CN115486443B - 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 PDF

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CN115486443B
CN115486443B CN202211129753.3A CN202211129753A CN115486443B CN 115486443 B CN115486443 B CN 115486443B CN 202211129753 A CN202211129753 A CN 202211129753A CN 115486443 B CN115486443 B CN 115486443B
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titanium dioxide
solution
mixed solution
polystyrene microsphere
cerium
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CN115486443A (en
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李国标
张传奇
万印华
胡凯博
刘玉城
赵伯峰
王东
宋伟杰
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Ganjiang Innovation Academy of CAS
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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
    • 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
    • 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
    • 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

Abstract

The invention provides a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance, 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 between 100 and 150 ℃ to obtain titanium dioxide-polystyrene microspheres, and finally doping cerium into the surface-coated anatase crystal form titanium dioxide to obtain cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial substances; 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, uniform particles, good dispersibility, difficult agglomeration and the like, has antibacterial functions under visible light and dark conditions, has high light energy utilization rate and excellent antibacterial performance, and can be widely applied to the antibacterial field.

Description

Cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material and preparation method and application thereof
Technical Field
The invention relates to the field of nano antibacterial material preparation, in particular to a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material, 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 wastewater is treated, 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 energy band of the nano titanium dioxide is wider and only the ultraviolet light part in sunlight can be absorbed. Therefore, the industrial application of the nano titanium dioxide photocatalyst is limited due to the low light energy utilization rate and antibacterial efficiency of the nano titanium dioxide.
The microsphere structure can effectively improve the antibacterial performance by increasing the load capacity of the semiconductor and the exposure of the active crystal face. For example, chinese patent No. CN 101659773B discloses nano TiO 2 Polystyrene microsphere compound, preparation method and application thereof, which is a nano TiO loaded on the surface of a carrier of polystyrene 2 The microsphere has very high specific surface area and semiconductor loading capacity, so that the microsphere can achieve fast, efficient and broad-spectrum antibacterial effect under ultraviolet light. However, the patent must achieve the antibacterial effect under the light, and is a solid sphere, which does not fully exert the scattering effect of the hollow structure on light, and fails to improve the light capturing capability of the material.
The doping of rare earth elements can increase the crystal defect of the semiconductor to narrow the energy band, and can cause optical transition between the orbitals of the semiconductor 4F to increase the light energy utilization range while generating more widely generated electrons and holes. For example, chinese patent No. CN 104069847B discloses rare earth europium doped nano TiO 2 The preparation method of the hollow glass microsphere is a photocatalysis microsphere with core-shell structure and doped with rare earth element europium, the microsphere has excellent light absorption performance, and the doping of the rare earth element enables TiO to be realized 2 The absorbed light is red shifted, the light response range is widened to visible light, and the catalytic activity and the light energy utilization rate of the semiconductor are effectively improved.
However, the above technical solutions related to the composite antibacterial microspheres have problems, nano TiO 2 The polystyrene microsphere compound can only have antibacterial performance under ultraviolet light, and rare earth europium doped nano TiO 2 The hollow glass microsphere has limited semiconductor load capacity, and the composite antibacterial microsphere has the defects of nonuniform particles, poor dispersibility and the like, so that the light energy utilization efficiency and antibacterial activity of the composite antibacterial microsphere are limited.
Therefore, how to design and prepare the composite antibacterial microsphere with controllable structure, good stability, high load and antibacterial function under the 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 existing in the prior art, the invention provides a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance, 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 between 100 and 150 ℃ to obtain titanium dioxide-polystyrene microspheres, and finally doping cerium into the surface-coated anatase crystal form titanium dioxide to obtain cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial substances; 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, uniform particles, good dispersibility, difficult agglomeration and the like, has antibacterial functions under visible light and dark conditions, has high light energy utilization rate and excellent antibacterial performance, and can be widely applied to the antibacterial field.
To achieve the purpose, the invention adopts the following technical scheme:
the invention aims at providing a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which comprises the following steps:
(1) Adding polystyrene microspheres and polyvinylpyrrolidone into a first solvent for heating for one time to obtain a first mixed solution;
(2) Adding 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 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, glycol, polyethylene glycol and the titanium dioxide-polystyrene microsphere in the step (3) into an ammonium cerium nitrate solution, stirring to obtain a sol system, and calcining to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
According to the preparation method, polystyrene microspheres are used as carriers, a large specific surface area can be provided for titanium dioxide loading, then a layer of anatase crystal form titanium dioxide is coated on the surfaces of the polystyrene microspheres by a solvothermal method at a temperature of 100-150 ℃ to obtain the titanium dioxide-polystyrene microspheres, finally rare earth ion cerium is used for doping modification on the anatase crystal form titanium dioxide coated on the surfaces, so that the photoresponse range of the titanium dioxide-polystyrene microspheres is widened to visible light, and cerium ions can be released to enable the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material to have an antibacterial effect in darkness. 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, uniform particles, good dispersibility, difficult agglomeration and the like, has an antibacterial function under visible light and dark conditions, has high light energy utilization rate and excellent antibacterial performance, and can be widely applied to the antibacterial field.
