CN118160747B - Magnetic carbon nitride/zinc selenide photocatalysis bactericide and preparation method and application thereof - Google Patents
Magnetic carbon nitride/zinc selenide photocatalysis bactericide and preparation method and application thereof Download PDFInfo
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- CN118160747B CN118160747B CN202410594151.8A CN202410594151A CN118160747B CN 118160747 B CN118160747 B CN 118160747B CN 202410594151 A CN202410594151 A CN 202410594151A CN 118160747 B CN118160747 B CN 118160747B
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- magnetic
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- composite
- zinc selenide
- carbon nitride
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 19
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000000696 magnetic material Substances 0.000 claims abstract description 33
- 239000004005 microsphere Substances 0.000 claims abstract description 29
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
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- 239000013078 crystal Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
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- 238000005406 washing Methods 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- SGZIYCCHNHOYKN-UHFFFAOYSA-N 2-benzo[e][1]benzothiol-1-ylacetic acid Chemical compound C1=CC=CC2=C3C(CC(=O)O)=CSC3=CC=C21 SGZIYCCHNHOYKN-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 239000003139 biocide Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 230000000855 fungicidal effect Effects 0.000 claims description 3
- 239000000417 fungicide Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
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- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 17
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 16
- 238000001228 spectrum Methods 0.000 abstract description 11
- 230000004044 response Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
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- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 8
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- 238000012512 characterization method Methods 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 230000001052 transient effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
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- 238000010521 absorption reaction Methods 0.000 description 3
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- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
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- 241001148471 unidentified anaerobic bacterium Species 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241001476727 Escherichia coli IS1 Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 208000037386 Typhoid Diseases 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 238000000985 reflectance spectrum Methods 0.000 description 1
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- 239000012488 sample solution Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 201000008297 typhoid fever Diseases 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/30—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/33—Electric or magnetic properties
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- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
- B01J35/505—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration with a non-spherical or unspecified core-shell structure
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- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
- A61L2101/28—Inorganic materials containing iron
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
- A61L2101/30—Inorganic materials containing zinc
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Medicinal Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Animal Behavior & Ethology (AREA)
- Environmental Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Physics & Mathematics (AREA)
- Zoology (AREA)
- Hydrology & Water Resources (AREA)
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- Plant Pathology (AREA)
- General Chemical & Material Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Communicable Diseases (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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- Epidemiology (AREA)
- Toxicology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention belongs to the field of bactericides, and relates to a magnetic carbon nitride/zinc selenide photocatalysis bactericide, a preparation method and application thereof, wherein the magnetic carbon nitride/zinc selenide photocatalysis bactericide comprises Fe 3O4@g-C3N4 @ZnSe composite magnetic material, and the Fe 3O4@g-C3N4 @ZnSe composite magnetic material is formed by wrapping g-C 3N4 and ZnSe heterojunction composite material outside a magnetic Fe 3O4 microsphere. The invention combines the magnetic Fe 3O4 microsphere with the g-C 3N4 and ZnSe material, effectively enhances the adsorption performance and the photocatalytic performance of the material, shows wide spectral response, can reduce the band gap of the obtained heterojunction composite, improves the photocatalytic efficiency, can achieve the high-efficiency sterilization effect of visible light catalysis under wide spectrum, can be fully recycled for cyclic utilization, is stable, low in toxicity and safe, is environment-friendly, and realizes the environment-friendly and high-efficiency sterilization water purification treatment or medical antibacterial treatment.
Description
Technical Field
The invention belongs to the field of bactericides, relates to a magnetic photocatalytic bactericide and a preparation method and application thereof, and in particular relates to a magnetic carbon nitride/zinc selenide photocatalytic bactericide and a preparation method thereof and application thereof in catalytic sterilization under visible light irradiation.
Background
Among the water pollutants, the organic pollutants have great ecological harm and the most spread, which not only harm the life of aquatic organisms, but also cause the mass breeding of anaerobic bacteria and facultative anaerobic bacteria including disease pathogens such as dysentery, typhoid and the like. The traditional bactericides (liquid chlorine and ozone) have strong killing effect on microorganisms, but can form various disinfection byproducts and cause secondary pollution to water. The use of silver and copper ion containing bactericides in large amounts also results in the deposition of heavy metals in organisms.
