CN115486443A - Cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material and preparation method and application thereof - Google Patents
Cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material and preparation method and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 163
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 154
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 154
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 99
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 86
- 239000010936 titanium Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000004729 solvothermal method Methods 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims description 82
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 55
- 238000005406 washing Methods 0.000 claims description 55
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 51
- 229910021641 deionized water Inorganic materials 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 40
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 29
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 28
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 238000003303 reheating Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- -1 cerium ions Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- A01N25/08—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
- A01N25/10—Macromolecular compounds
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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
- A01N25/26—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 in coated particulate form
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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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention provides a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material and a preparation method and application thereof, wherein the preparation method comprises the following steps: firstly, preparing polystyrene microspheres, then coating a layer of anatase crystal form titanium dioxide on the surfaces of the polystyrene microspheres by a solvothermal method at a temperature of 100-150 ℃ to obtain titanium dioxide-polystyrene microspheres, and finally doping cerium into the anatase crystal form titanium dioxide coated on the surfaces to obtain a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material; the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material is of a hollow spherical structure, has the advantages of controllable structure, good stability, high load capacity, uniform particles, good dispersibility, difficulty in agglomeration and the like, has an antibacterial function under visible light and dark conditions, is high in light energy utilization rate and excellent in antibacterial performance, and can be widely applied to the antibacterial field.
Description
Technical Field
The invention relates to the field of preparation of nano antibacterial materials, in particular to a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material and a preparation method and application thereof.
Background
The nano titanium dioxide has the advantages of good chemical stability, wide application range, no toxicity to human bodies and the like, and has wide application prospect in the fields of wastewater treatment, air purification, sterilization, disinfection and the like. However, when the nano titanium dioxide is used for treating wastewater, the nano titanium dioxide is easy to agglomerate into larger particles, so that the specific surface area is reduced, namely, the contact area with bacteria is reduced, and the nano titanium dioxide has a wider energy band and can only absorb the ultraviolet light part in sunlight. Therefore, the light energy utilization rate and the antibacterial efficiency of the nano titanium dioxide are low, so that the industrial application of the nano titanium dioxide photocatalyst is limited.
The microsphere structure can effectively improve the antibacterial performance by increasing the loading capacity of a semiconductor and the exposure of an active crystal face. For example, chinese invention patent CN 101659773B discloses nano TiO 2 A polystyrene microsphere compound, a preparation method and application thereof, which is a surface loaded nano TiO with polystyrene as a carrier 2 The microsphere has high specific surface area and semiconductor loading capacity, so that the rapid, efficient and broad-spectrum antibacterial effect can be achieved under ultraviolet light. However, the patent must be illuminated to achieve the antibacterial effect, and the hollow structure is a solid sphere, which does not fully exert the scattering effect of the light, and fails to improve the light capturing capability of the material.
Doping with rare earth elementsSo as to increase the crystal defects of the semiconductor to narrow the energy band, generate more widely generated electron-hole, and simultaneously cause the optical transition between 4F orbitals of the semiconductor, thereby increasing the light energy utilization range. For example, chinese patent CN 104069847B discloses rare earth europium doped nano TiO 2 The preparation method of hollow glass microsphere is characterized by that it is a rare earth element europium-doped photocatalytic microsphere with core-shell structure, said microsphere possesses excellent light-absorbing property, and the doping of rare earth element can make TiO be doped 2 Absorbed light is red-shifted, the photoresponse range of the semiconductor is widened to visible light, and the catalytic activity and the light energy utilization rate of the semiconductor are effectively improved.
However, the technical schemes related to the composite antibacterial microspheres have problems, namely the nano TiO has problems 2 The polystyrene microsphere compound has antibacterial performance only under ultraviolet light, and the rare earth europium is doped with nano TiO 2 The semiconductor loading capacity on the hollow glass microspheres is limited, and the composite antibacterial microspheres have the defects of non-uniform particles, poor dispersibility and the like, so that the light energy utilization efficiency and the antibacterial activity of the composite antibacterial microspheres are limited.
Therefore, how to design and prepare the composite antibacterial microsphere which has controllable structure, good stability and high load capacity and has antibacterial function under visible light and dark conditions has important significance for improving the practical application of the nano antibacterial material.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, a preparation method and application thereof, wherein the preparation method comprises the following steps: firstly, preparing polystyrene microspheres, then coating a layer of anatase crystal form titanium dioxide on the surfaces of the polystyrene microspheres by a solvothermal method at a temperature of 100-150 ℃ to obtain titanium dioxide-polystyrene microspheres, and finally doping cerium into the anatase crystal form titanium dioxide coated on the surfaces to obtain a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material; the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material is of a hollow spherical structure, has the advantages of controllable structure, good stability, high load capacity, uniform particles, good dispersibility, difficulty in agglomeration and the like, has an antibacterial function under visible light and dark conditions, is high in light energy utilization rate and excellent in antibacterial performance, and can be widely applied to the antibacterial field.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, which comprises the following steps:
(1) Adding polystyrene microspheres and polyvinylpyrrolidone into a first solvent for primary heating to obtain a first mixed solution;
(2) Adding a titanate solution into the first mixed solution obtained in the step (1) for secondary heating to obtain a second mixed solution;
(3) Reacting the second mixed solution obtained in the step (2) at 100-150 ℃ by a solvothermal method, and sequentially centrifuging, washing and drying to obtain titanium dioxide-polystyrene microspheres;
(4) And (3) respectively adding citric acid, ethylene glycol, polyethylene glycol and the titanium dioxide-polystyrene microspheres obtained in the step (3) into a ceric ammonium nitrate solution, stirring to obtain a sol system, and calcining to obtain the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material.
