CN114946857B - Hollow polythiophene photocatalysis antibacterial agent and preparation method thereof - Google Patents
Hollow polythiophene photocatalysis antibacterial agent and preparation method thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 34
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 26
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 18
- 229920000123 polythiophene Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000002077 nanosphere Substances 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 4
- 239000000969 carrier Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 3
- 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 18
- 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
- 238000000034 method Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 5
- -1 2, 5-dihydroxyphenyl Chemical group 0.000 claims description 4
- 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
- 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
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 13
- 239000011941 photocatalyst Substances 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 6
- 229910001308 Zinc ferrite Inorganic materials 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
- 230000000845 anti-microbial effect Effects 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 230000003115 biocidal effect Effects 0.000 description 3
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000007787 solid 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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 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
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 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
- 239000002114 nanocomposite Substances 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
- 238000002604 ultrasonography Methods 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
- 208000035143 Bacterial infection Diseases 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
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920000547 conjugated polymer Polymers 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
- 239000012530 fluid Substances 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
- 230000004298 light response Effects 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 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
- 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
- 229930192474 thiophene Natural products 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
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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
- 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
-
- 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
- B01J35/51—Spheres
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a hollow polythiophene photocatalysis antibacterial agent, belonging to the technical field of catalyst preparation. The antibacterial agent takes a thienyl polymer as an active component, hollow nanospheres as carriers, 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, dripping the obtained thienyl polymer dispersion liquid into the hollow nanosphere dispersion liquid dropwise, then continuously stirring for 120-150 min in the dark, removing the solvent by a rotary evaporator after the reaction is finished, and drying in a vacuum drying oven at 50-70 ℃ to obtain the hollow polythiophene photocatalysis antibacterial agent of the target product. The preparation method disclosed by the invention has the advantages of simple preparation process, convenience in synthesis, low material price, reduction in cost of the photocatalytic antibacterial agent, strong antibacterial effect, 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 (Mo Zunli, hu Re, wang Ya, etc.) with antibacterial or bactericidal performance]Material guide a: in the general description, 2014,28 (1): 50.). The antimicrobial properties of the antimicrobial material may 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 function of inhibiting and eliminating harmful microorganisms, and can effectively prevent the harmful microorganismsIs a breeding of (3). The photocatalysis antibacterial is that the photocatalyst absorbs light energy under the irradiation of light with a certain wavelength, and is excited by energy larger than the forbidden band broadband to form photo-generated electrons (e) - ) And 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.) can be separately reacted with water and oxygen to give them strong redox properties to form Reactive Oxygen Species (ROS), which can cooperate with each other to penetrate bacterial cell membranes, enter cells, destroy proteins, leave cell walls broken, kill bacteria (Karli Gold, buford Slay, mark Knackstedt, et al, antimicrobial Activity of Metal and Metal-Oxide Based Nanoparticles [ J]Advanced Therapeutics,2018,1 (3). The photocatalysis antibacterial agent can quickly sterilize, effectively and 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 application prospect (Liwei Zhai, ziqi Zhang, yantao Zhao, et al, efficacy Antibacterial Performance and Effect of Structure on Property Based on Cationic Conjugated Polymers [ J ]].Macromolecules,2018,51(18):7239–7247.)。
