CN112791724A - Nanotube photocatalytic bactericide, and preparation method and application thereof - Google Patents
Nanotube photocatalytic bactericide, and preparation method and application thereof Download PDFInfo
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- 239000002071 nanotube Substances 0.000 title claims abstract description 148
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 99
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 92
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 96
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- 238000003837 high-temperature calcination Methods 0.000 claims description 5
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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 discloses a nanotube photocatalytic bactericide, and a preparation method and application thereof, and belongs to the technical field of bactericides. The preparation method of the nanotube photocatalytic bactericide comprises the following steps: step 1: preparation of a catalyst having SnO2A porous alumina template of nanotubes; step 2: preparation of TiO2And SnO2A composite nanotube; and step 3: preparation of Ag-modified TiO2And SnO2Composite nanotube photocatalytic germicide. The invention also relates toDiscloses a nanotube photocatalytic bactericide and application thereof. The nanotube photocatalytic bactericide prepared by the invention has excellent photocatalytic activity and good antibacterial performance, can be used under visible light without being limited to the use condition of an ultraviolet light source, is a high-efficiency visible light-driven photocatalytic antibacterial agent, and has a wider application range.
Description
Technical Field
The invention relates to a nanotube photocatalytic bactericide, a preparation method and application thereof, and belongs to the technical field of bactericides.
Background
Various bacteria and viruses have been threatening the health of human beings all the time. With the increasing progress of science and technology, the requirement of people on environmental sanitation is further improved, and the antibacterial material is particularly important in life. In the present day that global environmental pollution is becoming more serious, the treatment of environmental pollution by means of photocatalysis technology has attracted extensive attention in all countries of the world. At present, WO of different morphologies3、SnO2、ZnO、SrTiO3、g-C3N4And TiO2And the like have been widely used for photodegradation of environmental pollutants. Wherein, TiO2As a classical photocatalyst, the photocatalyst is an inorganic antibacterial agent which is concerned by people due to the advantages of no toxicity, no odor, no irritation, good thermal stability and heat resistance, no combustion and white self. Nano TiO 22As a semiconductor photocatalytic inorganic antibacterial agent, the compound has broad-spectrum sterilization function and can inhibit and kill bacteria, germs and the like. However, TiO2The wide band gap energy (Eg 2.0-3.2eV) and the rapid recombination of photogenerated carriers limit the photocatalytic efficiency to uv light only, accounting for 3-5% of the entire solar spectrum. To enlarge TiO2The light absorption range of the compound can be prolonged, the service life of the photoexcited electron-hole pair can be prolonged, and TiO can be improved2Various strategies have been adopted for photocatalytic activity, such as surface modification, bandgap engineering by doping with transition metals (Cr, Mn, Co, Zn, Ni and Fe) and non-metals (N, P, S, C and B, etc.), plasma coupling (Au, Ag, Pt and Pd) and coupling with other semiconductors (ZnO, WO)3、SrTiO3、SnO2CdS, ZnS and CdS). Among these strategies, TiO2Coupling with other semiconductors can separate photo-generated electron-hole pairs and improve photocatalytic activity.
SnO2As an important transition metal-based semiconductor material, the material is widely applied to the fields of lithium ion batteries, gas sensors, photocatalysts and the like. When SnO2With TiO2When combined, SnO2Energy of guide belt (E)CB0V compared to NHE pH 7) to TiO2Energy of guide belt (E)CB0.5V, compared to NHE at pH 7) is low, facilitating carrier separation. And plasma noble metal nano particles are doped into a semiconductor to form a hybrid nano structure, so that the transfer of electrons and the high-efficiency acquisition of visible light can be assisted through surface plasma resonance, and the separation of carriers can be improved. Ag has good adsorption performance on oxygen, photo-generated electrons captured by Ag can be quickly transferred to oxygen adsorbed on the surface, the separation of electrons and holes is further promoted, Ag is a biological antibacterial material with excellent performance, and nano-silver has excellent sterilization performance and no selectivity on light sources.
High-activity free radicals generated in the process of photocatalytic reaction can thoroughly oxidize organic pollutants, especially some organic pollutants difficult to degrade into CO2、H2O and the like. The nanotube can be used as a metal conductor, and has strong transmission and transportation capacity to high-activity free radicals, but the nanotube photocatalysis bactericide is not available at present. In view of the above, there is a need to provide a new nanotube photocatalytic bactericide to solve the drawbacks of the prior art.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a nanotube photocatalytic bactericide. The nanotube photocatalytic bactericide prepared by the invention has excellent photocatalytic activity and good antibacterial performance, can be used under visible light without being limited to the use condition of an ultraviolet light source, is a high-efficiency visible light-driven photocatalytic antibacterial agent, and has a wider application range.
