CN113827726A - Ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity and preparation method and application thereof - Google Patents
Ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity and preparation method and application thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 67
- 239000011206 ternary composite Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 32
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000013179 MIL-101(Fe) Substances 0.000 claims abstract description 79
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- 238000006243 chemical reaction Methods 0.000 claims description 65
- 239000011259 mixed solution Substances 0.000 claims description 29
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 241000588724 Escherichia coli Species 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
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- 238000011049 filling Methods 0.000 claims description 5
- 241000191967 Staphylococcus aureus Species 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 244000052616 bacterial pathogen Species 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 39
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Abstract
The invention discloses a ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity, and a preparation method and application thereof2MoS loaded with MIL-101(Fe) as a support2Then, ZnO quantum dots are loaded on MoS2The surface of the nanosheet improves the separation efficiency of carriers, so that the photocatalytic antibacterial performance of the nanosheet is enhanced; NH (NH)2‑MIL‑101(Fe)、MoS2And the hetero-structure formed among the ZnO reduces the transition energy barrier of electrons, promotes the separation of photo-generated electrons and holes, promotes the generation of active oxygen, realizes the photocatalytic antibacterial effect, and has MoS2The photo-thermal property of the composite material enables the composite material to generate a large amount of heat and high temperature after being illuminated so as to inhibit the growth of bacteria, and the photocatalysis and photo-thermal synergistic effect enables the prepared composite material to show higher antibacterial activity.
Description
Technical Field
The invention belongs to the technical field of antibacterial materials and environmental protection, relates to a composite material and a preparation method thereof, and particularly relates to a ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity, and a preparation method and application thereof.
Background
Bacterial infections are a common problem in daily life, and the common bacteria causing infections are staphylococcus aureus and escherichia coli, which can cause wound inflammation, pneumonia, colitis, septicemia, and especially postoperative wound infections can cause high mortality and morbidity and pose serious threats to human life and health. Antibiotics are an effective method for treating bacterial infection problems, but the long-term use of antibiotics can cause drug resistance of bacteria, and seriously threatens the living environment and ecosystem of people. Therefore, the development of highly effective and environmentally friendly antibacterial agents is urgent. In recent years, inorganic nanocomposites have been extensively studied and used to effectively kill bacteria, avoid the generation of drug-resistant bacteria and protect public health.
Molybdenum disulfide has been widely used in the fields of solar energy conversion, photocatalytic antibacterial and organic matter degradation due to its unique two-dimensional lamellar structure, high photocatalytic activity and photo-thermal conversion capability and its property of generating oxidative stress. Using MoS2The photocatalytic activity and the photo-thermal conversion capability can achieve the synergistic sterilization effect. The high temperature generated by photo-thermal can accelerate ROS generated by photocatalysis to rapidly enter cells to oxidize enzymes, proteins and the like in the cells. Simultaneous, narrow bandgap MoS2Has wide photoresponse range from ultraviolet to near infrared, and has good photocatalytic performance when electron-hole separation is carried out under the excitation of light. But pure MoS2The low efficiency of electron-hole separation and the easy and rapid recombination lead to the limited photocatalytic antibacterial activity of molybdenum disulfide itself, which needs to be compounded with other materials to enhance its antibacterial performance. And the photocatalytic performance of molybdenum disulfide can be effectively improved by constructing a heterojunction through a semiconductor.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity, a preparation method and application thereof, which realize photodynamic-photothermal synergistic antibacterial and have the advantages of wide visible light absorption range, good antibacterial performance and low cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity comprises the following steps:
step one, FeCl3·6H2Adding O and 2-amino terephthalic acid into a solvent DMF, and stirring until the O and the 2-amino terephthalic acid are dissolved to obtain a first reaction mixed solution;
step two, transferring the first reaction mixed solution obtained in the step one into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 20-24 hours at 100-110 ℃, cooling to room temperature after the reaction is finished, centrifuging, washing with water, and drying to finally obtain a sample NH2-MIL-101(Fe)；
Step three, adding sodium molybdate dihydrate and thiourea into deionized water, and stirring until the sodium molybdate dihydrate and the thiourea are dissolved to obtain a second reaction mixed solution;
step four, the sample NH obtained in the step two2Dispersing MIL-101(Fe) in the second reaction mixed solution obtained in the third step, uniformly stirring and performing ultrasonic treatment; then, transferring the mixture into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 20-25 h at 180-220 ℃, cooling to room temperature after the reaction is finished, centrifuging, washing with water, and drying to finally obtain a sample NH2-MIL-101(Fe)/MoS2；
Step five, adding Zn (CH)3COO)2·2H2Adding O and KOH into the ethanol solution, and stirring at 32 ℃ until the O and the KOH are dissolved to obtain a third reaction mixed solution;
step six, taking the sample NH obtained in the step four2-MIL-101(Fe)/MoS2Adding the mixture into the third reaction mixed solution obtained in the fifth step, performing ultrasonic treatment until the mixture is uniformly dispersed, performing oil bath reaction at the temperature of 90-110 ℃, maintaining the reaction for 5 hours by magnetic stirring, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to finally obtain NH2-MIL-101(Fe)/MoS2the/ZnO ternary composite antibacterial material.