Under the irradiation of specific wave band, the photocatalytic material can produce active oxygen to play a role in sterilization, so as to realize pollutant removal, antibacterial sterilization, new energy production, clean chemical production and simulated photosynthesis, and has the characteristics of energy conservation, green, sustainability, low cost and the like. However, at present, the traditional photocatalysts such as zinc oxide and titanium dioxide can only be excited by ultraviolet light, the utilization rate of natural light is low, a large amount of photocatalytic materials are low in efficiency in the application of antibiosis and sterilization, and the problems of difficult recovery and use in water, relatively high cost and the like are solved.
Disclosure of Invention
Aiming at the antibacterial and bactericidal problems of water bodies, the invention provides a magnetic carbon nitride/zinc selenide photocatalysis bactericide (ferroferric oxide/graphite carbon nitride/zinc selenide, fe 3O4@g-C3N4 @ZnSe) which takes magnetic Fe 3O4 microspheres as cores and g-C 3N4 and ZnSe heterojunction composite materials as shells, a preparation method and application thereof, and the prepared composite bactericide (Fe 3O4@g-C3N4 @ZnSe) can be sterilized efficiently under visible light irradiation, has stable performance, can be recycled by magnetic separation, is safe and environment-friendly, and can be applied to water body disinfectants, medical antibacterial agents and the like.
The invention adopts the technical scheme that:
A magnetic carbon nitride/zinc selenide photocatalysis bactericide comprises Fe 3O4@g-C3N4 @ZnSe composite magnetic material, wherein the Fe 3O4@g-C3N4 @ZnSe composite magnetic material is formed by wrapping g-C 3N4 and ZnSe heterojunction composite material outside a magnetic Fe 3O4 microsphere to form a core-shell structure.
Preferably, the particle size of the Fe 3O4@g-C3N4 @ZnSe composite magnetic material is 1-2 mu m.
Preferably, the particle size of the magnetic Fe 3O4 microsphere is 100-800 nm.
The preparation method of the Fe 3O4@g-C3N4 @ZnSe composite magnetic material comprises the following steps:
S1, preparing the magnetic Fe 3O4 microsphere by taking FeCl 3·6H2 O and NaAc as raw materials.
S2, preparing g-C 3N4 by taking urea crystals as raw materials.
S3, preparing the Fe 3O4@g-C3N4 @ZnSe composite magnetic material by taking g-C 3N4, zinc acetate, selenium powder and magnetic Fe 3O4 microspheres as raw materials.
Preferably, in the step S1, the magnetic Fe 3O4 microsphere is prepared by a hydrothermal method: and (3) dissolving FeCl 3·6H2 O and NaAc in ethylene glycol, stirring until the solution is transparent, performing hydrothermal reaction for 6-10 h at 180-220 ℃ in a reaction kettle, centrifuging to obtain a hydrothermal product, washing with ethanol and deionized water, and drying to obtain the magnetic Fe 3O4 microsphere.
Preferably, in the step S2, the g-C 3N4 is prepared by a high-temperature calcination method: and (3) drying and grinding urea crystals, and then reacting in a muffle furnace at a high temperature of 400-650 ℃ for 2-6 h to obtain g-C 3N4, and grinding into powder for later use. There are other methods for preparing g-C 3N4, such as solvothermal method (complex synthesis process, low economic benefit), electrochemical deposition method (complex reactant), solid phase reaction method (high requirement on reaction environment and equipment), etc. The method is simple, convenient, economical and environment-friendly, and g-C 3N4 is preferably prepared by a muffle furnace high-temperature calcination method.
Preferably, in the step S2, the temperature rising rate of the muffle furnace isAnd (3) carrying out reaction heat preservation for 2-6 h.