The scheme for solving the technical problems is as follows: a preparation method of a nanotube photocatalytic bactericide comprises the following steps:
step 1: preparation of a catalyst having SnO2Nanotube and method of manufacturing the samePorous alumina template
Taking a porous alumina template, soaking in SnCl with the concentration of 0.02-0.1 mol/mL4·5H2O in water solution;
from the above SnCl4·5H2Taking out the porous alumina template from the O aqueous solution, and calcining at high temperature to obtain the porous alumina template with SnO2A porous alumina template of nanotubes;
the above-mentioned metal oxide powder is mixed with SnO2Washing the porous alumina template of the nanotube, and drying to obtain dry SnO2A porous alumina template of nanotubes;
step 2: preparation of TiO2And SnO2Composite nanotubes
Drying the SnO obtained in the step 12Soaking the porous alumina template of the nanotube in a tetrabutyl titanate solution with the concentration of 0.05mol/mL-0.15mol/mL to obtain the template with TiO2And SnO2A porous alumina template of composite nanotubes;
removing TiO from the solution of butyl titanate2And SnO2Removing the porous alumina template of the composite nanotube, washing, and drying to obtain TiO2And SnO2A composite nanotube;
and step 3: preparation of Ag-modified TiO2And SnO2Composite nanotube photocatalytic bactericide
TiO obtained in the step 22And SnO2The composite nano tube is dipped into AgNO with the concentration of 0.2mol/L-0.6mol/L in the same volume3Mixing the raw materials in water solution, filtering, taking precipitate, drying and annealing to obtain Ag modified TiO2And SnO2Composite nanotube photocatalytic germicide.
The principle of the preparation method of the nanotube photocatalytic bactericide is as follows:
in step 1 of the present invention, a porous anodized Aluminum Template, having the english name of Anodic Aluminum Oxide Template, is called AAO Template for short. The main component of the porous anodic aluminum oxide template is Al2O3Is made of high purityAluminum (99.999%) was prepared by anodic oxidation in a corresponding acidic electrolyte solution. The metal aluminum is used as an anode, and under the condition of applying a certain external electric field and specific working conditions, the reaction time is controlled, and an oxide film with the thickness of tens of microns to hundreds of microns is formed on the surface of the anode aluminum. The nano-pore arrangement in the finally formed alumina template has a highly ordered hexagonal periodic structure, the pore spacing and the pore diameter can be dozens to hundreds of nanometers, and the pore density is 109/cm2-1011/cm2. The porous anodic alumina template is widely used for preparing various ordered nano materials and devices, and has the characteristics of simple preparation process, large ratio of pore depth to pore diameter, high pore density, controllable pore diameter and the like. However, at present, a porous anodic alumina template and SnCl are not prepared4And (4) combining reports. Therefore, the invention utilizes the characteristics of small aperture of the porous anodic alumina template and the like as the hard template to prepare the photocatalytic bactericide with the double-layer nanotube morphology for the first time by compounding twice.
In step 1 of the invention, a porous alumina template is soaked in SnCl4·5H2Calcining at high temperature in O water solution, and oxidizing to obtain vertical SnO2A porous alumina template of nanotubes. The chemical reaction formula involved is:
SnCl4+H2O→Sn(OH)Cl
Sn(OH)Cl→SnO2+HCl
in step 2 of the present invention, the vertical SnO obtained in step 12Depositing TiO on the basis of the nano tube2. The chemical reaction formula involved is:
Ti(OC4H9)4+4H2O＝Ti(OH)4+4C4H9OH
Ti(OH)4+Ti(OC4H9)4＝2TiO2+4C4H9OH
adding TiO into the mixture2And SnO2The compound can promote the separation of photo-generated electrons and holes, not only improve the photo-catalytic activity, but also improve the antibacterial efficiency.
In step 3 of the present invention, TiO is used2And SnO2The composite nano tube is used as a carrier, the composite of the metal Ag and the carrier is realized for the first time, the metal Ag is deposited and uniformly distributed on the surface of the carrier, the nano Ag with small particle size can be obtained, no agglomeration exists, the specific surface area of the nano Ag can be increased, and the biological antibacterial performance of the nano Ag is improved. When the nano-Ag is irradiated by ultraviolet light, an energy barrier is formed between the nano-Ag and the nano-tube, the recombination of electrons and holes is inhibited, and the quantum efficiency and the photocatalytic activity of the nano-tube are improved.
