CN112010387A - Method for degrading dye through photocatalysis of rodlike zinc oxide assisted by ultrasound - Google Patents
Method for degrading dye through photocatalysis of rodlike zinc oxide assisted by ultrasound Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 188
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- 238000000034 method Methods 0.000 title claims abstract description 41
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- 230000000593 degrading effect Effects 0.000 title claims abstract description 28
- 230000015556 catabolic process Effects 0.000 claims abstract description 41
- 238000006731 degradation reaction Methods 0.000 claims abstract description 41
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 32
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
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- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
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- 239000000843 powder Substances 0.000 claims description 3
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- 238000001291 vacuum drying Methods 0.000 claims description 3
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 58
- 229940012189 methyl orange Drugs 0.000 description 58
- 239000000975 dye Substances 0.000 description 38
- 239000001048 orange dye Substances 0.000 description 11
- 239000010453 quartz Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
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- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a method for degrading dye by photocatalysis of rodlike zinc oxide assisted by ultrasound, which is implemented according to the following steps: the method comprises the steps of taking zinc oxide and dye, carrying out magnetic stirring in a dark state to achieve adsorption-desorption balance, turning on a xenon lamp and an ultrasonic emitter, carrying out ultraviolet irradiation and ultrasonic radiation synchronously, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and ultrasonic equipment to complete dye degradation, wherein when the photocatalyst is subjected to photocatalytic degradation, the cavitation effect of ultrasonic waves can generate active free radicals to assist in degrading the dye, the ultrasonic waves can continuously clean the surface of the catalyst to prevent inactivation, the contact area between the dispersed and aggregated catalyst and pollutants is increased, the potential gradient caused by bending deformation of the rodlike zinc oxide under the ultrasonic action improves the separation effect of photo-generated electrons and holes, and the method has the advantage of improving the catalytic effect. Thereby solving the problem that the dye wastewater can not be effectively treated in the prior art.
Description
Technical Field
The invention belongs to the technical field of dye wastewater treatment, and relates to a method for degrading a dye by photocatalysis of rodlike zinc oxide under the assistance of ultrasound.
Background
The textile industry is one of the dominant industries in China, and with the continuous emergence of various novel textiles, the textile process becomes more complicated. Among them, the dyeing of textile cloth requires the use of various dyes having complicated structures and the consequent generation of a large amount of dye waste water. Because the dyes are various in types, the generated wastewater has the characteristics of high organic matter content, deep chromaticity, complex components, difficult degradation and the like, and even part of the dye wastewater shows certain biological toxicity. If the wastewater cannot be effectively treated before being discharged into an environmental water area, not only the stability of the water environment is damaged, but also certain harm is caused to the survival of water organisms and even the health of human bodies. Currently, the main method for treating wastewater is a biodegradation method, however, the complex components of dye wastewater are not beneficial to the growth and reproduction of microorganisms, and cannot be effectively treated in the actual operation process. In order to find a more effective method for treating dye wastewater, a process capable of degrading dyes into non-toxic and harmless products has been the focus of research.
The photocatalysis method is a new advanced oxidation process, is often combined with various advanced oxidation technologies such as a Fenton method, ozone oxidation, electrochemical oxidation and the like, and is used as one of pretreatment measures for an inflow water sample. The photocatalytic technology is a method for degrading a target pollutant by reacting the pollutant with a catalytic material having a surface with strong oxidation-reduction properties under the irradiation of sunlight. Currently, numerous photocatalytic materials have been successfully prepared and exhibit good catalytic effects. The zinc oxide is one of the well-studied photocatalytic materials, and is widely applied to the field of photocatalysis due to the advantages of good chemical stability, no toxicity, simple preparation, low cost and the like. However, single zinc oxide has low light utilization, high volatility and low economic efficiency, which reduces the practical use value of zinc oxide. In order to improve the photocatalytic performance of zinc oxide, numerous zinc oxide modification methods including metal/nonmetal doping, noble metal deposition, semiconductor compounding, and the like are reported at home and abroad. Wu et al [ Type II hectohection in microwave nanoparticles/graphite carbon nitride promoting photocatalytic activity ] effectively improves the separation of carriers, improves the absorption efficiency of visible light, and enhances the degradation efficiency of target pollutants by compounding zinc oxide and graphite carbon nitride. The method effectively improves the separation effect of the photo-generated electrons and the holes and enlarges the photoresponse range. However, the modification method just improves the absorption capacity of the zinc oxide catalyst to light energy by performing certain modification on the zinc oxide catalyst, and fails to consider the capture of multi-level energy by the material to improve the catalytic degradation performance.
