuprous oxide antibacterial material while improving the antibacterial performance of the zinc oxide antibacterial material, so that the lasting antibacterial performance is achieved.
Disclosure of Invention
The invention provides a preparation method of a cuprous oxide-zinc oxide core-shell antibacterial material, which aims to solve the problems of short antibacterial period and unstable antibacterial effect of an antibacterial agent in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a cuprous oxide-zinc oxide core-shell antibacterial material is disclosed, wherein the composite antibacterial agent comprises a cuprous oxide core structure and a zinc oxide shell structure; the particle size of the composite antibacterial agent is 1-5 μm.
Further, the cuprous oxide inner core structure is arranged to be a cubic structure.
Furthermore, the thickness of the zinc oxide shell structure is 0.1-0.9 μm.
Furthermore, the zinc oxide shell structure is arranged into a polygonal irregular-shaped structure.
Further, the preparation method of the cuprous oxide-zinc oxide core-shell antibacterial material comprises the following steps:
s1, measuring 20-40mL of copper acetate solution, magnetically stirring at a constant temperature, and then dropping 60-80mL of sodium borohydride solution into the copper acetate solution by using a constant-pressure funnel;
s1, after the sodium borohydride solution is added dropwise, continuously stirring and reacting for 20-30min, and simultaneously preheating 120mL of 100-60 ℃ glucose solution for 10-20 min; then dropping a glucose solution into the flat-bottomed flask, reacting for 60-80min after the solution is dropped, centrifugally washing for 2-3 times after the reaction is finished, and finally drying in a vacuum drying oven at 60-80 ℃ for 8-9h to obtain cuprous oxide powder;
s3, taking 0.05g of cuprous oxide powder obtained in the step S2, placing the cuprous oxide powder in a beaker, adding 20-30mL of deionized water into the beaker, and performing ultrasonic dispersion for 10-20min under an ultrasonic condition to disperse the cuprous oxide powder in an aqueous solution;
s4, under the condition of magnetic stirring at 80-90 ℃, dropwise adding 10-20mL of sodium dodecyl sulfate into the solution obtained in the step S3, then sequentially dropwise adding 25mL of zinc acetate solution (with the molar concentration of 0.2moL/L) and 10mL of sodium borohydride solution (with the molar concentration of 1moL/L), after the reaction is finished, centrifugally washing for 2-3 times, and finally drying in a vacuum drying box at 60-80 ℃ for 8-9 hours to obtain the cuprous oxide-zinc oxide core-shell antibacterial material.
Further, the molar ratio of the copper acetate solution, the sodium borohydride solution and the glucose solution is 1: 5: 7.
further, in step S1, the water bath heating temperature is 80-90 ℃.
Further, the dropping speed of the constant pressure funnel in the step S1 is 6-8S/d.
Furthermore, the stirring speed is kept unchanged in the whole preparation process, and the stirring rotating speed is 600-800 r/min.
Furthermore, the concentration of the sodium dodecyl sulfate is 0.01-0.05 mol/L.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention discloses a preparation method of a cuprous oxide-zinc oxide core-shell antibacterial material. The material prepared by the invention combines the characteristics of N-type semiconductor zinc oxide and P-type semiconductor cuprous oxide, and the problems of sudden release, instability, short antibacterial timeliness and the like of the cuprous oxide are solved by wrapping the zinc oxide on the cuprous oxide, so that the cuprous oxide-zinc oxide core-shell antibacterial material prepared by the method has a good application prospect in the antibacterial field.
1) The cuprous oxide-zinc oxide core-shell antibacterial material is prepared by combining a liquid phase reduction method and a precipitation method, the release rate of copper ions is detected by ICP, the antibacterial durability of the material is explored by a coating flat plate method, and the material is found to have excellent antibacterial performance;
2) according to the invention, by controlling the reaction preparation method and related experimental parameters, the particle size of the antibacterial material is controlled to be in a micron level, and compared with a common nano-level antibacterial agent, the antibacterial material has a good dispersion effect, is not easy to agglomerate and is not easy to be adsorbed by bacteria, so that the slow release effect of the antibacterial material is promoted, and the lasting antibacterial effect of the antibacterial material is improved.
