CN114950492B - 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material for photoelectrocatalysis to kill bacteria - Google Patents
1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material for photoelectrocatalysis to kill bacteria Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- -1 1, 2-diaminoanthraquinone-molybdenum disulfide Chemical compound 0.000 title claims abstract description 19
- 241000894006 Bacteria Species 0.000 title claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 14
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001962 electrophoresis Methods 0.000 claims description 3
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 8
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 241000588724 Escherichia coli Species 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZGHDMISTQPRNRG-UHFFFAOYSA-N dimolybdenum Chemical compound [Mo]#[Mo] ZGHDMISTQPRNRG-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a 1, 2-diamino anthraquinone-molybdenum disulfide composite antibacterial material for killing bacteria by photoelectrocatalysis, which is obtained by dehydrating and condensing carboxyl functionalized molybdenum disulfide and 1, 2-diamino anthraquinone under EDC and HCl conditions, and loading the molybdenum disulfide onto ITO conductive glass to obtain a photoanode. The composite antibacterial material has high-efficiency sterilization effect, can still keep high-efficiency antibacterial after being recycled for many times, and has economic and environmental benefits compared with photocatalysis 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 photoelectrosterilization.
Background
In recent years, photocatalytic antibacterial has attracted much attention by virtue of no obvious drug resistance, few side effects and the like. However, most of photocatalytic sterilization materials are powder, and the problems of difficult recovery, water source pollution and the like are faced. To solve these drawbacks, researchers have focused on finding whether improved synthetic methods or materials exist that can both maintain the antibacterial properties of the materials and solve the problem of difficult material recovery.
The photoelectrocatalytic oxidation (PEC) is regarded as an efficient sterilization treatment method as a green efficient technology with controllable reaction, high oxidation speed and no need of chemical additives, and integrates the advantages of the photoelectrocatalytic method and the electrochemical method. For example under anodic illuminationThe generated electrons can move to the cathode under the drive of an external circuit, so that the problem of high recombination rate of electrons and holes is solved. Also because the photosensitizer is immobilized on the substrate, there is no need to recover the photocatalyst from the suspension after the end of the reaction, and the most alarming recovery problem is also solved. PEC technology, in which the catalyst is immobilized on the surface of a carrier as a photosensitive anode, is a key point of electrochemical antibacterial systems. 1, 2-diaminoanthraquinone is a photosensitizer that absorbs a wide range of visible light and readily interacts with semiconductors, and has been demonstrated for 1, 2-diaminoanthraquinone and MoS 2 Physical complexation has a better antibacterial effect but is still less than ideal from the end result. It has been found that the different modes of attachment between the same materials greatly affect the structure and properties 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 photoelectrocatalysis to kill bacteria, and the composite antibacterial material is loaded on ITO conductive glass to form a photoanode, so that the recycling of the material and the improvement of antibacterial efficiency are realized.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention firstly discloses a 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material for killing bacteria by photoelectrocatalysis, which comprises the following preparation method: firstly embedding thioglycollic acid into molybdenum disulfide by ultrasonic action to obtain carboxyl functionalized molybdenum disulfide; and then dehydrating and condensing the carboxyl functionalized molybdenum disulfide and 1, 2-diaminoanthraquinone under EDC and HCl conditions to obtain the covalent grafted 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material. The method specifically comprises the following steps:
step 1, preparing carboxyl functionalized molybdenum disulfide
50-150mg MoS is taken 2 Adding the powder into 50-100mL of ultrapure water, performing ultrasonic treatment for 2-4 hours to uniformly disperse, adding 200-600 mu L of thioglycollic acid, and performing ultrasonic treatment under ice cooling for 15-24 hours; dialyzing the obtained mixture with ultrapure water for 2-3 days, lyophilizing, and collecting solid to obtain carboxyl functionalized diMolybdenum sulfide, denoted MoS 2 -COOH；
Step 2, grafting 1, 2-diaminoanthraquinone
10-60mg MoS 2 Sequentially adding-COOH, 10-60mg of 1, 2-diaminoanthraquinone and 3-6mL of dry DMF into a three-necked 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 a nitrogen atmosphere; stirring at room temperature for 48-72h, centrifuging to collect solid product, washing with DMF, water and ethanol sequentially, and drying at 60deg.C to obtain target product 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material, which is 1,2-DAQ-MoS 2 。
The invention also discloses a photo-anode for photoelectrocatalysis and bacteria killing, which is loaded with the 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material on ITO conductive glass by an electrophoresis technology, and the specific preparation method comprises the following steps: 20-50mg of 1,2-DAQ-MoS 2 Ultrasonically dispersing in a mixed solution of ethanol and water, taking Pt sheets as anodes and ITO conductive glass as cathodes, and reacting at 40-60V to obtain 1,2-DAQ-MoS 2 And loading the photo-anode on ITO to obtain the photo-anode for killing bacteria by photoelectrocatalysis.