The invention also has the following technical characteristics:
preferably, in the first step, FeCl3·6H2The mass ratio of O to 2-amino terephthalic acid is 3: (1-1.2) FeCl3·6H2The mass ratio of O to DMF solvent is 1: 42.
preferably, in the third step, the mass ratio of the sodium molybdate dihydrate to the thiourea is 3: (4-6), wherein the mass ratio of the sodium molybdate dihydrate to the solvent deionized water is 3: (400-500).
Preferably, in the fourth step, sample NH2The mass ratio of the addition amount of MIL-101(Fe) to the sodium molybdate dihydrate is (1-2): 3.
preferably, in the fifth step, Zn (CH)3COO)2·2H2The mass ratio of O to KOH is (1.5-2.2): 1, wherein the mass ratio of the zinc acetate to the solvent ethanol is 1: (240-284).
Preferably, in the sixth step, sample NH2-MIL-101(Fe)/MoS2The addition amount of Zn (CH)3COO)2·2H2The mass ratio of O is (5-6): 6.
preferably, the filling ratio of the solution in the polytetrafluoroethylene high-pressure reaction kettle in the second step and the fourth step is 50 percent.
The invention also discloses a ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity, which is prepared by the method, and the structure of the ternary composite antibacterial material is in a flower ball shape.
The invention also discloses application of the ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity, and particularly the material is applied to the antibacterial field and can effectively kill pathogenic bacteria of escherichia coli and staphylococcus aureus.
Compared with the prior art, the invention has the following technical effects:
the invention utilizes NH prepared by a hydrothermal method2-MIL-101(Fe)/MoS2the/ZnO ternary composite antibacterial material has high specific surface area and wide photoresponse range, realizes the photocatalysis and photo-thermal synergistic effect, and has high antibacterial activity, wide visible light absorption range and low cost;
by using NH in the invention2MIL-101(Fe) as a support, mainly due to its high specific surface area and the abundance of active sites that can be MoS2The nano sheet grows on the surface to provide nucleation sites, so that MoS can be improved2The problem of stacking of nano-sheets, and then loading ZnO quantum dots on MoS2Nano sheet surface, ZnO as n-type semiconductor and p-type semiconductor MoS2A p-n heterojunction is formed, the separation efficiency of carriers is improved, and the photocatalytic antibacterial performance of the carriers is further enhanced;
NH prepared by the invention2-MIL-101(Fe)/MoS2the/ZnO ternary composite antibacterial material is prepared from MoS2NH wrapped by nanosheets2MIL-101(Fe) forms a structure similar to a flower ball, ZnO quantum dots are loaded on the surface of the structure to obtain a ternary composite material, the flower ball structure exposes more active sites and sharp edges, the specific surface area is larger, and the photocatalytic antibacterial activity is improved;
of importance is NH2-MIL-101(Fe)、MoS2The heterostructure formed by the ZnO crystal and the ZnO crystal reduces the transition energy barrier of electrons, promotes the separation of photo-generated electrons and holes, promotes the generation of active oxygen, and realizes the photocatalytic antibacterial effect; furthermore, MoS2The photo-thermal characteristic of the NH-containing material enables the NH-containing material to generate a large amount of heat and high temperature after being illuminated so as to inhibit the growth of bacteria, meanwhile, the higher temperature can improve the permeability of bacterial cell membranes, and is beneficial to promoting active oxygen to rapidly enter cells to damage the bacteria, and the prepared NH is caused by the synergistic effect of photocatalysis and photo-thermal2-MIL-101(Fe)/MoS2the/ZnO ternary composite material shows higher antibacterial activity under the action of short-time illumination, and has certain practical application value and application prospect.
