CN115067359A - Ag ion-loaded black TiO 2 Nano photocatalytic bactericidal material and preparation method thereof - Google Patents
Ag ion-loaded black TiO 2 Nano photocatalytic bactericidal material and preparation method thereof Download PDFInfo
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- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 43
- 150000002500 ions Chemical class 0.000 claims abstract description 38
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- 239000000843 powder Substances 0.000 claims abstract description 23
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- 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
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/48—Silver or gold
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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Abstract
The invention belongs to the technical field of photocatalytic sterilization materials, and relates to black TiO loaded with Ag ions 2 A nano photocatalytic sterilization material and a preparation method thereof. The preparation method comprises the following steps: (1) mixing benzalkonium chloride, nano titanium dioxide and a solvent to obtain a mixed solution; (2) performing ball milling treatment on the mixed solution, and then heating and drying to obtain a powder sample; (3) mixing the powder sample with NaBH 4 Mixing and grinding the powder, then placing the powder into a tubular furnace for heat treatment for a period of time, and introducing Ar gas for protection; (4) dispersing the heat-treated mixed powder in deionized water for centrifugal impurity-removing ion treatment, further ultrasonic treatment and stirringAdding silver ion-containing salt, and drying to obtain Ag @ b-TiO 2 . The preparation method of the invention has the advantages of simple and convenient operation, easy realization, low consumption, high yield, good repeatability, suitability for large-scale production and no secondary pollution to the environment.
Description
Technical Field
The invention belongs to the technical field of photocatalytic sterilization materials, and relates to black TiO loaded with Ag ions 2 A nano photocatalytic sterilization material and a preparation method thereof.
Background
The photocatalysis technology is a technology for efficiently solving the environmental pollution and improving the public health. Titanium dioxide (TiO) 2 ) Is a stable and cheap high-efficiency inorganic photocatalytic material, and TiO is a TiO material with the advantages of high photocatalytic performance, high stability, low toxicity, low price, environmental protection and the like 2 Can generate a photocatalytic reaction under the excitation of ultraviolet rays, and finally decompose organic matters into carbon dioxide and water without difference. Thus, TiO 2 Can be used in the fields of organic matter removal, sterilization, disinfection, sewage treatment and the like.
However, only 4-5% of the UV component of sunlight greatly limits TiO 2 The photocatalytic application of (1). To better realize TiO 2 Under the natural condition, the solar response can be realized by modifying the solar energy through metal/nonmetal ion doping, noble metal loading, heterojunction semiconductor structure and the like. In addition, to TiO 2 The visible light catalysis can be realized by modifying the catalyst per se.
Black nano titanium dioxide (b-TiO) 2 ) Is to use hydrogen to partially react Ti 4+ Reduction of ions to Ti 3+ Ions, making TiO 2 The absorption spectrum extends to the visible light region, and visible light response is realized. Thus, under visible light irradiation, black TiO 2 The nano photocatalytic material can realize the high-efficiency photocatalytic sterilization effect. However, the black nano titanium dioxide has poor dispersibility and poor ion resistance, is easy to agglomerate and settle, so that the specific surface area of the black nano titanium dioxide is reduced sharply, and the photocatalytic efficiency and the application range of the black nano titanium dioxide are greatly influenced.
Silver is used for sterilization and disinfection from old times and is an old bactericide. In comparison, the silver ions have higher safety, better killing effect, broad-spectrum killing property, no drug resistance and strong killing effect on super bacteria. However, silver ions are easily consumed by chloride ions and the like, are easily lost, are easily decomposed by light and are limited in absorption amount by cells, so that the killing effect of the disinfectant containing silver ions is greatly limited; if the killing effect is achieved by only increasing the dosage, the method can cause immeasurable damage to human bodies and the environment and does not meet the discharge standard of environmental protection. Therefore, how to prepare safe and stable silver-containing germicidal disinfectant is always the focus of research. The nano titanium dioxide can be used as an excellent carrier of silver ions, so that the stability of the ions can be enhanced, and the sterilization efficiency of the nano titanium dioxide can also be enhanced; meanwhile, the addition of silver ions also enables the nano titanium dioxide to obtain a sterilization effect under the condition of no light, and the metal ion loaded nano titanium dioxide has a more excellent sterilization effect than the metal ions and the nano titanium dioxide. However, due to the charge stability of the colloid, the concentration of silver ions that can be added to the nano titanium dioxide dispersion liquid is very limited, and how to increase the loading amount of the nano titanium dioxide to the silver ions is very critical.