Preferably, in the step S3, the Fe 3O4@g-C3N4 @ ZnSe composite magnetic material is prepared by a one-pot hydrothermal synthesis method: adding g-C 3N4, zinc acetate, selenium powder and Fe 3O4 into a KOH solution with the concentration of 4-10 mol/L, adding hydrazine hydrate with the concentration of 10-30% of the total liquid volume for dissolution assistance, stirring for 1-2 h until the suspension is uniform, transferring the mixture into a reaction kettle, and performing high-temperature reaction at 180-220 ℃ by a hydrothermal method to complete the synthesis of the zinc selenide and g-C 3N4 heterojunction composite material and the coating between the materials, and cooling, washing and drying the mixture to obtain the Fe 3O4@g-C3N4 @ZnSe composite magnetic material.
Preferably, in the step S3, in the Fe 3O4@g-C3N4 @ ZnSe composite magnetic material, znSe: the mass ratio of Fe 3O4 is 1:1 to 10:1, znSe: the molar ratio of g-C 3N4 is 1:1 to 10:1.
The application of the magnetic carbon nitride/zinc selenide photocatalysis bactericide in broad spectrum sterilization can be used for water sterilization treatment, medical antibacterial treatment and the like.
Preferably, the broad spectrum means that the illumination wavelength range is 420nm to 800nm.
Preferably, the sterilization refers to water sterilization or medical sterilization.
Compared with the prior art, the invention has the beneficial effects that;
1. According to the invention, the magnetic Fe 3O4 microsphere is compounded with the organic semiconductor photocatalyst graphite carbon nitride (g-C 3N4) and the ZnSe material of the narrow-band gap semiconductor, so that the adsorption performance and the photocatalytic performance of the material are effectively enhanced, the wide spectral response is displayed, the wide light response wavelength is up to 200-800 nm, the obtained heterojunction compound can reduce the band gap, improve the photocatalytic efficiency, achieve the high-efficiency sterilization effect of visible light catalysis under a wide spectrum, and can be fully recycled for cyclic utilization, so that the method is stable, low in toxicity, safe, environmentally friendly and environment-friendly, and the environment-friendly high-efficiency sterilization water purification treatment or medical antibacterial treatment is realized.
2. The ferroferric oxide with good magnetic responsiveness, monodispersity and superparamagnetism is used as a composite antibacterial base material, so that the recyclable and cyclic utilization of the antibacterial material is realized.
3. By utilizing the characteristic that the graphite carbon nitride has a narrower energy band gap (can utilize light energy with the wavelength smaller than 440 nm), the solar energy utilization rate of zinc selenide can be improved, and meanwhile, the graphite carbon nitride has the advantages of easiness in preparation, good stability, high photocatalytic activity and the like. By utilizing the characteristics of narrow band gap (band gap is 2.5-2.8 eV), high excitation energy (21 meV), excellent photosensitivity and the like of zinc selenide, a large number of energy level defects can be generated in a band gap region, all visible light radiation can be absorbed, the utilization rate of light is higher, excellent adsorption performance and photocatalysis performance are realized, and meanwhile, compared with other II-VI semiconductor materials, the zinc selenide has the advantages of low toxicity and environmental friendliness.
Drawings
FIG. 1 is a scanning electron microscope image of Fe 3O4@g-C3N4 @ ZnSe composite magnetic material (a) of example one and of ferroferric oxide (b) obtained in comparative example one.
FIG. 2 is an XPS spectrum of the Fe 3O4@g-C3N4 @ZnSe composite magnetic material obtained in example one.
Fig. 3 is a diagram showing the hysteresis loop (a) and the hysteresis loop partial enlargement (b) of the Fe 3O4@g-C3N4 @ ZnSe composite magnetic material obtained in example one and the ferroferric oxide obtained in comparative example one.
FIG. 4 is an ultraviolet visible diffuse reflectance spectrum of the Fe 3O4@g-C3N4 @ZnSe composite magnetic material obtained in example one and a comparative example two g-C 3N4/ZnSe heterojunction composite material.
FIG. 5 shows a concentration of 5 mg/mL -1 in example one, example two, example three, example four, comparative example one E.coli concentration obtained by antibacterial experiments on E.coli of 1×10 7CFU·mL- under 30min illumination condition of the materials obtained in comparative example II and comparative example IIIA histogram.
FIG. 6 shows the E.coli concentration of the Fe 3O4@g-C3N4 @ ZnSe composite magnetic material obtained in example one during 3 cyclesA curve of change in value.