3) The invention selects the cubic cuprous oxide as the core structure, compared with other structures, the cubic cuprous oxide has good dispersibility, relatively smaller specific surface area, small bulk density, good suspension property and low oil absorption, is very suitable to be used as an additive to be added into the ship antifouling paint, and can effectively prevent the ship from being invaded by microorganisms.
The preparation method of the invention provides a certain experimental basis for the research of recombining antibacterial components and constructing a multi-component multifunctional antibacterial material with a novel structure.
Drawings
Fig. 1 is an SEM image of cuprous oxide powder and cuprous oxide-zinc oxide core-shell antibacterial material.
FIG. 2 is SEM-EDS energy spectrum of cuprous oxide-zinc oxide core-shell antibacterial material.
FIG. 3 is a TEM image of cuprous oxide-zinc oxide core-shell antibacterial material;
FIG. 4 is a TEM-EDS energy spectrum of cuprous oxide-zinc oxide core-shell antibacterial material;
fig. 5 is a graph showing the release amount of copper ions of the cuprous oxide and cuprous oxide-zinc oxide core-shell antibacterial material.
FIG. 6 is a graph of the experimental antibacterial property of the cuprous oxide-zinc oxide core-shell antibacterial material by a coating plate method.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
As shown in the figure:
example 1:
a cuprous oxide-zinc oxide core-shell antibacterial material is disclosed, wherein the composite antibacterial agent comprises a cuprous oxide core structure and a zinc oxide shell structure; the particle size of the composite antibacterial agent is 1-5 μm.
Example 2:
on the basis of example 1, the cuprous oxide core structure is arranged to be a cubic structure.
Example 3:
on the basis of examples 1-2, the zinc oxide shell structure had a thickness of 0.1-0.9. mu.m.
Example 4:
on the basis of the examples 1 to 3, the zinc oxide shell structure is provided as a polygonal irregularly shaped structure.
Example 5:
on the basis of the embodiments 1 to 4, the preparation method of the cuprous oxide-zinc oxide core-shell antibacterial material comprises the following steps:
s1, measuring 20-40mL of copper acetate solution, magnetically stirring at a constant temperature, and then dropping 60-80mL of sodium borohydride solution into the copper acetate solution by using a constant-pressure funnel;
s1, after the sodium borohydride solution is added dropwise, continuously stirring and reacting for 20-30min, and simultaneously preheating 120mL of 100-60 ℃ glucose solution for 10-20 min; then dropping a glucose solution into the flat-bottomed flask, reacting for 60-80min after the solution is dropped, centrifugally washing for 2-3 times after the reaction is finished, and finally drying in a vacuum drying oven at 60-80 ℃ for 8-9h to obtain cuprous oxide powder;
s3, taking 0.05g of cuprous oxide powder obtained in the step S2, placing the cuprous oxide powder in a beaker, adding 20-30mL of deionized water into the beaker, and performing ultrasonic dispersion for 10-20min under an ultrasonic condition to disperse the cuprous oxide powder in an aqueous solution;
s4, under the condition of magnetic stirring at 80-90 ℃, dropwise adding 10-20mL of sodium dodecyl sulfate into the solution obtained in the step S3, then sequentially dropwise adding 25mL of zinc acetate solution (with the molar concentration of 0.2moL/L) and 10mL of sodium borohydride solution (with the molar concentration of 1moL/L), after the reaction is finished, centrifugally washing for 2-3 times, and finally drying in a vacuum drying box at 60-80 ℃ for 8-9 hours to obtain the cuprous oxide-zinc oxide core-shell antibacterial material.
Example 6:
based on the examples 1-5, the molar ratio of the copper acetate solution to the sodium borohydride solution to the glucose solution is 1: 5: 7.
example 7:
based on examples 1 to 6, step S1 was carried out at a water bath heating temperature of 80 to 90 ℃.
Example 8:
on the basis of examples 1 to 7, the dropping speed of the constant pressure funnel of step S1 was 6 to 8S/d.
Example 9:
on the basis of the examples 1-8, the stirring speed is kept unchanged in the whole preparation process, and the stirring rotating speed is 600-800 r/min.