Ultrasonic wave is vibration energy widely existing in nature, and under the irradiation of the ultrasonic wave with certain frequency, tiny bubbles existing in liquid are rapidly collapsed and closed and release huge energy, and a large amount of active free radicals are generated in the process and complex dyes can be effectively decomposed. However, the degradation of the dye by using the ultrasonic wave alone has problems of high energy consumption, low treatment rate, high cost, and the like, and the yield in practical use is too low. As a piezoelectric material with better prospect, the zinc oxide can absorb light energy and can also effectively absorb vibration energy so as to form a potential difference on the surface of the catalyst. In a wastewater environment, the zinc oxide catalyst generates slight bending deformation due to ultrasonic pressure, and the change of the appearance causes the change of the surface potential of the catalyst to form a certain electric field gradient. The existence of the electric field gradient can convert OH in water-And H+Inducing to form active free radical and acting on the degradation of dye in waste water. Meanwhile, when the light energy is synchronously captured, the existence of the electric field gradient can also promote the separation of the photo-generated electrons and the holes so as to improve the photocatalysis efficiency. While one-dimensional, as compared to two-dimensional, sheet-like and three-dimensional, flower-like morphologiesThe rod-like shape of (2) has more excellent piezoelectric properties. Therefore, the photocatalytic degradation of the dye by using the rod-shaped zinc oxide assisted by ultrasound is a feasible measure for improving the treatment efficiency of the dye wastewater.
Disclosure of Invention
The invention aims to provide a method for degrading dye by photocatalysis of rodlike zinc oxide assisted by ultrasound, which solves the problem that dye wastewater cannot be effectively treated in the prior art.
The technical scheme adopted by the invention is that the method for degrading the dye by photocatalysis of the rodlike zinc oxide assisted by ultrasound specifically comprises the following steps: and (3) magnetically stirring zinc oxide and dye in a dark state to achieve adsorption-desorption balance, turning on a xenon lamp and an ultrasonic emitter, synchronously carrying out ultraviolet irradiation and ultrasonic radiation, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, and finishing dye degradation.
The invention is also characterized in that:
the zinc oxide is rod-shaped, and the specific surface area is 4.24m2The grain size is 31.82nm, and the forbidden band width is 3.3 eV.
The power of the xenon lamp is 300W, and the power of the ultrasonic wave is 100-500W.
The time of magnetic stirring is not less than 30 minutes.
The preparation method of the rodlike zinc oxide comprises the steps of respectively dissolving zinc nitrate hexahydrate and hexamethylenetetramine into deionized water, uniformly stirring for 30 minutes, mixing the solutions to form a mixed solution, stirring for 20-30 minutes again, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, respectively keeping the mixed solution at 90 ℃ for 18-20 hours, washing white powder with deionized water and absolute ethyl alcohol for more than three times, and drying in vacuum for 12 hours to finally obtain the required rodlike zinc oxide.
The mass ratio of the zinc nitrate hexahydrate to the hexamethylenetetramine is 0.5-0.59: 0.25-0.28.
Deionized water is at least 20 mL.
The vacuum drying temperature is 60-80 ℃.
The invention has the beneficial effects that: the invention relates to a method for degrading dye by photocatalysis of rodlike zinc oxide assisted by ultrasound, which solves the problem that dye wastewater cannot be effectively treated in the prior art. The preparation process of the zinc oxide is simple, the raw material cost is low, the reaction conditions are mild and easy to meet, the zinc oxide photocatalyst has better significance for the application of the zinc oxide photocatalyst in the field of catalysis, and the cavitation effect caused by ultrasonic waves can generate active free radicals to assist in degrading the dye; the contact area between the dispersed and agglomerated catalyst and pollutants is increased, and the catalytic effect is improved; the potential gradient caused by bending deformation of the rodlike zinc oxide under the ultrasonic action improves the separation effect of photo-generated electrons and holes; continuous cleaning of the catalyst surface prevents deactivation. The photocatalytic degradation efficiency is far greater than the sum of the single photocatalytic and ultrasonic catalytic efficiencies. When the ultrasonic power is 200W and the xenon lamp illumination time is 100 minutes, the degradation efficiency of the methyl orange reaches 84.6 percent; when the catalytic degradation is carried out only by the illumination of a xenon lamp, the degradation efficiency of the methyl orange reaches 36 percent; when the catalytic degradation is carried out only by ultrasonic waves, the degradation efficiency of the methyl orange reaches 15.9 percent; the results show that the photocatalytic degradation efficiency of the rodlike zinc oxide can be remarkably promoted by ultrasonic assistance; compared with other multidimensional shapes, the rod-shaped zinc oxide has a simple shape and structure, is not easily damaged by ultrasonic waves, and can still keep the integrity of the shape after multiple experiments of degrading methyl orange by ultrasonic-assisted illumination. At the same time, the stability of degradation can also be maintained.
