CN117463350A - Cu (copper) alloy 2 O@ZnO visible light photocatalytic antibacterial material and preparation method thereof - Google Patents
Cu (copper) alloy 2 O@ZnO visible light photocatalytic antibacterial material and preparation method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 71
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 8
- 239000000956 alloy Substances 0.000 title claims description 8
- 229910045601 alloy Inorganic materials 0.000 title claims description 8
- 229910052802 copper Inorganic materials 0.000 title claims description 8
- 239000000243 solution Substances 0.000 claims abstract description 22
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 10
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 10
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
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- 150000003751 zinc Chemical class 0.000 claims abstract description 10
- 238000011534 incubation Methods 0.000 claims abstract description 9
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- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
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- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 229960004011 methenamine Drugs 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 239000003814 drug Substances 0.000 abstract description 8
- 229940079593 drug Drugs 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 73
- 239000011787 zinc oxide Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 9
- 239000002158 endotoxin Substances 0.000 description 7
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- 230000001580 bacterial effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 206010052428 Wound Diseases 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 208000035143 Bacterial infection Diseases 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 3
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- 238000013459 approach Methods 0.000 description 2
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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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
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Abstract
The invention discloses a Cu 2 O@ZnO visible light photocatalytic antibacterial material and preparation method thereof, and belongs to antibacterial materialsThe preparation technology field comprises the following specific steps: (1) Dissolving zinc salt in deionized water, adding alkaline solution to adjust the pH to 10-12, and adding organic solvent A under sealed condition to obtain solution I; (2) Adding copper salt and an organic solvent B into the solution I, performing constant-temperature reaction, and then adding alkali liquor for reaction to obtain a solution II; (3) Adding ascorbic acid into the solution II, and sequentially performing constant-temperature incubation, centrifugation, washing, freeze drying and microwave treatment to finally obtain the Cu 2 O@ZnO visible light photocatalytic antibacterial material. The porous hollow structure can be used as a drug load; and the invention combines ZnO and Cu 2 O coupling can improve the utilization rate of solar energy, further improve the photocatalysis efficiency and improve the photocatalysis antibacterial property of the material.
Description
Technical Field
The invention relates to the technical field of antibacterial material preparation, in particular to a Cu 2 O@ZnO visible light photocatalytic antibacterial material and a preparation method thereof.
Background
At present, bacterial infections pose a serious threat to human health, and have become the second leading cause of death worldwide, next to ischemic heart disease. In the clinic, once a bacterial infection occurs, the most common approach is to use antibiotics. However, abuse of antibiotics accelerates the production of drug-resistant bacteria, leads to reduced efficacy of the antibiotics, and makes common infectious diseases such as sepsis and pneumonia more difficult to treat. Therefore, there is an urgent need to develop a novel sterilization technique which is efficient, fast, nontoxic and harmless to overcome the problems of bacterial resistance and the like
In recent years, with the advancement of optical technology and the development of photocatalytic materials, photocatalytic sterilization technology has become one of the most promising methods for treating drug-resistant bacterial infections. Compared with the traditional sterilization technology, the photocatalysis sterilization has the characteristics of environmental protection, high efficiency, no drug resistance and the like. Among a large number of photocatalytic materials, zinc oxide has a wide prospect in the field of photocatalytic antibacterial due to its excellent chemical stability, photoelectric properties and good biocompatibility. ZnO as a photocatalytic antibacterial material, which is exposed to light having energy equal to or greater than its band gap, electrons on the valence band (e - ) Will be excited to the conduction band and generate corresponding electron holes (h + ). Reactive Oxygen Species (ROS) are generated. ROS have extremely strong oxidative activity and can break chemical bonds of most organic substances. Therefore, it can attack cell membrane, destroy protein, lipid, polysaccharide and other components of bacteria, and finally achieve ideal sterilizing effect. However, due to ZnO tapeThe gap is relatively wide and can only be activated by the ultraviolet region of the solar spectrum, which results in its relatively low photocatalytic efficiency.
