CN114950492A - 1, 2-diamino anthraquinone-molybdenum disulfide composite antibacterial material for killing bacteria by photoelectrocatalysis - Google Patents
1, 2-diamino anthraquinone-molybdenum disulfide composite antibacterial material for killing bacteria by photoelectrocatalysis Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
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Abstract
The invention discloses a 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material for killing bacteria by photoelectrocatalysis, which is obtained by dehydrating and condensing carboxyl functionalized molybdenum disulfide and 1, 2-diaminoanthraquinone under the condition of EDC & HCl, and loading the molybdenum disulfide on ITO conductive glass to obtain a photoanode. The composite antibacterial material has high-efficiency sterilization effect, can still maintain high-efficiency antibacterial after being recycled for multiple times, and has more economic and environmental-friendly benefits compared with photocatalytic antibacterial.
Description
Technical Field
The invention relates to a preparation method of a 1, 2-diaminoanthraquinone-molybdenum disulfide composite photo-anode for killing bacteria by photoelectrocatalysis, belonging to the field of photoelectricity sterilization.
Background
In recent years, photocatalytic antibacterial has attracted much attention due to the advantages of no obvious drug resistance, less side effects and the like. However, most of the photocatalytic sterilization materials are powders, which are difficult to recycle and pollute water sources. In order to solve these disadvantages, researchers have been devoted to search for improved synthetic methods or materials that can maintain the antibacterial properties of the materials and solve the problem of difficult material recycling.
The photoelectrocatalysis oxidation method (PEC) is a green high-efficiency technology which has controllable reaction and high oxidation speed and does not need chemical additives, integrates the advantages of the photocatalysis method and the electrochemical method, and is considered as a high-efficiency sterilization treatment method. For example, electrons generated by the illumination of the anode move to the cathode under the driving of an external circuit, and the problem of high recombination rate of the electrons and holes is reduced. Also, because the photosensitizer is immobilized on a substrate, there is no need to recover the photocatalyst from the suspension after the reaction is complete, and the most alarming recovery problem is readily solved. The PEC technology fixes a catalyst on the surface of a carrier to be used as a photosensitive anode, which is the key of an electrochemical antibacterial system. 1, 2-Diaminoanthraquinone is a photosensitizer that absorbs a wide range of visible light and readily interacts with semiconductors, and 1, 2-Diaminoanthraquinone and MoS have been demonstrated 2 Physical compounding has a good antimicrobial effect but is still less than ideal from the end result point of view. Researches show that different connection modes among the same raw materials can greatly influence the structure and the performance of the material, such as MoS 2 Covalent attachment to BCN proved to have higher HER activity than physical blending.
Disclosure of Invention
The invention aims to provide a 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material for killing bacteria by photoelectrocatalysis, and the material is loaded on ITO conductive glass to form a photo-anode, so that the material can be recycled, and the antibacterial efficiency is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly discloses a 1, 2-diamino anthraquinone-molybdenum disulfide composite antibacterial material for killing bacteria by photoelectrocatalysis, and the preparation method comprises the following steps: firstly, mercaptoacetic acid is embedded into molybdenum disulfide through ultrasonic action to obtain carboxyl functionalized molybdenum disulfide; and then dehydrating and condensing the carboxyl functionalized molybdenum disulfide and 1, 2-diaminoanthraquinone under the condition of EDC & HCl to obtain the covalently grafted 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material. The method specifically comprises the following steps:
Taking 50-150mg MoS 2 Adding the powder into 50-100mL of ultrapure water, performing ultrasonic treatment for 2-4h to uniformly disperse, adding 200-600 mu L of thioglycolic acid, and performing ultrasonic treatment for 15-24h under ice cooling; dialyzing the obtained mixture with ultrapure water for 2-3 days, freeze-drying and collecting solid, namely carboxyl functionalized molybdenum disulfide, which is recorded as MoS 2 -COOH；
Mixing 10-60mg of MoS 2 Sequentially adding 10-60mg of 1, 2-diaminoanthraquinone and 3-6mL of dry DMF into a three-neck flask, carrying out ultrasonic treatment for 2-4h, and then adding 10-60mg of EDC & HCl, 10-60mg of HOBt and 300-600 mu L of DIPEA under the nitrogen atmosphere; stirring for 48-72h at room temperature, centrifuging, collecting solid product, sequentially washing with DMF, water and ethanol, and drying at 60 deg.C to obtain 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material, which is recorded as 1,2-DAQ-MoS 2 。
The invention also discloses a photo-anode for killing bacteria by photoelectrocatalysis, the photo-anode is prepared by loading the 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material on ITO conductive glass by an electrophoresis technology, and the preparation method comprises the following steps: mixing 20-50mg of 1,2-DAQ-MoS 2 Ultrasonically dispersing in mixed solution of ethanol and water, reacting at 40-60V with Pt sheet as anode and ITO conductive glass as cathode to obtain 1,2-DAQ-MoS 2 Loaded on ITO to obtain the photo-anode for killing bacteria by photoelectrocatalysis.