Example 10:
in step S4, the concentration of sodium lauryl sulfate is 0.01-0.05mol/L based on examples 1-9.
Example 11:
the preparation method of the cuprous oxide-zinc oxide core-shell antibacterial material comprises the following specific operations:
(1) measuring 20mL of copper acetate solution, placing the copper acetate solution in a flat-bottomed flask, and stirring the solution at constant temperature and magnetically, and then dripping 60mL of sodium borohydride solution into the solution by using a constant-pressure funnel;
(2) after the sodium borohydride solution is dripped, reacting for 20min, and simultaneously preheating 100mL of glucose solution at 50 ℃ for 10 min; then dropping glucose solution into a flat-bottomed flask, reacting for 60min after the solution is completely dropped, centrifugally washing for 2 times after the reaction is finished, and finally drying in a vacuum drying oven at 60 ℃ for 9h to obtain cuprous oxide powder, wherein the shape of the cuprous oxide powder is shown in figure 1, and pure Cu can be seen by SEM2The shape of the O is cubic;
(3) putting 0.05g of cuprous oxide powder obtained in the step (2) into a beaker, adding 20 g of deionized water into the beaker, and ultrasonically dispersing for 10min under the ultrasonic condition to disperse the powder in the aqueous solution;
(4) and (3) under the constant-temperature magnetic stirring at 80 ℃, firstly dropwise adding 10mL of sodium dodecyl sulfate into the solution in the step (3), then sequentially dropwise adding 25mL of zinc acetate solution (with the molar concentration of 0.2moL/L) and 10mL of sodium borohydride solution (with the molar concentration of 1moL/L), after the reaction is finished, centrifugally washing for 2 times, and finally drying in a vacuum drying oven at 60 ℃ for 9 hours to obtain the cuprous oxide-zinc oxide core-shell antibacterial material.
Example 12:
the preparation method of the cuprous oxide-zinc oxide core-shell antibacterial material comprises the following specific operations:
(1) measuring 30mL of copper acetate solution, placing the solution in a flat-bottomed flask, and stirring the solution at constant temperature and magnetically, and then dropping 70mL of sodium borohydride solution into the solution by using a constant-pressure funnel;
(2) after the sodium borohydride solution is dripped, reacting for 25min, and simultaneously preheating 110mL of glucose solution at 55 ℃ for 15 min; then dropping a glucose solution into the flat-bottomed flask, reacting for 70 min after the solution is completely dropped, centrifugally washing for 3 times after the reaction is finished, and finally drying in a vacuum drying oven at 70 ℃ for 8.5h to obtain cubic cuprous oxide;
(3) putting 0.05g of cuprous oxide powder obtained in the step (2) into a beaker, adding 30mL of deionized water into the beaker, and ultrasonically dispersing for 15min under an ultrasonic condition to disperse the powder in an aqueous solution;
(4) and (2) under the condition of magnetic stirring at 85 ℃, dropwise adding 15mL of sodium dodecyl sulfate into the solution obtained in the step (3), then sequentially dropwise adding 25mL of zinc acetate solution (with the molar concentration of 0.2moL/L) and 10mL of sodium borohydride solution (with the molar concentration of 1moL/L), after the reaction is finished, centrifugally washing for 3 times, and finally drying in a vacuum drying oven at 70 ℃ for 8.5 hours to obtain the cuprous oxide-zinc oxide core-shell antibacterial material.
Example 13:
the preparation method of the cuprous oxide-zinc oxide core-shell antibacterial material comprises the following specific operations:
(1) measuring 40mL of copper acetate solution, placing the copper acetate solution in a flat-bottomed flask, and stirring the solution at constant temperature and magnetically, and then dropping 80mL of sodium borohydride solution into the solution by using a constant-pressure funnel;
(2) after the sodium borohydride solution is dripped, reacting for 30min, and simultaneously preheating 120mL of glucose solution at 60 ℃ for 20 min; then dropping a glucose solution into the flat-bottomed flask, reacting for 80min after the solution is completely dropped, centrifugally washing for 3 times after the reaction is finished, and finally drying in a vacuum drying oven at 80 ℃ for 8h to obtain cubic cuprous oxide;
(3) putting 0.05g of cuprous oxide powder obtained in the step (2) into a beaker, adding 25mL of deionized water into the beaker, and ultrasonically dispersing for 20min under the ultrasonic condition to disperse the powder in the aqueous solution;
(4) and (3) under the condition of magnetic stirring at 90 ℃, firstly dropwise adding 20mL of sodium dodecyl sulfate into the solution in the step (3), then sequentially dropwise adding 25mL of zinc acetate solution (with the molar concentration of 0.2moL/L) and 10mL of sodium borohydride solution (with the molar concentration of 1moL/L), after the reaction is finished, centrifugally washing for 3 times, and finally drying in a vacuum drying oven at 80 ℃ for 8 hours to obtain the cuprous oxide-zinc oxide core-shell antibacterial material.