The existing inorganic Metal oxide-based photocatalysts are mostly binary Metal oxides such as titanium dioxide, zinc oxide and the like, but the application of the Metal oxide photocatalysts has higher limitation due to the smaller light response range and lower photon utilization efficiency (Linxi Wang, jian jun Zhang, yong Zhang, et al, organic Metal-Oxide Photocatalyst for H 2 O 2 Production[J]Nano Micro Small,2022,18 (8): 2104561.); secondly, nonmetallic photocatalysts, such as the most widely studied carbon nitrides, but their application is also limited by factors such as small specific surface area and low carrier transport efficiency (Fubao Zhang, xiaoming Wang, haonan Liu, et al, recent Advances and Applications of Semiconductor Photocatalytic Technology [ J)]Applied Sciences-Basel,2019,9 (12): 2489.). Differently, organic photocatalysisThe agents such as thienyl polymer, quaternary ammonium salt polymer, pyrrole polymer and the like have higher antibacterial performance, can be used singly, and also can form novel efficient antibacterial agents through compounding with other types of photocatalytic materials, so that the novel efficient antibacterial agents have super-strong antibacterial effect, overcome the defects of other types of antibacterial agents, generally have wide light utilization rate, are environment-friendly, nontoxic and easy to degrade, and have the advantages compared with heavy metal and antibiotic antibacterial agents (Syafiqah Saidin, mohamad Amin Jumat, nur Ain Atiqah Mohd Amin, et al organic and inorganic antibacterial approaches in combating bacterial infection for biomedical application [ J ]].Materials Science and Engineering:C,2021,118:111382.)。
Chinese patent CN113477262a discloses a preparation method and application of silver chromate/zinc ferrite fibrous composite photocatalyst, in which zinc ferrite fiber prepared by electrostatic spinning and high-temperature calcination is used as a carrier, silver chromate particles are loaded on the surface of the zinc ferrite fiber by coprecipitation, so that the degradation of methylene blue and the killing efficiency of salmonella are improved, and the photocatalytic activity of the silver chromate/zinc ferrite composite fiber is promoted; chinese patent CN113215728B discloses a method for preparing a nonwoven fabric based on a copper oxide/graphene oxide composite antibacterial nanomaterial, and a nonwoven fabric based on a copper oxide/graphene oxide composite antibacterial nanomaterial prepared by the method for preparing a nonwoven fabric based on a copper oxide/graphene oxide composite antibacterial nanomaterial, so as to solve the defects of the existing nonwoven fabric, such as no antibacterial property, poor heat resistance, poor mechanical properties, and the like; 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 high-efficiency killing effect on harmful microorganisms in water; gu Yi Male [8] By ZnFe 2 O 4 As a matrix, a double-shell Ag/AgCl/G-ZnFe with photocatalytic antibacterial activity is constructed 2 O 4 Nanocubes, which have a certain antibacterial effect on E.coli (Gu Yi Man zinc ferrite nanocompositeControllable preparation of composite material and photocatalytic antibacterial property [ D ]]Lanzhou: university of lan traffic, 2021:1-69.); xu Hui et al prepared a copper oxide nanorod by a hydrothermal method, and then prepared a polyaniline/copper oxide nanocomposite by an in-situ polymerization method using the nanorod, which has an inhibitory effect on Escherichia coli and Staphylococcus aureus (Xu Hui, huang Jian, chen Yong, etc.. Preparation and antibacterial properties of the polyaniline/copper oxide nanocomposite [ J ]]Polymer materials science and engineering 2011,27 (10): 173-176.).
However, in general, the application and safety of the composite antibacterial polymer photocatalyst in the current patent and literature still have a certain problem, and the light utilization rate is poor, so that the practical application of the composite photocatalyst is restricted.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art, and provides a preparation method of a hollow polythiophene photocatalyst for photocatalysis and antibiosis and application of the hollow polythiophene photocatalyst for photocatalysis and antibiosis. The preparation process is simple, the price is low, the cost of the solid composite photocatalytic antibacterial agent is reduced to a certain extent, and the solid composite photocatalytic antibacterial agent can be applied to photocatalytic antibacterial in multiple fields and occasions.
The specific technical scheme of the invention is as follows:
a hollow polythiophene photocatalysis antibacterial agent is characterized in that a thienyl polymer is taken as an active component, hollow nanospheres are taken as carriers, 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), with no fixed morphology and size; the hollow nanospheres are g-ZnFe 2 O 4 The particle diameter of the hollow nanospheres or cuprous oxide hollow nanospheres is 500-900 nm, and the mass ratio of the active components to the carrier is 1:4.6-7.5.