Preferably, the reaction time is 30 to 60 minutes.
Preferably, the mixed solution of ethanol and water is formed by mixing ethanol and water according to a volume ratio of 1-2:1.
By utilizing the photoanode, an antibacterial system can be constructed by combining a light source and a power supply, and the system has high-efficiency inactivation effect on bacteria.
The beneficial effects of the invention are as follows:
1. the invention uses simple dehydration condensation method to covalently graft 1, 2-diamino anthraquinone and carboxyl functionalized molybdenum disulfide at normal temperature to obtain 1, 2-diamino anthraquinone-molybdenum disulfide composite antibacterial material, and then uses electrophoresis technology to load the material on ITO conductive glass to form the photo anode, the method is simple, and the manufacturing cost is low.
2. Compared with the 1, 2-diaminoanthraquinone/molybdenum disulfide composite material prepared by a physical mode, the 1, 2-diaminoanthraquinone/molybdenum disulfide composite material prepared by the method has the advantages that the crystallinity is improved, and the antibacterial property is optimized.
3. The photo-anode has high-efficiency sterilization effect on escherichia coli and staphylococcus aureus, and the existence of the electric bias promotes effective separation of carriers, so that compared with photocatalysis sterilization, the photo-anode realizes remarkable breakthrough in the antibacterial effect; meanwhile, the material can be recycled for many times and still keeps high-efficiency antibacterial performance, and has economic and environmental benefits.
4. According to the invention, the optimal raw material proportion and reaction conditions are selected, so that the obtained material has optimal antibacterial performance.
Drawings
FIG. 1 is a graph showing the results of comparative example 1 for 1,2-DAQ/MoS 2 (FIG. 1 a) and 1,2-DAQ-MoS obtained in example 1 2 (FIG. 1 b) SEM image.
FIG. 2 is a graph showing the results of comparative example 1 for 1,2-DAQ/MoS 2 And 1,2-DAQ-MoS obtained in example 1 2 Is a XRD pattern of (C).
FIG. 3 is a 1,2-DAQ/MoS obtained in comparative example 1 2 And 1,2-DAQ-MoS obtained in example 1 2 The antibacterial plate of the escherichia coli is coated with a pattern.
FIG. 4 is a block diagram of 1,2-DAQ-MoS obtained in example 1 2 Wherein fig. 4a is a full spectrum, fig. 4b is a C1s graph, and fig. 4C is an N1s graph.
FIG. 5 is a block diagram of 1,2-DAQ-MoS obtained in example 1 2 XPS spectrum of ITO.
FIG. 6 is a 1,2-DAQ-MoS obtained in example 1 2 SEM image of ITO.
FIG. 7 is a block diagram of 1,2-DAQ-MoS obtained in example 1 2 ITO to Escherichia coli antibacterial plate coating diagram, in the figure, L represents the photoreaction group, PEC represents the photoelectric reaction group.
FIG. 8 is a 1,2-DAQ-MoS obtained in example 1 2 ITO on Staphylococcus aureus antibacterial plate coating, in the figure, L represents a photoreaction group and PEC represents a photoelectric reaction group.
