CN114946857A - Hollow polythiophene photocatalytic antibacterial agent and preparation method thereof - Google Patents
Hollow polythiophene photocatalytic antibacterial agent and preparation method thereof Download PDFInfo
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- CN114946857A CN114946857A CN202210747285.XA CN202210747285A CN114946857A CN 114946857 A CN114946857 A CN 114946857A CN 202210747285 A CN202210747285 A CN 202210747285A CN 114946857 A CN114946857 A CN 114946857A
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- hollow
- thiophene
- antibacterial agent
- thienyl
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920000123 polythiophene Polymers 0.000 title claims abstract description 15
- 239000002077 nanosphere Substances 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 4
- -1 2, 5-dihydroxyphenyl Chemical group 0.000 claims description 3
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 12
- 239000011941 photocatalyst Substances 0.000 description 12
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 7
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910000431 copper oxide Inorganic materials 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/39—
-
- B01J35/51—
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a hollow polythiophene photocatalytic antibacterial agent, and belongs to the technical field of catalyst preparation. The antibacterial agent takes a thienyl polymer as an active component, hollow nanospheres as a carrier, and the hollow nanospheres are used for stabilizing the active component; the preparation method comprises the following steps: respectively dispersing the thienyl polymer and the hollow nanospheres in an organic solvent, stirring for 50-70 min in a dark place, dropwise adding the obtained thienyl polymer dispersion liquid into the hollow nanosphere dispersion liquid, then continuously stirring for 120-150 min in the dark, removing the solvent through a rotary evaporator after the reaction is finished, and drying in a vacuum drying oven at 50-70 ℃ to obtain the target product, namely the hollow polythiophene photocatalytic antibacterial agent. The preparation method has the advantages of simple preparation process, convenient synthesis, low material price, reduction of the cost of the photocatalytic antibacterial agent, strong antibacterial effect of the prepared catalyst, high light utilization rate, high safety and environmental friendliness.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a method for preparing a supported solid photocatalytic antibacterial agent by reacting hollow nanospheres with a thienyl polymer.
Background
The antibacterial material is a novel functional material with antibacterial or bactericidal properties (Mozun, Hu-Zi, Wang YaWen, etc.. antibacterial material and antibacterial mechanism thereof [ J]Material report a: for review, 2014,28(1): 50.). The antimicrobial properties of the antimicrobial material can be achieved by adding an appropriate amount of antimicrobial agent to the polymeric material, or otherwise introducing antimicrobial groups into the carrier material. The prepared antibacterial material has the functions of inhibiting and eliminating harmful microorganisms, and can effectively prevent the breeding of the harmful microorganisms. The photocatalytic antibacterial function is that the photocatalyst absorbs light energy under the irradiation of light with certain wavelength and is excited by the energy larger than the forbidden band to form photoproduction electrons (e) - ) And a cavity (h) + )(Junli Liu,Yuhan Wang,Jianzhong Ma,et al.A review on bidirectional analogies between the photocatalysis and antibacterial properties of ZnO[J]Journal of Alloys and Compounds,2019,783(30): 898-918), which can be generated with water and oxygen, respectively, to have strong redox properties to generate Reactive Oxygen Species (ROS), which can cooperate with each other to penetrate the bacterial cell membrane, enter the cell, destroy proteins, leave broken cell walls, and kill bacteria (Karli Gold, Buford slit, Mark Knackstedt, et al]Advanced Therapeutics,2018,1(3). The photocatalytic Antibacterial agent can quickly sterilize, is effective, can avoid the problem of biological drug resistance caused by antibiotics, has the advantages of high activity, good chemical stability, high selectivity, small damage to normal tissues, easy synthesis, low cost, no toxicity and the like, and has wide research and application prospects (Liwei Zhai, Ziqi Zhang, Yantao Zhao, et al. effective Antibacterial Performance and Effect of structural on Property base on Cationic connected Polymers [ J.].Macromolecules,2018,51(18):7239–7247.)。