Preferably, the reaction time is 30 to 60 min.
Preferably, the mixed solution of ethanol and water is prepared by mixing ethanol and water according to the volume ratio of 1-2: 1.
The light anode of the invention can be combined with a light source and a power supply to construct an antibacterial system, and the system has high-efficiency inactivation effect on bacteria.
The invention has the following beneficial effects:
1. the invention utilizes a simple dehydration condensation method to covalently graft 1, 2-diaminoanthraquinone and carboxyl functionalized molybdenum disulfide at normal temperature to obtain the 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material, and then utilizes an electrophoresis technology to load the material on ITO conductive glass to form a photo-anode, and the method is simple and has low manufacturing cost.
2. The 1, 2-diaminoanthraquinone-molybdenum disulfide is obtained by covalent grafting, and compared with a physically prepared 1, 2-diaminoanthraquinone/molybdenum disulfide composite material, the crystallinity is improved, and the antibacterial performance is optimized.
3. The photoanode has a high-efficiency sterilization effect on escherichia coli and staphylococcus aureus, the existence of electric bias promotes effective separation of carriers, and compared with photocatalytic sterilization, the photoanode realizes a significant breakthrough in the antibacterial effect; meanwhile, the material can be recycled for many times, still keeps high-efficiency antibacterial performance, and has economic and environmental benefits.
4. The invention ensures that the obtained material has the optimal antibacterial performance by screening the optimal raw material proportion and reaction conditions.
Drawings
FIG. 1 shows 1,2-DAQ/MoS obtained in comparative example 1 2 (FIG. 1a) and 1,2-DAQ-MoS obtained in example 1 2 (FIG. 1b) SEM image.
FIG. 2 shows 1,2-DAQ/MoS obtained in comparative example 1 2 And 1,2-DAQ-MoS obtained in example 1 2 XRD pattern of (a).
FIG. 3 shows 1,2-DAQ/MoS obtained in comparative example 1 2 And 1,2-DAQ-MoS obtained in example 1 2 The antibacterial plates of E.coli were plated.
FIG. 4 shows 1,2-DAQ-MoS obtained in example 1 2 Wherein FIG. 4a is a full spectrum, FIG. 4b is a C1s map, and FIG. 4C is an N1s map.
FIG. 5 shows 1,2-DAQ-MoS obtained in example 1 2 XPS spectrum of/ITO.
FIG. 6 shows 1,2-DAQ-MoS obtained in example 1 2 SEM image of/ITO.
FIG. 7 shows 1,2-DAQ-MoS obtained in example 1 2 The antibacterial plate of/ITO to Escherichia coli is coated with a pattern, wherein L represents a photoreaction group and PEC represents a photoreaction group.
FIG. 8 shows 1,2-DAQ-MoS obtained in example 1 2 The antibacterial plate of/ITO to staphylococcus aureus is coated, wherein L represents a photoreaction group and PEC represents a photoreaction group.