Drawings
FIG. 1 is NH2-Scanning Electron Micrograph (SEM) of MIL-101 (Fe);
FIG. 2 is NH2-MIL-101(Fe)/MoS2Scanning Electron Microscope (SEM);
FIG. 3 is NH2-MIL-101(Fe)/MoS2Scanning Electron Microscope (SEM) of the/ZnO ternary composite material;
FIG. 4 is NH2-Transmission Electron Micrograph (TEM) of MIL-101 (Fe);
FIG. 5 is NH2-MIL-101(Fe)/MoS2Transmission Electron Micrographs (TEMs);
FIG. 6 is NH2-MIL-101(Fe)/MoS2Transmission Electron Microscope (TEM) of the/ZnO ternary composite material;
FIG. 7 is NH2-MIL-101(Fe)、MoS2、NH2-MIL-101(Fe)/MoS2And NH2-MIL-101(Fe)/MoS2XRD diffraction pattern of the/ZnO ternary composite material;
FIG. 8 shows MoS2、NH2-MIL-101(Fe)/MoS2And NH2-MIL-101(Fe)/MoS2The photothermal effect spectrum of the/ZnO ternary composite material;
FIG. 9-FIG. 19 are NH2-MIL-101(Fe)/MoS2Antibacterial effect pair of/ZnO ternary composite material on escherichia coli in different illumination timeA comparison graph;
FIG. 20 is NH2-MIL-101(Fe)/MoS2The bacteriostasis rate of the/ZnO ternary composite material under the action of visible light is obtained.
Detailed Description
The present invention will be explained in further detail with reference to examples.
In the following examples, the mass fraction of the ethanol solution is not less than 99.7%, and the density is 0.789-0.791 g/mL.
Example 1:
step one, taking 4.16mmol FeCl3·6H2Adding O and 2.15mmol of 2-amino terephthalic acid into a beaker, adding 50mL of DMF (dimethyl formamide) solvent, and stirring until the DMF solvent is dissolved to obtain a first reaction mixed solution;
step two, transferring the first reaction mixed solution obtained in the step one into a polytetrafluoroethylene high-pressure reaction kettle (the filling ratio is 50%), reacting for 24 hours at 110 ℃, cooling to room temperature after the reaction is finished, centrifuging, washing, and drying for 12 hours at 50 ℃ to finally obtain a sample NH2-MIL-101(Fe)；
Step three, adding 0.3g of sodium molybdate dihydrate and 0.4g of thiourea into 40mL of deionized water, and stirring until the sodium molybdate dihydrate and the thiourea are dissolved to obtain a second reaction mixed solution;
step four, 0.1g of sample NH obtained in the step two2Dispersing MIL-101(Fe) in the second reaction mixed solution obtained in the third step, uniformly stirring and carrying out ultrasonic treatment for 30 min; then, transferring the mixture into a polytetrafluoroethylene high-pressure reaction kettle, reacting at 180 ℃ for 24h, cooling to room temperature after the reaction is finished, centrifuging, washing with water, and drying at 50 ℃ for 12h to finally obtain a sample NH2-MIL-101(Fe)/MoS2；
Step five, taking 0.36g of Zn (CH)3COO)2·2H2Adding O and 0.24g KOH into 150mL ethanol solution, and stirring for 30min at 32 ℃ until the O and the KOH are dissolved to obtain third reaction mixed solution;
step six, taking 0.36g of sample NH obtained in the step four2-MIL-101(Fe)/MoS2Adding into the third reaction mixture obtained in the fifth step, performing ultrasonic treatment for 40min, performing oil bath reaction at 95 deg.C, and magnetically stirring for maintainingCooling to room temperature after the reaction is finished, centrifuging, washing with ethanol for 3 times, and drying at 50 deg.C for 12h to obtain NH2-MIL-101(Fe)/MoS2the/ZnO ternary composite antibacterial material.