The preparation method provided by the invention adopts the polystyrene microsphere as a carrier, can provide a larger specific surface area for loading titanium dioxide, then adopts a solvothermal method and controls the temperature to be 100-150 ℃, coats a layer of anatase crystal form titanium dioxide on the surface of the polystyrene microsphere to obtain the titanium dioxide-polystyrene microsphere, finally uses rare earth ion cerium to dope and modify the anatase crystal form titanium dioxide coated on the surface, widens the photoresponse range of the anatase crystal form titanium dioxide to visible light, and can release cerium ions so that the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material still has an antibacterial effect in the dark. The cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material prepared by the preparation method is of a hollow spherical structure, has the advantages of controllable structure, good stability, high load capacity, uniform particles, good dispersibility, difficult agglomeration and the like, has an antibacterial function under visible light and dark conditions, is high in light energy utilization rate and excellent in antibacterial performance, and can be widely applied to the antibacterial field.
It should be noted that the temperature of the reaction in the step (3) of the present invention is 100 to 150 ℃, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the above-mentioned numerical range are also applicable.
As a preferred technical scheme of the invention, the preparation method of the polystyrene microsphere in the step (1) comprises the following steps:
(i) Sequentially adding sodium dodecyl sulfate and styrene into deionized water for primary heating to obtain a mixed solution a;
(ii) And (e) adding a potassium persulfate aqueous solution into the mixed solution a obtained in the step (i) for reheating to obtain a mixed solution b, and sequentially centrifuging, washing and drying to obtain the polystyrene microsphere.
It is worth to say that the preparation method of the polystyrene microsphere provided by the invention adopts styrene as a raw material, sodium dodecyl sulfate as a surfactant and potassium persulfate as an initiator, and adopts an emulsion polymerization method to prepare the polystyrene microsphere with uniform particles, so that a larger specific surface area is provided for subsequent titanium dioxide loading.
In a preferred embodiment of the present invention, the mass ratio of sodium dodecyl sulfate to styrene in step (i) is 1 (200 to 300), for example, 1.
Preferably, the solid-to-liquid ratio of sodium dodecyl sulfate to deionized water in step (i) is 1g (1500-2000) mL, such as 1g.
Preferably, the temperature of the first heating in step (i) is 30 to 100 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited within the above-mentioned range of values are equally applicable.
Preferably, the time for the first heating in step (i) is 30 to 60min, such as 30min, 35min, 40min, 45min, 50min, 55min or 60min, but is not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the solid-to-liquid ratio of the aqueous potassium persulfate solution in step (ii), i.e., the solid-to-liquid ratio of potassium persulfate to deionized water, is 1g (50 to 100) mL, for example, 1 g.
Preferably, in step (ii), the volume ratio of the mixed solution a to the aqueous potassium persulfate solution is (5 to 10) 1, for example, 5.
Preferably, the reheating temperature in step (ii) is 30 to 100 ℃, for example 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited within the above-mentioned range of values are also applicable.
Preferably, the reheating time in step (ii) is 300-500 min, such as 300min, 330min, 350min, 380min, 400min, 430min, 450min, 470min or 500min, but not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
Preferably, the centrifugation in step (ii) is performed at a speed of 10000 to 15000r/min, such as 10000, 11000, 12000, 13000, 14000 or 15000r/min, but not limited to the recited values, and other values not recited within the above-mentioned range of values are also applicable.
Preferably, the washing in step (ii) comprises washing with anhydrous ethanol and deionized water alternately for 2 to 4 times. It is to be noted that the cleaning with the absolute ethanol and the deionized water in this order is regarded as one alternate cleaning.
In a preferred embodiment of the present invention, the polyvinylpyrrolidone in step (1) has a molecular weight of 5000 to 25000, for example, 5000, 10000, 15000, 20000, 25000, etc., but the molecular weight is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
Preferably, in step (1), the mass ratio of the polystyrene microspheres to the polyvinylpyrrolidone is (1-2) 1, for example, 1.
Preferably, the first solvent of step (1) comprises absolute ethanol.
Preferably, the solid-to-liquid ratio of the polystyrene microspheres and the first solvent in step (1) is 1g (200 to 300) mL, for example, 1g.
Preferably, the temperature of the primary heating in the step (1) is 30 to 100 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
Preferably, the time for one heating in step (1) is 30 to 60min, such as 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the recited values, and other values not recited in the above range of values are also applicable.
As a preferable technical scheme of the invention, the titanate in the titanate solution in the step (2) is tetrabutyl titanate.
Preferably, the solvent of the titanate solution of step (2) comprises anhydrous ethanol.
Preferably, the titanate solution in step (2) has a solid-to-liquid ratio of 1g (50-100) mL, such as 1g.
Preferably, in step (2), the volume ratio of the titanate solution to the first mixed solution is (1-5): 1, for example, 1.
Preferably, the temperature of the secondary heating in the step (2) is 30 to 100 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the secondary heating time in step (2) is 200-300 min, such as 200min, 210min, 230min, 250min, 270min, 290min or 300min, but not limited to the recited values, and other unrecited values in the above-mentioned value range are also applicable.
In a preferred embodiment of the present invention, the reaction time in step (3) is 60 to 180min, for example, 60min, 80min, 100min, 120min, 140min, 150min, 160min, or 180min, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the centrifugation in step (3) is performed at a speed of 5000 to 10000r/min, such as 5000r/min, 6000r/min, 7000r/min, 8000r/min, 9000r/min or 10000r/min, but not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
Preferably, the washing in step (3) comprises washing with anhydrous ethanol and deionized water alternately for 2-4 times. It is to be noted that the cleaning with absolute ethanol and deionized water in this order is regarded as one-time alternate cleaning.
As a preferred embodiment of the present invention, the molecular weight of the polyethylene glycol in the step (4) is 10000 to 20000, for example 10000, 11000, 13000, 15000, 17000, 18000 or 20000, but the molecular weight is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
Preferably, in the step (4), the mass ratio of the citric acid, the glycol, the polyethylene glycol and the titanium dioxide-polystyrene microspheres is 5.
Preferably, the solvent of the ammonium cerium nitrate solution in the step (4) is a mixed solvent of anhydrous ethanol and deionized water in a volume ratio of (5-10) 1, such as 5.