The reaction temperature in the step (3) of the present invention is 100 to 150 ℃, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
As a preferable 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 first heating to obtain a mixed solution a;
(ii) And (3) adding a potassium persulfate aqueous solution into the mixed solution a in the step (i) for reheating to obtain a mixed solution b, and sequentially centrifuging, washing and drying to obtain the polystyrene microsphere.
The preparation method of the polystyrene microsphere takes styrene as a raw material, sodium dodecyl sulfate as a surfactant, potassium persulfate as an initiator, and adopts an emulsion polymerization method to prepare the polystyrene microsphere with uniform particles, thereby providing a larger specific surface area for subsequent titanium dioxide loading.
In the preferred embodiment of the present invention, the mass ratio of sodium dodecyl sulfate to styrene in step (i) is 1 (200-300), for example, 1:200, 1:210, 1:220, 1:230, 1:240, 1:250, 1:260, 1:270, 1:280, 1:290 or 1:300, etc., but not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
Preferably, the solid-to-liquid ratio of sodium dodecyl sulfate to deionized water in step (i) is 1g (1500-2000) mL, for example, 1g:1500mL, 1g:190 mL, or 1g:2000mL, etc., but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the temperature of the first heating in the step (i) is 30 to 100 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or the like, but the method is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
Preferably, the time of the first heating in step (i) is 30 to 60min, for example 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc., but not limited to the listed values, and other non-listed values within the above-mentioned range are equally 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 (50-100) mL, for example, 1g:50mL, 1g:60mL, 1g:70mL, 1g:80mL, 1g:90mL, or 1g:100mL, etc., but is not limited to the recited values, and other non-recited values within the above ranges are equally applicable.
Preferably, the volume ratio of the mixed solution a and the aqueous potassium persulfate solution in the step (ii) is (5-10): 1, for example, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but the present invention is not limited to the above-mentioned values, and other non-mentioned values within the above-mentioned ranges are equally applicable.
Preferably, the reheating temperature in step (ii) is 30 to 100 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, or 100 ℃, etc., but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the reheating time in step (ii) is 300-500 min, for example 300min, 330min, 350min, 380min, 400min, 430min, 450min, 470min or 500min, etc., but is not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
Preferably, the rotational speed of the centrifugation in step (ii) is 10000 to 15000r/min, for example 10000r/min, 11000r/min, 12000r/min, 13000r/min, 14000r/min or 15000r/min, etc., but is not limited to the values listed, and other non-listed values within the above-mentioned range are equally applicable.
Preferably, the washing of step (ii) comprises alternating washing with absolute ethanol and deionized water 2 to 4 times. It should be noted that the sequential washing with absolute ethanol and deionized water is considered to be an alternate washing.
In a preferred embodiment of the present invention, the polyvinylpyrrolidone in the step (1) has a molecular weight of 5000 to 25000, for example, 5000, 10000, 15000, 20000 or 25000, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
Preferably, the mass ratio of the polystyrene microsphere and the polyvinylpyrrolidone in the step (1) is (1-2): 1, for example, 1:1, 1.1:1, 1.3:1, 1.5:1, 1.6:1, 1.8:1 or 2:1, etc., but the invention is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the first solvent of step (1) comprises absolute ethanol.
Preferably, the solid-to-liquid ratio of the polystyrene microsphere and the first solvent in the step (1) is 1g (200 to 300) mL, for example, 1g:200mL, 1g:210mL, 1g:230mL, 1g:250mL, 1g:260mL, 1g:280mL or 1g:300mL, etc., but not limited to the recited values, and other non-recited values within the above-recited range are equally applicable.
Preferably, the temperature of the primary heating in the step (1) is 30 to 100 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or the like, but the temperature is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
Preferably, the time of the primary heating in the step (1) is 30 to 60min, for example, 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc., but not limited to the listed values, and other non-listed values within the above-mentioned range are equally 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 absolute ethanol.
Preferably, the solid-to-liquid ratio of the titanate solution in step (2) is 1g (50 to 100) mL, for example, 1g:50mL, 1g:60mL, 1g:70mL, 1g:80mL, 1g:90mL or 1g:100mL, etc., but not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the volume ratio of the titanate solution and the first mixed solution in the step (2) is (1-5): 1, for example, 1:1, 2:1, 3:1, 4:1 or 5:1, etc., but not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
Preferably, the temperature of the secondary heating in the step (2) is 30 to 100 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or the like, but the secondary heating is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
Preferably, the time of the secondary heating in the step (2) is 200 to 300min, for example, 200min, 210min, 230min, 250min, 270min, 290min or 300min, but not limited to the listed values, and other non-listed values in the above range are equally applicable.
In a preferred embodiment of the present invention, the reaction time in the step (3) is 60 to 180 minutes, for example, 60 minutes, 80 minutes, 100 minutes, 120 minutes, 140 minutes, 150 minutes, 160 minutes or 180 minutes, but the reaction time is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
Preferably, the rotational speed of the centrifugation in the step (3) is 5000 to 10000r/min, for example, 5000r/min, 6000r/min, 7000r/min, 8000r/min, 9000r/min or 10000r/min, etc., but not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
Preferably, the washing of step (3) comprises alternately washing with absolute ethanol and deionized water 2-4 times. It should be noted that the sequential washing with absolute ethanol and deionized water is considered to be an alternate washing.