Drawings
FIG. 1 is a scanning electron microscope image of rod-shaped zinc oxide prepared in a method for degrading dye by photocatalysis through ultrasound-assisted rod-shaped zinc oxide;
FIG. 2 is a scanning electron microscope image of rod-shaped zinc oxide after being degraded by the ultrasonic-assisted photocatalysis in the method for degrading the dye by the ultrasonic-assisted photocatalysis.
FIG. 3 is a graph showing the degradation rate of rod-shaped zinc oxide in a method for degrading dye by photocatalysis with ultrasound-assisted rod-shaped zinc oxide, wherein the rod-shaped zinc oxide degrades methyl orange by ultrasonic oxidation, photocatalytic oxidation and ultrasound-assisted photocatalytic oxidation;
FIG. 4 is a graph of the degradation rate of rod-shaped zinc oxide with different contents in a method for degrading dye by ultrasound-assisted rod-shaped zinc oxide photocatalysis in a synergistic manner;
FIG. 5 is a graph of the degradation rate of rod-shaped zinc oxide with different power ultrasonic synergistic photocatalytic degradation of dye in a method of ultrasonic-assisted rod-shaped zinc oxide photocatalytic degradation of dye;
FIG. 6 is a comparison of XRD of rod-shaped zinc oxide before and after being degraded by ultrasound in a method for degrading dye by ultrasound-assisted rod-shaped zinc oxide photocatalysis;
fig. 7 is a graph of the degradation efficiency of rodlike zinc oxide to methyl orange after three cycles of experiments in which rodlike zinc oxide is degraded by methyl orange under the assistance of ultrasound in a method for degrading dye by photocatalysis of rodlike zinc oxide under the assistance of ultrasound.
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 method for degrading dye by photocatalysis of rodlike zinc oxide assisted by ultrasound, which is implemented by the following steps: and (3) magnetically stirring zinc oxide and dye in a dark state to achieve adsorption-desorption balance, turning on a xenon lamp and an ultrasonic emitter, synchronously carrying out ultraviolet irradiation and ultrasonic radiation, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, and finishing dye degradation.
The zinc oxide is rod-shaped, and has a specific surface area of 4.24m2The grain size is 31.82nm, and the forbidden band width is 3.3 eV. The power of the xenon lamp is 300W, and the power of the ultrasonic wave is 100-500W. The magnetic stirring time is not less than 30 minutes, and the mass of the added rodlike zinc oxide is as follows: 20-50 mg.
The preparation method of the rodlike zinc oxide comprises the steps of respectively dissolving zinc nitrate hexahydrate and hexamethylenetetramine into deionized water, uniformly stirring for 30 minutes, mixing the solutions to form a mixed solution, stirring for 20-30 minutes again, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, respectively keeping the mixed solution at 90 ℃ for 18-20 hours, washing white powder with deionized water and absolute ethyl alcohol for more than three times, and drying in vacuum for 12 hours to finally obtain the required rodlike zinc oxide.
The mass ratio of zinc nitrate hexahydrate to hexamethylenetetramine is (0.5-0.59): 0.25-0.28. Deionized water is at least 20 mL. The vacuum drying temperature is 60-80 ℃.
The dye in the embodiment of the invention takes a methyl orange solution as an example, wherein the concentration of the methyl orange solution is 20-40mg/L, the addition amount is 40-80mL, and the mass of the added rod-shaped zinc oxide is as follows: and 20-50mg, after the dye degradation is completed, testing the concentration of the methyl orange, and further calculating the degradation rate of the methyl orange.