In conclusion, the nanotube photocatalytic bactericide prepared by the invention has excellent photocatalytic activity and good antibacterial performance, can be used under visible light without being limited to the use condition of an ultraviolet light source, is a high-efficiency visible light-driven photocatalytic antibacterial agent, and has wider application range.
The preparation method of the nanotube photocatalytic bactericide has the beneficial effects that:
1. firstly, TiO is mixed2And SnO2The compound can promote the separation of photo-generated electrons and holes, not only improve the photo-catalytic activity, but also improve the antibacterial efficiency. Then TiO is added2And SnO2The composite nano tube is used as a carrier, the composite of the metal Ag and the carrier is realized for the first time, the metal Ag is deposited and uniformly distributed on the surface of the carrier, the nano Ag with small particle size can be obtained, no agglomeration exists, the specific surface area of the nano Ag can be increased, and the biological antibacterial performance of the nano Ag is improved. When the nano-Ag is irradiated by ultraviolet light, an energy barrier is formed between the nano-Ag and the nano-tube, the recombination of electrons and holes is inhibited, and the quantum efficiency and the photocatalytic activity of the nano-tube are improved.
2. The nanotube photocatalytic bactericide prepared by the invention has excellent photocatalytic activity and good antibacterial performance, can be used under visible light without being limited to the use condition of an ultraviolet light source, is a high-efficiency visible light-driven photocatalytic antibacterial agent, and has a wider application range.
3. The preparation method of the nanotube photocatalytic bactericide is simple to operate, low in cost, wide in market prospect and suitable for large-scale popularization and application.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in the step 1, the porous alumina template is a single-pass template, the aperture is 30nm, the pore spacing is 65nm, and the pore depth is 5 μm +/-0.2 μm.
The adoption of the further beneficial effects is as follows: SnO prepared by adopting porous alumina template with the parameters2The performance of the porous alumina template of the nanotube is better, which is more beneficial to improving the performance parameters of the final finished product nanotube photocatalytic bactericide.
The porous anodized aluminum template is commercially available, for example, from marine woodwork, Inc.
Further, in the step 1, the soaking temperature is 25-30 ℃ and the time is 4 hours.
The adoption of the further beneficial effects is as follows: by adopting the parameters, SnCl can be realized4·5H2Combining the O aqueous solution with the porous alumina template so as to deposit a layer of SnO in the pores of the porous alumina template2To obtain vertical SnO2A nanotube.
Further, in the step 1, the temperature of the high-temperature calcination is 550 ℃, and the time is 2 h.
The adoption of the further beneficial effects is as follows: high-temperature calcination can remove impurities and oxidize Sn (OH) Cl nanoparticles to generate SnO with good crystallinity in the high-temperature calcination process2A nanotube.
Further, in the step 1, the washing is carried out for 3-4 times by adopting absolute ethyl alcohol, and then the washing is carried out for 3-4 times by adopting distilled water.
The adoption of the further beneficial effects is as follows: by adopting the mode, impurities brought by raw materials or templates and the like can be washed away.
Further, in the step 1, the drying temperature is 60 ℃ and the drying time is 6 hours.
The adoption of the further beneficial effects is as follows: by adopting the parameters, the drying effect is better.
Further, in the step 2, the soaking temperature is 25-30 ℃ and the time is 4 hours.
The adoption of the further beneficial effects is as follows: can better make TiO2Deposited on SnO2Inside the nanotube.
Further, in the step 2, the removing of the porous alumina template refers to dissolving the template with TiO by using a NaOH solution with a concentration of 2mol/L2And SnO2A porous alumina template of composite nanotubes.
The adoption of the further beneficial effects is as follows: in the above manner, the catalyst can have TiO2And SnO2And removing the porous alumina template in the porous alumina template of the composite nanotube.
Further, in the step 2, the washing is carried out for 3-4 times by adopting absolute ethyl alcohol, and then the washing is carried out for 3-4 times by adopting distilled water.
The adoption of the further beneficial effects is as follows: by adopting the mode, impurities can be washed away.
Further, in the step 2, the drying temperature is 60 ℃ and the drying time is 6 h.
The adoption of the further beneficial effects is as follows: by adopting the parameters, the drying effect is better.