Fig. 7 is a graph (a) of transient photocurrent response and electrochemical impedance (b) of the materials (bactericides) obtained in example one and comparative example two under intermittent irradiation of a xenon lamp.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention. The experimental methods in the following examples are conventional methods unless otherwise specified. Materials, reagents, and the like used in the examples described below are commercially available with analytically pure reagents as preferred reagents unless otherwise specified.
Example 1
(1) Weigh 2.7g FeCl 3 6H 2 0, dissolving in 80ml of ethylene glycol, continuously stirring to form a transparent solution, adding 7.2g of NaAc, continuously stirring the mixture for 0.5H to be uniform, transferring the mixture into a reaction kettle, and reacting for 9H at 200 ℃; cooling to room temperature, centrifuging to obtain a hydrothermal product, washing thoroughly with ethanol and deionized water, and then placing into a 60 ℃ vacuum drying device for 10 hours to obtain the black magnetic Fe 3O4 microsphere with the particle size of 100-800 nm.
(2) And (3) taking a certain amount of urea crystals, drying and grinding, placing the urea crystals in a muffle furnace for reacting for 2 hours at a high temperature of 550 ℃ to obtain pale yellow g-C 3N4, and grinding the pale yellow g-C 3N4 into powder for subsequent use.
(3) Weighing 16.128g of KOH, slowly adding the KOH into 48mL of deionized water, preparing a 6mol/L KOH solution, sequentially adding 1.2558g of zinc acetate dihydrate, 0.1464gg-C 3N4, 0.4518g of selenium powder and 0.1296g of magnetic Fe 3O4 microspheres, adding 12mL of hydrazine hydrate, mechanically stirring for 1h to be uniform, transferring to a reaction kettle, and carrying out hydrothermal treatment at 200 ℃ for 3h; cooling to room temperature, thoroughly washing, drying in a 55 ℃ drying box for 12 hours to obtain Fe 3O4@g-C3N4 @ZnSe composite magnetic material, wherein ZnSe in the product: the mass ratio of Fe 3O4 is 6:1.
Example two
The preparation process is the same as in example one, and the mass of the magnetic Fe 3O4 microsphere added in the step (3) is 0.111g, namely ZnSe in the product: the mass ratio of Fe 3O4 is 7:1.
Example III
The preparation process is the same as in example one, and the mass of the magnetic Fe 3O4 microsphere added in the step (3) is 1.5556g, namely ZnSe in the product: the mass ratio of Fe 3O4 is 0.5:1.
Example IV
The preparation process is the same as in the first example, and the mass of the magnetic Fe 3O4 microsphere added in the step (3) is 0.0707g, namely ZnSe in the product: the mass ratio of Fe 3O4 is 11:1.
Comparative example one
The preparation method is the same as in the first embodiment (1), and magnetic Fe 3O4 microspheres are obtained.
Comparative example two
The preparation process is the same as the steps (2) and (3) in the first embodiment, except that the magnetic Fe 3O4 microsphere is not added in the step (3), so as to obtain the nonmagnetic ZnSe@g-C 3N4 composite material.
Comparative example three
50Ml of solution is prepared by mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:2. 1.93g of Zn (NO 3)2·6H2 O,0.15g of g-C 3N4 and 0.05g of Fe 3O4@SiO2) are weighed, then 1.485g of urea is added, the materials are dissolved in a solution prepared in advance, mechanically stirred for 30min until the materials are completely dissolved, the materials are transferred into a hydrothermal reaction kettle for reacting at 180 ℃ for 18 h, the materials are taken out after being cooled to room temperature, cooled and placed at room temperature, washed thoroughly, dried for 12h in a 55 ℃ drying box, and impurities are removed and dried, thus obtaining the magnetic Fe 3O4@SiO2@g-C3N4/ZnO composite material.