Preferably, the molar concentration of the cerium ammonium nitrate solution in step (4) is 1 to 1.5mmol/L, such as 1mmol/L, 1.1mmol/L, 1.2mmol/L, 1.3mmol/L, 1.4mmol/L or 1.5mmol/L, but is not limited to the recited values, and other values not recited within the above numerical range are also applicable.
Preferably, in step (4), the mass ratio of cerium ammonium nitrate to citric acid in the cerium ammonium nitrate solution is (1.25 to 1.5): 1, for example, 1.25.
Preferably, the stirring time in step (4) is 400-500 min, such as 400min, 410min, 430min, 450min, 460min, 480min or 500min, but not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the temperature of the calcination in step (4) is 400 to 600 ℃, for example, 400 ℃, 430 ℃, 450 ℃, 480 ℃, 500 ℃, 530 ℃, 550 ℃, 580 ℃ or 600 ℃, but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the calcination temperature in step (4) is 120-240 min, such as 120min, 140min, 150min, 160min, 180min, 200min, 220min or 240min, but not limited to the recited values, and other unrecited values in the above-mentioned range of values are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Sequentially adding polystyrene microspheres and polyvinylpyrrolidone with the molecular weight of 5000-25000 into absolute ethyl alcohol according to the mass ratio of (1-2) to 1, controlling the solid-to-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g (200-300) mL, and carrying out primary heating at 30-100 ℃ for 30-60 min to obtain a first mixed solution;
the preparation method of the polystyrene microsphere comprises the following steps:
(i) Sequentially adding sodium dodecyl sulfate and styrene into deionized water according to the mass ratio of 1 (200-300), controlling the solid-to-liquid ratio of the sodium dodecyl sulfate to the deionized water to be 1g (1500-2000) mL, and carrying out primary heating at 30-100 ℃ for 30-60 min to obtain a mixed solution a;
(ii) Adding a potassium persulfate aqueous solution into the mixed solution a in the step (i), wherein the solid-to-liquid ratio of the potassium persulfate aqueous solution is 1g (50-100) mL, the volume ratio of the mixed solution a to the potassium persulfate aqueous solution is controlled to be (5-10): 1, reheating for 300-500 min at 30-100 ℃ to obtain a mixed solution b, sequentially centrifuging, washing and drying at the rotating speed of 10000-15000 r/min, wherein the washing comprises alternately washing 2-4 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres;
(2) Dissolving tetrabutyl titanate in absolute ethyl alcohol, controlling the solid-to-liquid ratio to be 1g (50-100) mL, adding the obtained tetrabutyl titanate solution into the first mixed solution obtained in the step (1), controlling the volume ratio of the titanate solution to the first mixed solution to be (1-5): 1, and carrying out secondary heating for 200-300 min at the temperature of 30-100 ℃ to obtain a second mixed solution;
(3) Reacting the second mixed solution obtained in the step (2) for 60-180 min at 100-150 ℃ by a solvothermal method, and sequentially performing centrifugation, washing and drying at the rotating speed of 5000-10000 r/min, wherein the washing comprises alternately washing with absolute ethyl alcohol and deionized water for 2-4 times to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding citric acid, ethylene glycol, polyethylene glycol with the molecular weight of 10000-20000 and the titanium dioxide-polystyrene microspheres in the step (3) into a ceric ammonium nitrate solution according to the mass ratio of 5-5 to 60, wherein the solvent of the ceric ammonium nitrate solution is a mixed solvent of absolute ethyl alcohol and deionized water in a volume ratio of (5-10) to 1, the molar concentration is 1-1.5 mmol/L, the mass ratio of the ceric ammonium nitrate to the citric acid in the ceric ammonium nitrate solution is controlled to be (1.25-1.5) to 1, stirring for 400-500 min to obtain a sol system, and calcining for 120-240 min at 400-600 ℃ to obtain the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material.
It is worth to be noted that the raw materials adopted in the preparation method of the invention comprise sodium dodecyl sulfate, styrene, potassium persulfate, polyvinylpyrrolidone, absolute ethyl alcohol, tetrabutyl titanate, citric acid, ethylene glycol, polyethylene glycol, ammonium ceric nitrate and the like, and the purity of the raw materials is above industrial grade.
It is worth to say that the preparation method of the invention comprises the following steps: firstly, styrene is taken as a raw material, sodium dodecyl sulfate is taken as a surfactant, potassium persulfate is taken as an initiator, and an emulsion polymerization method is adopted to prepare polystyrene microspheres with uniform particles, so that a larger specific surface area is provided for subsequent titanium dioxide loading; then, tetrabutyl titanate is used as a titanium source, and a layer of anatase crystal form titanium dioxide with a stable structure is coated on the surface of the polystyrene microsphere by adopting a solvothermal method, so that the agglomeration phenomenon of the nano titanium dioxide is reduced, and the exposure of an active crystal face of the nano titanium dioxide is increased; finally, cerium ammonium nitrate is used as a rare earth doping element, and cerium is doped into the anatase crystal type titanium dioxide coated on the surface by a sol-gel and hard template method by controlling reaction conditions and material ratio, so that the antibacterial activity of the titanium dioxide under visible light and darkness is improved; the prepared cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material is of a hollow spherical structure, has the advantages of controllable structure, good stability, high load capacity, uniform particles, good dispersibility, difficult agglomeration and the like, has an antibacterial function under visible light and dark conditions, is high in light energy utilization rate and excellent in antibacterial performance, and can be widely applied to the antibacterial field.
The second objective of the present invention is to provide a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial obtained by the preparation method of the first objective, wherein the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial has a hollow spherical structure, and the titanium dioxide is in an anatase crystal form.
It is worth to say that the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material is of a hollow structure obtained by calcination, and the stability of the structure and the utilization rate of light energy can be effectively guaranteed.