In order to better utilize the visible light region as a main component of solar energy, one of the most promising approaches is to use some narrow bandgap semiconductors as visible light photosensitizers to form coupling semiconductors, thereby achieving higher photocatalytic activity in sunlight. Cu (Cu) 2 O is a typical p-type narrow bandgap semiconductor, but pure Cu, although it can be excited directly by visible light 2 O is extremely unstable and is easily oxidized by humid air, so that the antibacterial effect is short. But it is suitable for the band gap width capable of capturing solar energy and is considered as the optimal semiconductor material for sensitizing a wide band gap semiconductor and improving photocatalytic efficiency. Thus, by combining ZnO with Cu 2 The O coupling mode improves the utilization rate of solar energy, further improves the photocatalysis efficiency, and has great application prospect.
In addition, most ZnO and Cu are now 2 O is a smooth and compact surface, so the specific surface area is small, and the adsorption efficiency is low. In antimicrobial applications, most antimicrobial agents only kill bacteria and do not effectively remove bacterial residues. It is well known that endotoxins in bacterial residues can lead to active substances produced by bacteria, which, if they are freely present in the wound, can attack cells and substances in the wound fluid that promote wound healing, thereby affecting the healing process of the wound.
Accordingly, there has been developed ZnO and Cu having a porous structure and having high photocatalytic efficiency and excellent antibacterial effect 2 O-composites are a problem that one skilled in the art would need to solve.
Disclosure of Invention
In view of this, the present invention discloses a Cu 2 O@ZnO visible light photocatalytic antibacterial material and preparation method thereof, znO and Cu are prepared by a hydrothermal method 2 O coupling to prepare ZnO and Cu with porous structure, high photocatalytic efficiency and excellent antibacterial effect 2 O composite material solves the problems that ZnO in the prior art has wider band gap and can only be used by ultraviolet rays in solar energy spectrumZone activation, resulting in lower photocatalytic efficiency; cu (Cu) 2 O has high photocatalytic efficiency in sunlight, but has the problems of poor stability, short antibacterial time and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
cu (copper) alloy 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material comprises the following steps:
(1) Dissolving zinc salt in deionized water, adding alkaline solution to adjust the pH to 10-12, slowly dripping organic solvent A, and uniformly stirring under a closed condition to obtain solution I;
(2) Adding copper salt and an organic solvent B into the solution I, performing constant-temperature reaction, and then adding alkali liquor for reaction to obtain a solution II;
(3) Adding ascorbic acid into the solution II, and sequentially performing constant-temperature incubation, centrifugation, washing, freeze drying and microwave treatment to obtain the Cu 2 O@ZnO visible light photocatalytic antibacterial material.
The beneficial effects that above-mentioned technical scheme reached are: the invention prepares Cu by a simple one-pot hydrothermal method 2 O@ZnO, the method firstly utilizes a hydrothermal method to prepare ZnO and Cu 2 O precursor, ascorbic acid as reducing agent, znO and Cu are reduced in situ 2 Reduction of O precursor to encapsulate ZnO seed crystal in Cu 2 The surface of O continuously grows under the hydrothermal condition, and ZnO continuously grows on Cu by microwave heat treatment after the product is freeze-dried 2 O surface growth up to cover the whole Cu 2 O surface, thereby obtaining Cu of core-shell structure 2 O@ZnO photocatalytic antibacterial material; and the finally prepared material combines the characteristics of n-type semiconductor zinc oxide and p-type semiconductor cuprous oxide, and in addition, the ascorbic acid is a vitamin, so that the biological safety is high, and the safety of the photocatalytic antibacterial material is further improved.
Preferably, the alkali liquor in the step (1) and the step (2) is any one of ammonia water and sodium hydroxide.
Further, the concentration of the lye was 4mM.
Preferably, the steps of(1) The zinc salt is Zn (NO) 3 ) 2 ·6H 2 O；
The organic solvent A is hexamethylene tetramine.
