CN112007668A - Preparation method of ZnO ternary composite photocatalyst - Google Patents
Preparation method of ZnO ternary composite photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000011206 ternary composite Substances 0.000 title claims abstract description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 244
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
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Abstract
The invention discloses a preparation method of a ZnO ternary composite photocatalyst, belonging to the technical field of environmental protection and photocatalysisThe composite photocatalyst has higher photodegradation and disinfection performance than single ZnO particles and ZnO/ZnSe composite materials, the degradation of methyl orange under visible light reaches 91.5 percent, and Escherichia coli with 4.95log can be inactivated, the preparation method is simple, the adopted raw materials are cheap, the cost is lower, the environmental benefit is good, and the application prospect is good2The advantage of good visible light response, thereby enlarging the visible light response range of ZnO/ZnSe and solving the problem of single MoSe2Is a problem of high recombination rate of electron-hole pairs of the catalyst.
Description
Technical Field
The invention belongs to the technical fields of material preparation, photocatalysis technology and environmental pollution treatment, and relates to a preparation method of a ZnO ternary composite photocatalyst.
Background
The problem of water pollution caused by organic contaminants associated with dyes and biological contamination associated with microorganisms has been of increasing concern. There are about 5,000-10,000 tons of dye released into the water from the textile industry worldwide every year, accounting for about 20% of industrial water pollution. Regarding biological contamination, for example, harmful bacteria in wastewater have been identified as one of the causes of infectious diseases. Therefore, there is an urgent need to develop an effective method for eliminating dyes and harmful bacteria in wastewater. The photocatalytic technology utilizes sunlight to the maximum extent to remove harmful organic pollutants, and the visible light-driven disinfection process is a promising advanced oxidation technology, can be used for eliminating pathogenic bacteria without ultraviolet rays, antibiotic resistance or carcinogenic disinfection byproducts, is harmless to the environment and the like, and is concerned.
The nano semiconductor material ZnO becomes the photocatalyst with the most application potential at present due to the advantages of good photocatalytic activity and antibacterial activity, no toxicity, low price, strong excitation binding energy (60meV) and the like. However, the band gap of ZnO is wide, and the ZnO responds to ultraviolet light (accounting for 3-5% of the energy of sunlight), and the quantum efficiency of the photocatalytic reaction is low, so that the ZnO is limited in practical application. The compounding of ZnO and narrow bandgap semiconductor is an effective method for preparing materials with visible light response. In recent years, ZnSe has a value of 2.70eVA band gap and excellent photosensitivity are considered as a good photocatalytic material. And researches show that the II-type structure formed by ZnO and ZnSe can remarkably promote the separation of photon-generated carriers, and expand the absorption range of ZnO on visible light, so that high catalytic performance is obtained. Muhammad et al (One-pot failure synthesis of the ZnO/ZnSe heterojunction for effective photocatalytic degradation of azo dye) designed that the degradation rate of Congo red at the optimum ZnO/ZnSe ratio was 3.8 times that of pure ZnO. However, ZnO/ZnSe has only a small absorption in the visible region, and thus its application is still limited. In order to solve this problem, the photocatalytic performance of the binary system still needs to be further improved. Recent studies have shown that coupling of more energy levels in the construction of heterostructure nanocomposites results not only in a reduction of the total bandgap energy but also in a reduction of the recombination rate of electron/hole pairs. In addition, the three-way photocatalyst utilizes multi-component synergy to replace simple single-component stacking to improve efficiency. The Chinese patent 201910000869.9 synthesizes ZnO/ZnS/ZnSe composite nanobelts, which show higher activity under the irradiation of sunlight. MoSe2The narrow band gap of the catalyst is 1.7-1.9eV, a wider range of light absorption can be generated, and the unique sandwich layer structure can provide a huge specific surface area, so the catalyst is proved to be a good catalyst promoter for visible light photocatalysis. But the optical quantum efficiency is low due to easy agglomeration and serious recombination of photon-generated carriers. Therefore, the invention synthesizes ZnO, ZnSe and MoSe2The heterostructure composite catalyst realizes that the catalyst has better photocatalytic activity under visible light.
Disclosure of Invention
The invention aims to provide a preparation method of a ZnO ternary composite photocatalyst, and solves the problem that ZnO in the prior art is low in degradation efficiency under the condition of visible low energy consumption.