Example 2:
step one, taking 4.16mmol FeCl3·6H2Adding O and 2.05mmol of 2-amino terephthalic acid into a beaker, adding 50mL of DMF (dimethyl formamide) solvent, and stirring until the DMF solvent is dissolved to obtain a first reaction mixed solution;
step two, transferring the first reaction mixed solution obtained in the step one into a polytetrafluoroethylene high-pressure reaction kettle (the filling ratio is 50%), reacting for 20 hours at 100 ℃, cooling to room temperature after the reaction is finished, centrifuging, washing, and drying for 12 hours at 50 ℃ to finally obtain a sample NH2-MIL-101(Fe)；
Step three, adding 0.3g of sodium molybdate dihydrate and 0.5g of thiourea into 45mL of deionized water, and stirring until the sodium molybdate dihydrate and the thiourea are dissolved to obtain a second reaction mixed solution;
step four, 0.1g of sample NH obtained in the step two2Dispersing MIL-101(Fe) in the second reaction mixed solution obtained in the third step, uniformly stirring and carrying out ultrasonic treatment for 30 min; then, transferring the mixture into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 20h at 200 ℃, cooling to room temperature after the reaction is finished, centrifuging, washing with water, and drying at 50 ℃ for 12h to finally obtain a sample NH2-MIL-101(Fe)/MoS2；
Step five, taking 0.48g of Zn (CH)3COO)2·2H2Adding O and 0.24g KOH into 150mL ethanol solution, and stirring for 30min at 32 ℃ until the O and the KOH are dissolved to obtain third reaction mixed solution;
step six, taking 0.44g of sample NH obtained in the step four2-MIL-101(Fe)/MoS2Adding into the third reaction mixed solution obtained in the fifth step, performing ultrasonic treatment for 40min, performing oil bath reaction at 90 ℃, maintaining magnetic stirring for 8h, cooling to room temperature after the reaction is finished, centrifuging, washing with ethanol for 3 times, and drying at 50 ℃ for 12h to obtain NH2-MIL-101(Fe)/MoS2the/ZnO ternary composite antibacterial material.
Example 3:
step one, taking 4.16mmol FeCl3·6H2Adding O and 2.47mmol of 2-amino terephthalic acid into a beaker, adding 50mL of DMF (dimethyl formamide) solvent, and stirring until the DMF solvent is dissolved to obtain a first reaction mixed solution;
step two, transferring the first reaction mixed solution obtained in the step one into a polytetrafluoroethylene high-pressure reaction kettle (the filling ratio is 50%), reacting for 22 hours at 105 ℃, cooling to room temperature after the reaction is finished, centrifuging, washing, and drying for 12 hours at 50 ℃ to finally obtain a sample NH2-MIL-101(Fe)；
Step three, adding 0.3g of sodium molybdate dihydrate and 0.6g of thiourea into 50mL of deionized water, and stirring until the sodium molybdate dihydrate and the thiourea are dissolved to obtain a second reaction mixed solution;
step four, 0.1g of sample NH obtained in the step two2Dispersing MIL-101(Fe) in the second reaction mixed solution obtained in the third step, uniformly stirring and carrying out ultrasonic treatment for 30 min; then, transferring the mixture into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 25h at 220 ℃, cooling to room temperature after the reaction is finished, centrifuging, washing with water, and drying at 50 ℃ for 12h to finally obtain a sample NH2-MIL-101(Fe)/MoS2；
Step five, taking 0.528g of Zn (CH)3COO)2·2H2Adding O and 0.24g KOH into 150mL ethanol solution, stirring and stirring for 30min at 32 ℃ until the O and the KOH are dissolved to obtain third reaction mixed solution;
step six, taking 0.44g of sample NH obtained in the step four2-MIL-101(Fe)/MoS2Adding into the third reaction mixed solution obtained in the fifth step, performing ultrasonic treatment for 40min, performing oil bath reaction at 110 ℃, maintaining magnetic stirring for 6h, cooling to room temperature after the reaction is finished, centrifuging, washing with ethanol for 3 times, and drying at 50 ℃ for 12h to obtain NH2-MIL-101(Fe)/MoS2the/ZnO ternary composite antibacterial material.