A preparation method of a hollow polythiophene photocatalysis antibacterial agent comprises the following steps: respectively dispersing thienyl polymer and hollow nanospheres in the presence ofDropwise dripping the obtained thienyl polymer dispersion liquid into the hollow nanosphere dispersion liquid in a solvent and stirring for 50-70 min in a dark place, continuously stirring for 120-150 min in the dark, removing the solvent by a rotary evaporator after the reaction is finished, and drying in a vacuum drying oven at 50-70 ℃ to obtain the hollow polythiophene photocatalysis antibacterial agent of the target product; the thienyl polymer is PTET-T-COOH- (OH) 2 Or PTET-T-COOH-OH, wherein 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 dispersing liquid is 0.6-1 mg/mL, and the organic solvent is THF, ethyl acetate, acetone or petroleum ether; the concentration of the hollow nanosphere dispersion is 1-1.2 mg/mL, and the used organic solvent is absolute ethyl alcohol, acetone or petroleum ether.
The beneficial effects are that:
the preparation method of the composite 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 outstanding technical progress of the thienyl polymer/hollow nanosphere photocatalysis antibacterial agent is reflected in strong antibacterial effect, high light utilization rate, high safety and environmental friendliness. Especially, the photocatalysis antibacterial agent using the hollow nanospheres as the carrier has the advantages of strongest antibacterial effect, highest light utilization rate and outstanding safety and environmental protection. These results are superior to the disclosed nanospheres, hollow nanospheres or other photocatalytic antimicrobial agents that support complex thiophene-based polymers.
The specific embodiment is as follows:
example 1:
3mg of PTET-T-COOH- (OH) 2 Dissolved in 5mL THF and dispersed ultrasonically in the dark for 50min while 20mg g-ZnFe was added 2 O 4 The hollow nanospheres were dispersed in 20mL absolute ethanol and stirred for 50min in the dark. Then the mixture containing PTET-T-COOH- (OH) 2 Is added dropwise to the g-ZnFe mixed solution 2 O 4 The hollow nanospheres were suspended in absolute ethanol and then stirred for a further 120min in the dark. Reverse-rotationAfter this, the solvent was removed by rotary evaporator and dried in a vacuum oven at 50 ℃ to give the final product.
Example 2:
4mg of PTET-T-COOH- (OH) 2 Dissolving in 6mL THF, dispersing in dark ultrasound for 55min, dispersing 23mg Cu 2 The O hollow nanospheres were dispersed in 22mL of acetone and stirred for 55min in the dark. Then the mixture containing PTET-T-COOH- (OH) 2 Is slowly dropped into the mixed solution of THF of Cu 2 The O hollow nanospheres are in acetone solution and then stirred for 125min in the dark. The solvent was removed by rotary evaporator and dried in a vacuum oven at 55deg.C to give the final product.
Example 3:
5mL of ethyl acetate was mixed with 4mg of PTET-T-COOH-OH and sonicated in the dark for 60min,26mg g-ZnFe 2 O 4 The hollow nanospheres were dissolved in 25mL absolute ethanol and stirred for 60min in the dark. Dripping ethyl acetate mixed solution containing PTET-T-COOH-OH into g-ZnFe dropwise 2 O 4 The hollow nanospheres were suspended in absolute ethanol and then stirred for a further 130min in the dark. After the reaction was completed, the solvent was removed by rotary evaporator and dried at 55 ℃ to obtain the final product.
Example 4:
6mg of PTET-T-COOH-OH were dissolved in 8mL of ethyl acetate and dispersed by ultrasound in the dark for 70min. 35mg of Cu 2 The O hollow nanospheres are dispersed in 30mL of absolute ethyl alcohol and stirred for 50-70 min in a dark place. Then the mixed solution of ethyl acetate containing PTET-T-COOH-OH is slowly dripped into Cu 2 The O hollow nanospheres are suspended in absolute ethanol and then stirred for 150min in the dark. After the reaction, the solvent was removed and dried at 70℃to give the final product.