In a preferred embodiment of the present invention, the polyethylene glycol in the step (4) has a molecular weight of 10000 to 20000, for example 10000, 11000, 13000, 15000, 17000, 18000 or 20000, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned numerical ranges are equally applicable.
Preferably, the mass ratio of the citric acid, the ethylene glycol, the polyethylene glycol and the titanium dioxide-polystyrene microsphere in the step (4) is 5:1000:60 (3-5), for example, 5:1000:60:3, 5:1000:60:3.5, 5:1000:60:4, 5:1000:60:4.5 or 5:1000:60:5, but not limited to the listed values, and other non-listed values in the above range are equally applicable.
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, for example, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but the present invention is not limited to the listed values, and other non-listed values in the above-mentioned range are equally applicable.
Preferably, the molar concentration of the ammonium cerium nitrate solution in the step (4) is 1 to 1.5mmol/L, for example, 1mmol/L, 1.1mmol/L, 1.2mmol/L, 1.3mmol/L, 1.4mmol/L, or 1.5mmol/L, etc., but not limited to the recited values, and other non-recited values within the above-recited range are equally applicable.
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, for example, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1 or 1.5:1, etc., but not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
Preferably, the stirring time in the step (4) is 400 to 500min, for example 400min, 410min, 430min, 450min, 460min, 480min or 500min, etc., but not limited to the listed values, and other non-listed values in the above-mentioned range are equally applicable.
Preferably, the temperature of the calcination in the step (4) is 400 to 600 ℃, for example 400 ℃, 430 ℃, 450 ℃, 480 ℃, 500 ℃, 530 ℃, 550 ℃, 580 ℃, 600 ℃, or the like, but the calcination is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
Preferably, the temperature of the calcination in the step (4) is 120 to 240min, for example 120min, 140min, 150min, 160min, 180min, 200min, 220min or 240min, etc., but the calcination is not limited to the listed values, and other non-listed values within the above-mentioned range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Sequentially adding polystyrene microspheres and polyvinylpyrrolidone with a molecular weight of 5000-25000 into absolute ethyl alcohol according to a mass ratio of (1-2) 1, controlling the solid-liquid ratio of the polystyrene microspheres and the absolute ethyl alcohol to be 1g (200-300) mL, and 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 (200-300), controlling the solid-liquid ratio of the sodium dodecyl sulfate and the deionized water to be 1g (1500-2000) mL, and heating for the first time 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, controlling the volume ratio of the mixed solution a to the potassium persulfate aqueous solution to be (5-10): 1, heating again at 30-100 ℃ for 300-500 min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at the rotating speed of 10000-15000 r/min, wherein the washing comprises alternately washing for 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 at 30-100 ℃ for 200-300 min to obtain a second mixed solution;
(3) Reacting the second mixed solution in the step (2) at 100-150 ℃ for 60-180 min by a solvothermal method, and sequentially centrifuging, washing and drying at a 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, glycol, polyethylene glycol with molecular weight of 10000-20000 and the titanium dioxide-polystyrene microsphere in the step (3) into a ceric ammonium nitrate solution according to the mass ratio of 5:1000:60, wherein the solvent of the ceric ammonium nitrate solution is a mixed solvent of absolute ethanol and deionized water with the volume ratio of (5-10): 1 and the molar concentration of 1-1.5 mmol/L, controlling the mass ratio of ceric ammonium nitrate and citric acid in the ceric ammonium nitrate solution to be (1.25-1.5): 1, stirring for 400-500 min to obtain a sol system, and calcining for 120-240 min at the temperature of 400-600 ℃ to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
The raw materials adopted in the preparation method comprise sodium dodecyl sulfate, styrene, potassium persulfate, polyvinylpyrrolidone, absolute ethyl alcohol, tetrabutyl titanate, citric acid, ethylene glycol, polyethylene glycol, ceric ammonium nitrate and the like, and the purities are all above industrial grade.
It is worth to say that the preparation method of the invention comprises the following steps: styrene is used as a raw material, sodium dodecyl sulfate is used as a surfactant, potassium persulfate is used 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, a layer of anatase crystal form titanium dioxide with 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 the active crystal face of the nano titanium dioxide is increased; finally, cerium is doped into the anatase crystal type titanium dioxide coated on the surface by using ceric ammonium nitrate as a rare earth doping element and controlling the reaction condition and the material proportion and adopting a sol-gel and hard template method, 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, uniform particles, good dispersibility, difficult agglomeration and the like, has antibacterial functions under visible light and dark conditions, has high light energy utilization rate and excellent antibacterial performance, and can be widely applied to the antibacterial field.
The second object of the present invention is to provide a cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained by the preparation method according to one of the objects, wherein the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material has a hollow spherical structure, and wherein titanium dioxide has an anatase crystal form.
The cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material is of a hollow structure obtained by calcining, so that the stability of the structure and the utilization rate of light energy can be effectively ensured.