Preferably, the copper salt in step (2) is CuSO 4 ；
The organic solvent B is ethylenediamine tetraacetic acid or EDTA-Na 2 。
Preferably, in 1L of the total mixed solution, the molar ratio of the zinc salt, the copper salt, the organic solvents A and B and the ascorbic acid is 25:5:12.5:2: (6.5-7.5).
Preferably, the constant temperature reaction temperature in the step (2) is 65 ℃, and the reaction time is 30min.
The beneficial effects that above-mentioned technical scheme reached are: the constant temperature reaction temperature is limited to 65 ℃, which is favorable for the generation of zinc oxide precursors.
Preferably, the constant temperature incubation temperature in the step (3) is 85 ℃, and the incubation time is 12 hours.
The beneficial effects that above-mentioned technical scheme reached are: the constant temperature incubation temperature is limited to be 85 ℃, is the most suitable temperature for zinc oxide growth, is favorable for forming a hollow porous structure, and can ensure that the zinc oxide has a higher growth speed in a limited incubation time.
Preferably, the washing conditions of step (3) are: the washing was performed twice with deionized water and ethanol.
Preferably, the microwave power in the step (3) is 500-800W, and the microwave treatment time is 30min.
The beneficial effects that above-mentioned technical scheme reached are: wherein the microwave heat treatment can promote Cu 2 The ZnO crystal seeds on the surface of O continuously grow, and have important influence on the porous and hollow structure of the finally formed material.
Cu (copper) alloy 2 O@ZnO visible light photocatalytic antibacterial material has a structure that the material is porous and hollow, and ZnO seed crystal is wrapped in Cu 2 Core-shell structure of the surface of O.
Preferably, the Cu 2 The forbidden bandwidth of the O@ZnO visible light photocatalytic antibacterial material is 2.13-2.2eV.
Preferably, the Cu 2 The particle size of the O@ZnO particles is 1-3 mu m.
Preferably, the pore size is 200-400nm.
Cu (copper) alloy 2 The O@ZnO visible light photocatalytic antibacterial material is applied to a wound medicine carrier.
Preferably, the drug is a vascular growth factor.
Cu (copper) alloy 2 Application of O@ZnO visible light photocatalytic antibacterial material in bone implantation drug carriers.
Preferably, the drug is a bone growth promoting drug.
Further, the bone growth promoting drug is BMP2.
As can be seen from the technical scheme, compared with the prior art, the invention discloses a Cu 2 The O@ZnO visible light photocatalytic antibacterial material and the preparation method thereof have the following beneficial effects:
1. conventionally synthesized Cu 2 The O-ZnO composite material is mostly solid and has no holes, and Cu prepared by the invention 2 O@ZnO has a hollow porous property and can be used as a drug carrier;
2. the preparation method disclosed by the invention is prepared by using a one-pot hydrothermal method, is simple and safe in process, simple in operation method, low in equipment requirement and low in cost, and is suitable for large-scale production and industrialization;
3. ZnO and Cu 2 O coupling can improve the utilization rate of solar energy, further improve the photocatalysis efficiency, improve the photocatalysis antibacterial property of the material, and solve the problem of Cu 2 O instability, short antibacterial time and other problems;
4. the yellow light responded by the material prepared finally has milder property and less harm to human bodies, so that the application range of photocatalysis and antibiosis can be enlarged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 shows Cu prepared in example 1 of the present invention 2 Scanning electron microscope image of O@ZnO.
FIG. 2 shows Cu prepared in example 1 of the present invention 2 Transmission electron microscopy of o@zno.
FIG. 3 shows Cu prepared in example 1 of the present invention 2 Energy band gap diagram of o@zno.
FIG. 4 shows Cu prepared in example 1 of the present invention 2 Photocatalytic antibacterial schematic diagram of O@ZnO under natural light and yellow light conditions.