Benzalkonium chloride is a cationic surfactant, can be used for surface modification of nano materials, and improves the dispersibility of the nano materials. Meanwhile, benzalkonium chloride is a common quaternary ammonium salt sterilization material, belongs to a low-efficiency disinfectant, is commonly used in food industry, drinking water, household detergents and the like, and has poor effect of killing part of microorganisms and is easy to generate drug resistance. The compound bactericide of the quaternary ammonium salt and the silver ions has good bactericidal effect, and researches show that the mixed effect of the quaternary ammonium salt of 3ppm and the Ag ions of 0.4ppm can achieve 99.97 percent of the killing efficiency of 1mim on the staphylococcus aureus, but any single component is ineffective. Therefore, the benzalkonium chloride and silver ions are combined, so that the sterilization efficiency can be enhanced, the dosage of each component can be greatly reduced, and higher biological safety is obtained.
Disclosure of Invention
The invention aims to provide black TiO loaded by Ag ions 2 The preparation method of the nano photocatalytic sterilization material has the advantages of simple and convenient operation, easy realization, low consumption, high yield, good repeatability, suitability for large-scale production and no secondary pollution to the environment 2 A nano photocatalytic sterilizing material.
To achieve this objectIn a basic embodiment, the present invention provides a black TiO supported by Ag ions 2 The preparation method of the nano photocatalytic sterilization material comprises the following steps:
(1) mixing benzalkonium chloride, nano titanium dioxide (preferably commercialized P25 type titanium dioxide with the grain size of 20nm) and a solvent to obtain a mixed solution;
(2) performing ball milling treatment on the mixed solution, and then heating and drying to obtain a powder sample;
(3) mixing the powder sample with NaBH 4 Mixing and grinding the powder, then placing the powder into a tubular furnace for heat treatment for a period of time, and introducing Ar gas for protection;
(4) dispersing the heat-treated mixed powder in deionized water for centrifugal impurity ion removal treatment, further performing ultrasonic treatment, adding silver ion-containing salt while stirring, and drying to obtain the black TiO loaded with Ag ions 2 Nano photocatalytic bactericidal material, i.e. Ag @ b-TiO 2 (preferably prepared to Ag @ b-TiO) 2 The average particle size of the nanomaterial is 20 nm).
In a preferred embodiment, the present invention provides a black TiO supported on Ag ions 2 The preparation method of the nano photocatalytic sterilization material comprises the step (1), wherein the mass ratio of benzalkonium chloride to nano titanium dioxide is 50-99: 1.
In a preferred embodiment, the present invention provides a black TiO supported on Ag ions 2 The preparation method of the nano photocatalytic sterilization material comprises the step (1), wherein the solvent is selected from one or more of water, ethanol and polyethylene glycol (preferably absolute ethanol).
In a preferred embodiment, the present invention provides a black TiO supported on Ag ions 2 The preparation method of the nano photocatalytic sterilization material comprises the step (2), wherein the ball milling treatment time is 2-6h (preferably 5 h).
In a preferred embodiment, the present invention provides a black TiO supported on Ag ions 2 A preparation method of a nano photocatalytic sterilization material, wherein in the step (2), the methodThe temperature for heating and drying is 40-100 deg.C (preferably 80 deg.C), and the time is 2-8h (preferably 4 h).
In a preferred embodiment, the present invention provides a black TiO supported on Ag ions 2 The preparation method of the nano photocatalytic sterilization material comprises the following steps of (3),
the titanium dioxide and NaBH in the powder sample 4 The mixing mass ratio of the powder is 4: (0.5-1) (preferably 4: 1);
the grinding time is 20-120min (preferably 30 min);
the temperature of the heat treatment is 200 ℃ to 400 ℃ (preferably 300 ℃), and the time is 0.5-3h (preferably 1 h);
the flow of the Ar gas is controlled to ensure that the cavity of the tube furnace keeps micro-positive pressure.
In a preferred embodiment, the present invention provides a black TiO supported on Ag ions 2 The preparation method of the nano photocatalytic sterilization material comprises the following steps of (4),
the mass ratio of the titanium dioxide to the deionized water in the mixed powder is 0.1-10:100 (preferably 1: 100);
the centrifugation rotation speed of the centrifugation impurity removal ion treatment is 500-5000rpm (preferably 5000rpm), and the time is 10-40min (preferably 30 min);
the ultrasonic treatment time is 1-4h (preferably 1h), and the power is 80-300W (preferably 240W).
In a preferred embodiment, the present invention provides a black TiO supported on Ag ions 2 The preparation method of the nano photocatalytic sterilization material comprises the following steps of (4),
the silver ion-containing salt is silver nitrate;
the concentration of Ag ions after addition of the silver ion-containing salt is 10 to 1000ppm (preferably 100 ppm);
the stirring speed is 100-1000rpm (preferably 500rpm), and the time is 10-120min (preferably 1 h).