Example 5:
4mg PTET-T-COOH- (OH) 2 Acetone 4mL is added, stirring is vigorously carried out for 120min, 30mg g-ZnFe2O4 hollow nanospheres are taken and dispersed in petroleum ether 25mL, and stirring is carried out for 80min. The two solutions were mixed and stirred for 150min. The solvent was removed and dried to give the final product.
Example 6:
adding 6mg PTET-T-COOH-OH to 8mL petroleumStirring with ether for 120min, and collecting 28mg Cu 2 The O hollow nanospheres were dissolved in 25mL absolute ethanol and stirred for 1.5h. The two solutions were slowly mixed and stirred for 40min after the dropwise addition was completed within 30min. The solvent was removed and dried to give the final product.
Example 7:
the samples prepared in examples 1 to 6 were tested for photocatalytic antimicrobial under the conditions of LED light source, light intensity: 150mW/cm 2 . Samples of the solution were collected every 15min using standard plate counting methods, 100 μl of bacterial fluid was taken and diluted. Serial dilutions of the surface-contacted solutions were plated onto sterile petri dishes, incubated overnight in a 37 ℃ incubator, and colony counted to determine the number of viable bacteria. The results are shown in Table 1.
TABLE 1 antibacterial effect and cycle stability of different examples of implementation
。
Claims (3)
1. A hollow polythiophene photocatalysis antibacterial agent is characterized in that a thienyl polymer is taken as an active component, hollow nanospheres are taken as carriers, 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 or 5- (3-hydroxyphenyl) -5' - (thiophene-ethylene-thiophene) -thiophene-3, 4-dicarboxylic acid, and has no fixed morphology and size; the hollow nanospheres are g-ZnFe 2 O 4 The particle diameter of the hollow nanospheres or cuprous oxide hollow nanospheres is 500-900 nm, and the mass ratio of the active components to the carrier is 1:4.6-7.5.
2. A method for preparing the hollow polythiophene photocatalysis antibacterial agent according to claim 1, comprising the following steps: respectively dispersing a thienyl polymer and hollow nanospheres in an organic solvent, stirring in a dark place for 50-70 min, dropwise dripping the obtained thienyl polymer dispersion liquid into the hollow nanosphere dispersion liquid, and then continuously stirring in the dark for 120-150 min, after the reaction is finished, removing the solvent by a rotary evaporator, and drying in a vacuum drying oven at 50-70 ℃ to obtain a target product hollow polythiophene photocatalysis 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, and 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 method for preparing a hollow polythiophene photocatalysis antibacterial agent according to claim 2, wherein the concentration of the thienyl polymer dispersion liquid is 0.6-1 mg/mL, and the organic solvent is THF, ethyl acetate, acetone or petroleum ether; the concentration of the hollow nanosphere dispersion is 1-1.2 mg/mL, and the used organic solvent is absolute ethyl alcohol, acetone or petroleum ether.
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| CN101177253A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院理化技术研究所 | Preparation method of hollow micron carbon spheres with regular size |
| CN106311109A (en) * | 2016-08-26 | 2017-01-11 | 江苏大学 | Embedded hollow magnetic imprinted photocatalytic nanoreactor and preparation method thereof |
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| JP2018076279A (en) * | 2016-06-29 | 2018-05-17 | 東ソー株式会社 | Optically active thiophene compound, optically active polythiophene, and production method thereof |
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| CN101177253A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院理化技术研究所 | Preparation method of hollow micron carbon spheres with regular size |
| JP2018076279A (en) * | 2016-06-29 | 2018-05-17 | 東ソー株式会社 | Optically active thiophene compound, optically active polythiophene, and production method thereof |
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