Another object of the present invention is to provide a use of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial substance for antibacterial purposes.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the preparation method, firstly, polystyrene microspheres are prepared, then, a layer of anatase crystal form titanium dioxide is coated on the surfaces of the polystyrene microspheres by a solvothermal method and the temperature is controlled to be 100-150 ℃ to obtain titanium dioxide-polystyrene microspheres, and finally cerium is doped in the anatase crystal form titanium dioxide coated on the surfaces, so that the prepared cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance is of a hollow spherical structure, has the advantages of controllable structure, good stability, high load, uniform particles, good dispersibility, difficult agglomeration and the like, has antibacterial functions under the conditions of visible light and darkness, has high light energy utilization rate and excellent antibacterial property, and can be widely used in the antibacterial field;
(2) The preparation method of the invention preferably uses styrene as raw material, sodium dodecyl sulfate as surfactant, potassium persulfate as initiator, and adopts emulsion polymerization to prepare polystyrene microsphere with uniform particles, thus providing larger specific surface area for subsequent titanium dioxide loading.
Drawings
FIG. 1 is a scanning electron microscope image of polystyrene microspheres in 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 material obtained in example 1;
FIG. 3 is an EDS spectrum of titanium element of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in example 1;
FIG. 4 is a cerium element EDS spectrum of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in example 1;
FIG. 5 is a graph showing the particle size distribution of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial obtained in example 1.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which comprises the following steps:
(1) Sequentially adding 0.08g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with molecular weight of 5000 into 20mL of absolute ethyl alcohol according to the mass ratio of 1.33:1, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g:250mL, and 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 1:300, namely controlling the solid-to-liquid ratio of the sodium dodecyl sulfate and the deionized water to be about 1g:1667mL, and performing primary heating at 30 ℃ for 30min to obtain a mixed solution a;
(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 to 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 5:1, reheating at 70 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotating speed of 10000r/min, wherein the washing comprises alternately cleaning for 3 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres; the scanning electron microscope image 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-to-liquid ratio to be 1g to 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 1.5:1, and carrying out secondary heating at 30 ℃ for 250min to obtain a second mixed solution;
(3) Reacting the second mixed solution in the step (2) at 100 ℃ for 60min by a solvothermal method, and sequentially centrifuging, washing and drying at a rotating speed of 5000r/min, wherein the washing comprises the steps of alternately washing with absolute ethyl alcohol and deionized water for 3 times to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with molecular weight of 10000 and 0.04g of titanium dioxide-polystyrene microsphere in the step (3) into a cerium ammonium nitrate solution according to the mass ratio of about 5:1000:60:4, wherein 0.0658g (0.12 mmol) of cerium ammonium nitrate is dissolved in 100mL of a mixed solvent of anhydrous ethanol and deionized water with volume ratio of 7:1, namely, the molar concentration of the cerium ammonium nitrate solution is 1.2mmol/L, the mass ratio of cerium ammonium nitrate and citric acid in the cerium ammonium nitrate solution is controlled to be 1.316:1, stirring for 450min to obtain a bright yellow sol system, and calcining at 400 ℃ for 120min to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
The scanning electron microscope image of the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in the embodiment 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 embodiment has the advantages of good stability, uniform particles, good dispersibility, difficult agglomeration and the like; the EDS energy spectrum of the titanium element of the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in the embodiment 1 is shown in figure 3, and it can be seen from figure 3 that the titanium dioxide is uniformly wrapped on the surface of the polystyrene microsphere; the EDS energy spectrum of cerium element of the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in the example 1 is shown in FIG. 4, and the successful doping of cerium into the titanium dioxide-polystyrene microsphere can be seen from FIG. 4; the particle size distribution of the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in example 1 is shown in fig. 5, and it can be seen from fig. 5 that the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in this example has a uniform particle size distribution and an average particle size of 270nm.