The technical scheme adopted by the invention is that the preparation method of the ZnO ternary composite photocatalyst is implemented according to the following steps:
preparing ZnO nanoparticles according to the following implementation, putting zinc acetate into absolute ethyl alcohol, and performing ultrasonic treatment to form a solution A; dissolving oxalic acid in absolute ethyl alcohol and stirring at room temperature to form a solution B; and (3) dripping the solution B into the solution A at the speed of 3-4 seconds under the condition of a hot water bath, continuously stirring to obtain sol, aging the sol for a period of time to obtain gel, drying the gel in a drying oven at 60 ℃, finally calcining in a muffle furnace, and obtaining ZnO after the calcination is finished.
The invention is also characterized in that:
in the step 1, the solution A is 1.83g of zinc acetate and 60ml of ethanol, the solution B is 5.04g of oxalic acid and 40ml of ethanol, the water bath temperature is 60 ℃, and the aging time is 24-36 h.
Preparation of MoSe in step 12The nanometer flower is specifically implemented as follows, sodium molybdate dihydrate and selenium powder are dissolved in 60mL of mixed solution of ethanol and deionized water, then the suspension is transferred to a 100mL polytetrafluoroethylene hydrothermal reaction kettle for constant-temperature thermal reaction, precipitates are obtained after cooling to the ambient temperature, and the precipitates are washed for several times by ethanol and distilled water in sequence, the obtained black solid is dried for 12 hours in a vacuum environment at 80 ℃, namely MoSe2And (4) nano flowers.
The ratio of the sodium molybdate dihydrate to the selenium powder is 3: 1-2: 1, the temperature of the constant-temperature thermal reaction is 180-200 ℃, and the reaction time is 18-22 h.
In the step 2, the dosage ratio of the selenium powder, the sodium borohydride and the zinc oxide is 0.076-0.24 g: 0.038-0.11 g: 0.1 to 0.4g of MoSe2The mass of (A) is 0.5-2 mg;
in the step 2, the mass ratio of water to ethylene glycol is 1:1, the temperature of the stainless steel autoclave is 180-240 ℃, and the reaction time is 18-24 hours.
And 2, centrifugally collecting the mixture at 4000-5000 r/min.
The method for calcining in the muffle furnace comprises the following steps: keeping the temperature at 300-700 ℃ for 2-4 h in an air atmosphere, wherein the heating rate is 3-5 ℃/min.
The invention has the beneficial effects that: the invention relates to a preparation method of a ZnO ternary composite photocatalyst, which solves the problem that ZnO in the prior art has low degradation efficiency under the condition of low visible energy consumption. Prepared ZnO/ZnSe/MoSe2The composite photocatalyst has higher photocatalytic capacity than single ZnO and ZnO/ZnSe, overcomes the defects of a single catalytic material, and promotes the charge separation effect by constructing a multi-heterojunction interface. The method has the advantages of less chemical reagents, simple preparation process, no need of complex and expensive equipment, and the prepared ZnO/ZnSe/MoSe2The composite catalyst does not introduce impurities, has high purity, has remarkable photocatalytic effects of degrading methyl orange and inhibiting escherichia coli, constructs a step-by-step electron transfer mechanism, and accelerates the separation of photon-generated carriers; using MoSe2The optical absorption broad spectrum property of the compound expands the optical absorption range, thereby improving the photocatalytic activity, ZnO is prepared by adopting a sol-gel method, and ZnO/ZnSe/MoSe are prepared by a hydrothermal method2A ternary complex. The preparation method is simple, the visible light catalysis efficiency is high, the preparation method has wide application prospect in the field of photocatalysis, and the prepared ZnO/ZnSe/MoSe2The composite photocatalytic material has excellent degradation performance on methyl orange under simulated visible light and good inhibition or sterilization performance on escherichia coli, the adopted raw materials are cheap, the cost is low, and the prepared ZnO/ZnSe/MoSe is2The composite photocatalyst has no pollution to the environment.
Drawings
FIG. 1 is a scanning electron microscope image of a composite photocatalyst prepared by the preparation method of a ZnO ternary composite photocatalyst;
FIG. 2 is a graph of degradation rates of different photocatalysts to methyl orange in the preparation method of the ZnO ternary composite photocatalyst.