Example 14:
the morphological structure of the cuprous oxide-zinc oxide core-shell antibacterial material prepared according to the embodiment 1 is characterized in that:
the left side of the figure 1 is a structural schematic diagram of a cuprous oxide powder SEM; the cuprous oxide-zinc oxide core-shell antibacterial material is arranged on the right side of the figure 1.
As seen in SEM picture, before wrapping ZnO, cuprous oxide is in cubic structure and has particle size of 1-2 μm; after wrapping ZnO, the shape of the material is changed, the cubic shape can not be seen, and the material is changed into a polygonal irregular structure which is beneficial to Cu2+Thereby achieving a lasting antibacterial effect;
FIG. 2 is an EDS energy spectrum of cuprous oxide-zinc oxide core-shell antibacterial material,
the left panel also shows that the material is composed mainly of C, O, Cu and Zn, Au is from the gold spraying treatment in SEM detection, and Cu is from cubic Cu2O, thereby indicating Cu2The surface of O is coated with ZnO;
FIG. 3 further demonstrates the prepared cuprous oxide-zinc oxide core-shell antibacterial material by TEM, from which Cu can be seen2ZnO is wrapped on the surface of the O, and the ZnO shell is of an angular irregular structure.
The EDS spectrum of fig. 4 shows that the material has Cu, O, Zn composition, further validating the previous conclusion.
Example 15:
the cuprous oxide-zinc oxide core-shell antibacterial material prepared according to the example 1 is used for testing the antibacterial performance:
the durable antibacterial performance of the material is determined by a coating flat plate method, and the experimental process is as follows:
coli is selected to carry out antibacterial detection on the material at different time periods. Firstly, all glass instruments and culture media used in the antibacterial experiment process need to be sterilized at high temperature in an autoclave in advance, the experiment operation needs to be carried out in a clean bench, and the used bacterial strains need to be activated in advance (OD600 is 1); secondly, diluting the activated bacterial liquid to 10 DEG5Adding 100 μ L diluted bacterial solution into test tubes containing 0.005g cuprous oxide powder and 10mL cuprous oxide-zinc oxide core-shell antibacterial material (the cuprous oxide powder and the cuprous oxide-zinc oxide core-shell antibacterial material are shaken in PBS solution for 0, 1, 2, 3, 7, 14, 21 and 28 days, and then centrifugally washingVacuum dried powder); placing the test tube on a shaking table, shaking for 15min, transferring 100 μ L of the solution from the test tube, inoculating on a solid culture medium, uniformly coating, writing numbers, and testing all samples at least three times; and finally, placing the coated plate in a constant-temperature incubator for culturing for 18-24h, observing the antibacterial action of the material through the number of bacterial colonies on the plate after 0, 1, 2, 3, 7, 14, 21 and 28 days, and calculating the antibacterial rate of the material by adopting a viable bacterial colony counting method, wherein the antibacterial rate AR is calculated according to the following formula:
in the formula: AR-antimicrobial Rate (%)
A-number of colonies of reference sample
B-number of colonies of test Material
The antibacterial rates of the cuprous oxide powder and the cuprous oxide-zinc oxide core-shell antibacterial material are shown in the following table 1:
table 1: antibacterial rate of cuprous oxide powder and cuprous oxide-zinc oxide core-shell antibacterial material
As can be seen from the table, the antibacterial rate of the pure cuprous oxide powder is reduced rapidly with the time being prolonged, after 28 days, the antibacterial rate is only 45.70%, while the antibacterial rate of the cuprous oxide-zinc oxide core-shell antibacterial material is higher and reaches 71.84%, which indicates that in Cu, the antibacterial rate of the cuprous oxide-zinc oxide core-shell antibacterial material is higher2ZnO is wrapped on the surface of O, which is beneficial to the slow release of copper ions, thereby leading Cu to be2O achieves a long-lasting antibacterial property.