In a preferred embodiment, the present invention provides a black TiO supported on Ag ions 2 Preparation method of nano photocatalytic sterilization materialWherein in the step (4), the drying temperature is 40-100 ℃ and the drying time is 2-6 h.
The second purpose of the invention is to provide black TiO loaded by Ag ions 2 The nano photocatalytic sterilization material has the advantages of uniform size, good dispersibility, good photocatalytic effect and good sterilization effect.
To achieve this object, in a basic embodiment, the present invention provides a black TiO supported by Ag ions 2 The nano photocatalytic sterilization material is prepared by the preparation method.
The Ag ion loaded black TiO2 nano photocatalytic sterilization material and the preparation method thereof have the advantages of simple and convenient operation, easy realization, low consumption, high yield, good repeatability, suitability for large-scale production and no secondary pollution to the environment 2 The nano photocatalytic sterilization material prepared from the nano photocatalytic sterilization material has the advantages of uniform size, good dispersibility, good photocatalytic effect and good sterilization effect.
The beneficial effects of the invention are embodied in that:
1) in the invention, the common ultraviolet light excited P25 nanometer titanium dioxide is replaced by the visible light responding black nanometer titanium dioxide for sterilization. In contrast, the black nano titanium dioxide can realize effective sterilization in a wider area, and has wider application prospect. In addition, in order to solve the problem of poor dispersibility of the black nano titanium dioxide, the quaternary ammonium salt surfactant benzalkonium chloride is used as a surface modifier to realize in-situ dispersion of the black nano titanium dioxide; inert gas argon is used as protective gas, which is favorable for obtaining black TiO by reduction 2 And can effectively inhibit the pyrolysis of the surfactant to make the surfactant exert the due effect. The black nano titanium dioxide dispersed in situ keeps large specific surface area, and the visible light response photocatalysis sterilization nano material is obtained.
2) In the present invention, Ag ions can be adsorbed not only on TiO 2 And can be effectively adsorbed on benzalkonium chloride. Benzalkonium chloride not only can inhibitPreparation of nano TiO 2 The aggregation of the composite material can also increase the adsorption capacity of the composite material on the nano titanium dioxide by adsorbing Ag ions through amino groups, prevent the loss of metal ions, further promote the slow release effect of the metal ions and enhance the long-term antibacterial effect of the composite material. In addition, the synergistic effect of benzalkonium chloride and Ag ions enables the composite nano material to have super-strong sterilization effect, and the composite nano material still has good sterilization effect even under the condition of no illumination. Due to the existence of the surfactant, the direct drying preparation of the powder material is realized, and the particle size of the powder material is not increased after the powder material is re-dispersed. In addition, the method is simple and convenient to operate, easy to implement, short in time consumption, low in cost, high in yield, good in repeatability and suitable for large-scale production or has no secondary pollution to the environment.
3) Based on the preparation method, the commercialized nano titanium dioxide can be modified, so that the titanium dioxide has the sterilization effect in any scene, and the titanium dioxide with the strong visible light catalytic sterilization capability further loads silver to further enhance the sterilization capability of the titanium dioxide. The preparation method has the capability of large-scale industrialization, and expands the application of the nano titanium dioxide in the aspects of air purification, sterilization and the like.
Drawings
FIG. 1 is the Ag @ b-TiO residue obtained in example 1 2 Transmission electron microscopy imaging of the nanomaterial.
FIG. 2 is the Ag @ b-TiO residue obtained in example 1 2 And (3) a characterization diagram of the killing effect of the nano material on staphylococcus aureus and escherichia coli.
Detailed Description
The following examples further illustrate specific embodiments of the present invention. Silver nitrate, sodium borohydride and benzalkonium chloride used in the examples were purchased from the Aladdin reagent, and P25 type nanometer titanium dioxide used was purchased from the winning Industrial group.
Example 1: ag @ b-TiO 2 Preparation of nanomaterials
(1) Putting 3g of P25 powder and 0.03g of benzalkonium chloride into an agate mortar, adding 5mL of absolute ethyl alcohol, uniformly mixing, and then transferring into a ball milling pot for ball milling for 5h (500 rpm);
(2) transferring the ball-milled sample into an oven, and drying for 4h at the temperature of 80 ℃;
(3) the dried powder was mixed with 0.8g of NaBH 4 Grinding in a mortar for 30 minutes, and then transferring to a tube furnace for heat treatment for 1h at 300 ℃ in an argon atmosphere;
(4) dispersing the heat-treated powder in deionized water, centrifuging at 2000rpm for 30min to remove excessive benzalkonium chloride, performing ultrasonic treatment for 1h (240W), and dispersing in deionized water to obtain TiO 2 The solid mass content of (A) is 1%;
(5) adding a certain amount of AgNO into the dispersion liquid after ultrasonic treatment under the condition of stirring 3 Continuously stirring the dispersion liquid for 1h at normal temperature and pressure, wherein the content of Ag ions in the dispersion liquid is 100 ppm;
(6) evaporating the obtained dispersion liquid to dryness at 100 ℃ to obtain the composite nano sterilizing material powder.