The third purpose of the invention is to provide the application of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material in the second purpose, and the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material is used for antibiosis.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) The preparation method comprises the steps of preparing polystyrene microspheres, coating a layer of anatase crystal form titanium dioxide on the surfaces of the polystyrene microspheres by a solvothermal method at a temperature of 100-150 ℃ to obtain titanium dioxide-polystyrene microspheres, and finally doping cerium into the anatase crystal form titanium dioxide coated on the surfaces of the polystyrene microspheres, so that the prepared cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material is of a hollow spherical structure, has the advantages of controllable structure, good stability, high load capacity, uniform particles, good dispersibility, difficult agglomeration and the like, has a function under visible light and dark antibacterial conditions, is high in light energy utilization rate and excellent in antibacterial performance, and can be widely applied to the antibacterial field;
(2) The preparation method provided by the invention preferably adopts styrene as a raw material, sodium dodecyl sulfate as a surfactant and potassium persulfate as an initiator, adopts an emulsion polymerization method to prepare the polystyrene microspheres with uniform particles, and can provide a larger specific surface area for subsequent titanium dioxide loading.
Drawings
FIG. 1 is a scanning electron micrograph of polystyrene microspheres obtained by the preparation method described in example 1;
FIG. 2 is a scanning electron microscope image of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial obtained in example 1;
FIG. 3 is an EDS (electron-directed Spectroscopy) spectrum of titanium element of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in example 1;
FIG. 4 is an EDS energy spectrum of cerium doped titanium dioxide-polystyrene microsphere composite antibacterial obtained in example 1;
FIG. 5 is a graph showing the distribution of the particle size of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial obtained in example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, which comprises the following steps:
(1) Sequentially adding 0.08g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with the molecular weight of 5000 into 20mL of absolute ethyl alcohol according to the mass ratio of 1.33, controlling the solid-to-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g and 250mL, and carrying out primary heating at 30 ℃ for 30min to obtain a first mixed solution;
the preparation method of the polystyrene microsphere comprises the following steps:
(i) Sequentially adding 0.03g of sodium dodecyl sulfate and 9.0g of styrene into 50mL of deionized water according to a mass ratio of 1;
(ii) Dissolving 0.1g of potassium persulfate in 10mL of deionized water to obtain a potassium persulfate aqueous solution with a solid-to-liquid ratio of 1g of 100mL, adding the potassium persulfate aqueous solution into the mixed solution a in the step (i), controlling the volume ratio of the mixed solution a to the potassium persulfate aqueous solution to be 5, reheating at 70 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at the rotation speed of 10000r/min, wherein the washing comprises alternately washing 3 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres; the scanning electron micrograph of the polystyrene microsphere is shown in figure 1, and as can be seen from figure 1, the polystyrene microsphere has uniform particles and good dispersibility;
(2) Dissolving 0.3g of tetrabutyl titanate in 30mL of absolute ethyl alcohol, controlling the solid-liquid ratio to be 1g of 100mL, adding the obtained tetrabutyl titanate solution into the first mixed solution in the step (1), controlling the volume ratio of the titanate solution to the first mixed solution to be 1.5;
(3) Reacting the second mixed solution obtained in the step (2) at 100 ℃ for 60min by a solvothermal method, and sequentially centrifuging, washing and drying at the rotating speed of 5000r/min, wherein the washing comprises alternately cleaning for 3 times by adopting absolute ethyl alcohol and deionized water to obtain titanium dioxide-polystyrene microspheres;
(4) Adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with the molecular weight of 10000 and 0.04g of the titanium dioxide-polystyrene microspheres obtained in the step (3) into a ceric ammonium nitrate solution in sequence according to a mass ratio of 5.
A scanning electron microscope image of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in the example 1 is shown in fig. 2, and it can be seen from fig. 2 that the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in the example has the advantages of good stability, uniform particles, good dispersibility, difficult agglomeration and the like; an EDS (electron-directed Spectroscopy) spectrum of the titanium element of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in example 1 is shown in FIG. 3, and it can be seen from FIG. 3 that titanium dioxide is uniformly coated on the surface of a polystyrene microsphere; an EDS (energy dispersive spectroscopy) of a cerium element of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in example 1 is shown in fig. 4, and as can be seen from fig. 4, cerium is successfully doped into the titanium dioxide-polystyrene microsphere; the distribution diagram of the particle size of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial obtained in example 1 is shown in fig. 5, and it can be seen from fig. 5 that the particle size distribution of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial obtained in this example is uniform and the average particle size is 270nm.
Example 2
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, which comprises the following steps:
(1) Sequentially adding 0.1g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with the molecular weight of 8000 into 20mL of absolute ethyl alcohol according to the mass ratio of 1.67 to 1, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g and 200mL, and carrying out primary heating at 30 ℃ for 30min to obtain a first mixed solution;
the preparation method of the polystyrene microsphere comprises the following steps:
(i) Sequentially adding 0.04g of sodium dodecyl sulfate and 10.0g of styrene into 60mL of deionized water according to a mass ratio of 1:250, namely, controlling the solid-to-liquid ratio of the sodium dodecyl sulfate to the deionized water to be about 1g;
(ii) Dissolving 0.1g of potassium persulfate in 10mL of deionized water to obtain a potassium persulfate aqueous solution with a solid-to-liquid ratio of 1g of 100mL, adding the potassium persulfate aqueous solution into the mixed solution a in the step (i), controlling the volume ratio of the mixed solution a to the potassium persulfate aqueous solution to be 6, reheating at 80 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotation speed of 10000r/min, wherein the washing comprises alternately washing 3 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres;
(2) Dissolving 0.3g of tetrabutyl titanate in 30mL of anhydrous ethanol, controlling the solid-to-liquid ratio to be 1g of 100100mL, adding the obtained tetrabutyl titanate solution into the first mixed solution in the step (1), controlling the volume ratio of the titanate solution to the first mixed solution to be 1.5;
(3) Reacting the second mixed solution obtained in the step (2) at 100 ℃ for 60min by a solvothermal method, and sequentially centrifuging, washing and drying at the rotating speed of 5000r/min, wherein the washing comprises alternately cleaning for 3 times by adopting absolute ethyl alcohol and deionized water to obtain titanium dioxide-polystyrene microspheres;
(4) Adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with the molecular weight of 10000 and 0.04g of the titanium dioxide-polystyrene microspheres obtained in the step (3) into a ceric ammonium nitrate solution in sequence according to a mass ratio of 5.