And (3) effect verification:
E.coli antibacterial experiments under photocatalysis are carried out on the materials obtained in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment, the first comparative embodiment, the second comparative embodiment and the third comparative embodiment, scanning electron microscope characterization is carried out on the materials obtained in the first embodiment and the first comparative embodiment, hysteresis loop characterization is carried out on the materials obtained in the first embodiment and the first comparative embodiment, ultraviolet visible diffuse reflection characterization is carried out on the materials obtained in the first embodiment and the second comparative embodiment, and transient photocurrent density characterization and electrochemical impedance characterization are carried out on the materials obtained in the first embodiment and the second comparative embodiment.
1. The characterization result of the scanning electron microscope is shown in fig. 1, the particle size of the magnetic Fe 3O4 microsphere with smaller diameter and better dispersity is 0.42+/-0.28 mu m, the g-C 3N4 and ZnSe of the composite magnetic material obtained in the first embodiment form heterojunction to better coat the magnetic Fe 3O4 microsphere, the surface of the material presents a stacked lamellar structure, the lamellar is compact, and the size of the lamellar is obviously increased to 1.28+/-0.07 mu m.
2. The surface element composition and chemical state of the material obtained in example one was characterized by XPS, as shown in FIG. 2. Fig. 2 (a) shows a full spectrum of elemental analysis of a sample, in which peaks of energy spectrum of C, N, O, fe, zn, se are present. The high resolution spectrum of C1s corresponds to (b) in FIG. 2, and the peaks at binding energies 284.83, 286.91eV correspond to carbon-carbon bonds and carbon-oxygen bonds, respectively. The high resolution spectrum of (C) in FIG. 2, corresponding to N1s, shows peaks at binding energies of 400.47,401.42,402.78eV, demonstrating the presence of g-C 3N4 in the complex fungicide. The high resolution spectrum of (d) in FIG. 2, corresponding to O1s, shows that the oxygen element exists in the metal oxide state with the binding energy at the peak at 530.59,532.07 eV. The high resolution spectrum of (e) in FIG. 2 corresponds to Fe2p, the peak at 711.48,723.68eV of the binding energy corresponds to Fe2p 3/2,Fe2p1/2, demonstrating successful coating of Fe 3O4 in the composite biocide. The high resolution spectrum of (f) in FIG. 2 corresponds to the peak at 1022.47,1045.49eV for Zn2p 3/2, and the high resolution spectrum of (g) in FIG. 2 corresponds to Se3d, and the peak at 53.09,54.45eV for Se3d 5/2, demonstrating that Zn and Se exist in the zinc selenide state.
3. The hysteresis loop results of the materials obtained in the first and the comparative examples are shown in fig. 3, and it can be seen from (a) in fig. 3 that the saturation magnetization of the Fe 3O4@g-C3N4 @znse composite magnetic material and the magnetic Fe 3O4 microsphere are 9.68 and 79.12, respectively (a·m 2)·kg-1, the saturation magnetization of the magnetic Fe 3O4 microsphere is far greater than that of the Fe 3O4@g-C3N4 @znse composite magnetic material, because g-C 3N4 and ZnSe are both non-magnetic materials, the magnetic properties of the composite material are reduced after the surface of the magnetic bead is wrapped up, and thus the saturation magnetization is significantly reduced, and as can be seen from (b) in fig. 3, the coercivity of the Fe 3O4@g-C3N4 @znse composite magnetic material and the magnetic Fe 3O4 microsphere are 52.06 and 22.07 (a·m -1), respectively, and the remanence is 0.541 and 3.166 (a·m 2)·kg-1), which proves that the Fe 3O4@g-C3N4 @znse composite magnetic material retains the excellent properties of part of the magnetic field 3O4 microsphere superparamagnetism, and can be recycled.
4. The characterization result of the ultraviolet-visible diffuse reflection is shown in fig. 4 by the optical characteristics of the ultraviolet-visible diffuse reflection spectrum reaction compound, and it is known from (a) in fig. 4 that the first embodiment shows strong light absorption in the range of 200-800nm, and the main absorption band without the absorption edge is slightly wider than that of the second embodiment, but the main absorption bands are basically overlapped, and the light absorption of the second embodiment is greatly reduced at 450nm, namely, the visible light absorption capability of the Fe 3O4@g-C3N4 @ZnSe composite magnetic material is slightly stronger than that of the nonmagnetic ZnSe@g-C 3N4 composite material. As can be seen from fig. 4 (b) and fig. 4 (C), the bandgap of the composite magnetic material is 2.44eV, and the bandgap of the nonmagnetic znse@g-C 3N4 is 2.49eV, i.e., the bandgap of the Fe 3O4@g-C3N4 @znse composite magnetic material is slightly narrower compared to the nonmagnetic znse@g-C 3N4 composite material, which indicates that the photocatalytic activity of znse@g-C 3N4 is slightly better than that of the Fe 3O4@g-C3N4 @znse composite magnetic material.