Further, in the step 3, the annealing temperature is 550 ℃ and the time is 2 h.
The adoption of the further beneficial effects is as follows: the purpose of the anneal is to remove impurities by high temperature calcination.
Further, in the step 3, the aperture of the screen used for filtering is 200 nm.
The adoption of the further beneficial effects is as follows: the sediment meeting the requirement can be obtained by adopting the filter pore size.
The second purpose of the invention is to provide the nanotube photocatalytic bactericide prepared by the preparation method. The nanotube photocatalytic bactericide has excellent photocatalytic activity and good antibacterial performance, can be used under visible light, and has a wider application range.
The scheme for solving the technical problems is as follows: the nanotube photocatalytic bactericide prepared by the preparation method.
The nanotube photocatalytic bactericide has the beneficial effects that:
the nanotube photocatalytic bactericide has excellent photocatalytic activity and good antibacterial performance, can be used under visible light, and has a wider application range.
The third purpose of the invention is to provide the application of the nanotube photocatalytic bactericide prepared by the preparation method. The nanotube photocatalytic bactericide prepared by the preparation method can be used for preparing bactericidal products and killing staphylococcus aureus, pseudomonas aeruginosa, candida albicans, bacillus subtilis and the like.
The scheme for solving the technical problems is as follows: the nanotube photocatalytic bactericide prepared by the preparation method is applied to preparation of bactericidal products.
The application of the nanotube photocatalytic bactericide in the preparation of bactericidal products has the following beneficial effects:
the nanotube photocatalytic bactericide prepared by the preparation method can be used for preparing bactericidal products and killing staphylococcus aureus, pseudomonas aeruginosa, candida albicans, bacillus subtilis and the like.
When the prepared nanotube photocatalytic bactericide is used for sterilization, the nanotube photocatalytic bactericide can be prepared into a solution, and an article to be sterilized or sterilized is soaked in the solution for several hours and removed when the sterilized or sterilized article reaches a sterile state.
The prepared nanotube photocatalytic bactericide can also be prepared into a spray or a wet tissue, when the surface of an article needs sterilization, the spray is sprayed on the surface of the article or the wet tissue covers the article, and when the wet tissue is quick-dried, the spray is used for supplementing a sterilization solution until the sterilized condition is reached.
Drawings
FIG. 1 shows Ag modified TiO compound prepared in example 1 of the present invention2And SnO2Composite nanotube photocatalytic bactericideSEM image of (d), scale bar 100 nm.
FIG. 2 shows Ag modified TiO compound prepared in example 1 of the present invention2And SnO2SEM image of the compounded nanotube photocatalytic bactericide with scale bar of 5 μm.
FIG. 3 shows Ag modified TiO prepared in example 1 of the present invention2And SnO2EDX spectra of the composite nanotube photocatalytic germicide. In the figure, the y-axis describes the number of X-rays, and the X-axis is the energy of the X-rays.
Detailed Description
The principles and features of this invention are described below in conjunction with the following detailed drawings, which are given by way of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the nanotube photocatalytic bactericide comprises the following steps:
step 1: preparation of a catalyst having SnO2Porous alumina template of nanotube
And (3) taking a porous alumina template, wherein the porous alumina template is a single-pass template, the aperture is 30nm, the pore spacing is 65nm, and the pore depth is 5 microns +/-0.2 microns. Soaking in SnCl with the concentration of 0.02mol/mL at the temperature of 25 DEG C4·5H2O aqueous solution for 4 h.
From the above SnCl4·5H2Taking out the porous alumina template from the O aqueous solution, calcining at 550 ℃ for 2h to obtain the porous alumina template with SnO2A porous alumina template of nanotubes.
The above-mentioned metal oxide powder is mixed with SnO2Washing the porous alumina template of the nanotube with absolute ethyl alcohol for 3 times, then washing with distilled water for 3 times, and drying at 60 ℃ for 6 hours to obtain dry SnO2A porous alumina template of nanotubes.
Step 2: preparation of TiO2And SnO2Composite nanotubes
Drying the SnO obtained in the step 12Soaking a porous alumina template of the nanotube in a tetrabutyl titanate solution with the concentration of 0.1mol/mL at the temperature of 25 ℃ to obtain the template with TiO2And SnO2A porous alumina template of composite nanotubes.