Most of the existing inorganic Metal Oxide-based photocatalysts are binary Metal oxides such as titanium dioxide and zinc Oxide, but due to the smaller photoresponse range and the lower photon utilization efficiency, the application of the Metal Oxide Photocatalyst has higher limitation (Linxi Wang, Jianjun Zhang, Yong Zhang, et al, inorganic Metal-Oxide Photocatalyst for H 2 O 2 Production[J]Nano Micro Small,2022,18(8): 2104561.); secondly, non-metallic photocatalysts, such as carbon nitride, are most widely studied, but their application is also limited by such factors as small specific surface area and low carrier transport efficiency (Fubao Zhang, Xiaoning Wang, Haonan Liu, et al. Recent Advances and Applications of Semiconductor Photonic Technology [ J]Applied Sciences-Basel,2019,9(12): 2489.). Different from the above, the organic photocatalysts such as thiophene-based polymers, quaternary ammonium salt polymers, pyrrole-based polymers and the like have high antibacterial performance, can be used alone, and can also be compounded with other types of photocatalytic materials to form a novel high-efficiency antibacterial agent, so that the novel high-efficiency antibacterial agent has a super-strong antibacterial effect, makes up the defects of other types of antibacterial agents, generally has wide light utilization rate, is environment-friendly, non-toxic and easy to degrade, and has advantages over heavy metal and antibiotic antibacterial agents (Syafiqah Saidin, Moha amine Jumat, Nur Aiiqah Mohd amine, et al].Materials Science and Engineering:C,2021,118:111382.)。
Chinese patent CN113477262A discloses a preparation method and application of a silver chromate/zinc ferrite fibrous composite photocatalyst, wherein the silver chromate/zinc ferrite fibrous composite photocatalyst takes zinc ferrite fibers prepared by electrostatic spinning and high-temperature calcination methods as a carrier, silver chromate particles are loaded on the surface of the zinc ferrite fibers by utilizing a coprecipitation method, so that the degradation efficiency of methylene blue and the killing efficiency of salmonella are improved, and the photocatalytic activity of the silver chromate/zinc ferrite composite fibers is promoted; chinese patent CN113215728B discloses a preparation method of non-woven fabric based on copper oxide/graphene oxide composite antibacterial nano material,the non-woven fabric based on the copper oxide/graphene oxide composite antibacterial nano material is prepared by the preparation method of the non-woven fabric based on the copper oxide/graphene oxide composite antibacterial nano material, so that the defects that the existing non-woven fabric has no antibacterial property, is not heat-resistant, has poor mechanical property and the like are overcome; chinese patent CV111213675A discloses a water-soluble conjugated polythiophene/molybdenum disulfide composite photocatalytic bactericide, a preparation method and application thereof, wherein the composite photocatalytic bactericide is prepared by loading water-soluble conjugated polythiophene on the surface of a molybdenum disulfide nanosheet, and has an efficient killing effect on harmful microorganisms in water; ancient man [8] With ZnFe 2 O 4 As a matrix, a double-shell Ag/AgCl/G-ZnFe with photocatalytic antibacterial activity is constructed 2 O 4 Nanocubes with a certain antibacterial effect on escherichia coli (controlled preparation of zinc ferrite nanocomposite and photocatalytic antibacterial property [ D ] thereof]In Lanzhou: lanzhou university of transportation, 2021: 1-69.); xuhui et al prepared a copper oxide nanorod by hydrothermal method, and then used this nanorod to obtain a polyaniline/copper oxide nanocomposite by in situ polymerization method, which has inhibitory effects on Escherichia coli and Staphylococcus aureus (Xuhui, Huangjian, Chenyu, etc. preparation of polyaniline/copper oxide nanocomposite and antibacterial properties [ J]Polymer materials science and engineering, 2011,27(10): 173-.
However, in general, the application and safety of the composite antibacterial polymer photocatalyst in the current patents and documents still have certain problems, and the light utilization rate is poor, so that the practical application of the composite photocatalyst is limited.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a preparation method of a hollow polythiophene photocatalyst for photocatalytic antibacterial and to apply the hollow polythiophene photocatalyst to photocatalytic antibacterial. The preparation process is simple, the price is low, the cost of the solid composite type photocatalytic antibacterial agent is reduced to a certain extent, and the composite type photocatalytic antibacterial agent can be applied to photocatalytic antibacterial in multiple fields and multiple occasions.