FIG. 3 is a bacteriostatic diagram of different photocatalysts in the preparation method of the ZnO ternary composite photocatalyst.
FIG. 4 shows the degradation efficiency of the composite photocatalyst prepared by the preparation method of the ZnO ternary composite photocatalyst to methyl oranges of different concentrations.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a ZnO ternary composite photocatalyst, which is implemented by the following steps:
preparing ZnO nanoparticles according to the following implementation, putting zinc acetate into absolute ethyl alcohol, and performing ultrasonic treatment to form a solution A; dissolving oxalic acid in absolute ethyl alcohol and stirring at room temperature to form a solution B; and (3) dripping the solution B into the solution A at the speed of 3-4 seconds under the condition of a hot water bath, continuously stirring to obtain sol, aging the sol for a period of time to obtain gel, drying the gel in a drying oven at 60 ℃, finally calcining in a muffle furnace, and obtaining ZnO after the calcination is finished. In the step 1, the solution A is 1.83g of zinc acetate and 60ml of ethanol, the solution B is 5.04g of oxalic acid and 40ml of ethanol, the water bath temperature is 60 ℃, and the aging time is 24-36 h. The method for calcining in the furnace comprises the following steps: keeping the temperature at 300-700 ℃ for 2-4 h in an air atmosphere, wherein the heating rate is 3-5 ℃/min.
Preparation of MoSe in step 12The nanometer flower is specifically implemented as follows, sodium molybdate dihydrate and selenium powder are dissolved in 60mL of mixed solution of ethanol and deionized water, then the suspension is transferred to a 100mL polytetrafluoroethylene hydrothermal reaction kettle for constant-temperature thermal reaction, precipitates are obtained after cooling to the ambient temperature, and the precipitates are washed for several times by ethanol and distilled water in sequence, the obtained black solid is dried for 12 hours in a vacuum environment at 80 ℃, namely MoSe2And (4) nano flowers. Specifically, the ratio of sodium molybdate dihydrate to selenium powder is 3: 1-2: 1, the temperature of the constant-temperature thermal reaction is 180-200 ℃, and the reaction time is 18-22 hours.
in the step 2, the dosage ratio of the selenium powder, the sodium borohydride and the zinc oxide is 0.076-0.24 g, 0.038-0.11 g, 0.1-0.4 g, and MoSe is2The mass of (A) is 0.5-2 mg; in the step 2, the mass ratio of water to ethylene glycol is 1:1, the volume of water is 50ml, the temperature of the stainless steel autoclave is 180-240 ℃, and the reaction time is 18-24 h. And 2, centrifugally collecting the mixture at 4000-5000 r/min.
The ZnO ternary composite photocatalyst prepared by the preparation method of the ZnO ternary composite photocatalyst is used for carrying out degradation calculation on methyl orange, and specifically, 0.03g of the prepared photocatalyst is dispersed in 50mL of methyl orange solution (with the concentration of 20-40 mg/L); then, the resulting suspension was stirred in the dark for 30 minutes to reach adsorption-desorption equilibrium; subsequently, the mixture was placed under visible light, sampled every 30min, centrifuged to separate the solid catalyst and collect the supernatant, and then measured with a UV-vis spectrophotometer for lambdamaxAbsorbance value of 464nm and by the formula: eta is 1-Ct/C0X 100% calculating the degradation rate, where C0And CtIs the initial concentration of methyl orange before irradiation and the concentration at a certain time of reaction.
The preparation method of the ZnO ternary composite photocatalyst comprises the steps of ultrasonically dispersing 10mg of a photocatalytic material in 9ml of 85% sterile saline, adding a proper amount of bacterial suspension with the concentration of 107cfu/ml, uniformly mixing, sampling every 30min under visible light irradiation, taking 0.1ml of diluted coating plate after gradient dilution, culturing at 37 ℃ for 18h, counting to determine the number of bacterial colonies, repeating each group of experiments for three times, and performing parallel experiments by light control and dark control.
