CN116440956A - MIL-based photocatalytic composite film with photo-thermal sterilization function and preparation method and application thereof - Google Patents
MIL-based photocatalytic composite film with photo-thermal sterilization function and preparation method and application thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 43
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000012528 membrane Substances 0.000 claims abstract description 101
- 229920000767 polyaniline Polymers 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000002121 nanofiber Substances 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 11
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract 2
- 239000000835 fiber Substances 0.000 claims description 73
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 49
- 229920000620 organic polymer Polymers 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 28
- 238000001523 electrospinning Methods 0.000 claims description 22
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 22
- 238000011068 loading method Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000009987 spinning Methods 0.000 claims description 17
- 238000000967 suction filtration Methods 0.000 claims description 13
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 12
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 12
- -1 polyethylene terephthalate Polymers 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000004729 solvothermal method Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000009736 wetting Methods 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 241000192125 Firmicutes Species 0.000 claims description 8
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 5
- 239000001263 FEMA 3042 Substances 0.000 claims description 5
- 239000013255 MILs Substances 0.000 claims description 5
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 5
- 230000003100 immobilizing effect Effects 0.000 claims description 5
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 5
- 229940033123 tannic acid Drugs 0.000 claims description 5
- 235000015523 tannic acid Nutrition 0.000 claims description 5
- 229920002258 tannic acid Polymers 0.000 claims description 5
- 239000013110 organic ligand Substances 0.000 claims description 3
- 229920001690 polydopamine Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 210000004379 membrane Anatomy 0.000 abstract description 45
- 230000002779 inactivation Effects 0.000 abstract description 23
- 241000894006 Bacteria Species 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 210000002469 basement membrane Anatomy 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 238000003828 vacuum filtration Methods 0.000 abstract 1
- 230000001580 bacterial effect Effects 0.000 description 43
- 239000007788 liquid Substances 0.000 description 25
- 238000005286 illumination Methods 0.000 description 16
- 229910052724 xenon Inorganic materials 0.000 description 16
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 16
- 241000588724 Escherichia coli Species 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 11
- 239000001963 growth medium Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 241000191967 Staphylococcus aureus Species 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- 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
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- 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
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- Hydrology & Water Resources (AREA)
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Abstract
The invention belongs to the technical field of sterilization materials, and particularly relates to an MIL-based photocatalytic composite membrane with a photo-thermal sterilization function, and a preparation method and application thereof. An organic nanofiber basement membrane is prepared by an electrostatic spinning method, and an MIL metal organic framework/polyaniline (MIL/PANI) heterojunction is prepared by a hydrothermal method. And then uniformly mixing the binder with catechol functional groups with an MIL/PANI heterojunction, depositing and fixing the binder on a bottom film in a vacuum filtration mode to prepare the MIL-based photocatalytic composite film. The composite membrane prepared by the invention can generate active oxygen species under visible light, the MIL/PANI heterojunction immobilized on the bottom membrane reduces the recombination rate of photogenerated carriers, enlarges the light absorption range, cooperatively exerts the photo-thermal conversion effect, shows high-efficiency photo-catalytic inactivation efficiency on harmful gram bacteria in water, and shows advantages in the aspects of convenient recovery and recycling, thereby having good application prospect.
Description
Technical Field
The invention belongs to the technical field of sterilization materials, and particularly relates to an MIL-based photocatalytic composite membrane with a photo-thermal sterilization function, and a preparation method and application thereof.
Background
The mass propagation and spread of pathogenic bacteria caused by bacterial contamination in water bodies creates potential public health safety problems. Traditional sterilization technologies such as chlorination, ozone oxidation, ultraviolet radiation and the like have shown good sterilization effects, but have the problems of high energy consumption, high cost, secondary pollution or bacterial light revitalization and the like. Therefore, there is an urgent need to develop novel sterilization materials and techniques to solve the problem of bacterial contamination of water bodies. The photocatalytic sterilization technology, which sterilizes by generating active species having strong oxidizing property from a photocatalytic material using sunlight, is regarded as a green, safe, and efficient sterilization technology, has attracted attention by researchers.