Example 1:
pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 30mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in a dark state to achieve adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp and a 200W ultrasonic emitter, carrying out ultraviolet irradiation and ultrasonic irradiation synchronously, keeping the temperature at 25 ℃, reacting for 100 minutes, collecting and centrifuging the rest catalyst, and observing the morphology change by using a scanning electron microscope.
As shown in figures 1 and 2, the shape of the rod-shaped zinc oxide is not changed after the methyl orange is degraded by the ultrasonic-assisted photocatalysis, and the rod-shaped zinc oxide is proved to have good stability.
Example 2
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 30mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in the dark state to achieve adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, opening a 200W ultrasonic emitter, carrying out ultrasonic radiation reaction for 100 minutes, keeping the temperature at 25 ℃, closing an ultrasonic device, testing the concentration of the methyl orange, and further calculating the degradation rate of the methyl orange.
As shown in fig. 3, the degradation efficiency of methyl orange by ultrasonic oxidation is 15.99%.
Example 3
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 50mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in a dark state to achieve the adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp, carrying out ultraviolet irradiation reaction for 100 minutes, keeping the temperature at 25 ℃, turning off the xenon lamp, testing the concentration of the methyl orange, and further calculating the degradation rate of the methyl orange.
As shown in fig. 3, the degradation efficiency of the rod-shaped zinc oxide photocatalyst on methyl orange is 36%.
Example 4
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 20mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in a dark state to achieve adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp and a 200W ultrasonic emitter, carrying out ultraviolet irradiation and ultrasonic irradiation synchronously, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, testing the concentration of the methyl orange, and further calculating the degradation rate of the methyl orange.
As shown in fig. 4, the degradation efficiency of the rod-shaped zinc oxide assisted by ultrasound on methyl orange is 58.28%.
Example 5
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 30mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in a dark state to achieve adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp and a 200W ultrasonic emitter, carrying out ultraviolet irradiation and ultrasonic irradiation synchronously, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, testing the concentration of the methyl orange, and further calculating the degradation rate of the methyl orange.
As shown in fig. 4, the degradation efficiency of the rod-shaped zinc oxide assisted by ultrasound on methyl orange is 84.57%.
Example 6
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 40mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in a dark state to achieve adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp and a 200W ultrasonic emitter, carrying out ultraviolet irradiation and ultrasonic irradiation synchronously, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, testing the concentration of the methyl orange, and further calculating the degradation rate of the methyl orange.
As shown in fig. 4, the degradation efficiency of the rod-shaped zinc oxide assisted by ultrasound on methyl orange is 96.2%.
Example 7
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 30mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in a dark state to achieve adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp and a 100W ultrasonic emitter, carrying out ultraviolet irradiation and ultrasonic irradiation synchronously, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, testing the concentration of the methyl orange, and further calculating the degradation rate of the methyl orange.
As shown in fig. 5, the degradation efficiency of the rod-shaped zinc oxide assisted by ultrasound on methyl orange is 53.28%.
Example 8
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 30mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in a dark state to achieve adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp and a 300W ultrasonic emitter, carrying out ultraviolet irradiation and ultrasonic irradiation synchronously, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, testing the concentration of the methyl orange, and further calculating the degradation rate of the methyl orange.
As shown in fig. 5, the degradation efficiency of the rod-shaped zinc oxide assisted by ultrasound on methyl orange is 90.38%.
Example 9
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 30mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in a dark state to achieve adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp and a 500W ultrasonic emitter, carrying out ultraviolet irradiation and ultrasonic irradiation synchronously, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, testing the concentration of the methyl orange, and further calculating the degradation rate of the methyl orange.
As shown in fig. 5, the degradation efficiency of the rod-shaped zinc oxide assisted by the ultrasound on the methyl orange is 97.29%.
Example 10
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 30mg of prepared rod-shaped zinc oxide, carrying out magnetic stirring for 30 minutes in the dark state to achieve the adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp and a 200W ultrasonic emitter, synchronously carrying out ultraviolet irradiation and ultrasonic irradiation, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, centrifuging, collecting the residual catalyst, and analyzing the phase structure by utilizing X diffraction.
As shown in fig. 6, after the methyl orange is degraded by the ultrasonic-assisted photocatalysis, the crystal structure of the rod-shaped zinc oxide is not changed, which indicates that the rod-shaped zinc oxide has a stable crystal structure in the ultrasonic environment.