Example 1:
preparing ZnO nanoparticles: ultrasonically dispersing 1.83g of zinc acetate in 60ml of absolute ethyl alcohol to form a solution A; dissolving oxalic acid in 40ml of absolute ethyl alcohol to form a solution B; dripping the solution B into the solution A at the speed of 3-4 seconds under the water bath temperature of 60 ℃, continuously stirring to obtain sol, aging the sol for a period of time to obtain gel, heating to 400 ℃ at the heating rate of 5 ℃/min in a muffle furnace, keeping the temperature for 2 hours, naturally cooling to room temperature, grinding to obtain ZnO, and storing for later use.
Preparing MoSe2 nanoflowers: 5mmol of sodium molybdate dihydrate and 15mmol of selenium powder are dissolved in 60mL of mixed solution of ethanol and deionized water (volume ratio is 1: 1). Then, the suspension was transferred to a 100ml stainless steel autoclave and thermally reacted at a constant temperature of 200 ℃ for 18h, after cooling to ambient temperature, a precipitate was obtained and washed with ethanol and distilled water in sequence for 3 times, and the black product was vacuum-dried at 80 ℃ for 12h to obtain MoSe2 nanoflower.
Preparing a ZnO/ZnSe/MoSe2 composite photocatalyst: 0.076g of selenium powder, 0.038g of sodium borohydride and 0.2g of zinc oxide are dispersed in a mixed solution of ethanol (25ml) and distilled water (25ml), 0.5mg of molybdenum diselenide is ultrasonically dispersed in the mixed solution for 1h, and then the mixture is transferred into a stainless steel autoclave to be sealed and reacted for 24h at 200 ℃. And after the reaction is finished, cooling to room temperature, centrifugally collecting the precipitate, repeatedly washing with deionized water and ethanol, and vacuum-drying at 60 ℃ for 12h to obtain the ZnO/ZnSe/MoSe2 (0.5%) ternary composite photocatalyst.
As shown in fig. 1, which is a projection electron micrograph of ZnO/ZnSe/MoSe2 (1%), the image shows the hexawurtzite structure of ZnO, with ZnSe particles and MoSe2 nanosheets tightly bound together, which facilitates charge transfer between them and accelerates the separation of electron-hole pairs, thus enhancing photocatalytic activity.
And (3) observing the photocatalytic activity of the prepared composite catalyst by taking degraded Methyl Orange (MO) as a model: 0.03g of catalyst was dispersed in 50ml of a 30mg/L aqueous methyl orange solution. Before illumination, the sample is stirred for 30min in a dark place to achieve adsorption-desorption balance, and then sampling is carried out; after illumination, 4ml samples were taken every 30min, the catalyst was removed by centrifugation, and the supernatant was measured for absorbance at the characteristic absorption wavelength of MO (464nm) using an ultraviolet-visible spectrophotometer and its concentration was determined by a methyl orange standard curve. As shown in FIG. 2, the degradation rate of methyl orange by ZnO/ZnSe/MoSe2 (0.5%) under illumination for 180min is 76%.
Example 2:
preparing ZnO nanoparticles: ultrasonically dispersing 1.83g of zinc acetate in 60ml of absolute ethyl alcohol to form a solution A; dissolving oxalic acid in 40ml of absolute ethyl alcohol to form a solution B; dripping the solution B into the solution A at the speed of 3-4 seconds under the water bath temperature of 60 ℃, continuously stirring to obtain sol, aging the sol for a period of time to obtain gel, heating to 400 ℃ at the heating rate of 5 ℃/min in a muffle furnace, keeping the temperature for 2 hours, naturally cooling to room temperature, grinding to obtain ZnO, and storing for later use.
Preparing MoSe2 nanoflowers: 5mmol of sodium molybdate dihydrate and 15mmol of selenium powder are dissolved in 60mL of mixed solution of ethanol and deionized water (volume ratio is 1: 1). Then, the suspension was transferred to a 100ml stainless steel autoclave and thermally reacted at a constant temperature of 200 ℃ for 18h, after cooling to ambient temperature, a precipitate was obtained and washed with ethanol and distilled water in sequence for 3 times, and the black product was vacuum-dried at 80 ℃ for 12h to obtain MoSe2 nanoflower.
