CN108772084B - TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3Preparation method and application of composite nano material - Google Patents
TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3Preparation method and application of composite nano material Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 42
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 35
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- B01J35/39—
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- 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
- A01N59/20—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
Abstract
The invention discloses TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3A preparation method and application of a composite nano material, belonging to the technical field of synthesis of photocatalytic antibacterial materials. With nano TiO2And Cu (NO)3)2Adding Na as main material in certain proportion2CO3Solution, and water bath method to obtain TiO with high antibacterial activity2/Cu2(OH)2CO3A composite nanomaterial. The invention adopts an in-situ growth method to prepare the nano-titanium oxide on TiO2Cu grown on surface of nano-particles2(OH)2CO3The method is simple and easy to implement, the raw materials are cheap and easy to obtain, and the equipment and the process are simple and easy to operate; the method has the advantages of small reagent pollution, good reaction repeatability, mild preparation conditions and the like. The resulting TiO2/Cu2(OH)2CO3The composite nano material shows good bacteriostasis and sterilization performance in the photocatalysis antibacterial process, and has stable performance and good repeatability.
Description
Technical Field
The invention belongs to the technical field of solar energy, photocatalytic materials and environmental pollution treatment, and particularly relates to TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3Composite nano material and its preparation process.
Background
Since Japan scientist Matsunaga [ ]FEMS Microbiology letters, 1985, 29(1-2): 211-214]First reported TiO2After having good bactericidal performance under ultraviolet irradiation, photocatalytic antibacterial materials have received great attention from researchers and have been extensively studied. Research shows that the photocatalytic antibacterial material has broad-spectrum antibacterial performance, can kill various microorganisms, has no specificity on harmful substances released by the microorganisms, can be completely oxidized and decomposed, and does not cause secondary pollution. Therefore, the photocatalytic antibacterial material has the advantages of high antibacterial performance, lasting effect, low drug resistance, no pollution, no toxicity, broad-spectrum antibacterial property and the like, and has good application prospect in the field of water purificationApplied microbiology and biotechnology, 2011, 90(6): 1847-1868]. At present, TiO2The photocatalyst antibacterial material has the advantages of stable chemical property, no toxicity, low cost and the like, and is the most widely used photocatalytic antibacterial material. However, TiO alone2The photoproduction electrons and holes generated in the material are easy to recombine, so that the quantum efficiency and the catalytic activity are reduced, and the practical application of the photocatalysis antibacterial material is restricted.
To achieve higher photocatalytic efficiency, many researchers have includedTo TiO in2Modification research of the photocatalyst. It has been found that in TiO2The surface of the photocatalyst is loaded with a small amount of noble metal as a cocatalyst, so that the recombination of photogenerated electrons and holes can be effectively inhibited, and the photocatalytic performance of the photocatalyst is improved. Zhao [ 2 ]Biomaterials, 2011, 32(24): 5706-5716]The Ag/TiO is synthesized by using a photo-reduction method2The results of antibacterial experiments on the nanotube composite show that the prepared composite has excellent antibacterial property. However, the noble metal is very expensive, and the noble metal used as the promoter has a high cost, so that it is an important research direction to improve the photocatalytic performance and reduce the cost. Recently, Cu compound promoters have been reported in many reports because of their low cost and high efficiency. Xu 2International Journal of Hydrogen Energy, 2010, 35(11): 5254-5261]Etc. report TiO of composite Cu-based cocatalyst2Photocatalytic materials even more noble than some noble metal-supported TiO2The photocatalytic efficiency of the photocatalytic material is higher. However, to date, TiO has been used2The research of the Cu-series cocatalyst for photocatalytic antibacterial has not been reported.
Disclosure of Invention
Aiming at the existing TiO2The photocatalytic material has the defects of complex preparation process, high cost and easy recombination of photo-generated electron-hole pairs, and the technical problem to be solved by the invention is to synthesize TiO with excellent photocatalytic antibacterial property and low cost by using a simple method2/Cu2(OH)2CO3Composite nano material and its preparation process.
In order to solve the technical problems, the invention adopts the following technical scheme:
TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3The preparation method of the composite nano material comprises the following steps:
(1) adding TiO into the mixture2Adding the nano particles into deionized water; then Cu (NO) is added3)2٠3H2O solid, transferring the O solid to a 60 ℃ water bath kettle after ultrasonic stirring uniformly, and keeping the temperature for 10 min to obtain a mixed solution;
(2) mixing Na2CO3Dissolving in deionized water, placing the beaker in 60 deg.C water bath, and maintaining the temperature for 10 min to obtain Na2CO3A solution;
(3) quickly pouring the mixed solution in the step (1) into Na in the step (2)2CO3Stirring in the solution at constant temperature in a 60 deg.C water bath for 30 min; after the reaction, centrifugally separating the product, washing the product twice with deionized water and absolute ethyl alcohol respectively, and drying the product for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain TiO2/Cu2(OH)2CO3A composite photocatalytic material.