Removing TiO from the solution of butyl titanate2And SnO2Removing the porous alumina template by using NaOH solution with the concentration of 2mol/L, washing the porous alumina template for 3 times by using absolute ethyl alcohol, washing the porous alumina template for 3 times by using distilled water, and drying the porous alumina template for 6 hours at the temperature of 60 ℃ to obtain TiO2And SnO2Composite nanotubes.
And step 3: preparation of nanotube photocatalytic bactericide
TiO obtained in the step 22And SnO2The composite nano tube is dipped into AgNO with the concentration of 0.2mol/L in the same volume3Mixing the above materials in water solution, filtering with 200nm filter screen, collecting precipitate, drying at 60 deg.C for 6 hr, and annealing at 550 deg.C for 2 hr to obtain Ag modified TiO2And SnO2Composite nanotube photocatalytic germicide.
Ag modified TiO prepared in this example2And SnO2SEM image of the compounded nanotube photocatalytic germicide, as shown in fig. 1.
Ag modified TiO prepared in this example2And SnO2SEM image of the compounded nanotube photocatalytic germicide, as shown in fig. 2.
Ag modified TiO prepared in this example2And SnO2The EDX spectrum of the compounded nanotube photocatalytic germicide is shown in fig. 3.
The nanotube photocatalytic bactericide prepared by the preparation method.
The nanotube photocatalytic bactericide prepared by the preparation method is applied to preparation of bactericidal products.
Example 2
The preparation method of the nanotube photocatalytic bactericide comprises the following steps:
step 1: preparation of a catalyst having SnO2Porous alumina template of nanotube
Taking a porous alumina template, wherein the porous alumina template is a single-pass template, the aperture is 30nm, the hole spacing is 65nm, and holes are arrangedThe depth is 5 μm. + -. 0.2. mu.m. Soaking in SnCl with the concentration of 0.5mol/mL at the temperature of 25-30 DEG C4·5H2O aqueous solution for 4 h.
From the above SnCl4·5H2Taking out the porous alumina template from the O aqueous solution, calcining at 550 ℃ for 2h to obtain the porous alumina template with SnO2A porous alumina template of nanotubes.
The above-mentioned metal oxide powder is mixed with SnO2Washing the porous alumina template of the nanotube with absolute ethyl alcohol for 4 times, then washing with distilled water for 3 times, and drying at 60 ℃ for 6 hours to obtain dry SnO2A porous alumina template of nanotubes.
Step 2: preparation of TiO2And SnO2Composite nanotubes
Drying the SnO obtained in the step 12Soaking a porous alumina template of the nanotube in a tetrabutyl titanate solution with the concentration of 0.1mol/mL at the temperature of 28 ℃ to obtain the template with TiO2And SnO2A porous alumina template of composite nanotubes.
Removing TiO from the solution of butyl titanate2And SnO2Removing the porous alumina template with NaOH solution with concentration of 2mol/L, washing with anhydrous ethanol for 4 times, washing with distilled water for 3 times, and drying at 60 deg.C for 6 hr to obtain TiO2And SnO2Composite nanotubes.
And step 3: preparation of nanotube photocatalytic bactericide
TiO obtained in the step 22And SnO2The composite nano tube is dipped into AgNO with the concentration of 0.4mol/L in the same volume3Mixing the above materials in water solution, filtering with 200nm filter screen, collecting precipitate, drying at 60 deg.C for 6 hr, and annealing at 550 deg.C for 2 hr to obtain Ag modified TiO2And SnO2Composite nanotube photocatalytic germicide.
The nanotube photocatalytic bactericide prepared by the preparation method.
The nanotube photocatalytic bactericide prepared by the preparation method is applied to preparation of bactericidal products.
Example 3
The preparation method of the nanotube photocatalytic bactericide comprises the following steps:
step 1: preparation of a catalyst having SnO2Porous alumina template of nanotube
And (3) taking a porous alumina template, wherein the porous alumina template is a single-pass template, the aperture is 30nm, the pore spacing is 65nm, and the pore depth is 5 microns +/-0.2 microns. Soaking in SnCl with the concentration of 0.1mol/mL at the temperature of 25-30 DEG C4·5H2O aqueous solution for 4 h.
From the above SnCl4·5H2Taking out the porous alumina template from the O aqueous solution, calcining at 550 ℃ for 2h to obtain the porous alumina template with SnO2A porous alumina template of nanotubes.
The above-mentioned metal oxide powder is mixed with SnO2Washing the porous alumina template of the nanotube with absolute ethyl alcohol for 3 times, then washing with distilled water for 4 times, and drying at 60 ℃ for 6 hours to obtain dry SnO2A porous alumina template of nanotubes.