The specific technical scheme of the invention is as follows:
a hollow polythiophene photocatalytic antibacterial agent is characterized in that a thienyl polymer is used as an active component, hollow nanospheres are used as a carrier, and the hollow nanospheres are used for stabilizing the active component; the thienyl polymer is poly 5- (2, 5-dihydroxyphenyl) -5' - (thiophene-ethylene-thiophene) -thiophene-3, 4-dicarboxylic acid (PTET-T-COOH- (OH) 2 ) Or 5- (3-hydroxyphenyl) -5' - (thiophene-ethylene-thiophene) -thiophene-3, 4-dicarboxylic acid (PTET-T-COOH-OH), without fixed morphology and size; the hollow nanospheres are g-ZnFe 2 O 4 The hollow nanospheres or cuprous oxide hollow nanospheres have the particle size of 500-900 nm, and the mass ratio of the active component to the carrier is 1: 4.6-7.5.
A preparation method of a hollow polythiophene photocatalytic antibacterial agent comprises the following steps: respectively dispersing a thienyl polymer and hollow nanospheres in an organic solvent, stirring for 50-70 min in a dark place, dropwise adding the obtained thienyl polymer dispersion liquid into the hollow nanosphere dispersion liquid, continuously stirring for 120-150 min in the dark place, removing the solvent through a rotary evaporator after the reaction is finished, and drying in a vacuum drying oven at 50-70 ℃ to obtain a target product, namely a hollow polythiophene photocatalytic antibacterial agent; the thienyl polymer is PTET-T-COOH- (OH) 2 Or PTET-T-COOH-OH, the hollow nanospheres are g-ZnFe 2 O 4 Hollow nanospheres or Cu 2 O hollow nanospheres; the mass ratio of the thienyl polymer to the hollow nanospheres is 1: 4.6-7.5.
Preferably, the concentration of the thienyl polymer dispersion liquid is 0.6-1 mg/mL, and the used organic solvent is THF, ethyl acetate, acetone or petroleum ether; the concentration of the hollow nanosphere dispersion liquid is 1-1.2 mg/mL, and the used organic solvent is absolute ethyl alcohol, acetone or petroleum ether.
Has the advantages that:
the preparation method of the compound photocatalytic antibacterial agent has the advantages of simple process, convenient synthesis and low material price, and reduces the cost of the photocatalytic antibacterial agent. The invention has the advantages of strong antibacterial effect, high light utilization rate, high safety and environmental protection. Especially, the photocatalysis antibacterial agent using the hollow nanosphere as the carrier has the strongest antibacterial effect, the highest light utilization rate and the most outstanding safety and environmental protection. These results are superior to the disclosed photocatalytic antibacterial agents of nanospheres, hollow nanospheres or other supported complex thiophene-based polymers.
The specific implementation mode is as follows:
example 1:
3mg of PTET-T-COOH- (OH) 2 Dissolving in 5mL THF and ultrasonically dispersing for 50min in the dark while adding 20mg g-ZnFe 2 O 4 The hollow nanospheres were dispersed in 20mL of absolute ethanol and stirred for 50min in the dark. Then containing PTET-T-COOH- (OH) 2 The THF mixed solution of (1) was dropwise added to g-ZnFe 2 O 4 The hollow nanospheres are suspended in absolute ethanol and then stirred for 120min in the dark. After the reaction was completed, the solvent was removed by a rotary evaporator and dried in a vacuum oven at 50 ℃ to obtain the final product.
Example 2:
4mg of PTET-T-COOH- (OH) 2 Dissolving in 6mL THF, ultrasonic dispersing for 55min in dark place, and adding 23mg Cu 2 The O hollow nanospheres were dispersed in 22mL acetone and stirred for 55min away from light. Then containing PTET-T-COOH- (OH) 2 The THF mixed solution of (1) was slowly dropped to Cu 2 O hollow nanospheres in acetone solution, and then stirring in the dark for 125 min. The solvent was removed by rotary evaporator and dried in a vacuum oven at 55 deg.C to give the final product.
Example 3:
5mL of ethyl acetate and 4mg of PTET-T-COOH-OH are mixed and are ultrasonically dispersed for 60min in dark place, 26mg of g-ZnFe 2 O 4 The hollow nanospheres were dissolved in 25mL of absolute ethanol and stirred for 60min in the dark. Dropwise adding the mixed solution of ethyl acetate containing PTET-T-COOH-OH to g-ZnFe 2 O 4 The suspension of the hollow nanospheres in absolute ethanol is stirred for 130min in the dark. After the reaction was completed, the solvent was removed by a rotary evaporator and dried at 55 ℃ to obtain the final product.