Example 2
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which comprises the following steps:
(1) Sequentially adding 0.1g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with molecular weight of 8000 into 20mL of absolute ethyl alcohol according to the mass ratio of 1.67:1, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g:200mL, and 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 and the deionized water to be about 1g:1500mL, and performing primary heating at 30 ℃ for 30min to obtain a mixed solution a;
(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 to 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 6:1, reheating at 80 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotating speed of 10000r/min, wherein the washing comprises alternately cleaning for 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-to-liquid ratio to be 1g to 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 1.5:1, and carrying out secondary heating at 30 ℃ for 200min to obtain a second mixed solution;
(3) Reacting the second mixed solution in the step (2) at 100 ℃ for 60min by a solvothermal method, and sequentially centrifuging, washing and drying at a rotating speed of 5000r/min, wherein the washing comprises the steps of alternately washing with absolute ethyl alcohol and deionized water for 3 times to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with molecular weight of 10000 and 0.04g of titanium dioxide-polystyrene microsphere in the step (3) into a cerium ammonium nitrate solution according to the mass ratio of about 5:1000:60:4, wherein 0.0658g (0.12 mmol) of cerium ammonium nitrate is dissolved in 100mL of a mixed solvent of anhydrous ethanol and deionized water with volume ratio of 7:1, namely, the molar concentration of the cerium ammonium nitrate solution is 1.2mmol/L, the mass ratio of cerium ammonium nitrate and citric acid in the cerium ammonium nitrate solution is controlled to be 1.316:1, stirring for 450min to obtain a bright yellow sol system, and calcining at 450 ℃ for 120min to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
Example 3
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which comprises the following steps:
(1) Sequentially adding 0.1g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with molecular weight of 8000 into 20mL of absolute ethyl alcohol according to the mass ratio of 1.67:1, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g:200mL, and 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 and the deionized water to be about 1g:1500mL, and performing primary heating at 30 ℃ for 30min to obtain a mixed solution a;
(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 to 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 10:1, reheating at 80 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotating speed of 10000r/min, wherein the washing comprises alternately cleaning for 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-to-liquid ratio to be 1g to 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 1.5:1, and performing secondary heating at 30 ℃ for 300min to obtain a second mixed solution;
(3) Reacting the second mixed solution in the step (2) for 90min at the temperature of 100 ℃ by a solvothermal method, and sequentially centrifuging, washing and drying at the rotating speed of 5000r/min, wherein the washing comprises the steps of alternately cleaning with absolute ethyl alcohol and deionized water for 3 times to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with molecular weight of 10000 and 0.04g of titanium dioxide-polystyrene microsphere in the step (3) into a cerium ammonium nitrate solution according to the mass ratio of about 5:1000:60:4, wherein 0.0658g (0.12 mmol) of cerium ammonium nitrate is dissolved in 100mL of a mixed solvent of anhydrous ethanol and deionized water with the volume ratio of 7:1, namely, the molar concentration of the cerium ammonium nitrate solution is 1.2mmol/L, the mass ratio of cerium ammonium nitrate and citric acid in the cerium ammonium nitrate solution is controlled to be 1.316:1, stirring for 500min to obtain a bright yellow sol system, and calcining at 450 ℃ for 180min to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
Example 4
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which comprises the following steps:
(1) Sequentially adding 0.1g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with a molecular weight of 24000 into 20mL of absolute ethyl alcohol according to a mass ratio of 1.67:1, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g:200mL, and 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 1:250, namely controlling the solid-to-liquid ratio of the sodium dodecyl sulfate and the deionized water to be about 1g:1750mL, and performing primary heating at 30 ℃ for 30min to obtain a mixed solution a;
(ii) Dissolving 0.1g of potassium persulfate in 7mL of deionized water to obtain a potassium persulfate aqueous solution with a solid-to-liquid ratio of 1g to 70mL, 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 10:1, reheating at 100 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotating speed of 15000r/min, wherein the washing comprises alternately cleaning for 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-to-liquid ratio to be 1g to 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 1.5:1, and performing secondary heating at 30 ℃ for 300min to obtain a second mixed solution;
(3) Reacting the second mixed solution in the step (2) at 150 ℃ for 60min by a solvothermal method, and sequentially centrifuging, washing and drying at a rotating speed of 5000r/min, wherein the washing comprises the steps of alternately washing with absolute ethyl alcohol and deionized water for 3 times to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with molecular weight of 20000 and 0.04g of the titanium dioxide-polystyrene microsphere in the step (3) into a cerium ammonium nitrate solution according to the mass ratio of about 5:1000:60:4, wherein 0.0658g (0.12 mmol) of cerium ammonium nitrate is dissolved in 100mL of a mixed solvent of anhydrous ethanol and deionized water with the volume ratio of 7:1, namely, the molar concentration of the cerium ammonium nitrate solution is 1.2mmol/L, the mass ratio of cerium ammonium nitrate and citric acid in the cerium ammonium nitrate solution is controlled to be 1.316:1, stirring for 450min to obtain a bright yellow sol system, and calcining at 500 ℃ for 120min to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
Example 5
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which comprises the following steps:
(1) Sequentially adding 0.12g of polystyrene microspheres and 0.08g of polyvinylpyrrolidone with molecular weight of 8000 into 25mL of absolute ethyl alcohol according to a mass ratio of 1.5:1, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g:208mL, and performing 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 1:200, namely controlling the solid-to-liquid ratio of the sodium dodecyl sulfate and the deionized water to be about 1g:2000mL, and performing primary heating at 30 ℃ for 30min to obtain a mixed solution a;