For NH prepared in example 22-MIL-101(Fe)/MoS2The characterization and antibacterial test result analysis of the/ZnO ternary composite material are as follows:
1. scanning Electron Microscope (SEM) and electron microscope (TEM) analysis:
using a scanning electron microscope and a transmission electron microscope pairNH obtained in this example2-MIL-101(Fe)/MoS2The shape observation of the/ZnO ternary composite antibacterial material is carried out, and the results are shown in figures 1 to 6;
FIG. 1 shows NH prepared2Scanning electron micrograph of the MIL-101(Fe) morphology, NH being observed from FIG. 12MIL-101(Fe) is rhombohedral octahedral structure.
FIGS. 2 and 3 are each NH2-MIL-101(Fe)/MoS2And NH2-MIL-101(Fe)/MoS2The scanning electron micrograph of the/ZnO shows that NH is2-MIL-101(Fe)/MoS2the/ZnO presents a flower-like spherical structure and the MoS of which the surface is provided with a plurality of folds2The nanosheets were of overlapping composition and sharp edged with an average size of 1 μm.
FIG. 4 is NH2Transmission electron micrograph of MIL-101(Fe) showing rhombohedral octahedral structures in agreement with the SEM photograph results;
FIG. 5 is NH2-MIL-101(Fe)/MoS2In a Transmission Electron Microscope (TEM) image, MoS can be seen from an observation of FIG. 52The nano-sheet is successfully wrapped in NH2-MIL-101(Fe) surface;
FIG. 6 is NH2-MIL-101(Fe)/MoS2Transmission Electron Microscope (TEM) image of/ZnO ternary composite material, and careful observation of FIG. 6 can find flower-ball-shaped NH2-MIL-101(Fe)/MoS2The surface is distributed with fine ZnO quantum dots, which shows NH in the example2-MIL-101(Fe)/MoS2The preparation of the ternary composite material of/ZnO is successful.
XRD analysis
The NH prepared in this example was measured by X-ray diffractometer (XRD)2-MIL-101(Fe)、MoS2、NH2-MIL-101(Fe)/MoS2And NH2-MIL-101(Fe)/MoS2The crystal structure of the/ZnO ternary composite material is analyzed, and the result is shown in the attached figure 7:
FIG. 7 is NH respectively2-MIL-101(Fe)、MoS2、NH2-MIL-101(Fe)/MoS2And NH2-MIL-101(Fe)/MoS2XRD pattern of/ZnO; MoS at values of 2 theta of 14.3, 32.8 and 58.52(PDF #73-1508) (002), (100) and (110) crystal planes characteristic diffraction peaks；MoS2The characteristic diffraction peak of (A) is wide and is not obvious because the crystallinity of the molybdenum disulfide synthesized by a hydrothermal method is incomplete; however, characteristic diffraction peaks of the crystal planes of ZnO (PDF #36-1451) (101), (102), (103), and (112) were detected at 2 θ values of 36.3 °, 47.5 °, 63.1 °, and 67.9 °, indicating that the ZnO quantum dots were successfully loaded to NH2-MIL-101(Fe)/MoS2Further proved to successfully prepare NH2-MIL-101(Fe)/MoS2The ternary composite material/ZnO.