5. Antibacterial effect of the material. Under the irradiation of a PL-XQ 500 w xenon lamp (with a visible light 420nm filter), the concentration of a test sample is 5 mg.mL -1, and the final concentration of the bacterial liquid of Escherichia coli is 1×10 7 CFU mL-1. 1mL of the mixed solution is placed in an ep tube, light is mechanically shaken under a xenon lamp for 30min times, the solution is diluted for 500 times after the light is finished, 200 mu L of the mixed solution is uniformly coated on an LB solid culture medium, the mixed solution is placed in a 37 ℃ incubator for 12 hours of incubation, the result is observed and counted, the colony count of the mixed solution which is not illuminated by the xenon lamp is compared, and the bacteriostasis rate of the material is calculated. All photocatalytic bacterial inactivation experiments were repeated three times. The cyclic antibacterial test was carried out in a glass conical flask with 10 mg/mL -1 sample solution mixed, the total volume of the antibacterial system was 50mL, the system was subjected to light under a solar simulator for 60min while maintaining mechanical shaking, and samples were taken 3 times at 0min,30min, and 60min, respectively. After the illumination is finished, the mixed solution is diluted by 500 times, 200 mu L of the mixed solution is evenly coated on LB solid culture medium, the mixed solution is placed in a 37 ℃ incubator for 12 hours of incubation, the colony count is observed, the colony count is compared with the colony count of the mixed solution which is not illuminated by a xenon lamp, and the bacteriostasis rate of the material is calculated. After the mixture of the residual bacterial liquid and the material is sterilized, washed and dried, the experimental steps are repeated twice, all the photocatalysis bacteria inactivation experiments are repeated for 3 times in parallel, namely three antibacterial cycles are total, an escherichia coli antibacterial effect curve of three cycles is drawn, and the antibacterial performance of the material is evaluated.
The antibacterial results are shown in fig. 5 and 6. Under the irradiation of visible light, the magnetic beads of the first magnetic Fe 3O4 of the comparative example and the magnetic Fe 3O4@SiO2@g-C3N4/ZnO composite material of the third magnetic example have almost no antibacterial effect, and the sterilizing rate of the composite material of the second ZnSe@g-C 3N4 of the comparative example is lower; the composite materials obtained in the first and second embodiments can achieve complete antibiosis under the condition of illumination for 30min, and the bacteriostasis rate of the third cycle of the embodiment reaches 99.99%, but the antibiosis effect of the third embodiment (ZnSe: fe 3O4 mass ratio is 0.5:1) and the fourth embodiment (ZnSe: fe 3O4 mass ratio is 11:1) is poor, and the composite materials are characterized in that: the mass ratio of Fe 3O4 is 1: 1-10: 1, the Fe 3O4@g-C3N4 @ZnSe material with a core-shell structure can improve the sterilization rate, the element proportion has a remarkable influence on the sterilization effect, the antibacterial effect of the composite material is obviously reduced after the element proportion exceeds a specific proportion range, and the Fe 3O4@g-C3N4 @ZnSe material can be used for sterilizing the escherichia coli efficiently under the irradiation of visible light and has stable performance and can be recycled.
6. The photoelectrochemical property test results are shown in FIG. 7, the test is carried out under a three-electrode system, the light source used is a PL-XQ500W xenon lamp, a counter electrode is a Pt electrode, a reference electrode is an Ag/AgCl electrode, fluorine doped tin oxide (FTO) conductive glass coated by a photocatalyst is used as a working electrode, and the electrolyte is 0.5 mol.L -1Na2SO4 solution.