(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 to 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 10:1, reheating at 80 ℃ for 500min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotating speed of 10000r/min, wherein the washing comprises alternately cleaning for 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 1 g/75 mL, 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 1.2:1, and performing secondary heating at 30 ℃ for 250min to obtain a second mixed solution;
(3) Reacting the second mixed solution in the step (2) at 100 ℃ for 60min by a solvothermal method, and sequentially centrifuging, washing and drying at the rotating speed of 10000r/min, wherein the washing comprises the steps of alternately washing with absolute ethyl alcohol and deionized water for 3 times to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with molecular weight of 10000 and 0.04g of titanium dioxide-polystyrene microsphere in the step (3) into a cerium ammonium nitrate solution according to the mass ratio of about 5:1000:60:4, wherein 0.0658g (0.12 mmol) of cerium ammonium nitrate is dissolved in 100mL of a mixed solvent of anhydrous ethanol and deionized water with volume ratio of 7:1, namely, the molar concentration of the cerium ammonium nitrate solution is 1.2mmol/L, the mass ratio of cerium ammonium nitrate and citric acid in the cerium ammonium nitrate solution is controlled to be 1.316:1, stirring for 450min to obtain a bright yellow sol system, and calcining at 500 ℃ for 120min to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
Example 6
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which comprises the following steps:
(1) Sequentially adding 0.12g of polystyrene microspheres and 0.08g of polyvinylpyrrolidone with molecular weight of 12000 into 25mL of absolute ethyl alcohol according to a mass ratio of 1.5:1, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g:208mL, and 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 1:200, namely controlling the solid-to-liquid ratio of the sodium dodecyl sulfate and the deionized water to be about 1g:160 mL, and performing primary heating at 30 ℃ for 30min to obtain a mixed solution a;
(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 to 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 8:1, reheating at 85 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotating speed of 10000r/min, wherein the washing comprises alternately cleaning for 3 times by adopting absolute ethyl alcohol and deionized water to obtain the polystyrene microspheres;
(2) Dissolving 0.5g of tetrabutyl titanate in 30mL of absolute ethyl alcohol, controlling the solid-to-liquid ratio to be 1 g/60 mL, 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 1.2:1, and performing secondary heating at 30 ℃ for 300min to obtain a second mixed solution;
(3) Reacting the second mixed solution in the step (2) for 90min at 110 ℃ by a solvothermal method, and sequentially centrifuging, washing and drying at the rotating speed of 10000r/min, wherein the washing comprises the steps of alternately washing with absolute ethyl alcohol and deionized water for 3 times to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with molecular weight of 10000 and 0.04g of titanium dioxide-polystyrene microsphere in the step (3) into a cerium ammonium nitrate solution according to the mass ratio of about 5:1000:60:4, wherein 0.0658g (0.12 mmol) of cerium ammonium nitrate is dissolved in 100mL of a mixed solvent of anhydrous ethanol and deionized water with volume ratio of 7:1, namely, the molar concentration of the cerium ammonium nitrate solution is 1.2mmol/L, the mass ratio of cerium ammonium nitrate and citric acid in the cerium ammonium nitrate solution is controlled to be 1.316:1, stirring for 500min to obtain a bright yellow sol system, and calcining at 600 ℃ for 120min to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
Example 7
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which comprises the following steps:
(1) Sequentially adding 0.1g of polystyrene microspheres and 0.06g of polyvinylpyrrolidone with molecular weight of 12000 into 20mL of absolute ethyl alcohol according to the mass ratio of 1.67:1, controlling the solid-liquid ratio of the polystyrene microspheres to the absolute ethyl alcohol to be 1g:200mL, and 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 1:200, namely controlling the solid-to-liquid ratio of the sodium dodecyl sulfate and the deionized water to be about 1g:1667mL, and performing primary heating at 30 ℃ for 30min to obtain a mixed solution a;
(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 to 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 5:1, reheating at 85 ℃ for 400min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at a rotating speed of 10000r/min, wherein the washing comprises alternately cleaning for 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 1 g/75 mL, 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 1.5:1, and performing secondary heating at 30 ℃ for 300min to obtain a second mixed solution;
(3) Reacting the second mixed solution in the step (2) for 90min at 105 ℃ by a solvothermal method, and sequentially centrifuging, washing and drying at the rotating speed of 10000r/min, wherein the washing comprises the steps of alternately washing with absolute ethyl alcohol and deionized water for 3 times to obtain titanium dioxide-polystyrene microspheres;
(4) Sequentially adding 0.05g of citric acid, 10mL of ethylene glycol, 0.6g of polyethylene glycol with molecular weight of 10000 and 0.04g of titanium dioxide-polystyrene microsphere in the step (3) into a cerium ammonium nitrate solution according to the mass ratio of about 5:1000:60:4, wherein 0.0658g (0.12 mmol) of cerium ammonium nitrate is dissolved in 100mL of a mixed solvent of anhydrous ethanol and deionized water with the volume ratio of 7:1, namely, the molar concentration of the cerium ammonium nitrate solution is 1.2mmol/L, the mass ratio of cerium ammonium nitrate and citric acid in the cerium ammonium nitrate solution is controlled to be 1.316:1, stirring for 500min to obtain a bright yellow sol system, and calcining at 500 ℃ for 120min to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
Example 8
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material, which is different from embodiment 7 only in that: the amount of tetrabutyl titanate used in the step (2) is reduced from 0.4g to 0.2g, i.e. the solid-to-liquid ratio of the tetrabutyl titanate solution is adjusted from 1g to 75mL to 1g to 120 mL.
Example 9
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material, which is different from embodiment 7 only in that: the amount of tetrabutyl titanate used in the step (2) was increased from "0.4g" to "0.7g", i.e., the solid-to-liquid ratio of the tetrabutyl titanate solution was adjusted from "1g:75mL" to "1g:43mL".