Preparing a ZnO/ZnSe/MoSe2 composite photocatalyst: 0.076g of selenium powder, 0.038g of sodium borohydride and 0.2g of zinc oxide are dispersed in a mixed solution of ethanol (25ml) and distilled water (25ml), 1mg of molybdenum diselenide is ultrasonically dispersed in the mixed solution for 1h, and then the mixture is transferred into a stainless steel autoclave to be sealed and reacted for 24h at 200 ℃. And after the reaction is finished, cooling to room temperature, centrifugally collecting the precipitate, repeatedly washing for 3 times by using deionized water and ethanol, and drying for 12 hours in vacuum at 60 ℃ to obtain the ZnO/ZnSe/MoSe2 (1%) ternary composite photocatalyst.
The photocatalytic activity of the prepared composite catalyst is examined by taking degraded Methyl Orange (MO) as a model, the evaluation conditions are the same as those of the example 1, and as shown in figure 2, the degradation efficiency of ZnO/ZnSe/MoSe2 (1%) to the methyl orange is 91.5 percent when the illumination is 180min
Coli (e.coli) was used as a model strain to investigate the antibacterial properties of the prepared composite catalyst: ultrasonically dispersing 10mg of photocatalytic material in 9ml of 85% sterile saline, then adding a proper amount of bacterial suspension with the concentration of 107cfu/ml, uniformly mixing, then sampling every 30min under the irradiation of visible light, taking 0.1ml of diluted plating plate after adopting gradient dilution, culturing at 37 ℃ for 18h, and counting to determine the colony count. As shown in FIG. 3, the presence of only the ZnO/ZnSe/MoSe2 (1%) catalyst was free of light, and after 120min approximately 1.6log of E.coli was inactivated; the antibacterial effect of ZnO/ZnSe/MoSe2 (1%) in the presence of a ZnO/ZnSe/MoSe2 (1%) catalyst after 120min of light exposure was 4.97log of E.coli inactivated.
Example 3
Preparing ZnO nanoparticles: ultrasonically dispersing 1.83g of zinc acetate in 60ml of absolute ethyl alcohol to form a solution A; dissolving oxalic acid in 40ml of absolute ethyl alcohol to form a solution B; dripping the solution B into the solution A at the speed of 3-4 seconds under the water bath temperature of 60 ℃, continuously stirring to obtain sol, aging the sol for a period of time to obtain gel, heating to 400 ℃ at the heating rate of 5 ℃/min in a muffle furnace, keeping the temperature for 2 hours, naturally cooling to room temperature, grinding to obtain ZnO, and storing for later use.
Preparing MoSe2 nanoflowers: 5mmol of sodium molybdate dihydrate and 15mmol of selenium powder are dissolved in 60mL of mixed solution of ethanol and deionized water (volume ratio is 1: 1). Then, the suspension was transferred to a 100ml stainless steel autoclave and thermally reacted at a constant temperature of 200 ℃ for 18h, after cooling to ambient temperature, a precipitate was obtained and washed with ethanol and distilled water in sequence for 3 times, and the black product was vacuum-dried at 80 ℃ for 12h to obtain MoSe2 nanoflower.
Preparing a ZnO/ZnSe/MoSe2 composite photocatalyst: 0.076g of selenium powder, 0.038g of sodium borohydride and 0.2g of zinc oxide are dispersed in a mixed solution of ethanol (25ml) and distilled water (25ml), 2mg of molybdenum diselenide is ultrasonically dispersed in the mixed solution for 1h, and then the mixture is transferred into a stainless steel autoclave to be sealed and reacted for 24h at 200 ℃. And after the reaction is finished, cooling to room temperature, centrifugally collecting the precipitate, repeatedly washing for 3 times by using deionized water and ethanol, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the ZnO/ZnSe/MoSe2 (2%) ternary composite photocatalyst.
The photocatalytic activity of the prepared composite catalyst is examined by taking degraded Methyl Orange (MO) as a model, the evaluation conditions are the same as those of the example 1, and as shown in figure 2, the degradation efficiency of ZnO/ZnSe/MoSe2 (2%) to the methyl orange is 86.4 percent when the illumination is 180min
Example 4
Preparing ZnO nanoparticles: ultrasonically dispersing 1.83g of zinc acetate in 60ml of absolute ethyl alcohol to form a solution A; dissolving oxalic acid in 40ml of absolute ethyl alcohol to form a solution B; dripping the solution B into the solution A at the speed of 3-4 seconds under the water bath temperature of 60 ℃, continuously stirring to obtain sol, aging the sol for a period of time to obtain gel, heating to 400 ℃ at the heating rate of 5 ℃/min in a muffle furnace, keeping the temperature for 2 hours, naturally cooling to room temperature, grinding to obtain ZnO, and storing for later use.