Step 2: preparation of TiO2And SnO2Composite nanotubes
Drying the SnO obtained in the step 12Soaking a porous alumina template of the nanotube in a tetrabutyl titanate solution with the concentration of 0.1mol/mL at the temperature of 30 ℃ to obtain the template with TiO2And SnO2A porous alumina template of composite nanotubes.
Removing TiO from the solution of butyl titanate2And SnO2Removing the porous alumina template with NaOH solution with concentration of 2mol/L, washing with anhydrous ethanol for 3 times, washing with distilled water for 4 times, and drying at 60 deg.C for 6 hr to obtain TiO2And SnO2Composite nanotubes.
And step 3: preparation of nanotube photocatalytic bactericide
TiO obtained in the step 22And SnO2The composite nano tube is dipped into AgNO with the concentration of 0.6mol/L in the same volume3In aqueous solutionMixing, filtering with 200nm filter screen, collecting precipitate, drying at 60 deg.C for 6 hr, and annealing at 550 deg.C for 2 hr to obtain Ag modified TiO2And SnO2Composite nanotube photocatalytic germicide.
The nanotube photocatalytic bactericide prepared by the preparation method.
The nanotube photocatalytic bactericide prepared by the preparation method is applied to preparation of bactericidal products.
Comparative example 1
The difference from example 1 is that in step 1 of comparative example 1, coal-based columnar activated carbon was used instead of the porous alumina template, and the rest was the same. Specifically, Ag-modified TiO of comparative example 12And SnO2The preparation method of the compound comprises the following steps:
step 1: impregnating with Sn-containing solutions
Soaking coal columnar activated carbon in SnCl with the concentration of 0.02mol/mL at the temperature of 25 DEG C4·5H2O aqueous solution for 4 h.
The parameters of the coal columnar activated carbon are as follows: the iodine adsorption value is 800-850MG/G, and the carbon tetrachloride adsorption rate is more than or equal to 40 percent; specific surface area: 800-850m2(ii)/g; water content: less than or equal to 5 percent; ash content: less than or equal to 10 percent; pH value: 9-10; particle diameter: 1.5-4 mm; distribution force: 1.5-10 mm; the bulk density is 530 g/L; the wear-resistant strength is more than or equal to 98 percent.
From the above SnCl4·5H2Taking out the coal columnar activated carbon from the O water solution, calcining at 550 ℃ for 2h to obtain the SnO2The activated carbon of (1).
The above-mentioned metal oxide powder is mixed with SnO2The active carbon is firstly washed by absolute ethyl alcohol for 3 times, then washed by distilled water for 3 times, and dried for 6 hours at the temperature of 60 ℃ to obtain the dried SnO2The activated carbon of (1).
Step 2: impregnating titaniferous solutions
Drying the SnO obtained in the step 12The activated carbon is soaked in a butyl titanate solution with the concentration of 0.1mol/mL at the temperature of 25 ℃ to obtain the SnO2And TiO2The activated carbon of (1).
Taking out SnO from the butyl titanate solution2And TiO2Roasting at 1100 deg.C to remove active carbon to obtain TiO2And SnO2The complex of (1).
And step 3: preparation of Ag-modified TiO2And SnO2Composite material
TiO obtained in the step 22And SnO2The compound is impregnated with AgNO with the same volume to the concentration of 0.2mol/L3Mixing the above materials in water solution, filtering with 200nm filter screen, collecting precipitate, drying at 60 deg.C for 6 hr, and annealing at 550 deg.C for 2 hr to obtain Ag modified TiO2And SnO2And (c) a complex.
Comparative example 2
The difference from example 1 is that in step 1 of comparative example 2, a solution of butyl titanate is used instead of SnCl4·5H2O aqueous solution, the rest being the same. Specifically, Ag-modified TiO of comparative example 22The preparation method of the nanotube photocatalytic bactericide comprises the following steps:
step 1: preparation of a catalyst having TiO2Porous alumina template of nanotube
And (3) taking a porous alumina template, wherein the porous alumina template is a single-pass template, the aperture is 30nm, the pore spacing is 65nm, and the pore depth is 5 microns +/-0.2 microns. Soaking in 0.1mol/mL solution of butyl titanate at 25 deg.C for 4 h.