Ag @ b-TiO prepared in this example 2 The nano material is stable, and the dispersion liquid can be stored at room temperature for more than 1 year without precipitation. The Ag @ b-TiO obtained in the example 2 The nanomaterial was characterized and the results are shown in fig. 1-2. Wherein FIG. 1 shows Ag @ b-TiO 2 Imaging of the nanomaterial by low-power transmission electron microscope; FIG. 2 is Ag @ b-TiO 2 The killing effect of the nano material on staphylococcus aureus and escherichia coli in an indoor light environment is shown and compared with that of a single component.
As can be seen from FIG. 1, Ag @ b-TiO 2 The nano material has no agglomeration phenomenon.
FIG. 2 compares Ag @ b-TiO 2 The killing rate of each single component to staphylococcus aureus and escherichia coli. It can be seen that, according to the test method specified in the GB 30706-2014 standard, under the environment of the illumination intensity of 1500 lux, when the concentration of the composite nano material is only 1ppm, the 30-min killing rate of the two bacteria reaches 95 percent, and the antibacterial effect is achieved; ag ion alone (20 ppm concentration), b-TiO under the same test environment 2 (0.1 wt%) and DDBAC (100ppm) at higher concentrationsThe sterilization rate of the antibacterial agent does not exceed 50 percent, and the antibacterial agent does not have an antibacterial effect.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (10)
1. Ag ion-loaded black TiO 2 The preparation method of the nano photocatalytic sterilization material is characterized by comprising the following steps:
(1) mixing benzalkonium chloride, nano titanium dioxide and a solvent to obtain a mixed solution;
(2) performing ball milling treatment on the mixed solution, and then heating and drying to obtain a powder sample;
(3) mixing the powder sample with NaBH 4 Mixing and grinding the powder, then placing the powder into a tubular furnace for heat treatment for a period of time, and introducing Ar gas for protection;
(4) dispersing the heat-treated mixed powder in deionized water for centrifugal impurity ion removal treatment, further performing ultrasonic treatment, adding silver ion-containing salt while stirring, and drying to obtain the black TiO loaded with Ag ions 2 Nano photocatalytic bactericidal material, i.e. Ag @ b-TiO 2 。
2. The method of claim 1, wherein: in the step (1), the mass ratio of benzalkonium chloride to nano titanium dioxide is 50-99: 1.
3. The method of claim 1, wherein: in the step (1), the solvent is selected from one or more of water, ethanol and polyethylene glycol.
4. The method of claim 1, wherein: in the step (2), the ball milling time is 2-6 h.
5. The method of claim 1, wherein: in the step (2), the temperature for heating and drying is 40-100 ℃ and the time is 2-8 h.
6. The method of claim 1, wherein: in the step (3), the step (c),
the titanium dioxide and NaBH in the powder sample 4 The mixing mass ratio of the powder is 4: (0.5-1);
the grinding time is 20-120 min;
the temperature of the heat treatment is 200-400 ℃, and the time is 0.5-3 h;
the flow of the Ar gas is controlled to ensure that the cavity of the tube furnace keeps micro-positive pressure.
7. The method of claim 1, wherein: in the step (4), the step (c),
the mass ratio of the titanium dioxide to the deionized water in the mixed powder is 0.1-10: 100;
the centrifugal rotation speed of the centrifugal impurity removal ion treatment is 500-5000rpm, and the time is 10-40 min;
the ultrasonic treatment time is 1-4h, and the power is 80-300W.
8. The method of claim 1, wherein: in the step (4), the step (c),
the silver ion-containing salt is silver nitrate;
the concentration of Ag ions is 10-1000ppm after the salt containing silver ions is added;
the rotation speed of the stirring is 100-1000rpm, and the time is 10-120 min.
9. The method of claim 1, wherein: in the step (4), the drying temperature is 40-100 ℃, and the drying time is 2-6 h.
10. Ag ion-loaded black TiO 2 The nano photocatalytic sterilization material is characterized in that: the nano photocatalytic sterilization material is prepared by the preparation method according to any one of claims 1 to 9.
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