3. Photothermal analysis:
FIG. 8 shows MoS2、NH2-MIL-101(Fe)/MoS2And NH2-MIL-101(Fe)/MoS2Photothermal spectroscopy of ZnO; the figures clearly show that: with illumination (18W cm)-2) Prolongation of NH time2-MIL-101(Fe)/MoS2The temperature of the/ZnO composite material is gradually increased, and the highest temperature reaches 62 ℃. The composite material has good photo-thermal effect, and the higher temperature can inhibit the propagation and growth of bacteria, thereby being beneficial to improving the antibacterial activity.
4. And (3) antibacterial activity analysis:
bacterial suspensions of escherichia coli and staphylococcus aureus at OD ═ 0.1 were diluted 100-fold. Bacterial suspension and certain concentration of MoS2、NH2-MIL-101(Fe)/MoS2And NH2-MIL-101(Fe)/MoS2the/ZnO nanocomposite was transferred to a 5ml centrifuge tube and then shaken for 30min to bring the bacteria and sample into full contact. Subsequently, the sample was passed through at a power of 18 W.cm-2Respectively irradiating for 6, 12, 18, 22 and 30 min. Finally, 25. mu.L of the bacterial suspensions treated with different light exposure times were inoculated onto agar medium from a 5mL centrifuge tube and incubated at 37 ℃ for 24 h. The antibacterial activity was judged by observing the growth of colonies on agar medium and the results are reported in FIGS. 9 to 19;
as can be seen from FIGS. 9 to 19, the presence of E.coli in a large amount on the medium with only light exposure did not decrease the bacteria with the increase of light exposure time, as shown in FIGS. 10 to 15, which indicates that the single light exposure did not have the antibacterial effect. In contrast, it is apparent from FIGS. 16 to 19 that E.coli treated with the sample was exposed to lightThe increase in time, the number of colonies on the medium, which confirmed NH, was significantly reduced2-MIL-101(Fe)/MoS2The antibacterial effect of the/ZnO ternary composite material is gradually enhanced along with the prolonging of the light irradiation time.
FIG. 20 is NH2-MIL-101(Fe)/MoS2The bacteriostasis rate of the/ZnO ternary composite material under the illumination effect is obtained; as is clear from the figure, the power is 18W cm-2NH after 30min of visible light irradiation2-MIL-101(Fe)/MoS2The bacteriostasis rate of the/ZnO ternary composite material to escherichia coli reaches 98.7 percent, which shows that the composite material has high-efficiency antibacterial effect.
The results of the above examples show that the NH prepared in example 22-MIL-101(Fe)/MoS2the/ZnO ternary composite material has efficient photocatalysis and photo-thermal synergistic antibacterial effects, and the preparation process is simple, low in cost and beneficial to application in the fields of environment and medical treatment.
It should be noted that, the present invention is described in detail with reference to the above embodiments, and those skilled in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which should be construed broadly as set forth in the claims.
Claims (9)
1. A preparation method of a ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity is characterized by comprising the following steps:
step one, FeCl3·6H2Adding O and 2-amino terephthalic acid into a solvent DMF, and stirring until the O and the 2-amino terephthalic acid are dissolved to obtain a first reaction mixed solution;
step two, transferring the first reaction mixed solution obtained in the step one into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 20-24 hours at 100-110 ℃, cooling to room temperature after the reaction is finished, centrifuging, washing with water, and drying to finally obtain a sample NH2-MIL-101(Fe)；
Step three, adding sodium molybdate dihydrate and thiourea into deionized water, and stirring until the sodium molybdate dihydrate and the thiourea are dissolved to obtain a second reaction mixed solution;
step four, the sample NH obtained in the step two2Dispersing MIL-101(Fe) in the second reaction mixed solution obtained in the third step, uniformly stirring and performing ultrasonic treatment; then, transferring the mixture into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 20-25 h at 180-220 ℃, cooling to room temperature after the reaction is finished, centrifuging, washing with water, and drying to finally obtain a sample NH2-MIL-101(Fe)/MoS2；
Step five, adding Zn (CH)3COO)2·2H2Adding O and KOH into the ethanol solution, and stirring at 32 ℃ until the O and the KOH are dissolved to obtain a third reaction mixed solution;
step six, taking the sample NH obtained in the step four2-MIL-101(Fe)/MoS2Adding the mixture into the third reaction mixed solution obtained in the fifth step, performing ultrasonic treatment until the mixture is uniformly dispersed, performing oil bath reaction at the temperature of 90-110 ℃, maintaining the reaction for 5-8 hours by magnetic stirring, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to finally obtain NH2-MIL-101(Fe)/MoS2the/ZnO ternary composite antibacterial material.