At present, the photocatalysis sterilization material mainly adopts TiO 2 ZnO and C 3 N 4 Etc., the sterilization function of which is based on the photocatalytic reaction. Reactive Oxygen Species (ROS) generated by photocatalytic materials under light can attack bacteria, causing damage to the cell wall membrane, interfering with the normal vital activity of the bacteria and causing its inactivation. In recent years, metal organic framework Materials (MOFs) formed by self-assembling metal ions or clusters and organic ligands are attracting attention for application in photocatalytic reactions due to the characteristics of high porosity, large specific surface area, low toxicity, abundant surface active groups and the like. However, the metal organic frame material still has the bottleneck problems of narrow photoresponse range and low photo-generated carrier separation rate, and the powder property of the metal organic frame material also affects the recycling performance of the sterilization material.
Disclosure of Invention
The invention aims to provide an MIL-based photocatalytic composite membrane with a photo-thermal sterilization function, which has high-efficiency inactivation capability on gram bacteria in a water body under visible light and has practical application prospect.
The invention relates to a preparation method of an MIL-based photocatalytic composite film with a photo-thermal sterilization function, which comprises the following steps:
(1) Preparation of organic Polymer fiber film
And dissolving the organic polymer in DMF solution to obtain uniform electrospinning solution, loading the prepared organic polymer electrospinning solution into electrostatic spinning equipment for spinning film forming, and drying the spun organic nanofiber film in a vacuum oven.
Wherein the organic polymer is one of polyvinylidene fluoride, polyacrylonitrile or polyethylene terephthalate;
the concentration of the electrospinning solution is 10% -15%, and the diameter of single nanofiber in the organic polymer fiber membrane prepared by electrospinning is 200-500nm.
(2) Preparation of MIL/PANI heterojunction
Polyaniline (PANI) is added into a mixed solvent of DMF and methanol, and metered 2-amino terephthalic acid and tetrabutyl titanate are added and mixed evenly by ultrasonic. The solution was transferred to a reaction vessel and heated in an oven at 150 ℃ for solvothermal reaction. And after the reaction is finished, centrifuging, washing and drying the reaction precipitate to obtain the MIL/PANI heterojunction.
Wherein the addition amount of PANI is 2-10% of the mass of the organic ligand 2-amino terephthalic acid.
(3) Preparation of MIL-based photocatalytic composite membrane material
And (3) wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, dispersing the binder and the MIL/PANI heterojunction prepared in the step (2) into the deionized water, and carrying out ultrasonic treatment on the mixed suspension for 10min by using an ultrasonic cell disruption instrument, wherein the ultrasonic power ratio is 100%. And depositing and fixedly carrying the treated mixed solution on the pre-wetted organic polymer fiber membrane by adopting a vacuum auxiliary suction filtration method. Drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite film material.
Wherein the binder is one of polydopamine, tannic acid or protocatechuic acid;
the vacuum auxiliary suction filtration method comprises the following steps: the membrane is wetted by water or ethanol in advance and fixed on a sand core filtering device, the obtained suspension is poured into the device to turn on a switch for suction filtration, the switch is turned off after all liquid on the membrane is suction filtered, and the membrane is taken down.
The loading of MILs/PANI heterojunction on the organic polymer fiber membrane was 5-15mg relative to 60mg fiber membrane.
The composite membrane provided by the invention is applied to the inactivation of gram-negative bacteria and gram-positive bacteria in water under low-power visible light irradiation.
The invention has the technical effects that:
(1) The MIL-based photocatalytic composite membrane prepared by the invention has rich pore diameter structure, higher light absorption capacity in an ultraviolet-visible light region, and the construction of MIL/PANI heterojunction solves the problem that photogenerated carriers in a single semiconductor photocatalyst are easy to compound, can generate more effective photogenerated electrons and holes, and are respectively combined with O 2 And H 2 O reacts to obtain active oxygen species with higher concentration, and the photocatalysis efficiency is improved.
(2) According to the invention, the binder and the MIL/PANI heterojunction are immobilized on the organic polymer base film by a vacuum auxiliary suction filtration method, so that the catalyst has good stability, the problem that the powder catalyst is difficult to recycle is solved, and the recycling rate of the catalyst is improved. MIL/PANI heterojunction loaded on the basement membrane plays a role in photocatalysis and photothermal conversion simultaneously, and the sterilization efficiency is synergistically improved, and the inactivation efficiency on gram negative bacteria and positive bacteria can reach 99.99 percent optimally.
Description of the drawings:
FIG. 1 is a Scanning Electron Microscope (SEM) image of a polyacrylonitrile fiber membrane prepared in example 1 of the present invention.