Cu (NO) in the step (1)3)2٠3H2O and TiO2The amount ratio of the substances (A) to (B) is 1:13.3 to 53.8.
Cu(NO3)2٠3H2O and Na2CO3The ratio of the amounts of the substances of (a) to (b) is 1: 1.2.
The TiO is2/Cu2(OH)2CO3Cu in composite photocatalytic material2(OH)2CO3The mole percentage of the component (A) is 0.9% -3.6%.
The TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3The application of the composite nano material as a photocatalytic antibacterial agent comprises the following steps: adding 10 mg of TiO2/Cu2(OH)2CO3Placing the composite photocatalytic material and 9.9 mL of PBS in a 60 mm multiplied by 15 mm dish, dispersing and mixing uniformly by ultrasonic for 10 min by an ultrasonic instrument, and then adding 0.1 mL of 10-concentration 107And (3) fully and uniformly mixing the bacterial suspension of CFU/mL, and then placing the mixture under a light source for a photocatalytic antibacterial experiment.
The invention has the beneficial effects that: 1. the invention makes use of TiO2、Cu(NO3)2٠3H2O and Na2CO3Preparing TiO by low-temperature water bath method as a precursor2/Cu2(OH)2CO3A composite photocatalytic material.
2. TiO prepared by the method provided by the invention2/Cu2(OH)2CO3Composite photocatalytic material in mouldHas good inhibition or killing performance to colibacillus under simulated sunlight.
3. The invention has the advantages of cheap raw materials, low cost, simple operation and easy control.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of various samples prepared according to examples 1-5 of the present invention;
FIG. 2 is a TEM photograph of a composite prepared in example 3 of the present invention;
FIG. 3 is an EDX spectrum of a composite prepared in example 3 of the present invention;
FIG. 4 is an XPS spectrum of a composite prepared in example 3 of the present invention;
FIG. 5 is a photograph showing the result of an antibacterial test of the composite material prepared in example 3 of the present invention;
FIG. 6 is a graph showing the photocatalytic antibiotic curves of various samples prepared in examples 1 to 5 of the present invention and a control experiment.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
0.24 g (1 mmol) of Cu (NO) was weighed3)2٠3H2Adding the O solid into 20 mL of deionized water, uniformly stirring by ultrasonic waves, and transferring the O solid into a water bath kettle at 60 ℃ to keep the temperature for 10 min; 0.13 g (1.2 mmol) of Na was weighed2CO3Dissolving in 24 ml deionized water, ultrasonic stirring, and placing in 60 deg.C water bath kettle for 10 min. Then adding Cu (NO)3)2The aqueous solution is poured rapidly over Na2CO3Stirring in water solution at constant temperature of 60 deg.C for 30 min. After the reaction is finished, cooling the reaction product to room temperature, washing the reaction product twice by using deionized water and absolute ethyl alcohol respectively, and drying the reaction product for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain Cu2(OH)2CO3A material.
Example 2
TiO having photocatalytic antibacterial Properties of the example2/Cu2(OH)2CO3The preparation method of the composite nano material comprises the following steps:
(1) 4.30 g (53.8 mmol) TiO were weighed2Adding the nanoparticles into 20 mL of deionized water; then 0.24 g (1 mmol) of Cu (NO) was added3)2٠3H2O solid, ultrasonic stirring, transferring to a 60 ℃ water bath kettle, and keeping the temperature for 10 min;
(2) 0.13 g (1.2 mmol) of Na was weighed2CO3Dissolving in 24 ml deionized water, placing the beaker in a 60 deg.C water bath, and keeping the temperature for 10 min;
(3) then TiO is filled in2And Cu (NO)3)2The mixed aqueous solution of (A) is poured into Na rapidly2CO3Stirring in water solution at constant temperature of 60 deg.C for 30 min; after the reaction, centrifugally separating the product, washing the product twice with deionized water and absolute ethyl alcohol respectively, and drying the product for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to prepare TiO2/Cu2(OH)2CO3-0.9% of composite photocatalytic material.