Removing TiO from the solution of butyl titanate2Removing the porous alumina template with NaOH solution with concentration of 2mol/L, washing with anhydrous ethanol for 3 times, washing with distilled water for 3 times, and drying at 60 deg.C for 6 hr to obtain TiO2A nanotube.
Step 2: preparation of Ag-modified TiO2Nanotube photocatalytic bactericide
The TiO obtained in the step 12Soaking the nanotube into AgNO with the equal volume and the concentration of 0.2mol/L3Mixing the above solutions, filtering with 200nm filter screen, collecting precipitate, drying at 60 deg.C for 6 hr, and annealing at 550 deg.C for 2 hr to obtain AgModified TiO2Nanotube photocatalytic germicide.
Experimental example 1
The Ag-modified TiO compounds prepared in examples 1-3 were collected2And SnO2The composite nanotube photocatalytic bactericide is prepared into solutions with the concentration of 50mg/mL by using clear water, and the solutions are named as solution 1, solution 2 and solution 3 respectively.
Meanwhile, the Ag modified TiO prepared in comparative example 1 was taken2And SnO2Composite and Ag modified TiO prepared in comparative example 22The nanotube photocatalytic bactericide is prepared into solutions with the concentration of 50mg/mL by using clear water, and the solutions are named as a solution 4 and a solution 5 respectively.
Determination of biological Activity: ag-modified TiO compounds prepared in examples 1 to 3 were measured by the hyphal growth rate method under in vitro conditions2And SnO2Composite nanotube photocatalytic bactericide and Ag modified TiO prepared in comparative example 12And SnO2Composite and Ag modified TiO prepared in comparative example 22The antibacterial activity of the nanotube photocatalytic bactericide.
The culture medium is prepared from solution 1-solution 5 (mass concentration is 50mg/mL) to obtain 5 concentration gradients, i.e., 8mg/mL, 4mg/mL, 2mg/mL, 1mg/mL and 0.5 mg/mL. After the plate is solidified, the well-cultured staphylococcus aureus cake (d is 5.0mm) with consistent growth is inoculated into the center of the plate. Each dish was inoculated with one cake of bacteria, inoculated with sterile aqueous medium as a blank Control (CK), 3 replicates were set for each treatment, incubated at 26 ℃ in a constant temperature incubator, and data was recorded when the control dish was about to grow full of colonies. Each colony was measured twice according to the cross method, and the average number represents the colony size, and the formula for calculating the inhibition rate is as follows:
the diameter (mm) of the colony is the average diameter of the colony-the diameter of the cake (5.0mm),
the bacteriostatic ratio (%) - (control colony diameter-treated colony diameter) ÷ control colony diameter × 100%.
The results of the experiment are shown in tables 1 and 2.
TABLE 1 inhibitory Effect of solution 1-solution 3 on Staphylococcus aureus
TABLE 2 inhibitory Effect of solution 4 to solution 5 on Staphylococcus aureus
Experimental example 2
The Ag-modified TiO compounds prepared in examples 1-3 were collected2And SnO2The composite nanotube photocatalytic bactericide is prepared into solutions with the concentration of 50mg/mL by using clear water, and the solutions are named as solution 1, solution 2 and solution 3 respectively.
Meanwhile, the Ag modified TiO prepared in comparative example 1 was taken2And SnO2Composite and Ag modified TiO prepared in comparative example 22The nanotube photocatalytic bactericide is prepared into solutions with the concentration of 50mg/mL by using clear water, and the solutions are named as a solution 4 and a solution 5 respectively.
Determination of biological Activity: ag-modified TiO compounds prepared in examples 1 to 3 were measured by the hyphal growth rate method under in vitro conditions2And SnO2Composite nanotube photocatalytic bactericide and Ag modified TiO prepared in comparative example 12And SnO2Composite and Ag modified TiO prepared in comparative example 22The antibacterial activity of the nanotube photocatalytic bactericide.
The culture medium is prepared from solution 1-solution 5 (mass concentration is 50mg/mL) to obtain 5 concentration gradients, i.e., 8mg/mL, 4mg/mL, 2mg/mL, 1mg/mL and 0.5 mg/mL. After the plate is solidified, the well-cultured bacillus pyocyaneus cake (d is 5.0mm) with consistent growth is inoculated into the center of the plate. Each dish was inoculated with one cake of bacteria, inoculated with sterile aqueous medium as a blank Control (CK), 3 replicates were set for each treatment, incubated at 26 ℃ in a constant temperature incubator, and data was recorded when the control dish was about to grow full of colonies. Each colony was measured twice according to the cross method, and the average number represents the colony size, and the formula for calculating the inhibition rate is as follows:
the diameter (mm) of the colony is the average diameter of the colony-the diameter of the cake (5.0mm),
the bacteriostatic ratio (%) - (control colony diameter-treated colony diameter) ÷ control colony diameter × 100%.