FIG. 9 is a graph showing the 1,2-DAQ-MoS obtained in example 1 of the present invention 2 Graph of antibacterial cycling stability of ITO.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Comparative example 1
150mg of lamellar molybdenum disulfide is added into 5mL of water and is subjected to ultrasonic treatment for 30min, 10mg of 1, 2-aminoanthraquinone is added and is subjected to ultrasonic treatment for 30min, stirring is carried out at normal temperature for 12h, then the product is centrifugally collected and freeze-dried, and the 1, 2-aminoanthraquinone sensitized molybdenum disulfide composite photocatalytic antibacterial material is obtained and is recorded as 1,2-DAQ/MoS 2 。
Example 1
The 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material is prepared according to the following steps:
step 1, preparing carboxyl functionalized molybdenum disulfide
50mg MoS is taken 2 Adding the powder into 50mL of ultrapure water, carrying out ultrasonic treatment for 2 hours to uniformly disperse, adding 200 mu L of thioglycollic acid, and carrying out ultrasonic treatment under ice cooling for 15 hours; dialyzing the obtained mixture with ultrapure water for 2 days, lyophilizing to collect solid, namely carboxyl functionalized molybdenum disulfide, denoted as MoS 2 -COOH。
Step 2, grafting 1, 2-diaminoanthraquinone
20mg of MoS 2 Sequentially adding-COOH, 20mg of 1, 2-diaminoanthraquinone and 3mL of dry DMF into a three-necked flask, carrying out ultrasonic treatment for 2 hours, and then adding 20mg of EDC.HCl, 20mg of HOBt and 300 mu LDIPEA under a nitrogen atmosphere; stirring at room temperature for 48h, centrifuging to collect solid product, washing with DMF, water and ethanol sequentially, and drying at 60deg.C to obtain target product 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material, denoted 1,2-DAQ-MoS 2 。
Step 3, loading the ITO conductive glass
20mg of 1,2-DAQ-MoS 2 Ultrasonically dispersing in a mixed solution of ethanol and water, taking Pt sheets as an anode and ITO conductive glass as a cathode, and reacting for 40min under the voltage of 60V to obtain 1,2-DAQ-MoS 2 The photo anode for photoelectrocatalysis and bacteria killing is carried on ITO and is marked as 1,2-DAQ-MoS 2 /ITO。
FIG. 1 is a graph showing the results of comparative example 1 for 1,2-DAQ/MoS 2 (FIG. 1 a) and 1,2-DAQ-MoS obtained in example 1 2 SEM image of (fig. 1 b), from which it can be seen: 1,2-DAQ/MoS 2 And 1,2-DAQ-MoS 2 Are all lamellar structures, but 1,2-DAQ-MoS 2 The surface is rougher and the crystallization is more obvious.
FIG. 2 is a graph showing the results of comparative example 1 for 1,2-DAQ/MoS 2 And 1,2-DAQ-MoS obtained in example 1 2 From the XRD pattern of (C), 1,2-DAQ/MoS can be seen 2 And 1,2-DAQ-MoS 2 Is consistent with the peak position of (1, 2-DAQ-MoS) 2 The peak intensity is greater, which means that its crystallinity is better.
FIG. 3 is a 1,2-DAQ/MoS obtained in comparative example 1 2 And 1,2-DAQ-MoS obtained in example 1 2 The specific test method for the photocatalysis sterilization of the antibacterial flat plate coating pattern of the escherichia coli comprises the following steps: 50. Mu.L of E.coli dilution (bacterial solution concentration 10) 5 CFU/mL) was mixed with 1mL of an aqueous solution of 0.1mg/mL of an antibacterial material and added to 50mL of PBS buffer, and a photoreaction group and a dark reaction group were set. The plate before the start of the reaction was coated as a control group, and after 80 minutes of the reaction, 30. Mu.L of PBS solution uniformly mixed was applied to the plate from the photoreaction group and the dark reaction group, respectively. Plate inversion incubation in biological incubator for 18h, 1,2-DAQ/MoS qualitative assessment by counting colony counts before and after plate plating 2 And 1,2-DAQ-MoS 2 Is used for the antibacterial property of the composition. As can be seen from the figures: 1,2-DAQ-MoS 2 The antibacterial agent has better antibacterial performance under illumination conditions, and is particularly characterized in that bacteria in a system are effectively inactivated after 80min of illumination.
FIG. 4 is a block diagram of 1,2-DAQ-MoS obtained in example 1 2 Is a XPS spectrum of (C). It can be seen from fig. 4a that the composite material has Mo, S, C, N, O elements present. FIG. 4b is a 1,2-DAQ-MoS 2 It can be seen that the 286.2eV has c=o bonds. FIG. 4c is a 1,2-DAQ-MoS 2 It can be seen from the N1s plot of (2), that 399.35eV has N-H bonds.
FIG. 5 is a block diagram of 1,2-DAQ-MoS obtained in example 1 2 XPS spectrum of ITO, from which it can be seen that there is 1,2-DAQ-MoS 2 Mo, S, C, N, O elements of (2) and In and Sn elements of the ITO conductive glass are also present.