FIG. 2 is an X-ray diffraction (XRD) pattern of MIL/PANI heterojunction prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
(1) Preparation of organic Polymer fiber film
Dissolving polyacrylonitrile in DMF solution to obtain uniform electrospun solution, and loading the prepared polyacrylonitrile electrospun solution (10%) into electrostatic spinning equipment for spinning film forming under the spinning conditions: the prepared electrospinning solution was charged into a syringe, and electrospinning was performed at a positive voltage of 15 kV. The spinning solution was fed at a rate of 0.8mL/h and the drum speed was 90rpm. The temperature was set to 25.+ -. 5 ℃ and the humidity was maintained at 40.+ -. 5%. Finally, the prepared polyacrylonitrile electrospun fiber membrane is dried in a vacuum oven at 50 ℃ for 12 hours. The average width of the single nano-fiber in the polyacrylonitrile fiber membrane is 200-300nm.
The Scanning Electron Microscope (SEM) image of the polyacrylonitrile fiber membrane prepared in this example is shown in fig. 1.
(2) Preparation of MIL/PANI heterojunction
0.011g of PANI was added to a mixed solvent of DMF and methanol (VDMF/V methanol=9:1, 50 mL), and 2-amino terephthalic acid (0.55 g,3 mmol) and tetrabutyl titanate (0.51 mL,1.5 mmol) were added and mixed well by sonication. The solution was transferred to a reaction vessel and heated in an oven at 150 ℃ for solvothermal reaction for 24h. And after the reaction is finished, centrifuging, washing and drying the reaction precipitate to obtain the MIL/PANI heterojunction.
The X-ray diffraction (XRD) pattern of the MIL/PANI heterojunction prepared in this example is shown in FIG. 2.
(3) Preparation of MIL-based photocatalytic composite membrane material
Wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, dispersing 5mg of protocatechuic acid binder and 10mg of MIL/PANI heterojunction prepared in the step (2) into the deionized water, and carrying out ultrasonic treatment on the mixed suspension by using an ultrasonic cytoclasis instrument. And depositing and immobilizing the treated mixed solution on a pre-wetted organic polymer fiber membrane by adopting a vacuum assisted suction filtration method, wherein the loading capacity of the MIL/PANI heterojunction on a polyacrylonitrile fiber membrane base membrane (60 mg fiber membrane) is 10mg. Drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite film material.
In addition, 5mg of MILs/PANI heterojunction was loaded onto a polyacrylonitrile fiber membrane (60 mg of fiber membrane) base membrane under the same conditions;
15mg of MIL/PANI heterojunction was supported on a polyacrylonitrile fiber membrane (60 mg of fiber membrane) base membrane under the same conditions.
(4) Bacterial inactivation process
Using filters (lambda. Is greater than or equal to 420 nm)Xenon lamps as visible light sources (light intensity: 0.3 Wcm) -2 ). The MIL-based photocatalytic composite film material prepared above (with the effective diameter of 4 cm) is placed at a concentration of 10 6 CFU/mL of E.coli solution (gram negative bacteria). Starting a xenon lamp to perform photocatalysis sterilization reaction, sucking 0.1mL of diluted bacterial liquid every 20min during illumination, inoculating the bacterial liquid on an LB solid culture medium, incubating the bacterial liquid in a biochemical incubator at 37 ℃ for 24 hours, and finally counting formed bacterial colonies. Through statistics, the inactivation rate of the MIL-based photocatalytic composite membrane material with the heterojunction load of 10mg to escherichia coli reaches 99.99% after the visible light irradiates for 60 minutes, which indicates that the MIL-based photocatalytic composite material prepared by the method has a certain sterilization performance to gram-negative bacteria. And the inactivation rate of the MIL-based photocatalytic composite membrane material with the heterojunction loading capacity to the escherichia coli after 60 minutes of visible light irradiation is 69.50%, and the inactivation rate of the MIL-based photocatalytic composite membrane material with the heterojunction loading capacity to the escherichia coli after 50 minutes of visible light irradiation is 99.99%. The method shows that the amount of the heterojunction loading obviously influences the efficiency of inactivating the escherichia coli of the MIL-based photocatalytic composite membrane material, however, excessive loading can cause the shedding of powder on the surface of the membrane and the increase of cost.