The results of the experiments are shown in tables 3 and 4.
TABLE 3 inhibitory Effect of solution 1 to solution 3 on Pseudomonas aeruginosa
TABLE 4 inhibitory Effect of solution 4 to solution 5 on Pseudomonas aeruginosa
In conclusion, the nanotube photocatalytic bactericide prepared in examples 1 to 3 has a good bactericidal effect on staphylococcus aureus, pseudomonas aeruginosa and the like, and can be used for preparing bactericidal products.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a nanotube photocatalytic bactericide is characterized by comprising the following steps:
step 1: preparation of a catalyst having SnO2Porous alumina template of nanotube
Taking a porous alumina template, soaking in SnCl with the concentration of 0.02-0.1 mol/mL4·5H2O in water solution;
from the above SnCl4·5H2Taking out the porous alumina template from the O aqueous solution, and calcining at high temperature to obtain the porous alumina template with SnO2A porous alumina template of nanotubes;
the above-mentioned metal oxide powder is mixed with SnO2Washing the porous alumina template of the nanotube, and drying to obtain dry SnO2A porous alumina template of nanotubes;
step 2: preparation of TiO2And SnO2Composite nanotubes
Drying the SnO obtained in the step 12Soaking the porous alumina template of the nanotube in a tetrabutyl titanate solution with the concentration of 0.05mol/mL-0.15mol/mL to obtain the template with TiO2And SnO2A porous alumina template of composite nanotubes;
removing TiO from the solution of butyl titanate2And SnO2Removing the porous alumina template of the composite nanotube, washing, and drying to obtain TiO2And SnO2A composite nanotube;
and step 3: preparation of Ag-modified TiO2And SnO2Composite nanotube photocatalytic bactericide
TiO obtained in the step 22And SnO2The composite nano tube is dipped into AgNO with the concentration of 0.2mol/L-0.6mol/L in the same volume3Mixing the raw materials in water solution, filtering, taking precipitate, drying and annealing to obtain Ag modified TiO2And SnO2Composite nanotube photocatalytic germicide.
2. The method for preparing nanotube photocatalytic bactericide according to claim 1, wherein in step 1, the porous alumina template is a single pass, the pore diameter is 30nm, the pore spacing is 65nm, and the pore depth is 5 μm ± 0.2 μm.
3. The preparation method of the nanotube photocatalytic bactericide as claimed in claim 1, wherein in step 1, the soaking temperature is 25-30 ℃ and the time is 4 h; the high-temperature calcination is carried out at 550 ℃ for 2 h.
4. The method for preparing the nanotube photocatalytic bactericide as claimed in claim 1, wherein in step 1, the washing is performed by washing with absolute ethanol for 3-4 times, and then washing with distilled water for 3-4 times; the drying temperature is 60 ℃ and the drying time is 6 h.
5. The method for preparing the nanotube photocatalytic bactericide according to claim 1, wherein in the step 2, the soaking temperature is 25 ℃ to 30 ℃ and the soaking time is 4 hours; the step of removing the porous alumina template refers to dissolving the TiO by using NaOH solution with the concentration of 2mol/L2And SnO2A porous alumina template of composite nanotubes.
6. The method for preparing the nanotube photocatalytic bactericide according to claim 1, wherein in the step 2, the washing is performed by washing with absolute ethyl alcohol for 3 to 4 times and then washing with distilled water for 3 to 4 times; the drying temperature is 60 ℃ and the drying time is 6 h.
7. The method for preparing nanotube photocatalytic bactericide as claimed in claim 1, wherein in step 3, the mesh used for filtration has a pore size of 200 nm; the drying temperature is 60 ℃ and the drying time is 6 h.
8. The method for preparing nanotube photocatalytic bactericide as claimed in claim 1, wherein in step 3, the annealing temperature is 550 ℃ and the annealing time is 2 hours.
9. The prepared nanotube photocatalytic bactericide of any one of claims 1 to 8.
10. Use of the nanotube photocatalytic fungicide prepared by the preparation method according to any one of claims 1 to 8 in the preparation of a fungicidal product.
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Application publication date: 20210514 |