Example 4:
6mg of PTET-T-COOH-OH was dissolved in 8mL of ethyl acetateAnd ultrasonically dispersing in ester for 70min in the dark. 35mg of Cu 2 Dispersing the O hollow nanospheres in 30mL of absolute ethyl alcohol, and stirring for 50-70 min in a dark place. Then slowly dripping the mixed solution of ethyl acetate containing PTET-T-COOH-OH to Cu 2 And (3) adding the O hollow nanospheres into an absolute ethanol suspension, and then continuing to stir in the dark for 150 min. After the reaction is finished, the solvent is removed, and the final product is obtained after drying at 70 ℃.
Example 5:
taking 4mg PTET-T-COOH- (OH) 2 Adding 4mL of acetone, stirring vigorously for 120min, taking 30mg of the hollow nanospheres of ZnFe2O4 to disperse in 25mL of petroleum ether, and stirring for 80 min. The two solutions were mixed and stirred for 150 min. Removing the solvent and drying to obtain the final product.
Example 6:
adding 6mg PTET-T-COOH-OH into 8mL petroleum ether, stirring vigorously for 120min, and taking 28mg Cu 2 The O hollow nanospheres are dissolved in 25mL of absolute ethanol and stirred for 1.5 h. Slowly mixing the two solutions, adding dropwise within 30min, and stirring for 40 min. Removing the solvent and drying to obtain the final product.
Example 7:
the samples prepared in the above embodiments 1 to 6 were subjected to photocatalytic antibacterial testing under the conditions of LED light source and light intensity: 150mW/cm 2 . Samples of the solution were collected every 15min using standard plate counting, 100. mu.L of the bacterial suspension was taken and diluted. Serial dilutions of the surface-contacting solutions were plated on sterile petri dishes, incubated overnight in a 37 ℃ incubator, and colony counts were performed to determine the number of viable bacteria. The results are shown in Table 1.
TABLE 1 antimicrobial efficacy and circulation stability of various examples
Claims (3)
1. A hollow polythiophene photocatalysis antibacterial agent is characterized in that a thiophene-based polymer is used as an active component, hollow nanospheres are used as a carrier, and the hollow nanospheres are used forStabilizing the active ingredient; the thienyl polymer is poly 5- (2, 5-dihydroxyphenyl) -5 '- (thiophene-ethylene-thiophene) -thiophene-3, 4-dicarboxylic acid or 5- (3-hydroxyphenyl) -5' - (thiophene-ethylene-thiophene) -thiophene-3, 4-dicarboxylic acid, and has no fixed shape and size; the hollow nanospheres are g-ZnFe 2 O 4 The hollow nanospheres or cuprous oxide hollow nanospheres have the particle size of 500-900 nm, and the mass ratio of the active component to the carrier is 1: 4.6-7.5.
2. A method for preparing the hollow polythiophene photocatalytic antibacterial agent in claim 1, comprising the following steps: respectively dispersing a thienyl polymer and hollow nanospheres in an organic solvent, stirring for 50-70 min in a dark place, dropwise adding the obtained thienyl polymer dispersion liquid into the hollow nanosphere dispersion liquid, continuously stirring for 120-150 min in the dark place, removing the solvent through a rotary evaporator after the reaction is finished, and drying in a vacuum drying oven at 50-70 ℃ to obtain a target product, namely a hollow polythiophene photocatalytic antibacterial agent; the thienyl polymer is poly 5- (2, 5-dihydroxyphenyl) -5 '- (thiophene-ethylene-thiophene) -thiophene-3, 4-dicarboxylic acid or 5- (3-hydroxyphenyl) -5' - (thiophene-ethylene-thiophene) -thiophene-3, 4-dicarboxylic acid, the hollow nanospheres are g-ZnFe 2 O 4 Hollow nanospheres or Cu 2 O hollow nanospheres; the mass ratio of the thienyl polymer to the hollow nanospheres is 1: 4.6-7.5.
3. The preparation method of the hollow polythiophene photocatalytic antibacterial agent according to claim 2, wherein the concentration of the thiophene-based polymer dispersion is 0.6-1 mg/mL, and the used organic solvent is THF, ethyl acetate, acetone or petroleum ether; the concentration of the hollow nanosphere dispersion liquid is 1-1.2 mg/mL, and the used organic solvent is absolute ethyl alcohol, acetone or petroleum ether.
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