Example 2
(1) Preparation of organic Polymer fiber film
And (3) dissolving polyacrylonitrile in a DMF solution to obtain a uniform electrospinning solution, loading the prepared polyacrylonitrile electrospinning solution (15%) into an electrostatic spinning device for spinning to form a film (spinning conditions are the same as in example 1), and drying the spun polyacrylonitrile fiber film in a vacuum oven, wherein the average width of single nanofibers in the polyacrylonitrile fiber film is 300-500nm.
(2) Preparation of MIL/PANI heterojunction
0.011g of PANI was added to a mixed solvent of DMF and methanol (V DMF /V Methanol =9:1, 50 mL) and 2-amino terephthalic acid (0.55 g,3 mmol) and tetrabutyl titanate (0.51 mL,1.5 mmol) were added and mixed well by ultrasound. The solution was transferred to a reaction vessel and heated in an oven at 150 ℃ for solvothermal reaction for 24h. After the reaction is finished, centrifuging, washing and drying the reaction precipitate to obtain the MIL/PANI heterojunction。
(3) Preparation of MIL-based photocatalytic composite membrane material
Wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, dispersing 5mg of binder polydopamine and 15mg of MIL/PANI heterojunction prepared in the step (2) into the deionized water, and carrying out ultrasonic treatment on the mixed suspension by using an ultrasonic cytoclasis instrument. And depositing and fixedly supporting the treated mixed solution on a pre-wetted organic polymer fiber membrane by adopting a vacuum auxiliary suction filtration method, wherein the load capacity of the MIL/PANI heterojunction on a polyacrylonitrile fiber membrane (60 mg fiber membrane) bottom membrane is 15mg, and drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite membrane material.
(4) Bacterial inactivation process
A xenon lamp with a filter (lambda. Is 420 nm) was used as a visible light source (light intensity: 0.3 Wcm) -2 ). The MIL-based photocatalytic composite film material prepared above (with the effective diameter of 4 cm) is placed at a concentration of 10 6 CFU/mL staphylococcus aureus solution (gram positive bacteria). Starting a xenon lamp to perform photocatalysis sterilization reaction, sucking 0.1mL of diluted bacterial liquid every 20min during illumination, inoculating the bacterial liquid on an LB solid culture medium, incubating the bacterial liquid in a biochemical incubator at 37 ℃ for 24 hours, and finally counting formed bacterial colonies. Through statistics, the inactivation rate of the MIL-based photocatalytic composite membrane material to staphylococcus aureus reaches 99.99% after 60 minutes of visible light illumination, which proves that the MIL-based photocatalytic composite material prepared by the method has a certain sterilization performance to gram-positive bacteria.
Example 3
(1) Preparation of organic Polymer fiber film
And (3) dissolving polyvinylidene fluoride in DMF (dimethyl formamide) solution to obtain uniform electrospinning solution, loading the prepared polyvinylidene fluoride electrospinning solution (10%) into electrostatic spinning equipment for spinning to form a film (spinning conditions are the same as in example 1), and drying the spun polyvinylidene fluoride fiber film in a vacuum oven, wherein the average width of single nano fibers in the polyvinylidene fluoride fiber film is 200-400nm.
(2) Preparation of MIL/PANI heterojunction
0.011g of PANI was added to DMF and methanolIn a mixed solvent (V) DMF /V Methanol =9:1, 50 mL) and 2-amino terephthalic acid (0.55 g,3 mmol) and tetrabutyl titanate (0.51 mL,1.5 mmol) were added and mixed well by ultrasound. The solution was transferred to a reaction vessel and heated in an oven at 150 ℃ for solvothermal reaction for 24h. And after the reaction is finished, centrifuging, washing and drying the reaction precipitate to obtain the MIL/PANI heterojunction.
(3) Preparation of MIL-based photocatalytic composite membrane material
Wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, dispersing 5mg of protocatechuic acid binder and 10mg of MIL/PANI heterojunction prepared in the step (2) into the deionized water, and carrying out ultrasonic treatment on the mixed suspension by using an ultrasonic cytoclasis instrument. And depositing and fixedly supporting the treated mixed solution on a pre-wetted organic polymer fiber membrane by adopting a vacuum auxiliary suction filtration method, wherein the load capacity of the MIL/PANI heterojunction on a polyvinylidene fluoride fiber membrane (60 mg fiber membrane) base membrane is 10mg. Drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite film material.