Preparing an LB culture medium: weighing 10 g of sodium chloride, 10 g of tryptone and 5 g of yeast extract powder, adding water to 1000 mL, and adjusting the pH value to 7.0 by using NaOH solution to obtain an LB liquid culture medium; adding 15 g of agar into the liquid culture medium to obtain solid culture medium, sterilizing the culture medium in a high-pressure steam sterilization kettle at 121 deg.C for 25 min, and refrigerating for use.
And (3) antibacterial experiment: 1) taking a refrigerator preserved Escherichia coli K12 strain, streaking on a solid LB culture medium plate at 37 ℃, culturing overnight, activating twice, taking an activated single colony in a liquid LB culture medium at 37 ℃, carrying out shake culture at 150 rpm for 12 h, carrying out shake culture twice, taking a bacterium liquid obtained by last shake culture at 6000 rpm, carrying out 5 min, centrifuging, collecting the bacterium, washing the bacterium with a PBS buffer solution for three times, suspending the bacterium in the PBS, and adjusting the concentration of the bacterium to be about 107CFU/mL for photocatalytic experiments. All consumables required in the experiment are placed in a sterilization pot for sterilization for 30min at the temperature of 121 ℃.
2) Concentration of materials used in the experimentIs 1 mg/mL. Firstly, 10 mg of material powder and 9.9 mL of PBS are placed in a 60 mm multiplied by 15 mm dish, dispersed and mixed evenly by ultrasonic for 10 min by an ultrasonic instrument, and then 0.1 mL of 10-concentration 10-component solution is added7And (3) fully and uniformly mixing the bacterial suspension of CFU/mL, and then placing the mixture under a light source for a photocatalytic sterilization experiment. And secondly, taking out 0.1 ml of mixed liquor at different time points, diluting the mixed liquor in a PBS buffer solution in a gradient manner, uniformly coating the mixed liquor on an LB (Langmuir-Blodgett) plate, culturing the mixed liquor at 37 ℃ for 24 hours, and calculating the number of single colonies of escherichia coli and the sterilization rate at different time points. Control experiments included pure TiO2And Cu2(OH)2CO3Killing effect on escherichia coli under illumination and TiO2/Cu2(OH)2CO3Survival of E.coli in the absence of light and in the absence of material only. All photocatalytic experiments were repeated three times, and the entire experimental environment was performed at room temperature.
The obtained sample was subjected to XRD analysis using X-ray diffractometer model D8 Advance of Bruker, Germany. FIG. 1 is an XRD spectrum of a sample showing that the prepared sample is pure phase Cu2(OH)2CO3. The antimicrobial curves of FIG. 6 show that Cu2(OH)2CO3After the material is illuminated for 80 min, about 44.9 percent of escherichia coli survive, and the photocatalytic antibacterial rate is only 55.1 percent.
The antibacterial curve shows (fig. 6), the composite material of the embodiment shows good photocatalytic antibacterial performance under simulated sunlight, after 80 min of reaction, about 1.2 log of escherichia coli survive, and the photocatalytic antibacterial rate can reach 99.99%.
Example 3
TiO having photocatalytic antibacterial Properties of the example2/Cu2(OH)2CO3The preparation method of the composite nano material comprises the following steps:
(1) 2.15 g (26.9 mmol) TiO are weighed2Adding the nanoparticles into 20 mL of deionized water; then 0.24 g (1 mmol) of Cu (NO) was added3)2٠3H2O solid, ultrasonic stirring, transferring to a 60 ℃ water bath kettle, and keeping the temperature for 10 min;
(2) 0.13 g (1.2 mmol) of Na was weighed2CO3Dissolving in 24 ml deionized water, placing the beaker in a 60 deg.C water bath, and keeping the temperature for 10 min;
(3) then TiO is filled in2And Cu (NO)3)2The mixed aqueous solution of (A) is poured into Na rapidly2CO3Stirring in water solution at constant temperature of 60 deg.C for 30 min; after the reaction, centrifugally separating the product, washing the product twice with deionized water and absolute ethyl alcohol respectively, and drying the product for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to prepare TiO2/Cu2(OH)2CO3-1.8% of composite photocatalytic material.
By TEM image (FIG. 2), it can be found that TiO is present2The surface of the nano-particle is loaded with 1-2 nm nano-clusters, and EDX and XPS tests prove that the nano-particle is Cu2(OH)2CO3Nanoclusters (fig. 3 and 4).
The photocatalysis antibacterial experiment result shows that Cu2(OH)2CO3Nanocluster supported TiO2The photocatalytic antibacterial performance is greatly improved. As shown in FIG. 5, the original concentration was 107 cfu mL-1The Escherichia coli was almost completely killed after 80 min of light irradiation. Compared with pure TiO2And Cu2(OH)2CO3The photocatalytic sterilization effect is improved by 6 log units. The remarkable improvement of the photocatalytic bactericidal activity of the composite material is mainly attributed to Cu2(OH)2CO3Can trap TiO as a cocatalyst2Electrons in conduction band to effectively inhibit TiO2The recombination of electrons and holes is beneficial to the separation of photo-generated electron-hole pairs.