FIG. 6 is a 1,2-DAQ-MoS obtained in example 1 2 SEM image of ITO shows that 1, 2-diaminoanthraquinone-molybdenum disulfide with 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, and the specific test method of the photoelectric catalytic sterilization of the material is as follows: 50. Mu.L of E.coli dilution (bacterial solution concentration 10) 5 CFU/mL) was added to 50mL of PBS buffer as a bacterial environment at 1,2-DAQ-MoS 2 ITO is used as a photo-anode, pt sheets are used as photocathodes, 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 group, and after 10min of the reaction, 30. Mu.L of PBS solution uniformly mixed was taken from the photoreaction group and the photoreaction group, respectively, and coated on the plate. Plate inversion culture in a biological incubator for 18h, qualitative assessment of 1,2-DAQ-MoS by counting the colony numbers before and after plate coating 2 Antibacterial properties of ITO.
FIG. 7 is a 1,2-DAQ-MoS of example 1 2 ITO to Escherichia coli antibacterial plate coating pattern. It can be seen that after 5 minutes, 1,2-DAQ-MoS 2 Bacteria of the ITO photovoltaic group (PEC) die entirely.
FIG. 8 is a 1,2-DAQ-MoS of example 1 2 ITO-on-Staphylococcus aureus antibacterial plate coating, the test method is the same as that of Escherichia coli. It can be seen that after 10 minutes, 1,2-DAQ-MoS 2 Bacteria of the ITO photovoltaic group (PEC) die entirely.
1,2-DAQ-MoS 2 After the first antibacterial operation (i.e. after the reaction of the illumination group and the photoelectric group for 5 min), the ITO is subjected to the second and more antibacterial operations by collecting solids through centrifugation. FIG. 9 is a 1,2-DAQ-MoS 2 The antibacterial cycle stability chart of ITO shows the antibacterial ratio calculated by (the number of E.coli before the start of the reaction-the number of E.coli after the end of the reaction for 5 minutes)/the number of E.coli before the start of the reaction. It can be seen from the figure that after three cycles the antimicrobial properties of the material have not been changed. 1,2-DAQ-MoS 2 ITO has very excellent antibacterial stability.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Any person skilled in the art may make variations or modifications to the equivalent embodiments using the teachings disclosed above. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (3)
1. A photoanode for photoelectrocatalytic killing of bacteria, characterized by: the photo-anode is prepared by loading a 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material on ITO conductive glass;
the preparation method of the 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material comprises the following steps:
step 1, embedding thioglycollic acid into molybdenum disulfide through ultrasonic action to obtain carboxyl functionalized molybdenum disulfide:
50-150mg MoS is taken 2 Adding the powder into 50-100mL ultrapure water, performing ultrasonic treatment for 2-4h to uniformly disperse, adding 200-600 mu L of thioglycollic acid, and performing ultrasonic treatment for 15-24h under ice cooling; dialyzing the obtained mixture with ultrapure water for 2-3 days, lyophilizing to collect solid, namely carboxyl functionalized molybdenum disulfide, denoted as MoS 2 -COOH；
Step 2, dehydrating and condensing the carboxyl functionalized molybdenum disulfide and 1, 2-diaminoanthraquinone under EDC and HCl conditions to obtain a covalent grafted 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material:
will be 10-60 MoS 60mg 2 Sequentially adding-COOH, 10-60mg of 1, 2-diaminoanthraquinone and 3-6mL of dry DMF into a three-neck flask, carrying out ultrasonic treatment on the mixture to obtain 2-4h, and then adding 10-60mg of EDC and HCl, 10-60mg of HOBt and 300-600 mu L of DIPEA under a nitrogen atmosphere; stirring at room temperature for 48-72 deg.C and h, centrifuging to collect solid product, washing with DMF, water and ethanol sequentially, and drying at 60deg.C to obtain target product 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material, which is 1,2-DAQ-MoS 2 ；
The photoanode is prepared by loading 1, 2-diaminoanthraquinone-molybdenum disulfide composite antibacterial material by electrophoresis technologyOnto ITO conductive glass, thereby obtaining the conductive glass, specifically comprising the following steps: 20-50 of mg of 1,2-DAQ-MoS 2 Ultrasonically dispersing in a mixed solution of ethanol and water, taking Pt sheets as anodes and ITO conductive glass as cathodes, and reacting under the voltage of 40-60V to obtain 1,2-DAQ-MoS 2 And loading the photo-anode on ITO to obtain the photo-anode for killing bacteria by photoelectrocatalysis.
2. The photoanode for photoelectrocatalytic killing of bacteria of claim 1, wherein: the reaction time is 30-60min.
3. The photoanode for photoelectrocatalytic killing of bacteria of claim 1, wherein: the mixed solution of ethanol and water is formed by mixing ethanol and water according to a volume ratio of 1-2:1.
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