(4) Bacterial inactivation process
A xenon lamp with a filter (lambda. Is 420 nm) was used as a visible light source (light intensity: 0.3 Wcm) -2 ). The MIL-based photocatalytic composite film material prepared above (with the effective diameter of 4 cm) is placed at a concentration of 10 6 CFU/mL of E.coli solution (gram negative bacteria). Starting a xenon lamp to perform photocatalysis sterilization reaction, sucking 0.1mL of diluted bacterial liquid every 20min during illumination, inoculating the bacterial liquid on an LB solid culture medium, incubating the bacterial liquid in a biochemical incubator at 37 ℃ for 24 hours, and finally counting formed bacterial colonies. Through statistics, the inactivation rate of the MIL-based photocatalytic composite membrane material to escherichia coli reaches 99.99% after 60 minutes of visible light illumination, which shows that the MIL-based photocatalytic composite membrane material prepared by the method has a certain sterilization performance to gram-negative bacteria. The sterilization performance of the MIL-based photocatalytic composite material is mainly determined by the photocatalytic activity of the prepared MIL/PANI heterojunction, the organic polymer film material has no influence on the sterilization performance, and the photocatalyst is loaded on the organic polymer film material so as to be convenient for material recovery and recycling.
Example 4
(1) Preparation of organic Polymer fiber film
And (3) dissolving polyvinylidene fluoride in DMF (dimethyl formamide) solution to obtain uniform electrospinning solution, loading the prepared polyvinylidene fluoride electrospinning solution (10%) into electrostatic spinning equipment for spinning to form a film (spinning conditions are the same as in example 1), and drying the spun polyvinylidene fluoride fiber film in a vacuum oven, wherein the average width of single nano fibers in the polyvinylidene fluoride fiber film is 200-400nm.
(2) Preparation of MIL/PANI heterojunction
0.022g of PANI was added to a mixed solvent of DMF and methanol (V DMF /V Methanol =9:1, 50 mL) and 2-amino terephthalic acid (0.55 g,3 mmol) and tetrabutyl titanate (0.51 mL,1.5 mmol) were added and mixed well by ultrasound. The solution was transferred to a reaction vessel and heated in an oven at 150 ℃ for solvothermal reaction. And after the reaction is finished, centrifuging, washing and drying the reaction precipitate to obtain the MIL/PANI heterojunction.
(3) Preparation of MIL-based photocatalytic composite membrane material
Wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, dispersing 5mg of binder tannic acid and 5mg of MIL/PANI heterojunction prepared in the step (2) into the deionized water, and carrying out ultrasonic treatment on the mixed suspension by using an ultrasonic cytoclasis instrument. And depositing and fixedly supporting the treated mixed solution on a pre-wetted organic polymer fiber membrane by adopting a vacuum auxiliary suction filtration method, wherein the load capacity of the MIL/PANI heterojunction on a polyvinylidene fluoride fiber membrane bottom (60 mg fiber membrane) membrane is 5mg. Drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite film material. The MILs/PANI heterojunction prepared in this example showed enhanced photocatalytic activity compared to example 1, and still showed good sterilization ability under the same illumination time with reduced loading.
(4) Bacterial inactivation process
A xenon lamp with a filter (lambda. Is 420 nm) was used as a visible light source (light intensity: 0.3 Wcm) -2 ). Placing the MIL-based photocatalytic composite membrane material (with the effective diameter of 4 cm) prepared in the above way at a concentration of10 6 CFU/mL of E.coli solution (gram negative bacteria). Starting a xenon lamp to perform photocatalysis sterilization reaction, sucking 0.1mL of diluted bacterial liquid every 20min during illumination, inoculating the bacterial liquid on an LB solid culture medium, incubating the bacterial liquid in a biochemical incubator at 37 ℃ for 24 hours, and finally counting formed bacterial colonies. Through statistics, the inactivation rate of the MIL-based photocatalytic composite membrane material to escherichia coli reaches 99.32% after 60 minutes of visible light illumination, which proves that the MIL-based photocatalytic composite material prepared by the method has a certain sterilization performance to gram-negative bacteria.
Example 5
(1) Preparation of organic Polymer fiber film
And (3) dissolving polyethylene terephthalate in DMF (dimethyl formamide) solution to obtain uniform electrospinning solution, loading the prepared polyethylene terephthalate electrospinning solution (13%) into electrostatic spinning equipment for spinning film forming (spinning conditions are the same as in example 1), and drying the spun polyethylene terephthalate fiber film in a vacuum oven, wherein the average width of single nanofibers in the polyethylene terephthalate fiber film is 400-500nm.