Example 4
TiO having photocatalytic antibacterial Properties of the example2/Cu2(OH)2CO3The preparation method of the composite nano material comprises the following steps:
(1) 1.45 g (18.2 mmol) TiO are weighed2Adding the nanoparticles into 20 mL of deionized water; then 0.24 g (1 mmol) of Cu (NO) was added3)2٠3H2O solid, ultrasonic stirring, transferring to a 60 ℃ water bath kettle, and keeping the temperature for 10 min;
(2) 0.13 g (1.2 mmol) of Na was weighed2CO3Dissolving in 24 ml deionized water, placing the beaker in a 60 deg.C water bath, and keeping the temperature for 10 min;
(3) then TiO is filled in2And Cu (NO)3)2The mixed aqueous solution of (A) is poured into Na rapidly2CO3Stirring in water solution at constant temperature of 60 deg.C for 30 min; after the reaction, centrifugally separating the product, washing the product twice with deionized water and absolute ethyl alcohol respectively, and drying the product for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to prepare TiO2/Cu2(OH)2CO3-2.7% of composite photocatalytic material.
Example 5
TiO having photocatalytic antibacterial Properties of the example2/Cu2(OH)2CO3The preparation method of the composite nano material comprises the following steps:
(1) 1.06 g (13.3 mmol) TiO are weighed2Adding the nanoparticles into 20 mL of deionized water; then 0.24 g (1 mmol) of Cu (NO) was added3)2٠3H2O solid, ultrasonic stirring, transferring to a 60 ℃ water bath kettle, and keeping the temperature for 10 min;
(2) 0.13 g (1.2 mmol) of Na was weighed2CO3Dissolving in 24 ml deionized water, placing the beaker in a 60 deg.C water bath, and keeping the temperature for 10 min;
(3) then TiO is filled in2And Cu (NO)3)2The mixed aqueous solution of (A) is poured into Na rapidly2CO3Stirring in water solution at constant temperature of 60 deg.C for 30 min; after the reaction, centrifugally separating the product, washing the product twice with deionized water and absolute ethyl alcohol respectively, and drying the product for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to prepare TiO2/Cu2(OH)2CO3-3.6% of composite photocatalytic material. The antibacterial curve shows (figure 6) that the composite material also shows better photocatalytic antibacterial performance under simulated sunlight. After 80 min of light, only about 3.48 log of E.coli survived.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (1)
1. TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3The application of the composite nano material as a photocatalytic antibacterial agent comprises the following steps: adding 10 mg of TiO2/Cu2(OH)2CO3Placing the composite photocatalytic material and 9.9 mL of PBS in a 60 mm multiplied by 15 mm dish, dispersing and mixing uniformly by ultrasonic for 10 min by an ultrasonic instrument, and then adding 0.1 mL of 10-concentration 107Fully and uniformly mixing the bacterial suspension of CFU/mL, and then placing the mixture under a light source for a photocatalytic antibacterial experiment;
the TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3The preparation method of the composite nano material comprises the following steps:
(1) adding TiO into the mixture2Adding the nano particles into deionized water; then Cu (NO) is added3)2٠3H2O solid, transferring the O solid to a 60 ℃ water bath kettle after ultrasonic stirring uniformly, and keeping the temperature for 10 min to obtain a mixed solution;
(2) mixing Na2CO3Dissolving in deionized water, placing the beaker in 60 deg.C water bath, and maintaining the temperature for 10 min to obtain Na2CO3A solution;
(3) quickly pouring the mixed solution in the step (1) into Na in the step (2)2CO3Stirring in the solution at constant temperature in a 60 deg.C water bath for 30 min; after the reaction, centrifugally separating the product, washing the product twice with deionized water and absolute ethyl alcohol respectively, and drying the product for 12 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain TiO2/Cu2(OH)2CO3A composite photocatalytic material;
c in the step (1)u(NO3)2٠3H2O and TiO2The amount ratio of the substances is 1: 13.3-53.8; cu (NO)3)2٠3H2O and Na2CO3The ratio of the amount of the substances of (a) to (b) is 1: 1.2;
the TiO is2/Cu2(OH)2CO3Cu in composite photocatalytic material2(OH)2CO3The mole percentage of the component (A) is 0.9% -3.6%.
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