Example 11
Pouring 50mL (30mg/L) of prepared methyl orange dye into a quartz reactor, adding 30mg of prepared rodlike zinc oxide, carrying out magnetic stirring for 30 minutes in a dark state to achieve adsorption-desorption balance of the methyl orange on the surface of the photocatalyst, turning on a 300W xenon lamp and a 200W ultrasonic emitter, carrying out ultraviolet irradiation and ultrasonic irradiation synchronously, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, centrifuging, collecting the rest catalyst, and carrying out multiple circulation experiments.
As shown in fig. 7, the rod-shaped zinc oxide maintained a stable degradation efficiency for methyl orange after three cycles of experiments.
The invention relates to a method for degrading dye by photocatalysis of rodlike zinc oxide assisted by ultrasound, and experimental results show that: compared with the method of singly using the ultrasonic catalytic degradation dye, the removal rate of the method of using the ultrasonic-assisted rod-shaped zinc oxide to carry out photocatalytic degradation is improved by 68.7 percent; compared with the method using photocatalytic degradation alone, the removal rate of the method using ultrasonic-assisted rod-shaped zinc oxide photocatalytic degradation is improved by 48.6%; the results show that the degradation efficiency of the dye is greatly improved by the ultrasonic synergistic photocatalysis. Meanwhile, the shape, crystal structure and degradation activity of the rodlike zinc oxide after the rodlike zinc oxide is subjected to photocatalytic degradation by the aid of ultrasound maintain good stability, and the rodlike zinc oxide is an excellent catalyst capable of improving photocatalytic activity by the aid of ultrasound.
Claims (8)
1. A method for degrading dye by photocatalysis of rodlike zinc oxide assisted by ultrasound is characterized by comprising the following steps: and (3) magnetically stirring zinc oxide and the dye in a dark state to achieve adsorption-desorption balance, turning on a xenon lamp and an ultrasonic emitter, synchronously carrying out ultraviolet irradiation and ultrasonic radiation, keeping the temperature at 25 ℃, reacting for 100 minutes, turning off the xenon lamp and the ultrasonic equipment, and finishing dye degradation.
2. The method for degrading dye through photocatalysis of rod-shaped zinc oxide assisted by ultrasonic waves according to claim 1, wherein the zinc oxide is rod-shaped and has a specific surface area of 4.24m2The grain size is 31.82nm, and the forbidden band width is 3.3 eV.
3. The method for degrading dye by photocatalysis of rod-shaped zinc oxide assisted by ultrasonic waves according to claim 1, wherein the power of the xenon lamp is 300W, and the power of the ultrasonic waves is 100-500W.
4. The method for degrading the dye through photocatalysis of the rod-shaped zinc oxide under the assistance of the ultrasonic waves as claimed in claim 1, wherein the time of the magnetic stirring is not less than 30 minutes, and the mass of the rod-shaped zinc oxide added is as follows: 20-50 mg.
5. The method for degrading dye through photocatalysis of rod-shaped zinc oxide assisted by ultrasonic according to any one of claims 1 to 4, wherein the rod-shaped zinc oxide is prepared by respectively dissolving zinc nitrate hexahydrate and hexamethylenetetramine in deionized water, uniformly stirring for 30 minutes, mixing the above solutions to form a mixed solution, stirring again for 20 to 30 minutes, transferring into a reaction kettle with a polytetrafluoroethylene lining, keeping the reaction kettle at 90 ℃ for 18 to 20 hours, washing white powder with deionized water and absolute ethyl alcohol for more than three times, and drying in vacuum for 12 hours to finally obtain the required rod-shaped zinc oxide.
6. The method for degrading the dye through the photocatalysis of the rod-shaped zinc oxide assisted by the ultrasonic wave according to claim 5, wherein the mass ratio of the zinc nitrate hexahydrate to the hexamethylenetetramine is 0.5-0.59: 0.25-0.28.
7. The method for degrading dye through photocatalysis of rod-shaped zinc oxide assisted by ultrasound according to claim 5, wherein the deionized water is at least 20 mL.
8. The method for degrading dye through photocatalysis of rod-shaped zinc oxide assisted by ultrasound according to claim 5, wherein the vacuum drying temperature is 60-80 ℃.
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