Example 16:
cuprous oxide-Zinc oxide core-Shell antibacterial Material Cu prepared in examples 11 to 132+The slow release performance research:
material Cu prepared by ICP inspection2+The slow release performance is tested as follows:
weighing 7 parts of 0015g of cuprous oxide powder and 7 parts of 0.015g of cuprous oxide-zinc oxide core-shell antibacterial material are placed in 14 test tubes filled with 20mL of PBS solution, then the test tubes are placed on a shaking table to be respectively shaken for 0d, 1d, 2d, 3d, 7d, 14d, 21d and 28d, then the test tubes are centrifuged to obtain supernatant, and HNO is used for3The solution was made acidic and Cu was detected by ICP2+The copper ion release amount of (b) is shown in FIG. 5. As can be observed from FIG. 5, in the first 3 days, Cu was present2O-released Cu2+The rate of (A) is fast, however ZnO/Cu2Cu in O core-shell antibacterial material2+The release rate of (a) is slowed.
Cu2O shows faster release of Cu2+Rate of (A) indicates Cu2The stability of O is reduced; ZnO/Cu2Cu capable of keeping lasting and mild of O composite antibacterial material2+Release mainly due to tight encapsulation of Cu by ZnO2O forms a protective barrier and reduces Cu2Possibility of contact reaction of O with external solution, in addition to that, ZnO is wrapped in Cu2The surface of O particles forms a large number of ion release channels, so that Cu2+A good slow release effect is achieved, and finally a durable antibacterial effect is achieved.
Example 17:
the antibacterial performance of the cuprous oxide-zinc oxide core-shell antibacterial material prepared in examples 11 to 13 is studied:
the antimicrobial performance of examples 11, 12, 13 was tested at 0d using the flat coating method described in example 15, and the results, as shown in fig. 6, indicate that:
the antibacterial ratio of example 11 was 95.61%,
example 12 had an antibacterial rate of 91.70%,
the antibacterial rate of example 13 was 85.25%.
According to the antibacterial effect of the embodiment, the optimal preparation conditions of the core-shell antibacterial material are as follows: placing 0.05g of Cu2O in a beaker, adding 25mL of deionized water in the beaker, and ultrasonically dispersing for 20min under the ultrasonic condition to disperse the powder in the aqueous solution; and dropwise adding 20mL of sodium dodecyl sulfate, then sequentially dropwise adding 25mL of zinc acetate solution (with the molar concentration of 0.2moL/L) and 10mL of sodium borohydride solution (with the molar concentration of 1moL/L), after the reaction is finished, centrifugally washing for 3 times, and finally drying in a vacuum drying oven at 80 ℃ for 8 hours to obtain the excellent cuprous oxide-zinc oxide core-shell antibacterial material.
Example 18:
the research on the lasting antibacterial performance of the cuprous oxide-zinc oxide core-shell antibacterial material prepared in the embodiments 11 to 13 comprises the following steps:
using the method of example 15 and example 16, the antibacterial rate and Cu were combined for different days2+Sustained release data, which are obtained by respectively carrying out the research on the lasting antibacterial performance of the examples 11, 12 and 13, and the results show that:
example 11, as can be seen from Table 1, pure Cu is present over time2The antibacterial rate of O is reduced rapidly, after 28 days, the antibacterial rate is only 45.70 percent, however, ZnO/Cu2The antibacterial rate of O is higher and reaches 71.84 percent; material Cu prepared by ICP inspection2+The procedure is as in example 11, and the results are shown in FIG. 4; is shown in Cu2ZnO is wrapped on the surface of O, which is beneficial to the slow release of copper ions, thereby leading Cu to be2O achieves a long-lasting antibacterial property.
