CN112007668B - Preparation method of ZnO ternary composite photocatalyst - Google Patents

Preparation method of ZnO ternary composite photocatalyst Download PDF

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CN112007668B
CN112007668B CN202010812581.4A CN202010812581A CN112007668B CN 112007668 B CN112007668 B CN 112007668B CN 202010812581 A CN202010812581 A CN 202010812581A CN 112007668 B CN112007668 B CN 112007668B
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武占省
杨燕
李云锋
刘啸尘
张洛红
武峥
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Xian Polytechnic University
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Abstract

The invention discloses a preparation method of a ZnO ternary composite photocatalyst, which belongs to the technical field of environmental protection and photocatalysis, wherein the prepared ZnO ternary 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%, and Escherichia coli with 4.95log can be inactivated, the preparation method is simple, the adopted raw materials are cheap, the cost is low, and the preparation method has good environmental benefit and good application prospect 2 The advantage of good visible light response, thereby enlarging the visible light response range of ZnO/ZnSe and solving the problem of single MoSe 2 Is a problem of high recombination rate of electron-hole pairs of the catalyst.

Description

Preparation method of ZnO ternary composite photocatalyst
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 is becoming a growing concern. About 5,000-10,000 tons of dye are released from the textile industry into the water bodies worldwide each year, accounting for about 20% of industrial water pollution. Regarding biological contamination, harmful bacteria in wastewater, for example, 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 (60 meV) 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 been considered as a good photocatalytic material because it has a band gap of 2.70eV and has excellent photosensitivity. 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 effect photocatalytic degradation of azo dye) designed the degradation rate of Congo red at the optimum ratio of ZnO/ZnSe3.8 times 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, and shows higher activity under the irradiation of sunlight. MoSe 2 The 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 MoSe 2 The 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:
step 1, preparing ZnO nanoparticles; preparation of MoSe 2 A 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 the temperature of 60 ℃, finally calcining in a muffle furnace, and obtaining ZnO after the calcination is finished.
Step 2, znO powder, se powder and NaBH 4 Dispersing in mixed solution of ethanol and deionized water; then adding MoSe 2 And (3) stirring the nanoflower ultrasonically, transferring the nanoflower into a 100ml stainless steel autoclave for constant-temperature thermal reaction, cooling to room temperature after the reaction is finished, centrifugally collecting the mixture, repeatedly washing 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.
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 1 2 Dissolving sodium molybdate dihydrate and selenium powder in 60mL of mixed solution of ethanol and deionized water, then transferring the suspension into a 100mL polytetrafluoroethylene hydrothermal reaction kettle for constant-temperature thermal reaction, cooling to the ambient temperature to obtain a precipitate, washing the precipitate with ethanol and distilled water for several times in sequence, and drying the obtained black solid for 12 hours in a vacuum environment at 80 ℃ to obtain MoSe 2 And (4) nano flowers.
The proportion of sodium molybdate dihydrate to selenium powder is 3.
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: 0.1-0.4g of MoSe 2 The mass of (A) is 0.5-2 mg;
in the step 2, the mass ratio of water to glycol is 1, the temperature of the stainless steel autoclave is 180-240 ℃, and the reaction time is 18-24 h.
In step 2, the mixture is centrifugally collected at 4000-5000 r/min.
The method for calcining in the muffle furnace comprises the following steps: keeping the temperature for 2 to 4 hours at the constant temperature of between 300 and 700 ℃ in the air atmosphere, wherein the heating rate is 3 to 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 the degradation efficiency of ZnO is low under the condition of low energy consumption in the prior art. Prepared ZnO/ZnSe/MoSe 2 The 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/MoSe 2 The 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; by using MoSe 2 The 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 method 2 A 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/MoSe 2 The 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 is 2 The 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 according to the following steps:
step 1, preparing ZnO nanoparticles; preparation of MoSe 2 Nano flower;
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 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 under the air atmosphere, and the heating rate is 3-5 ℃/min.
Preparation of MoSe in step 1 2 The 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 ℃, and the MoSe is obtained 2 And (4) nano flowers. Specifically, the ratio of sodium molybdate dihydrate to selenium powder is 3.
Step 2, znO powder, se powder and NaBH 4 Dispersing in mixed solution of ethanol and deionized water; then adding MoSe 2 And (3) carrying out ultrasonic stirring on the nanoflowers, transferring the nanoflowers into a 100ml stainless steel autoclave for constant-temperature thermal reaction, cooling to room temperature after the reaction is finished, 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. Noted as seed ZnO/ZnSe/MoSe 2 A composite photocatalyst of a compound light source and a compound light source,
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 and 0.1-0.4 g, moSe is added 2 The mass of (A) is 0.5-2 mg; step 2Wherein the mass ratio of water to glycol is 1:1, the water is 50ml, the temperature of the stainless steel autoclave is 180-240 ℃, and the reaction time is 18-24 h. In step 2, the mixture is centrifugally collected 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 lambda max Absorbance value of 464nm and by the formula: eta =1-C t /C 0 X 100% calculating the degradation rate, where C 0 And C t Is 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 were dissolved in 60mL of a mixed solution of ethanol and deionized water (volume ratio of 1. Then, the suspension was transferred to a 100ml stainless steel autoclave for isothermal thermal reaction at 200 ℃ for 18h, after cooling to ambient temperature, a precipitate was obtained, and washed with ethanol and distilled water sequentially for 3 times, and the black product was vacuum-dried at 80 ℃ for 12h to obtain MoSe2 nanoflower.