FIG. 9 shows 1,2-DAQ-MoS obtained in example 1 of the present invention 2 The antibacterial cycle stability of ITO.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Comparative example 1
Adding 150mg of lamellar molybdenum disulfide into 5mL of water, performing ultrasonic treatment for 30min, adding 10mg of 1, 2-aminoanthraquinone, performing ultrasonic treatment for 30min, stirring at normal temperature for 12h, centrifuging, collecting a product, and performing freeze drying to obtain the 1, 2-aminoanthraquinone-sensitized molybdenum disulfide composite photocatalytic antibacterial material, which is recorded as 1,2-DAQ/MoS 2 。
Example 1
In this example, the 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material was prepared as follows:
50mg of MoS is taken 2 Adding the powder into 50mL of ultrapure water, performing ultrasonic treatment for 2h to uniformly disperse the powder, adding 200 mu L of thioglycolic acid, and performing ultrasonic treatment for 15h under ice cooling; dialyzing the obtained mixture with ultrapure water for 2 days, freeze-drying and collecting solid, namely carboxyl functionalized molybdenum disulfide recorded as MoS 2 -COOH。
20mg of MoS 2 -COOH, 20mg of 1,sequentially adding 2-diaminoanthraquinone and 3mL of dry DMF into a three-neck flask, carrying out ultrasonic treatment for 2h, and then adding 20mg of EDC & HCl, 20mg of HOBt and 300 mu of LDIPEA under the nitrogen atmosphere; stirring for 48h at room temperature, centrifuging, collecting solid product, sequentially washing with DMF, water and ethanol, and drying at 60 deg.C to obtain 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material, which is recorded as 1,2-DAQ-MoS 2 。
20mg of 1,2-DAQ-MoS 2 Ultrasonically dispersing in mixed solution of ethanol and water, reacting for 40min at 60V with Pt sheet as anode and ITO conductive glass as cathode to obtain 1,2-DAQ-MoS 2 Loaded on ITO, i.e. photoanode for photoelectrocatalysis sterilization, and is marked as 1,2-DAQ-MoS 2 /ITO。
FIG. 1 shows 1,2-DAQ/MoS obtained in comparative example 1 2 (FIG. 1a) and 1,2-DAQ-MoS obtained in example 1 2 (FIG. 1b) SEM picture, from which it can be seen that: 1,2-DAQ/MoS 2 And 1,2-DAQ-MoS 2 Are all of lamellar structure, but 1,2-DAQ-MoS 2 The surface is rougher and the crystallization is more obvious.
FIG. 2 shows 1,2-DAQ/MoS obtained in comparative example 1 2 And 1,2-DAQ-MoS obtained in example 1 2 The XRD pattern of (A) shows that 1,2-DAQ/MoS can be seen 2 And 1,2-DAQ-MoS 2 Are consistent in peak position, but 1,2-DAQ-MoS 2 The greater the peak intensity, which means that it is more crystalline.
FIG. 3 shows 1,2-DAQ/MoS obtained in comparative example 1 2 And 1,2-DAQ-MoS obtained in example 1 2 The antibacterial flat plate of the escherichia coli is coated with a pattern, and the specific test method of the photocatalytic sterilization comprises the following steps: taking 50 μ L of Escherichia coli diluent (bacterial liquid concentration is 10) 5 CFU/mL) was mixed with 1mL of a 0.1mg/mL aqueous solution of the antibacterial material and added to 50mL of PBS buffer, and a light reaction group and a dark reaction group were set. The plate before the start of the reaction was coated as a control, and after 80min of reaction, 30. mu.L of a well-mixed PBS solution was applied to the plate from each of the light reaction group and the dark reaction group. The plates were cultured in an inverted manner in a biological incubator for 18 hours, and the number of colonies before and after plate coating was counted by a counting method to qualitatively evaluate 1,2-DAQ/MoS 2 And 1,2-DAQ-MoS 2 The antibacterial property of (1). As can be seen from the figure: 1,2-DAQ-MoS 2 Has better antibacterial performance under the condition of illumination, and particularly shows that the bacteria in the system are effectively inactivated by illumination for 80 min.
FIG. 4 shows 1,2-DAQ-MoS obtained in example 1 2 XPS spectra of (A). From FIG. 4a, it can be seen that Mo, S, C, N, O elements exist in the composite material. FIG. 4b is 1,2-DAQ-MoS 2 In the C1s diagram, it can be seen that 286.2eV has a C ═ O bond. FIG. 4c is 1,2-DAQ-MoS 2 In N1s, it can be seen that 399.35eV has an N-H bond.
FIG. 5 shows 1,2-DAQ-MoS obtained in example 1 2 XPS spectrum of/ITO, it can be seen that it is both 1,2-DAQ-MoS 2 The elements Mo, S, C, N and O In the ITO conductive glass also exist.
FIG. 6 shows 1,2-DAQ-MoS obtained in example 1 2 SEM image of/ITO, it can be seen that 1, 2-diaminoanthraquinone-molybdenum disulfide of lamellar structure grows on the surface of ITO conductive glass.
The 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material of the embodiment is loaded on ITO conductive glass to construct a photoelectric sterilization system, and can be applied to killing harmful microorganisms in water environment, taking Escherichia coli as an example, the specific test method of the photoelectric catalytic sterilization is as follows: taking 50 μ L of Escherichia coli diluent (bacterial liquid concentration is 10) 5 CFU/mL) was added to 50mL of PBS buffer as a bacterial environment, and 1,2-DAQ-MoS was added 2 the/ITO is used as a photo-anode, the Pt sheet is used as a photo-cathode, and a photo-reaction group and a photoelectric reaction group are arranged. The plate before the start of the reaction was coated as a control, and after 10min of reaction, 30. mu.L of a uniformly mixed PBS solution was applied to the plate from each of the photoreactive group and the photoreactive group. The plates were cultured in an inverted manner in a biological incubator for 18 hours, and the number of colonies before and after plate coating was counted by a counting method to qualitatively evaluate 1,2-DAQ-MoS 2 Antibacterial property of ITO.