Example 12 Cu test of the prepared Material by ICP2+The procedure is as in example 1, and the results are shown in FIG. 4; the durable antibacterial properties of the materials were determined by the flat-bed coating method, as in example 11, to obtain pure Cu2After 28d of O, the antibacterial rate is only 43.32 percent, however, ZnO/Cu2The antibacterial rate of O is higher and reaches 69.54 percent.
Example 13 durable antimicrobial Properties of the materials measured by the spread plate method, as in example 11, pure Cu was measured2After 28d of O, the antibacterial rate is only 40.69%, however, ZnO/Cu2The antibacterial rate of O is higher and reaches 66.85 percent. Material Cu prepared by ICP inspection2+The procedure is as in example 11, and the results are shown in FIG. 4.
The durable antimicrobial performance of example 11 was optimal.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. The cuprous oxide-zinc oxide core-shell antibacterial material is characterized in that the composite antibacterial agent comprises a cuprous oxide core structure and a zinc oxide shell structure; the particle size of the composite antibacterial agent is 1-5 μm.
2. A cuprous oxide-zinc oxide core-shell antibacterial material according to claim 1, wherein the cuprous oxide core structure is provided as a cubic structure.
3. A cuprous oxide-zinc oxide core-shell antibacterial material according to claim 1, wherein the thickness of zinc oxide shell structure is 0.1-0.9 μm.
4. A cuprous oxide-zinc oxide core-shell antibacterial material according to claim 1, wherein zinc oxide shell structure is arranged as polygonal irregular shape structure.
5. The preparation method of cuprous oxide-zinc oxide core-shell antibacterial material according to any of claims 1 to 4, characterized by comprising the following steps:
s1, measuring 20-40mL of copper acetate solution, magnetically stirring at a constant temperature, and then dropping 60-80mL of sodium borohydride solution into the copper acetate solution by using a constant-pressure funnel;
s2, after the sodium borohydride solution is added dropwise, continuously stirring and reacting for 20-30 min;
preheating 100-120mL of glucose solution at 50-60 ℃ for 10-20 min; then dropping the preheated glucose solution into a flat-bottomed flask, reacting for 60-80min after the solution is dropped, centrifugally washing for 2-3 times after the reaction is finished, and finally drying in a vacuum drying oven at 60-80 ℃ for 8-9h to obtain cuprous oxide powder;
s3, taking 0.05g of cuprous oxide powder obtained in the step S2, placing the cuprous oxide powder in a beaker, adding 20-30mL of deionized water into the beaker, and performing ultrasonic dispersion for 10-20min under an ultrasonic condition to disperse the cuprous oxide powder in an aqueous solution;
s4, under the condition of magnetic stirring at 80-90 ℃, firstly dripping 10-20mL of sodium dodecyl sulfate into the solution obtained in the step S3, then dripping 25mL of zinc acetate solution with the molar concentration of 0.2moL/L and 10mL of sodium borohydride solution with the molar concentration of 1moL/L in sequence, after the reaction is finished, centrifugally washing for 2-3 times, and finally drying in a vacuum drying box at 60-80 ℃ for 8-9 hours to obtain the cuprous oxide-zinc oxide core-shell antibacterial material.
6. The preparation method of cuprous oxide-zinc oxide core-shell antibacterial material according to claim 5, wherein the molar ratio of copper acetate solution, sodium borohydride solution, glucose solution is 1: 5: 7.
7. the preparation method of cuprous oxide-zinc oxide core-shell antibacterial material according to claim 5, wherein the water bath heating temperature of step S1 is 80-90 ℃.
8. The preparation method of cuprous oxide-zinc oxide core-shell antibacterial material according to claim 5, wherein the dropping speed of constant pressure funnel in step S1 is 6-8S/d.
9. The preparation method of cuprous oxide-zinc oxide core-shell antibacterial material according to claim 5, wherein the stirring speed is kept constant during the whole preparation process, and the stirring rotation speed is 600-800 r/min.
10. The method for preparing cuprous oxide-zinc oxide core-shell antibacterial material according to claim 5, wherein in step S4, the concentration of sodium dodecyl sulfate is 0.01-0.05 mol/L.
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