Example 3
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, which comprises the following steps:
(1) Sequentially adding 0.1g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with the molecular weight of 8000 into 20mL of absolute ethyl alcohol according to the mass ratio of 1.67, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1 g;
the preparation method of the polystyrene microsphere comprises the following steps:
(i) Sequentially adding 0.04g of sodium dodecyl sulfate and 10.0g of styrene into 60mL of deionized water according to a mass ratio of 1;
(ii) Dissolving 0.1g of potassium persulfate in 6mL of deionized water to obtain a potassium persulfate aqueous solution with a solid-to-liquid ratio of 1g of 60mL, adding the potassium persulfate aqueous solution into the mixed solution a in the step (i), controlling the volume ratio of the mixed solution a to the potassium persulfate aqueous solution to be 10, reheating at 80 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at the rotation speed of 10000r/min, wherein the washing comprises alternately washing 3 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres;
(2) Dissolving 0.3g of tetrabutyl titanate in 30mL of absolute ethyl alcohol, controlling the solid-liquid ratio to be 1g of 100mL, adding the obtained tetrabutyl titanate solution into the first mixed solution in the step (1), controlling the volume ratio of the titanate solution to the first mixed solution to be 1.5;
(3) Reacting the second mixed solution obtained in the step (2) at 100 ℃ for 90min by a solvothermal method, and sequentially centrifuging, washing and drying at the rotating speed of 5000r/min, wherein the washing comprises alternately cleaning for 3 times by adopting absolute ethyl alcohol and deionized water to obtain titanium dioxide-polystyrene microspheres;
(4) Adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with the molecular weight of 10000 and 0.04g of the titanium dioxide-polystyrene microspheres obtained in the step (3) into a ceric ammonium nitrate solution in sequence according to a mass ratio of 5.
Example 4
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, which comprises the following steps:
(1) Sequentially adding 0.1g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with the molecular weight of 24000 into 20mL of absolute ethyl alcohol according to the mass ratio of 1.67 to 1, controlling the solid-to-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g and 200mL, and carrying out primary heating at 50 ℃ for 30min to obtain a first mixed solution;
the preparation method of the polystyrene microsphere comprises the following steps:
(i) Sequentially adding 0.04g of sodium dodecyl sulfate and 10.0g of styrene into 70mL of deionized water according to a mass ratio of 1;
(ii) Dissolving 0.1g of potassium persulfate in 7mL of deionized water to obtain a 1 g/70mL potassium persulfate aqueous solution, adding the potassium persulfate aqueous solution into the mixed solution a in the step (i), controlling the volume ratio of the mixed solution a to the potassium persulfate aqueous solution to be 10, heating again at 100 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at the rotation speed of 15000r/min, wherein the washing comprises alternately washing 3 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres;
(2) Dissolving 0.3g of tetrabutyl titanate in 30mL of absolute ethyl alcohol, controlling the solid-liquid ratio to be 1g of 100mL, adding the obtained tetrabutyl titanate solution into the first mixed solution in the step (1), controlling the volume ratio of the titanate solution to the first mixed solution to be 1.5;
(3) Reacting the second mixed solution obtained in the step (2) at 150 ℃ for 60min by a solvothermal method, and sequentially centrifuging, washing and drying at the rotating speed of 5000r/min, wherein the washing comprises alternately cleaning for 3 times by adopting absolute ethyl alcohol and deionized water to obtain titanium dioxide-polystyrene microspheres;
(4) Adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with the molecular weight of 20000 and 0.04g of the titanium dioxide-polystyrene microspheres obtained in the step (3) into a ceric ammonium nitrate solution in sequence according to a mass ratio of 5.
Example 5
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, which comprises the following steps:
(1) Sequentially adding 0.12g of polystyrene microspheres and 0.08g of polyvinylpyrrolidone with the molecular weight of 8000 into 25mL of absolute ethyl alcohol according to the mass ratio of 1.5, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g and 208mL, and carrying out primary heating at 30 ℃ for 30min to obtain a first mixed solution;
the preparation method of the polystyrene microsphere comprises the following steps:
(i) Sequentially adding 0.05g of sodium dodecyl sulfate and 10.0g of styrene into 100mL of deionized water according to a mass ratio of 1;
(ii) Dissolving 0.1g of potassium persulfate in 10mL of deionized water to obtain a potassium persulfate aqueous solution with a solid-to-liquid ratio of 1g of 100mL, adding the potassium persulfate aqueous solution into the mixed solution a in the step (i), controlling the volume ratio of the mixed solution a to the potassium persulfate aqueous solution to be 10, reheating for 500min at 80 ℃ to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotation speed of 10000r/min, wherein the washing comprises alternately washing 3 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres;
(2) Dissolving 0.4g of tetrabutyl titanate in 30mL of anhydrous ethanol, controlling the solid-to-liquid ratio to be 1g of 75mL, adding the obtained tetrabutyl titanate solution into the first mixed solution in the step (1), controlling the volume ratio of the titanate solution to the first mixed solution to be 1.2;
(3) Reacting the second mixed solution obtained in the step (2) at 100 ℃ for 60min by a solvothermal method, and sequentially performing centrifugation, washing and drying at the rotating speed of 10000r/min, wherein the washing comprises alternately cleaning for 3 times by adopting absolute ethyl alcohol and deionized water to obtain titanium dioxide-polystyrene microspheres;
(4) Adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with the molecular weight of 10000 and 0.04g of the titanium dioxide-polystyrene microspheres obtained in the step (3) into a ceric ammonium nitrate solution in sequence according to a mass ratio of 5.