Preparing MoSe2 nanoflowers: 2.5-7.5 mmol of sodium molybdate dihydrate and 7.5-20 mmol of selenium powder are dissolved in 60mL of mixed solution of ethanol and deionized water (volume ratio is 1: 1). And then, transferring the suspension into a 100ml stainless steel autoclave for carrying out a constant temperature thermal reaction at 200 ℃ for 18-22 h, cooling to ambient temperature to obtain a precipitate, sequentially washing with ethanol and distilled water for 3 times, and carrying out vacuum drying on a black product at 80 ℃ for 12h to obtain the MoSe2 nanoflower.
Preparing a ZnO/ZnSe/MoSe2 composite photocatalyst: 0.076g of selenium powder, 0.038g of sodium borohydride and 0.2g of zinc oxide are dispersed in a mixed solution of ethanol and distilled water, 1mg of MoSe2 is ultrasonically dispersed in the mixed solution, and the mixture is transferred to a stainless steel autoclave to be sealed and reacted for 24 hours at 200 ℃. And after the reaction is finished, cooling to room temperature, centrifugally collecting the precipitate, repeatedly washing for 3 times by using deionized water and ethanol, and drying for 12 hours in vacuum at 60 ℃ to obtain the ZnO/ZnSe/MoSe2 (1%) ternary composite photocatalyst.
And (3) observing the photocatalytic activity of the prepared composite catalyst by taking degraded Methyl Orange (MO) as a model: 0.03g of catalyst was dispersed in 50ml of a 20mg/L methyl orange aqueous solution. Before illumination, the sample is stirred for 30min in a dark place to achieve adsorption-desorption balance, and then sampling is carried out; after illumination, 4ml samples were taken every 30min, the catalyst was removed by centrifugation, and the supernatant was measured for absorbance at the characteristic absorption wavelength of MO (464nm) using an ultraviolet-visible spectrophotometer and its concentration was determined by a methyl orange standard curve. As shown in FIG. 4, the degradation rate of methyl orange by ZnO/ZnSe/MoSe2 (1%) under illumination for 180min was 87%.
Example 5
Preparing ZnO nanoparticles: ultrasonically dispersing 1.83g of zinc acetate in 60ml of absolute ethyl alcohol to form a solution A; dissolving oxalic acid in 40ml of absolute ethyl alcohol to form a solution B; dripping the solution B into the solution A at the speed of 3-4 seconds under the water bath temperature of 60 ℃, continuously stirring to obtain sol, aging the sol for a period of time to obtain gel, heating to 400 ℃ at the heating rate of 5 ℃/min in a muffle furnace, keeping the temperature for 2 hours, naturally cooling to room temperature, grinding to obtain ZnO, and storing for later use.
Preparing MoSe2 nanoflowers: 5mmol of sodium molybdate dihydrate and 15mmol of selenium powder are dissolved in 60mL of mixed solution of ethanol and deionized water (volume ratio is 1: 1). Then, the suspension is transferred into a stainless steel autoclave for constant-temperature thermal reaction for 18h, after cooling to the ambient temperature, precipitate is obtained, the precipitate is sequentially washed by ethanol and distilled water for 3 times, and the black product is dried in vacuum at 80 ℃ for 12h to obtain the MoSe2 nanoflower.
Preparing a ZnO/ZnSe/MoSe2 composite photocatalyst: 0.076g of selenium powder, 0.038g of sodium borohydride and 0.2g of zinc oxide are dispersed in a mixed solution of ethanol and distilled water, 1mg of MoSe2 is ultrasonically dispersed in the mixed solution, and the mixture is transferred to a stainless steel autoclave to be sealed and reacted for 24 hours at 200 ℃. And after the reaction is finished, cooling to room temperature, centrifugally collecting the precipitate, repeatedly washing for 3 times by using deionized water and ethanol, and drying for 12 hours in vacuum at 60 ℃ to obtain the ZnO/ZnSe/MoSe2 (1%) ternary composite photocatalyst.