2. The method for preparing the ternary composite antibacterial material with photodynamic-photothermal synergetic antibacterial activity as claimed in claim 1, wherein in the first step, FeCl is used3·6H2The mass ratio of O to 2-amino terephthalic acid is 3: (1-1.2) FeCl3·6H2The mass ratio of O to DMF solvent is 1: 42.
3. the method for preparing the ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity as claimed in claim 1, wherein in the third step, the mass ratio of sodium molybdate dihydrate to thiourea is 3: (4-6), wherein the mass ratio of the sodium molybdate dihydrate to the solvent deionized water is 3: (400-500).
4. The method for preparing the ternary composite antibacterial material with photodynamic-photothermal synergetic antibacterial activity as claimed in claim 1, wherein in the fourth step, sample NH is added2-MThe mass ratio of the added amount of IL-101(Fe) to the sodium molybdate dihydrate is (1-2): 3.
5. the method for preparing a ternary composite antibacterial material having photodynamic-photothermal synergistic antibacterial activity as claimed in claim 1, wherein in said step five, Zn (CH)3COO)2·2H2The mass ratio of O to KOH is (1.5-2.2): 1, wherein the mass ratio of the zinc acetate to the solvent ethanol is 1: (240-284).
6. The method for preparing a ternary composite antibacterial material having photodynamic-photothermal synergistic antibacterial activity as claimed in claim 1, wherein in the sixth step, sample NH is added2-MIL-101(Fe)/MoS2The addition amount of Zn (CH)3COO)2·2H2The mass ratio of O is (5-6): 6.
7. the method for preparing a ternary composite antibacterial material with photodynamic-photothermal synergetic antibacterial activity as claimed in claim 1, wherein the filling ratio of the solution in the polytetrafluoroethylene autoclave in the second step and the fourth step is 50%.
8. A ternary composite antibacterial material having photodynamic-photothermal synergistic antibacterial activity prepared by the method of any one of claims 1 to 7, wherein the structure thereof is in the shape of a flower ball.
9. The use of the ternary composite antibacterial material with photodynamic-photothermal synergistic antibacterial activity as claimed in claim 8, wherein the material is used in the antibacterial field, and can effectively kill pathogenic bacteria of escherichia coli and staphylococcus aureus.
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| CN115722234A (en) * | 2022-11-15 | 2023-03-03 | 陕西科技大学 | Ce-MoS with photodynamic-enzyme activity 2 /WO 3 Preparation method and application of nano composite antibacterial material |
| CN116326594A (en) * | 2023-05-25 | 2023-06-27 | 中国海洋大学 | Composite material for ocean corrosion prevention and pollution prevention as well as preparation method and application thereof |
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| CN115722234A (en) * | 2022-11-15 | 2023-03-03 | 陕西科技大学 | Ce-MoS with photodynamic-enzyme activity 2 /WO 3 Preparation method and application of nano composite antibacterial material |
| CN116326594A (en) * | 2023-05-25 | 2023-06-27 | 中国海洋大学 | Composite material for ocean corrosion prevention and pollution prevention as well as preparation method and application thereof |
| CN116326594B (en) * | 2023-05-25 | 2023-09-15 | 中国海洋大学 | Composite material for ocean corrosion prevention and pollution prevention as well as preparation method and application thereof |
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