FIG. 7 shows 1,2-DAQ-MoS in example 1 2 The antibacterial plate of ITO to Escherichia coli is coated. As can be seen, after 5 minutes, 1,2-DAQ-MoS 2 The bacteria of the/ITO photovoltaic group (PEC) all died.
FIG. 8 shows 1,2-DAQ-MoS in example 1 2 The antibacterial plate of ITO to staphylococcus aureus is coated, and the test method is the same as that of escherichia coli. As can be seen, after 10 minutes, 1,2-DAQ-MoS 2 The bacteria of the/ITO photovoltaic group (PEC) all died.
1,2-DAQ-MoS 2 After the first antibacterial operation is finished (namely the illumination group and the photoelectric group react for 5 min), the solid is collected by centrifugation, and the second and above antibacterial operations are carried out. FIG. 9 shows 1,2-DAQ-MoS 2 ITO antibacterial cycling stability chart, wherein the antibacterial rate is calculated by the method of (number of escherichia coli before reaction starts-number of escherichia coli after 5min of reaction finishes)/number of escherichia coli before reaction starts. From the figure, it can be seen that after three cycles, the antibacterial performance of the material is not changed. 1,2-DAQ-MoS 2 The ITO has excellent antibacterial stability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Any person skilled in the art may, using the teachings disclosed above, change or modify the equivalent embodiments with equivalent changes. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material for killing bacteria by photoelectrocatalysis is characterized in that: firstly, mercaptoacetic acid is embedded into molybdenum disulfide through ultrasonic action to obtain carboxyl functionalized molybdenum disulfide; and then dehydrating and condensing the carboxyl functionalized molybdenum disulfide and 1, 2-diaminoanthraquinone under the condition of EDC & HCl to obtain the covalently grafted 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material.
2. The preparation method of the 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material according to claim 1, characterized by comprising the following steps:
step 1, preparation of carboxyl functionalized molybdenum disulfide
Taking 50-150mg MoS 2 Adding the powder into 50-100mL of ultrapure water, performing ultrasonic treatment for 2-4h to uniformly disperse, adding 200-600 mu L of thioglycolic acid, and performing ultrasonic treatment for 15-24h under ice cooling; dialyzing the obtained mixture with ultrapure water for 2-3 days, freeze-drying and collecting solid, namely carboxyl functionalized molybdenum disulfide, which is recorded as MoS 2 -COOH；
Step 2, grafting 1, 2-diamino anthraquinone
Mixing 10-60mg of MoS 2 Sequentially adding 10-60mg of 1, 2-diaminoanthraquinone and 3-6mL of dry DMF into a three-neck flask, carrying out ultrasonic treatment for 2-4h, and then adding 10-60mg of EDC & HCl, 10-60mg of HOBt and 300-600 mu L of DIPEA under the nitrogen atmosphere; stirring for 48-72h at room temperature, centrifuging, collecting solid product, sequentially washing with DMF, water and ethanol, and drying at 60 deg.C to obtain 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material, which is recorded as 1,2-DAQ-MoS 2 。
3. A1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material prepared by the preparation method of claim 1 or 2.
4. A photoanode for photoelectrocatalysis sterilization, which is characterized in that: the photo-anode is formed by loading the 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material as claimed in claim 3 on ITO conductive glass.
5. A method for preparing the photoanode of claim 4, wherein the method comprises the following steps: the method comprises the step of loading a 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material on ITO conductive glass by an electrophoresis technology to obtain the photo-anode.
6. The method of claim 5, wherein: mixing 20-50mg of 1,2-DAQ-MoS 2 Ultrasonically dispersing in mixed solution of ethanol and water, reacting at 40-60V with Pt sheet as anode and ITO conductive glass as cathode to obtain 1,2-DAQ-MoS 2 Loaded on ITO to obtain the photo-anode for killing bacteria by photoelectrocatalysis.
7. The method of claim 6, wherein: the reaction time is 30-60 min.
8. The method of claim 6, wherein: the mixed solution of the ethanol and the water is formed by mixing the ethanol and the water according to the volume ratio of 1-2: 1.
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