Preparing ZnO/ZnSe/MoSe2 composite photocatalyst: dispersing 0.076g of selenium powder, 0.038g of sodium borohydride and 0.2g of zinc oxide in a mixed solution of ethanol (25 ml) and distilled water (25 ml), ultrasonically dispersing 0.5mg of molybdenum diselenide in the mixed solution for 1h, transferring the mixture into a stainless steel autoclave, sealing, and reacting at 200 ℃ for 24h. 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 a hexagonal wurtzite structure of ZnO, with ZnSe particles and MoSe2 nanosheets being 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 solution of methyl orange. Before illumination, the sample is stirred for 30min in a dark place to achieve adsorption-desorption balance, and then the sample is taken; after illumination, 4ml of samples are taken every 30min, the catalyst is removed by centrifugation, and the supernatant is subjected to ultraviolet-visible spectrophotometer to determine the absorbance at the characteristic absorption wavelength (464 nm) of MO, and the concentration of the supernatant can be determined by a methyl orange standard curve. As shown in FIG. 2, the degradation rate of methyl orange by light irradiation of 180min and ZnO/ZnSe/MoSe2 (0.5%) 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; and (3) dripping the solution B into the solution A at the speed of 3-4 seconds in a water bath at 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 constant 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 were dissolved in 60mL of a mixed solution of ethanol and deionized water (volume ratio 1. Then, the suspension was transferred to a 100ml stainless steel autoclave for isothermal thermal reaction at 200 ℃ for 18h, after cooling to ambient temperature, a precipitate was obtained, and washed with ethanol and distilled water sequentially 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: dispersing 0.076g of selenium powder, 0.038g of sodium borohydride and 0.2g of zinc oxide in a mixed solution of ethanol (25 ml) and distilled water (25 ml), ultrasonically dispersing 1mg of molybdenum diselenide in the mixed solution for 1h, transferring the mixture into a stainless steel autoclave, sealing, and reacting at 200 ℃ for 24h. And cooling to room temperature after the reaction is finished, centrifugally collecting the precipitate, repeatedly washing for 3 times by using deionized water and ethanol, and drying in vacuum for 12 hours at the temperature of 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, as shown in figure 2, the degradation efficiency of ZnO/ZnSe/MoSe2 (1%) to the methyl orange is 91.5 percent when the composite catalyst is illuminated for 180min
The antibacterial property of the prepared composite catalyst is investigated by taking escherichia coli (e.coli) as a model strain: 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 without light inactivated approximately 1.6log of E.coli after 120 min; the antibacterial effect of ZnO/ZnSe/MoSe2 (1%) in the presence of the 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; and (3) dripping the solution B into the solution A at the speed of 3-4 seconds in a water bath at 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 constant 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 were dissolved in 60mL of a mixed solution of ethanol and deionized water (volume ratio of 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 nanoflowers.
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 (25 ml) and distilled water (25 ml), 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 cooling to room temperature after the reaction is finished, 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 composite catalyst is illuminated for 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. And then, transferring the suspension into a 100ml stainless steel autoclave for carrying out constant temperature thermal reaction at 200 ℃ for 18-22 h, cooling to the ambient temperature to obtain a precipitate, washing with ethanol and distilled water for 3 times in sequence, 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 cooling to room temperature after the reaction is finished, centrifugally collecting the precipitate, repeatedly washing for 3 times by using deionized water and ethanol, and drying in vacuum for 12 hours at the temperature of 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: 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 the sample is taken; after illumination, 4ml of sample was taken every 30min, the catalyst was removed by centrifugation, and the supernatant was measured for absorbance at the characteristic absorption wavelength of MO (464 nm) 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%) is 87% under 180min of illumination.
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 were dissolved in 60mL of a mixed solution of ethanol and deionized water (volume ratio 1. And then, transferring the suspension into a stainless steel high-pressure kettle for constant-temperature thermal reaction for 18h, cooling to the ambient temperature to obtain a precipitate, washing the precipitate with ethanol and distilled water for 3 times in sequence, and drying the black product at 80 ℃ in vacuum 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 cooling to room temperature after the reaction is finished, centrifugally collecting the precipitate, repeatedly washing for 3 times by using deionized water and ethanol, and drying in vacuum for 12 hours at the temperature of 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 40mg/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 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 180min.
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 comprises the following specific steps:
comparative example 1
Taking ZnO as a catalyst, and performing ultrasonic dispersion on 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; and (3) dripping the solution B into the solution A at the speed of 3-4 seconds in a water bath at 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 constant 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 the methyl orange are examined by taking the methyl orange and escherichia coli as models, the evaluation conditions are the same as those in example 1, as shown in figure 2, the light irradiation is 180min, and the degradation rate of ZnO on the methyl orange is 9.8%; 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 irradiation, 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 (25 ml) and deionized water (25 ml); adding 0.2g of ZnO into the solution and stirring for 1 hour; 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 the methyl orange are examined by taking the methyl orange and 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 180min under illumination, and 52%; as shown in FIG. 3, when no light was applied only to the ZnO/ZnSe catalyst, about 1.34log of E.coli was inactivated after 120 min; in the presence of ZnO/ZnSe and after 120min of illumination, approximately 3.21log of E.coli was inactivated.
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/MoSe 2 The composite photocatalyst has higher photocatalytic capability 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/MoSe 2 The 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(ii) a By using MoSe 2 The optical absorption broad spectrum property of the compound expands the optical absorption range, thereby improving the photocatalytic activity, znO is firstly prepared by adopting a sol-gel method, and then ZnO/ZnSe and ZnO/ZnSe/MoSe are prepared by a hydrothermal method 2 A 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/MoSe 2 The 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 is 2 The composite photocatalyst has no pollution to the environment.