Example 6
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, which comprises the following steps:
(1) Sequentially adding 0.12g of polystyrene microspheres and 0.08g of polyvinylpyrrolidone with the molecular weight of 12000 into 25mL of absolute ethyl alcohol according to the mass ratio of 1.5, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g and 208mL, and carrying out primary heating at 30 ℃ for 30min to obtain a first mixed solution;
the preparation method of the polystyrene microsphere comprises the following steps:
(i) Sequentially adding 0.05g of sodium dodecyl sulfate and 10.0g of styrene into 80mL of deionized water according to a mass ratio of 1;
(ii) Dissolving 0.1g of potassium persulfate in 10mL of deionized water to obtain a potassium persulfate aqueous solution with a solid-to-liquid ratio of 1g;
(2) Dissolving 0.5g of tetrabutyl titanate in 30mL of anhydrous ethanol, controlling a solid-to-liquid ratio to be 1g and 60mL, adding the obtained tetrabutyl titanate solution into the first mixed solution obtained in the step (1), controlling a volume ratio of the titanate solution to the first mixed solution to be 1.2;
(3) Reacting the second mixed solution obtained in the step (2) at 110 ℃ for 90min by a solvothermal method, and sequentially performing centrifugation, washing and drying at the rotating speed of 10000r/min, wherein the washing comprises alternately cleaning for 3 times by adopting absolute ethyl alcohol and deionized water to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with the molecular weight of 10000 and 0.04g of the titanium dioxide-polystyrene microspheres obtained in the step (3) into a cerium ammonium nitrate solution according to a mass ratio of 5.
Example 7
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, which comprises the following steps:
(1) Sequentially adding 0.1g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with the molecular weight of 12000 into 20mL of absolute ethyl alcohol according to the mass ratio of 1.67, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g and 200mL, and carrying out primary heating at 30 ℃ for 30min to obtain a first mixed solution;
the preparation method of the polystyrene microsphere comprises the following steps:
(i) Sequentially adding 0.03g of sodium dodecyl sulfate and 6.0g of styrene into 50mL of deionized water according to a mass ratio of 1;
(ii) Dissolving 0.1g of potassium persulfate in 10mL of deionized water to obtain a potassium persulfate aqueous solution with a solid-to-liquid ratio of 1g of 100mL, adding the potassium persulfate aqueous solution into the mixed solution a in the step (i), controlling the volume ratio of the mixed solution a to the potassium persulfate aqueous solution to be 5, reheating at 85 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotation speed of 10000r/min, wherein the washing comprises alternately washing 3 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres;
(2) Dissolving 0.4g of tetrabutyl titanate in 30mL of absolute ethyl alcohol, controlling the solid-to-liquid ratio to be 1g of 75mL, adding the obtained tetrabutyl titanate solution into the first mixed solution in the step (1), controlling the volume ratio of the titanate solution to the first mixed solution to be 1.5;
(3) Reacting the second mixed solution obtained in the step (2) at 105 ℃ for 90min by a solvothermal method, and sequentially performing centrifugation, washing and drying at the rotating speed of 10000r/min, wherein the washing comprises alternately cleaning for 3 times by adopting absolute ethyl alcohol and deionized water to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with the molecular weight of 10000 and 0.04g of the titanium dioxide-polystyrene microspheres obtained in the step (3) into a cerium ammonium nitrate solution according to a mass ratio of 5.
Example 8
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial, and compared with embodiment 7, the difference is only that: reducing the dosage of the tetrabutyl titanate in the step (2) from "0.4g" to "0.2g", namely, adjusting the solid-to-liquid ratio of the tetrabutyl titanate solution from "1 g.
Example 9
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial, and compared with embodiment 7, the difference is only that: increasing the dosage of the tetrabutyl titanate in the step (2) from ' 0.4g ' to ' 0.7g ', namely, adjusting the solid-to-liquid ratio of the tetrabutyl titanate solution from ' 1g.
Example 10
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial, and compared with embodiment 7, the difference is only that: reducing the calcining temperature of the step (4) from '500 ℃ to' 300 ℃.
Example 11
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material, which is different from the preparation method of embodiment 7 only in that: raising the calcination temperature of the step (4) from 500 ℃ to 700 ℃.
Example 12
The embodiment provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial, and compared with embodiment 7, the difference is only that: and (3) reducing the first heating time in the step (i) from '30 min' to '20 min'.
Comparative example 1
The comparative example provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial, and compared with example 7, the differences are only that: adjusting the temperature of the solvothermal reaction in the step (3) from 105 ℃ to 80 ℃.
Comparative example 2
The comparative example provides a preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial, and compared with example 7, the differences are only that: adjusting the temperature of the solvothermal reaction in the step (3) from 105 ℃ to 170 ℃.
Respectively weighing two 0.01g samples of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in the above examples and comparative examples, and respectively putting the two 0.01g samples into two 10mL samples containing 10 7 cfu/mL escherichia coli physiological saline solution and stirring and balancing for 30min; simulating sunlight by using a 500W xenon lamp, and stirring and irradiating for 30min under the irradiation of visible light to obtain the antibacterial rate A of escherichia coli; stirring the other part for 30min in the dark to obtain the antibacterial rate B of the Escherichia coli; specific results are shown in table 1.