And (3) observing the photocatalytic activity of the prepared composite catalyst by taking degraded Methyl Orange (MO) as a model: 0.03g of catalyst was dispersed in 50ml of an aqueous methyl orange solution having a concentration of 40 mg/L. Before illumination, the sample is stirred for 30min in a dark place to achieve adsorption-desorption balance, and then sampling is carried out; after the light irradiation, 4ml of the sample was taken every 30min, and the catalyst was removed by centrifugation to measure the absorbance. As shown in FIG. 4, the degradation efficiency of ZnO/ZnSe/MoSe2 (1%) on methyl orange is 71% when the light is irradiated for 180 min.
Coli (e.coli) was used as a model strain to examine the antibacterial activity of the prepared composite catalyst, the evaluation conditions were the same as in example 1, and about 2.6log of e.coli was inactivated by 120min of light irradiation.
The performance of the ZnO ternary composite photocatalyst prepared by the preparation method of the ZnO ternary composite photocatalyst is analyzed by adopting a comparative example, and the method specifically comprises the following steps:
comparative example 1
Taking ZnO as a catalyst, and the preparation process is as follows, 1.83g of zinc acetate is ultrasonically dispersed in 60ml of absolute ethyl alcohol to form a solution A; dissolving oxalic acid in 40ml of absolute ethyl alcohol to form a solution B; dripping the solution B into the solution A at the speed of 3-4 seconds under the water bath temperature of 60 ℃, continuously stirring to obtain sol, aging the sol for a period of time to obtain gel, heating to 400 ℃ at the heating rate of 5 ℃/min in a muffle furnace, keeping the temperature for 2 hours, naturally cooling to room temperature, grinding to obtain ZnO, and storing for later use.
The photocatalytic degradation and bacteriostatic performance of methyl orange and escherichia coli are examined by taking the methyl orange and the escherichia coli as models, the evaluation conditions are the same as those in example 1, as shown in figure 2, the degradation rate of ZnO on the methyl orange is 9.8% after illumination for 180 min; as shown in FIG. 3, in the absence of light with ZnO catalyst alone, after 120min, approximately 0.96log of E.coli was inactivated; in the presence of ZnO and after 120min of light, approximately 1.4log of E.coli was inactivated.
Comparative example 2
ZnO/ZnSe photocatalyst was prepared by dispersing 0.076g of selenium powder and 0.038g of sodium borohydride in a mixed solution of absolute ethanol (25ml) and deionized water (25 ml); adding 0.2g of ZnO into the solution and stirring for 1 hour; and after uniform dispersion, transferring the mixture to a 100ml stainless steel high-temperature reaction kettle, heating to 200 ℃ for reaction for 18-20 h, washing the obtained solid product with water and ethanol after the reaction is finished, and putting the solid product into a vacuum drying oven for drying overnight to obtain ZnO/ZnSe.
The photocatalytic degradation and bacteriostatic performance of methyl orange and escherichia coli are examined by taking the methyl orange and the escherichia coli as models, the evaluation conditions are the same as those in example 1, as shown in figure 2, the degradation rate of ZnO/ZnSe to the methyl orange is 52% after illumination for 180 min; as shown in FIG. 3, in the absence of light only in the presence of the ZnO/ZnSe catalyst, after 120min, about 1.34log of E.coli was inactivated; approximately 3.21log of E.coli was inactivated after 120min of light exposure in the presence of ZnO/ZnSe.
The invention relates to a preparation method of a ZnO ternary composite photocatalyst, which solves the problem that ZnO in the prior art has low degradation efficiency under the condition of low visible energy consumption. Prepared ZnO/ZnSe/MoSe2The composite photocatalyst has higher ZnO content than that of single ZnO,The ZnO/ZnSe has higher photocatalysis capability, which overcomes the defects of a single catalytic material and promotes the charge separation effect by constructing a multi-heterojunction interface. The method has the advantages of less chemical reagents, simple preparation process, no need of complex and expensive equipment, and the prepared ZnO/ZnSe/MoSe2The composite catalyst does not introduce impurities, has high purity, has remarkable photocatalytic effects of degrading methyl orange and inhibiting escherichia coli, constructs a step-by-step electron transfer mechanism, and accelerates the separation of photon-generated carriers; using MoSe2The optical absorption broad spectrum property of the compound expands the optical absorption range, thereby improving the photocatalytic activity, ZnO is prepared by adopting a sol-gel method, and ZnO/ZnSe/MoSe are prepared by a hydrothermal method2A ternary complex. The preparation method is simple, the visible light catalysis efficiency is high, the preparation method has wide application prospect in the field of photocatalysis, and the prepared ZnO/ZnSe/MoSe2The composite photocatalytic material has excellent degradation performance on methyl orange under simulated visible light and good inhibition or sterilization performance on escherichia coli, the adopted raw materials are cheap, the cost is low, and the prepared ZnO/ZnSe/MoSe is2The composite photocatalyst has no pollution to the environment.