Claims (1)

1. The preparation method of the ZnO ternary composite photocatalyst is characterized by comprising the following steps:
step 1, preparing ZnO nanoparticles; preparation of MoSe 2 A 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; dripping the solution B into the solution A at the speed of 3-4 seconds under the condition of 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 NaBH 4 Dispersing in mixed solution of ethanol and deionized water; then adding MoSe 2 Carrying out ultrasonic stirring on the nanoflower, transferring the nanoflower into a 100mL stainless steel autoclave for constant-temperature thermal reaction, cooling to room temperature after the reaction is finished, centrifuging and collecting the mixture, repeatedly washing for 3 times by using deionized water and ethanol, and drying the obtained light green precipitate at 60 ℃ for 12 hours to obtain a ZnO ternary composite photocatalyst;
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 MoSe is prepared in the step 1 2 The nanometer flower is implemented as followsDissolving sodium molybdate hydrate and selenium powder in 60mL of mixed solution of absolute ethyl alcohol and deionized water, then transferring the suspension into a 100mL polytetrafluoroethylene hydrothermal reaction kettle for constant-temperature thermal reaction, cooling to the ambient temperature to obtain a precipitate, washing the precipitate with absolute ethyl alcohol and distilled water for several times in sequence, and drying the obtained black solid for 12 hours in a vacuum environment at 80 ℃ to obtain MoSe 2 A nanoflower;
the method for calcining in the muffle furnace comprises the following steps: keeping the temperature at 300-700 ℃ for 2-4 h in air atmosphere, wherein the heating rate is 3-5 ℃/min;
in the step 2, se powder and NaBH are used 4 And ZnO powder in a dosage ratio of 0.076-0.24 g: 0.038-0.11 g: 0.1-0.4g of MoSe 2 The mass of (A) is 0.5-2 mg; the temperature of the constant temperature thermal reaction is 180-200 ℃, and the reaction time is 18-22 h;
in the step 2, the mass ratio of the deionized water to the ethanol is 1, the temperature of the stainless steel autoclave is 180-240 ℃, and the reaction time is 18-24 h;
in the step 2, the mixture is centrifugally collected at 4000-5000 r/min.
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