FIG. 5 shows Cu prepared in comparative example 1 of the present invention 2 Scanning electron microscope image of O@ZnO.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention discloses a Cu 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material comprises the following steps:
(1) Dissolving zinc salt in deionized water, adding alkaline solution to adjust the pH to 10-12, and adding organic solvent A under sealed condition to obtain solution I;
(2) Adding copper salt and an organic solvent B into the solution I, performing constant-temperature reaction at 65 ℃ for 30min, and then adding alkali liquor for reaction to obtain a solution II;
(3) Adding ascorbic acid into the solution II, incubating at constant temperature of 85 ℃ for 12h, centrifuging, washing with deionized water and ethanol twice, freeze drying, and microwave treating under microwave power of 500-800W for 30min to obtain Cu 2 O@ZnO visible light photocatalytic antibacterial material.
Further, the zinc salt is Zn (NO 3 ) 2 ·6H 2 O; the organic solvent A is hexamethylene tetramine; the copper salt is CuSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The organic solvent B is ethylenediamine tetraacetic acid or EDTA-Na 2 ；
The alkali liquor is any one of ammonia water and sodium hydroxide.
Wherein, in 1L of total mixed solution, the molar ratio of zinc salt, copper salt, organic solvents A and B and ascorbic acid is 25:5:12.5:2: (6.5-7.5).
Finally prepared Cu 2 O@ZnO visible light photocatalytic antibacterial material has a structure that the material is porous and hollow, and ZnO seed crystal is wrapped in Cu 2 Core-shell structure of the surface of O.
Further, the pore diameter is 200-400nm, cu 2 The particle size of the O@ZnO particles is 1-3 mu m, and Cu 2 The forbidden bandwidth of the O@ZnO visible light photocatalytic antibacterial material is 2.13-2.2eV.
Example 1
Cu (copper) alloy 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material comprises the following steps:
(1) 50mM Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 200mL of deionized water, then ammonia was added to adjust the pH of the solution to 10-12, then 25mM hexamethylenetetramine was dissolved in deionized water, and stirred until completely dissolved, and the process was completely sealed with a cap to prevent evaporation of ammonia.
(2) 10mM CuSO under stirring 4 And 4mM ethylenediamine tetraacetic acid are added into the solution in the step (1) and placed in a constant temperature water bath kettle at 65 ℃ for reaction for 30min.
(3) 40mL of 20wt% NaOH solution was added dropwise to the solution in step (2) at a constant temperature of 65℃with stirring, and reacted for 5min.
(4) Then, 14mM ascorbic acid was added to the solution of step (3), and the mixed solution was incubated in a constant temperature water bath at 85℃for 12 hours.
(5) The product was collected by centrifugation and washed twice with deionized water and ethanol each.
(6) Freeze drying the washed product, and performing microwave treatment in a microwave oven with microwave power of 500-800W for 30min to obtain the final productCu excited by visible light 2 O@ZnO visible light photocatalytic antibacterial material.
Wherein the molar volume concentration of each raw material component represents the amount of the substance containing each component in 1L of the total mixed solution.
Summarizing: cu finally prepared by the invention 2 The O@ZnO photocatalysis antibacterial material is arranged under an electron microscope for observation, the whole structure is porous and hollow, and ZnO seed crystal is wrapped on Cu 2 Core-shell structure of the surface of O. See in particular figures 1-2.
Comparative example 1
The procedure and condition parameters were the same as in example 1 except that the microwave treatment in step (6) was not performed, as in example 1.
Comparative example 1 finally prepared Cu 2 The structure of the O@ZnO visible light photocatalytic antibacterial material is shown in detail in fig. 5, and it can be seen that ZnO growing on the surface of a sample obtained without microwave treatment is less.
Effect verification
Test 1 antibacterial Effect
Coli (e.coli) and staphylococcus aureus (s.aureus) were used as models of gram negative and gram positive strains to evaluate the bactericidal activity of the prepared samples. The method comprises the following specific steps: cu is added with 2 The O@ZnO visible light photocatalytic antibacterial material was dispersed in 10mL of a bacterial suspension, and then the mixture was irradiated with yellow light or natural light for 3 hours; then, the number of colonies on the plate was counted, and the survival rate was calculated by plate counting.