TABLE 1
As can be seen from table 1:
(1) The cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material prepared by the preparation method is of a hollow spherical structure, has the advantages of controllable structure, good stability, high load capacity, uniform particles, good dispersibility, difficult agglomeration and the like, has an antibacterial function under visible light and dark conditions, has the antibacterial rate A of escherichia coli under visible light irradiation up to 99.81 percent and the antibacterial rate B of escherichia coli under dark conditions up to 35.41 percent, has high light energy utilization rate and excellent antibacterial performance, and can be widely applied to the antibacterial field;
(2) Comparing the example 7 with the examples 8 and 9, the antibacterial effect is obviously reduced due to the reduction of the dosage of tetrabutyl titanate corresponding to the example 8, while the antibacterial effect is deteriorated due to the excessive dosage of tetrabutyl titanate corresponding to the example 9, the generated anatase crystal form titanium dioxide is easy to agglomerate, and the surface of the polystyrene microsphere is coated unevenly;
(3) Comparing the example 7 with the examples 10 and 11, the calcining temperature of the example 10 is reduced to 300 ℃, which results in lower hollow degree of the prepared cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material and obviously reduced antibacterial effect, while the calcining temperature of the example 11 is increased to 700 ℃, which results in the destruction of the shape of anatase crystal form titanium dioxide and further results in the deterioration of the antibacterial effect of the prepared cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material due to the rupture;
(4) Comparing example 7 with example 12, since the first heating time in step (i) is related to the final aging degree of the mixed solution a, and further to the mechanical stability of the polystyrene microspheres as the carrier, example 12 reduces the first heating time in step (i) from "30min" to "20min", resulting in a deterioration of the antibacterial effect;
(5) Comparing example 7 with comparative examples 1 and 2, in the preparation method of the present invention, a layer of anatase crystal form titanium dioxide with a stable structure is coated on the surface of the polystyrene microsphere by using a solvothermal method, and both comparative examples 1 and 2 can cause a part of the generated titanium dioxide to be still amorphous, thereby causing the antibacterial effect to be poor.
The present invention is described in detail by the above embodiments, but the present invention is not limited to the above detailed structural features, which means that the present invention must not be implemented by the above detailed structural features. It should be understood by those skilled in the art that any modifications, equivalent substitutions of selected elements of the present invention, additions of auxiliary elements, selection of specific forms, etc., are intended to fall within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (10)
1. A preparation method of a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material is characterized by comprising the following steps:
(1) Adding polystyrene microspheres and polyvinylpyrrolidone into a first solvent for primary heating to obtain a first mixed solution;
(2) Adding a titanate solution into the first mixed solution obtained in the step (1) for secondary heating to obtain a second mixed solution;
(3) Reacting the second mixed solution obtained in the step (2) at 100-150 ℃ by a solvothermal method, and sequentially centrifuging, washing and drying to obtain titanium dioxide-polystyrene microspheres;
(4) And (3) respectively adding citric acid, ethylene glycol, polyethylene glycol and the titanium dioxide-polystyrene microspheres obtained in the step (3) into a ceric ammonium nitrate solution, stirring to obtain a sol system, and calcining to obtain the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material.
2. The method according to claim 1, wherein the method for preparing polystyrene microspheres in step (1) comprises the following steps:
(i) Sequentially adding sodium dodecyl sulfate and styrene into deionized water for primary heating to obtain a mixed solution a;
(ii) And (e) adding a potassium persulfate aqueous solution into the mixed solution a obtained in the step (i) for reheating to obtain a mixed solution b, and sequentially centrifuging, washing and drying to obtain the polystyrene microsphere.
3. The method according to claim 2, wherein the mass ratio of sodium lauryl sulfate to styrene in step (i) is 1 (200-300);
preferably, the solid-to-liquid ratio of the sodium dodecyl sulfate to the deionized water in the step (i) is 1g (1500-2000) mL;
preferably, the temperature of the first heating in the step (i) is 30 to 100 ℃;
preferably, the time for the first heating in step (i) is 30-60 min;
preferably, the solid-to-liquid ratio of the potassium persulfate aqueous solution in the step (ii) is 1g (50-100) mL;
preferably, the volume ratio of the mixed solution a to the potassium persulfate aqueous solution in the step (ii) is (5-10): 1;
preferably, the reheating temperature in the step (ii) is 30-100 ℃;
preferably, the reheating time in step (ii) is 300-500 min;
preferably, the rotation speed of the centrifugation in the step (ii) is 10000-15000 r/min;
preferably, the washing in step (ii) comprises washing with absolute ethyl alcohol and deionized water alternately for 2 to 4 times.
4. The process according to any one of claims 1 to 3, wherein the polyvinylpyrrolidone of step (1) has a molecular weight of 5000 to 25000;
preferably, the mass ratio of the polystyrene microspheres to the polyvinylpyrrolidone in the step (1) is (1-2): 1;
preferably, the first solvent of step (1) comprises absolute ethanol;
preferably, the solid-to-liquid ratio of the polystyrene microspheres and the first solvent in the step (1) is 1g (200-300) mL;
preferably, the temperature of the primary heating in the step (1) is 30-100 ℃;
preferably, the time for one heating in the step (1) is 30-60 min.
5. The method according to any one of claims 1 to 4, wherein the titanate in the titanate solution of step (2) is tetrabutyl titanate;
preferably, the solvent of the titanate solution of step (2) comprises anhydrous ethanol;
preferably, the solid-to-liquid ratio of the titanate solution in the step (2) is 1g (50-100) mL;
preferably, the volume ratio of the titanate solution to the first mixed solution in the step (2) is (1-5): 1;
preferably, the temperature of the secondary heating in the step (2) is 30-100 ℃;
preferably, the time of the secondary heating in the step (2) is 200-300 min.
6. The process according to any one of claims 1 to 5, wherein the reaction time in the step (3) is 60 to 180min;
preferably, the rotation speed of the centrifugation in the step (3) is 5000-10000 r/min;
preferably, the washing in step (3) comprises washing with absolute ethyl alcohol and deionized water alternately for 2-4 times.