The transient photocurrent response diagrams of the materials obtained in the first and the second examples under intermittent irradiation of a xenon lamp are shown in (a) of fig. 7, and the photocurrent response of the Fe 3O4@g-C3N4 @ZnSe material has good reproducibility and stability, and the transient photocurrent response value reaches 3.73The composite bactericide material has high-efficiency photocatalysis performance, and the transient photocurrent response value of the first embodiment is far greater than that of the second embodiment, which shows that the doping of Fe 3O4 greatly promotes the charge separation of the composite bactericide and improves the light utilization rate of the composite bactericide. The electrochemical impedance of the material is shown in (b) in fig. 7, the arc radius of comparative example 2 is slightly smaller than that of example 1, and the smaller the arc radius of the material curve is, the better the conductivity and the charge transfer performance are, which shows that the Fe 3O4@g-C3N4 @ZnSe material still has good electron-hole separation efficiency.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (5)
1. The magnetic carbon nitride/zinc selenide photocatalysis bactericide is characterized by comprising Fe 3O4@g-C3N4 @ZnSe composite magnetic material, wherein the Fe 3O4@g-C3N4 @ZnSe composite magnetic material is formed by wrapping g-C 3N4 and ZnSe heterojunction composite material outside a magnetic Fe 3O4 microsphere to form a core-shell structure;
the preparation method of the Fe 3O4@g-C3N4 @ZnSe composite magnetic material comprises the following steps:
S1, preparing magnetic Fe 3O4 microspheres by taking FeCl 3·6H2 O and NaAc as raw materials, wherein the specific process comprises the following steps: dissolving FeCl 3·6H2 O and NaAc in glycol, stirring until the solution is transparent, performing hydrothermal reaction for 6-10 h at 180-220 ℃ in a reaction kettle, centrifuging to obtain a hydrothermal product, washing with ethanol and deionized water, and drying to obtain the magnetic Fe 3O4 microsphere;
S2, preparing g-C 3N4 by taking urea crystals as raw materials, wherein the specific process is as follows: taking urea crystals, drying and grinding, and then reacting in a muffle furnace at a high temperature of 400-650 ℃ for 2-6 hours to obtain g-C 3N4, and grinding into powder for later use;
S3, preparing a Fe 3O4@g-C3N4 @ZnSe composite magnetic material by taking g-C 3N4, zinc acetate, selenium powder and magnetic Fe 3O4 microspheres as raw materials, wherein the specific process comprises the following steps: adding g-C 3N4, zinc acetate, selenium powder and magnetic Fe 3O4 microspheres into a KOH solution with the concentration of 4-10 mol/L, adding hydrazine hydrate with the concentration of 10-30% of the total liquid volume for dissolution assistance, stirring for 1-2 hours until the suspension is uniform, transferring the mixture into a reaction kettle, performing high-temperature reaction for 3 hours at 180-220 ℃ by a hydrothermal method, completing the synthesis of zinc selenide and g-C 3N4 heterojunction composite materials and the coating among the materials, cooling, washing and drying to obtain Fe 3O4@g-C3N4 @ZnSe composite magnetic materials; in the Fe 3O4@g-C3N4 @ZnSe composite magnetic material, znSe: the mass ratio of Fe 3O4 is 1:1 to 10:1, znSe: the molar ratio of g-C 3N4 is 1:1 to 10:1.
2. The magnetic carbon nitride/zinc selenide photocatalytic biocide of claim 1, wherein: the particle size of the Fe 3O4@g-C3N4 @ZnSe composite magnetic material is 1-2 mu m.
3. The magnetic carbon nitride/zinc selenide photocatalytic biocide of claim 1, wherein: the particle size of the magnetic Fe 3O4 microsphere is 100-800 nm.
4. The magnetic carbon nitride/zinc selenide photocatalyst according to claim 1, wherein in the step S2, the temperature rising rate of the muffle furnace is 10 ℃ min −1, and the reaction is kept for 2-6 h.
5. Use of a magnetic carbon nitride/zinc selenide photocatalytic fungicide according to claim 1 for the preparation of a broad spectrum photocatalytic fungicide, said broad spectrum being in the range of light wavelengths from 420nm to 800nm.
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