In detail, see fig. 4, wherein the control group in fig. 4 is bacteria without any treatment; the natural light group is the antibacterial effect of Cu2O@ZnO prepared in example 1 under the natural light condition; the yellow group is the antimicrobial effect under yellow light conditions using cu2o@zno prepared in example 1.
Summarizing: 1. cu prepared by the invention 2 The O@ZnO visible light photocatalytic antibacterial material has a good antibacterial effect; 2. yellow light responded by the antibacterial material has milder property, is less harmful to human body, and expands the application range of photocatalysis antibacterial.
Test 2 removal of bacterial residues
Cu prepared in example 1 above 2 O@zno was added to the bacterial suspension and after co-cultivation at 37 ℃ for 24 hours the bacterial endotoxin content in the co-culture was determined using a bacterial endotoxin determinator. The method comprises the following steps:
firstly, a bacterial endotoxin working standard with a concentration of 100EU/mL is taken, diluted into 10, 1.0, 0.1 and 0.01EU/mL standard series aqueous solutions by using limulus reagent dissolved water according to a 10-fold dilution method, the limulus test method is used for operation, the gel time is measured on a bacterial endotoxin tester, and a standard curve can be drawn on the basis of the logarithm of the gel time (lgt) and the logarithm of the bacterial endotoxin concentration (lgc). Then, cu under certain operating conditions was detected in the same manner 2 The bacterial endotoxin content in the water before and after O@ZnO treatment is calculated to be 94.67%. Observing the number of live bacteria and dead bacteria by using a fluorescence microscope, observing the number of bacteria on the surface of a sample, and evaluating Cu 2 Adsorption ability of o@zno to bacteria.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. Cu (copper) alloy 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material is characterized by comprising the following steps of:
(1) Dissolving zinc salt in deionized water, adding alkaline solution to adjust the pH to 10-12, adding organic solvent A, and stirring uniformly under a closed condition to obtain solution I;
(2) Adding copper salt and an organic solvent B into the solution I, performing constant-temperature reaction, and then adding alkali liquor for reaction to obtain a solution II;
(3) Adding ascorbic acid into the solution II, and sequentially performing constant-temperature incubation, centrifugation, washing, freeze drying and microwave treatment to obtain the Cu 2 O@ZnO visible light photocatalytic antibacterial material.
2. A Cu according to claim 1 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material is characterized by comprising the step (1) of preparing zinc salt from Zn (NO) 3 ) 2 ·6H 2 O；
The organic solvent A is hexamethylene tetramine.
3. A Cu according to claim 1 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material is characterized by comprising the step (2) of preparing a copper salt from CuSO 4 ；
The organic solvent B is ethylenediamine tetraacetic acid or EDTA-Na 2 。
4. A Cu according to any one of claims 1-3 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material is characterized by comprising the following steps of in 1L of total mixed solution, the molar ratio of zinc salt to copper salt to organic solvents A and B to ascorbic acid is 25:5:12.5:2: (6.5-7.5).
5. A Cu according to claim 1 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material is characterized in that the constant temperature reaction temperature in the step (2) is 65 ℃ and the reaction time is 30min.
6. A Cu according to claim 1 2 Preparation method of O@ZnO visible light photocatalytic antibacterial materialThe method is characterized in that the constant temperature incubation temperature in the step (3) is 85 ℃, and the incubation time is 12 hours.
7. A Cu according to claim 1 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material is characterized by comprising the following steps of: the washing was performed twice with deionized water and ethanol.
8. A Cu according to claim 1 2 The preparation method of the O@ZnO visible light photocatalytic antibacterial material is characterized in that the microwave power in the step (3) is 500-800W, and the microwave treatment time is 30min.
9. Cu prepared by the preparation method according to any one of claims 1 to 8 2 The O@ZnO visible light photocatalytic antibacterial material is characterized by comprising a porous hollow ZnO seed crystal wrapped in Cu 2 Core-shell structure of the surface of O.
10. Cu according to claim 9 2 The O@ZnO visible light photocatalytic antibacterial material is characterized in that,
the pore diameter is 200-400nm.
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