7. The method according to any one of claims 1 to 6, wherein the polyethylene glycol of step (4) has a molecular weight of 10000 to 20000;
preferably, the mass ratio of the citric acid, the glycol, the polyethylene glycol and the titanium dioxide-polystyrene microspheres in the step (4) is (5);
preferably, the solvent of the ammonium ceric nitrate solution in the step (4) is a mixed solvent of absolute ethyl alcohol and deionized water in a volume ratio of (5-10): 1;
preferably, the molar concentration of the ammonium cerium nitrate solution in the step (4) is 1-1.5 mmol/L;
preferably, in the step (4), the mass ratio of the ammonium cerium nitrate and the citric acid in the ammonium cerium nitrate solution is (1.25-1.5): 1;
preferably, the stirring time in the step (4) is 400-500 min;
preferably, the calcining temperature in the step (4) is 400-600 ℃;
preferably, the calcining temperature in the step (4) is 120-240 min.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) Sequentially adding polystyrene microspheres and polyvinylpyrrolidone with the molecular weight of 5000-25000 into absolute ethyl alcohol according to the mass ratio of (1-2) to 1, controlling the solid-to-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g (200-300) mL, and carrying out primary heating at 30-100 ℃ for 30-60 min to obtain a first mixed solution;
the preparation method of the polystyrene microsphere comprises the following steps:
(i) Sequentially adding sodium dodecyl sulfate and styrene into deionized water according to the mass ratio of 1 (200-300), controlling the solid-to-liquid ratio of the sodium dodecyl sulfate to the deionized water to be 1g (1500-2000) mL, and carrying out primary heating at 30-100 ℃ for 30-60 min to obtain a mixed solution a;
(ii) Adding a potassium persulfate aqueous solution into the mixed solution a obtained in the step (i), wherein the solid-to-liquid ratio of the potassium persulfate aqueous solution is 1g (50-100) mL, the volume ratio of the mixed solution a to the potassium persulfate aqueous solution is controlled to be (5-10): 1, reheating is carried out for 300-500 min at the temperature of 30-100 ℃ to obtain a mixed solution b, and centrifuging, washing and drying are sequentially carried out at the rotating speed of 10000-15000 r/min, wherein the washing comprises alternately cleaning 2-4 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres;
(2) Dissolving tetrabutyl titanate in absolute ethyl alcohol, controlling the solid-to-liquid ratio to be 1g (50-100) mL, adding the obtained tetrabutyl titanate solution into the first mixed solution obtained in the step (1), controlling the volume ratio of the titanate solution to the first mixed solution to be (1-5): 1, and carrying out secondary heating for 200-300 min at the temperature of 30-100 ℃ to obtain a second mixed solution;
(3) Reacting the second mixed solution obtained in the step (2) for 60-180 min at 100-150 ℃ by a solvothermal method, and sequentially performing centrifugation, washing and drying at the rotating speed of 5000-10000 r/min, wherein the washing comprises alternately washing with absolute ethyl alcohol and deionized water for 2-4 times to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding citric acid, ethylene glycol, polyethylene glycol with the molecular weight of 10000-20000 and the titanium dioxide-polystyrene microspheres in the step (3) into a ceric ammonium nitrate solution according to the mass ratio of 5-5 to 60, wherein the solvent of the ceric ammonium nitrate solution is a mixed solvent of absolute ethyl alcohol and deionized water in a volume ratio of (5-10) to 1, the molar concentration is 1-1.5 mmol/L, the mass ratio of the ceric ammonium nitrate to the citric acid in the ceric ammonium nitrate solution is controlled to be (1.25-1.5) to 1, stirring for 400-500 min to obtain a sol system, and calcining for 120-240 min at 400-600 ℃ to obtain the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material.
9. The cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained by the preparation method of any one of claims 1 to 8, wherein the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material is of a hollow spherical structure, and titanium dioxide is in an anatase crystal form.
10. The use of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material according to claim 9, wherein the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material is used for antibiosis.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07196424A (en) * | 1993-12-28 | 1995-08-01 | Japan Synthetic Rubber Co Ltd | Antimicrobial agent consisting of complex particle or hollow particle |
| CN101274246A (en) * | 2007-12-26 | 2008-10-01 | 中国科学院上海硅酸盐研究所 | Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon |
| CN101659773A (en) * | 2009-09-28 | 2010-03-03 | 浙江理工大学 | Nano TiO2-polystyrene microsphere compound and preparation method and application thereof |
| CN104761741A (en) * | 2015-04-17 | 2015-07-08 | 陕西科技大学 | Preparation method for hollow titanium dioxide/polyacrylate composite film with insulation performance |
| CN112225247A (en) * | 2020-10-20 | 2021-01-15 | 桂林理工大学 | Nano titanium dioxide open hollow sphere and preparation method thereof |
| CN113287635A (en) * | 2021-05-12 | 2021-08-24 | 湘潭大学 | Preparation method of doped metal oxide nano-particles, dispersion or powder for resisting bacteria and preventing mildew |
-
2022
- 2022-09-16 CN CN202211129753.3A patent/CN115486443B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07196424A (en) * | 1993-12-28 | 1995-08-01 | Japan Synthetic Rubber Co Ltd | Antimicrobial agent consisting of complex particle or hollow particle |
| CN101274246A (en) * | 2007-12-26 | 2008-10-01 | 中国科学院上海硅酸盐研究所 | Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon |
| CN101659773A (en) * | 2009-09-28 | 2010-03-03 | 浙江理工大学 | Nano TiO2-polystyrene microsphere compound and preparation method and application thereof |
| CN104761741A (en) * | 2015-04-17 | 2015-07-08 | 陕西科技大学 | Preparation method for hollow titanium dioxide/polyacrylate composite film with insulation performance |
| CN112225247A (en) * | 2020-10-20 | 2021-01-15 | 桂林理工大学 | Nano titanium dioxide open hollow sphere and preparation method thereof |
| CN113287635A (en) * | 2021-05-12 | 2021-08-24 | 湘潭大学 | Preparation method of doped metal oxide nano-particles, dispersion or powder for resisting bacteria and preventing mildew |
Non-Patent Citations (3)
| Title |
|---|
| ARNOUT IMHOF: ""Preparation and Characterization of Titania-Coated Polystyrene Spheres and Hollow Titania Shells"", 《LANGMUIR》, vol. 17, pages 3580 * |
| 冯炫;杨泠;关秋;刘应亮;: "掺银二氧化钛空心球的制备及其抗菌性能研究", 生态科学, no. 03, pages 145 - 147 * |
| 刘雪峰;涂铭旌;: "稀土负载型纳米二氧化钛抗菌剂的研制", 现代化工, no. 1, pages 145 * |
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