(2) Preparation of MIL/PANI heterojunction
0.033g PANI was added to a mixed solvent of DMF and methanol (V DMF /V Methanol =9:1, 50 mL) and 2-amino terephthalic acid (0.55 g,3 mmol) and tetrabutyl titanate (0.51 mL,1.5 mmol) were added and mixed well by ultrasound. The solution was transferred to a reaction vessel and heated in an oven at 150 ℃ for solvothermal reaction for 24h. And after the reaction is finished, centrifuging, washing and drying the reaction precipitate to obtain the MIL/PANI heterojunction.
(3) Preparation of MIL-based photocatalytic composite membrane material
Wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, dispersing 5mg of binder tannic acid and 10mg of MIL/PANI heterojunction prepared in the step (2) into the deionized water, and carrying out ultrasonic treatment on the mixed suspension by using an ultrasonic cytoclasis instrument. And depositing and immobilizing the treated mixed solution on a pre-wetted organic polymer fiber membrane by adopting a vacuum assisted suction filtration method, wherein the loading capacity of the MIL/PANI heterojunction on a polyethylene terephthalate fiber membrane (60 mg fiber membrane) base membrane is 10mg. Drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite film material.
(4) Bacterial inactivation process
A xenon lamp with a filter (lambda. Is 420 nm) was used as a visible light source (light intensity: 0.3 Wcm) -2 ). The MIL-based photocatalytic composite film material prepared above (with the effective diameter of 4 cm) is placed at a concentration of 10 6 CFU/mL staphylococcus aureus solution (gram positive bacteria). Starting a xenon lamp to perform photocatalysis sterilization reaction, sucking 0.1mL of diluted bacterial liquid every 20min during illumination, inoculating the bacterial liquid on an LB solid culture medium, incubating the bacterial liquid in a biochemical incubator at 37 ℃ for 24 hours, and finally counting formed bacterial colonies. Through statistics, the inactivation rate of the MIL-based photocatalytic composite membrane material to staphylococcus aureus reaches 99.50% after 60 minutes of visible light illumination, which proves that the MIL-based photocatalytic composite material prepared by the method has a certain sterilization performance to gram-positive bacteria.
Example 6
(1) Preparation of organic Polymer fiber film
And (3) dissolving the polyethylene terephthalate in DMF (dimethyl formamide) solution to obtain uniform electrospinning solution, loading the prepared polyethylene terephthalate electrospinning solution (10%) into electrostatic spinning equipment for spinning film forming (spinning conditions are the same as in example 1), and drying the spun polyethylene terephthalate fiber film in a vacuum oven, wherein the average width of single nanofibers in the polyethylene terephthalate fiber film is 350-450nm.
(2) Preparation of MIL/PANI heterojunction
0.044g of PANI was added to a mixed solvent of DMF and methanol (V DMF /V Methanol =9:1, 50 mL) and 2-amino terephthalic acid (0.55 g,3 mmol) and tetrabutyl titanate (0.51 mL,1.5 mmol) were added and mixed well by ultrasound. The solution was transferred to a reaction vessel and heated in an oven at 150 ℃ for solvothermal reaction for 24h. And after the reaction is finished, centrifuging, washing and drying the reaction precipitate to obtain the MIL/PANI heterojunction.
(3) Preparation of MIL-based photocatalytic composite membrane material
Wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, dispersing 5mg of binder tannic acid and 10mg of MIL/PANI heterojunction prepared in the step (2) into the deionized water, and carrying out ultrasonic treatment on the mixed suspension by using an ultrasonic cytoclasis instrument. And depositing and immobilizing the treated mixed solution on a pre-wetted organic polymer fiber membrane by adopting a vacuum assisted suction filtration method, wherein the loading capacity of the MIL/PANI heterojunction on a polyethylene terephthalate fiber membrane (60 mg fiber membrane) base membrane is 10mg. Drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite film material.
(4) Bacterial inactivation process
A xenon lamp with a filter (lambda. Is 420 nm) was used as a visible light source (light intensity: 0.3 Wcm) -2 ). The MIL-based photocatalytic composite film material prepared above (with the effective diameter of 4 cm) is placed at a concentration of 10 6 CFU/mL staphylococcus aureus solution (gram positive bacteria). Starting a xenon lamp to perform photocatalysis sterilization reaction, sucking 0.1mL of diluted bacterial liquid every 20min during illumination, inoculating the bacterial liquid on an LB solid culture medium, incubating the bacterial liquid in a biochemical incubator at 37 ℃ for 24 hours, and finally counting formed bacterial colonies. Through statistics, the inactivation rate of the MIL-based photocatalytic composite membrane material to staphylococcus aureus reaches 99.25 percent after 60 minutes of visible light illumination, the MIL-based photocatalytic composite material prepared by the method has a certain sterilization performance on gram-positive bacteria.