Example 10
The embodiment provides a preparation method of a cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material, which is different from embodiment 7 only in that: and (3) reducing the calcining temperature in 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 embodiment 7 only in that: and (3) increasing the calcining 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 material, which is different from embodiment 7 only in that: reducing the first heating time in step (i) from "30min" to "20min".
Comparative example 1
The comparative example provides a preparation method of cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which is different from example 7 only in that: the temperature of the solvothermal reaction in the step (3) is adjusted from 105 ℃ to 80 ℃.
Comparative example 2
The comparative example provides a preparation method of cerium doped titanium dioxide-polystyrene microsphere composite antibacterial, which is different from example 7 only in that: the temperature of the solvothermal reaction in the step (3) is adjusted from 105 ℃ to 170 ℃.
The cerium doped titanium dioxide-polystyrene microsphere composite antibacterial material obtained in the example and the comparative example is usedTwo 0.01g samples were weighed separately and two 0.01g samples were added to two 10mL portions containing 10 7 cfu/mL of the escherichia coli physiological saline solution and stirring and balancing for 30min; simulating sunlight by a 500W xenon lamp, and stirring and irradiating for 30min under visible light irradiation to obtain the antibacterial rate A of the escherichia coli; stirring the other part for 30min under dark condition to obtain antibacterial rate B of Escherichia coli; the 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 disclosed by the invention has a hollow spherical structure, has the advantages of controllable structure, good stability, high load, uniform particles, good dispersibility, difficulty in aggregation 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 of up to 99.81%, has the antibacterial rate B of up to 35.41% under dark conditions, has high light energy utilization rate and excellent antibacterial property, and can be widely applied to the antibacterial field;
(2) Comparing example 7 with examples 8 and 9, the antibacterial effect is obviously reduced due to the reduction of the amount of tetrabutyl titanate corresponding to example 8, while the generated anatase titanium dioxide is easy to agglomerate due to the excessively high amount of tetrabutyl titanate corresponding to example 9, and the antibacterial effect is also deteriorated due to uneven coating on the surface of polystyrene microspheres;
(3) Comparing example 7 with examples 10 and 11, the calcination temperature in example 10 is lowered to 300 ℃ to cause lower hollow degree of the prepared cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial substance, so that the antibacterial effect is obviously reduced, while in example 11, the calcination temperature is raised to 700 ℃ to cause the morphology of anatase crystal type titanium dioxide to be destroyed, so that the antibacterial effect of the prepared cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial substance is deteriorated due to cracking;
(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 thus to the mechanical stability of the polystyrene microsphere as a carrier, example 12 reduces the first heating time from "30min" to "20min" in step (i), resulting in deterioration of antibacterial effect;
(5) Comparing example 7 with comparative examples 1 and 2, the preparation method of the invention adopts a solvothermal method to coat a layer of anatase crystal form titanium dioxide with stable structure on the surface of polystyrene microsphere, and both comparative example 1 and comparative example 2 can lead to that part of generated titanium dioxide is still amorphous, thereby further leading to poor antibacterial effect.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (29)

1. The preparation method of the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial is characterized by comprising the following steps of:
(1) Adding polystyrene microspheres and polyvinylpyrrolidone into a first solvent for heating for one time to obtain a first mixed solution; wherein the temperature of the primary heating is 30-100 ℃, and the time of the primary heating is 30-60 min;
(2) Adding titanate solution into the first mixed solution obtained in the step (1) for secondary heating to obtain a second mixed solution; wherein the solid-to-liquid ratio of the titanate solution is 1g (50-100 mL); the volume ratio of the titanate solution to the first mixed solution is (1-5): 1; the temperature of the secondary heating is 30-100 ℃; the secondary heating time is 200-300 min;
(3) Reacting the second mixed solution 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, glycol, polyethylene glycol and the titanium dioxide-polystyrene microsphere in the step (3) into an ammonium cerium nitrate solution, stirring to obtain a sol system, and calcining to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
2. The method of claim 1, wherein the method of preparing polystyrene microspheres in step (1) comprises the steps of:
(i) Sequentially adding sodium dodecyl sulfate and styrene into deionized water for first heating to obtain a mixed solution a;
(ii) And (3) adding a potassium persulfate aqueous solution into the mixed solution a 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 preparation method according to claim 2, wherein the mass ratio of sodium dodecyl sulfate to styrene in the step (i) is 1 (200-300).
4. The method according to claim 2, wherein the solid-to-liquid ratio of sodium dodecyl sulfate to deionized water in step (i) is 1g (1500-2000) mL.
5. The method of claim 2, wherein the first heating in step (i) is at a temperature of 30-100 ℃; the time of the first heating in the step (i) is 30-60 min.
6. The method according to claim 2, wherein the solid-to-liquid ratio of the aqueous potassium persulfate solution in the step (ii) is 1g (50 to 100 mL).
7. The method according to claim 2, wherein the volume ratio of the mixed solution a to the aqueous potassium persulfate solution in the step (ii) is (5 to 10): 1.
8. The method of claim 2, wherein the reheating in step (ii) is at a temperature of 30-100 ℃; and (3) reheating in the step (ii) for 300-500 min.