Claims (8)
1. The preparation method of the ZnO ternary composite photocatalyst is characterized by comprising the following steps:
step 1, preparing ZnO nanoparticles; preparation of MoSe2A nanoflower;
preparing ZnO nanoparticles according to the following implementation, putting zinc acetate into absolute ethyl alcohol, and performing ultrasonic treatment to form a solution A; dissolving oxalic acid in absolute ethyl alcohol and stirring at room temperature to form a solution B; and (3) dripping the solution B into the solution A at the speed of 3-4 seconds under the condition of a hot water bath, continuously stirring to obtain sol, aging the sol for a period of time to obtain gel, drying the gel in a drying oven at 60 ℃, finally calcining in a muffle furnace, and obtaining ZnO after the calcination is finished.
Step 2, ZnO powder, Se powder and NaBH4Dispersing in mixed solution of ethanol and deionized water; then adding MoSe2Stirring with ultrasonic wave, transferring into 100ml stainless steel autoclave for constant temperature thermal reaction, cooling to room temperature after reactionAnd centrifuging and collecting the mixture, repeatedly washing the mixture for 3 times by using deionized water and ethanol, and drying the obtained light green precipitate at 60 ℃ for 12 hours to obtain the ZnO ternary composite photocatalyst.
2. The method for preparing the ZnO ternary composite photocatalyst as claimed in claim 1, wherein in the step 1, the solution A is 1.83g of zinc acetate and 60ml of ethanol, the solution B is 5.04g of oxalic acid and 40ml of ethanol, the water bath temperature is 60 ℃, and the aging time is 24-36 hours.
3. The method for preparing the ZnO ternary composite photocatalyst according to claim 1, wherein MoSe is prepared in the step 12The nanometer flower is specifically implemented as follows, sodium molybdate dihydrate and selenium powder are dissolved in 60mL of mixed solution of ethanol and deionized water, then the suspension is transferred to a 100mL polytetrafluoroethylene hydrothermal reaction kettle for constant-temperature thermal reaction, precipitates are obtained after cooling to the ambient temperature, and the precipitates are washed for several times by ethanol and distilled water in sequence, the obtained black solid is dried for 12 hours in a vacuum environment at 80 ℃, namely MoSe2And (4) nano flowers.
4. The preparation method of the ZnO ternary composite photocatalyst, according to claim 2, is characterized in that the ratio of sodium molybdate dihydrate to selenium powder is 3: 1-2: 1, the temperature of the isothermal thermal reaction is 180-200 ℃, and the reaction time is 18-22 h.
5. The preparation method of the ZnO ternary composite photocatalyst according to claim 1, wherein in the step 2, the dosage ratio of the selenium powder, the sodium borohydride and the zinc oxide is 0.076-0.24 g: 0.038-0.11 g: 0.1 to 0.4g of MoSe2The mass of (A) is 0.5-2 mg.
6. The preparation method of the ZnO ternary composite photocatalyst, according to claim 1, is characterized in that in the step 2, the mass ratio of water to ethylene glycol is 1:1, the temperature of a stainless steel autoclave is 180-240 ℃, and the reaction time is 18-24 hours.
7. The method for preparing the ZnO ternary composite photocatalyst according to claim 1, wherein in the step 2, the mixture is centrifugally collected at 4000 to 5000 r/min.
8. The preparation method of the ZnO ternary composite photocatalyst as claimed in claim 1, wherein the method for calcining in a muffle furnace comprises the following steps: keeping the temperature at 300-700 ℃ for 2-4 h in an air atmosphere, wherein the heating rate is 3-5 ℃/min.
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