Example 7
(1) Preparation of organic Polymer fiber film
And (3) dissolving polyacrylonitrile in a DMF solution to obtain a uniform electrospinning solution, loading the prepared polyacrylonitrile electrospinning solution (10%) into an electrostatic spinning device for spinning to form a film (spinning conditions are the same as in example 1), and drying the spun polyacrylonitrile fiber film in a vacuum oven, wherein the average width of single nanofibers in the polyacrylonitrile fiber film is 200-300nm.
(2) Preparation of MIL/PANI heterojunction
0.055g PANI was added to a mixed solvent of DMF and methanol (V DMF /V Methanol =9:1, 50 mL) and 2-amino terephthalic acid (0.55 g,3 mmol) and tetra titanate were addedButyl ester (0.51 mL,1.5 mmol) was mixed well by sonication. The solution was transferred to a reaction vessel and heated in an oven at 150 ℃ for solvothermal reaction for 24h. And after the reaction is finished, centrifuging, washing and drying the reaction precipitate to obtain the MIL/PANI heterojunction.
(3) Preparation of MIL-based photocatalytic composite membrane material
Wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, dispersing 5mg of protocatechuic acid binder and 10mg of MIL/PANI heterojunction prepared in the step (2) into the deionized water, and carrying out ultrasonic treatment on the mixed suspension by using an ultrasonic cytoclasis instrument. And depositing and fixedly supporting the treated mixed solution on a pre-wetted organic polymer fiber membrane by adopting a vacuum auxiliary suction filtration method, wherein the load capacity of the MIL/PANI heterojunction on a polyacrylonitrile fiber membrane (60 mg fiber membrane) bottom membrane is 10mg, and drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite membrane material.
(4) Bacterial inactivation process
A xenon lamp with a filter (lambda. Is 420 nm) was used as a visible light source (light intensity: 0.3 Wcm) -2 ). The MIL-based photocatalytic composite film material prepared above (with the effective diameter of 4 cm) is placed at a concentration of 10 6 CFU/mL of E.coli solution (gram negative bacteria). Starting a xenon lamp to perform photocatalysis sterilization reaction, sucking 0.1mL of diluted bacterial liquid every 20min during illumination, inoculating the bacterial liquid on an LB solid culture medium, incubating the bacterial liquid in a biochemical incubator at 37 ℃ for 24 hours, and finally counting formed bacterial colonies. Through statistics, the inactivation rate of the MIL-based photocatalytic composite membrane material with the heterojunction load of 10mg to escherichia coli reaches 99.37% after the visible light irradiates for 60 minutes, which indicates that the MIL-based photocatalytic composite material prepared by the method has a certain sterilization performance to gram-negative bacteria.
Comparative example 1
(1) Preparation of organic Polymer fiber film
As in example 1.
(2) Preparation of NH 2 -MIL-125
2-amino terephthalic acid (0.55 g,3 mmol) and tetrabutyl titanate (0.51 mL,1.5 mmol) were added to a mixed solvent of DMF and methanol (V DMF /V Methanol =9:1, 50 mL), and was mixed well by ultrasound. The solution was transferred to a reaction vessel and heated in an oven at 150 ℃ for solvothermal reaction for 24h. After the reaction is finished, centrifuging, washing and drying the reaction precipitate to obtain NH 2 -MIL-125。
(3) Preparation of MIL-based photocatalytic composite membrane material
Wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, and simultaneously, adding 5mg of protocatechuic acid binder and 10mg of NH obtained in the step (2) 2 MIL-125 was dispersed in deionized water and the mixed suspension was sonicated with a sonicator. Depositing and immobilizing the treated mixed solution on a pre-wetted organic polymer fiber membrane by adopting a vacuum assisted suction filtration method, and carrying out NH (NH) 2 MIL-125 was supported on the polyacrylonitrile fiber membrane base film (60 mg of fiber membrane) at a loading of 10mg. Drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite film material.