9. The method according to claim 2, wherein the rotational speed of the centrifugation in step (ii) is 10000 to 15000r/min.
10. The method of claim 2, wherein the washing of step (ii) comprises alternating washing with absolute ethanol and deionized water between 2 and 4 times.
11. The method according to claim 1, wherein the polyvinylpyrrolidone in step (1) has a molecular weight of 5000 to 25000.
12. The preparation method according to claim 1, wherein the mass ratio of the polystyrene microsphere to the polyvinylpyrrolidone in the step (1) is (1-2): 1.
13. The method of claim 1, wherein the first solvent of step (1) comprises absolute ethanol.
14. The method according to claim 1, wherein the solid-to-liquid ratio of the polystyrene microsphere and the first solvent in the step (1) is 1g (200 to 300) mL.
15. The method of claim 1, wherein the titanate in the titanate solution of step (2) is tetrabutyl titanate.
16. The method of claim 1, wherein the solvent of the titanate solution of step (2) comprises absolute ethanol.
17. The method according to claim 1, wherein the reaction time in the step (3) is 60 to 180 minutes.
18. The method according to claim 1, wherein the rotational speed of the centrifugation in the step (3) is 5000 to 10000r/min.
19. The method of claim 1, wherein the washing in step (3) comprises alternately washing with absolute ethanol and deionized water 2 to 4 times.
20. The method according to claim 1, wherein the polyethylene glycol in the step (4) has a molecular weight of 10000 to 20000.
21. The preparation method according to claim 1, wherein the mass ratio of the citric acid, the ethylene glycol, the polyethylene glycol and the titanium dioxide-polystyrene microsphere in the step (4) is 5:1000:60 (3-5).
22. The preparation method according to claim 1, wherein the solvent of the ammonium cerium nitrate solution in the step (4) is a mixed solvent of absolute ethanol and deionized water in a volume ratio of (5-10): 1.
23. The method according to claim 1, wherein the ceric ammonium nitrate solution in the step (4) has a molar concentration of 1 to 1.5mmol/L.
24. The method according to claim 1, wherein in the step (4), the mass ratio of the ammonium cerium nitrate to the citric acid in the ammonium cerium nitrate solution is 1.25 to 1.5.
25. The method according to claim 1, wherein the stirring time in the step (4) is 400 to 500 minutes.
26. The method of claim 1, wherein the calcining in step (4) is carried out at a temperature of 400-600 ℃; and (3) calcining for 120-240 min in the step (4).
27. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Sequentially adding polystyrene microspheres and polyvinylpyrrolidone with a molecular weight of 5000-25000 into absolute ethyl alcohol according to a mass ratio of (1-2) 1, controlling the solid-liquid ratio of the polystyrene microspheres and the absolute ethyl alcohol to be 1g (200-300) mL, and 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 (200-300), controlling the solid-liquid ratio of the sodium dodecyl sulfate and the deionized water to be 1g (1500-2000) mL, and heating for the first time 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, controlling the volume ratio of the mixed solution a to the potassium persulfate aqueous solution to be (5-10): 1, heating again at 30-100 ℃ for 300-500 min to obtain a mixed solution b, and sequentially centrifuging, washing and drying at the rotating speed of 10000-15000 r/min, wherein the washing comprises alternately washing for 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 at 30-100 ℃ for 200-300 min to obtain a second mixed solution;
(3) Reacting the second mixed solution in the step (2) at 100-150 ℃ for 60-180 min by a solvothermal method, and sequentially centrifuging, washing and drying at a 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, glycol, polyethylene glycol with molecular weight of 10000-20000 and the titanium dioxide-polystyrene microsphere in the step (3) into a ceric ammonium nitrate solution according to the mass ratio of 5:1000:60, wherein the solvent of the ceric ammonium nitrate solution is a mixed solvent of absolute ethanol and deionized water with the volume ratio of (5-10): 1 and the molar concentration of 1-1.5 mmol/L, controlling the mass ratio of ceric ammonium nitrate and citric acid in the ceric ammonium nitrate solution to be (1.25-1.5): 1, stirring for 400-500 min to obtain a sol system, and calcining for 120-240 min at the temperature of 400-600 ℃ to obtain the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial substance.
28. The cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial substance obtained by the preparation method according to claim 1, wherein the cerium-doped titanium dioxide-polystyrene microsphere composite antibacterial substance has a hollow spherical structure, and the titanium dioxide is in an anatase crystal form.
29. Use of the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial according to claim 28, wherein the cerium doped titanium dioxide-polystyrene microsphere composite antibacterial is used for antibacterial purposes.
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Citations (6)

* Cited by examiner, † Cited by third party
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
"Preparation and Characterization of Titania-Coated Polystyrene Spheres and Hollow Titania Shells";Arnout Imhof;《Langmuir》;第17卷;第3580页 *
掺银二氧化钛空心球的制备及其抗菌性能研究;冯炫;杨泠;关秋;刘应亮;;生态科学(第03期);第145-147页 *
稀土负载型纳米二氧化钛抗菌剂的研制;刘雪峰;涂铭旌;;现代化工(第S1期);第145页 *

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