(4) Bacterial inactivation process
A xenon lamp with a filter (lambda. Is 420 nm) was used as a visible light source (light intensity: 0.3 Wcm) -2 ). The MIL-based photocatalytic composite film material prepared above (with the effective diameter of 4 cm) is placed at a concentration of 10 6 CFU/mL of E.coli solution (gram negative bacteria). Starting a xenon lamp to perform photocatalysis sterilization reaction, sucking 0.1mL of diluted bacterial liquid every 20min during illumination, inoculating the bacterial liquid on an LB solid culture medium, incubating the bacterial liquid in a biochemical incubator at 37 ℃ for 24 hours, and finally counting formed bacterial colonies. Through statistics, 10mg NH 2 The inactivation rate of the MIL-125 loaded MIL-based photocatalytic composite membrane material to the escherichia coli reaches 62.75% after 60 minutes of visible light illumination. As can be seen from comparative example 1, the MIL/PANI heterojunction was more NH than that of the MIL/PANI heterojunction at the same loading and illumination time 2 MILs-125 exhibits enhanced photocatalytic sterilization properties.
Claims (8)
1. A MIL-based photocatalytic composite membrane with a photo-thermal sterilization function is characterized in that a bottom membrane of the MIL-based photocatalytic composite membrane is an organic polymer fiber membrane, and a functional unit immobilized on the bottom membrane is a photo-responsive MIL/Polyaniline (PANI) heterojunctionThe method comprises the steps of carrying out a first treatment on the surface of the Wherein MIL is NH 2 MILs-125 metal-organic framework material with a diameter of 500-600nm.
2. The preparation method of the MIL-based photocatalytic composite film with the photo-thermal sterilization function is characterized by comprising the following steps:
(1) Preparation of organic Polymer fiber film
Dissolving an organic polymer in a DMF solution to obtain a uniform electrospinning solution, loading the organic polymer electrospinning solution into electrostatic spinning equipment for spinning film forming, and drying the spun organic nanofiber film in a vacuum oven;
(2) Preparation of MIL/PANI heterojunction
Adding Polyaniline (PANI) into a mixed solvent of DMF and methanol, adding metered 2-amino terephthalic acid and tetrabutyl titanate, carrying out ultrasonic mixing uniformly, transferring the solution to a reaction kettle, heating in a baking oven at 150 ℃ for solvothermal reaction, centrifuging, washing and drying a reaction precipitate after the reaction is finished to obtain an MIL/PANI heterojunction;
(3) Preparation of MIL-based photocatalytic composite film
Wetting the organic polymer fiber membrane prepared in the step (1) with deionized water, dispersing the binder and the MIL/PANI heterojunction prepared in the step (2) into the deionized water, performing ultrasonic treatment on the mixed suspension by using an ultrasonic cell disruption instrument, depositing and immobilizing the treated mixed solution on the pre-wetted organic polymer fiber membrane by using a vacuum auxiliary suction filtration method, and drying in a vacuum drying oven to obtain the MIL-based photocatalytic composite membrane.
3. The method for preparing an MIL-based photocatalytic composite film with a photo-thermal sterilization function according to claim 2, wherein the organic polymer in the step (1) is one of polyvinylidene fluoride, polyacrylonitrile or polyethylene terephthalate.
4. The preparation method of the MIL-based photocatalytic composite film with the photo-thermal sterilization function according to claim 2, wherein the concentration of the electrospinning solution in the step (1) is 10% -15%, and the diameter of single nanofiber in the organic polymer fiber film prepared by electrospinning is 200-300nm.
5. The preparation method of the MILs-based photocatalytic composite film with the photo-thermal sterilization function according to claim 2, wherein the addition amount of PANI in the step (2) is 2% -10% of the mass of the organic ligand 2-amino terephthalic acid.
6. The method for preparing the MILs-based photocatalytic composite membrane with the photo-thermal sterilization function according to claim 2, wherein the binder in the step (3) is one of polydopamine, tannic acid or protocatechuic acid.
7. The method for preparing an MIL-based photocatalytic composite film having a photo-thermal sterilization function according to claim 2, wherein the loading amount of MIL/PANI heterojunction on the organic polymer fiber film is 5-15mg with respect to 60mg of the fiber film in the step (3).
8. Use of an MIL-based photocatalytic composite membrane according to claim 1, characterized in that the composite membrane is applied to deactivate gram-negative and gram-positive bacteria in water under low power visible light irradiation.
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