CN115121257A - Copper-doped zinc oxide nanorod, preparation method and application thereof in piezoelectric-photocatalytic removal of organic pollutants - Google Patents
Copper-doped zinc oxide nanorod, preparation method and application thereof in piezoelectric-photocatalytic removal of organic pollutants Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 155
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- 238000005286 illumination Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 26
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 9
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004122 cyclic group Chemical group 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
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- 229910052724 xenon Inorganic materials 0.000 description 3
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a copper-doped zinc oxide nanorod, a preparation method and application thereof in removing organic pollutants through piezoelectric-photocatalysis. And (3) placing the copper-doped zinc oxide nano rod into a water body containing organic pollutants, and performing illumination and/or ultrasonic treatment to finish the removal of the organic pollutants in the water body. Under the combined action of illumination and ultrasonic vibration, the material is excited by light to generate photo-generated charges, and a polarization electric field is generated under the ultrasonic action to promote the migration and separation of the photo-generated charges, so that the photocatalytic performance is effectively enhanced. The nano material prepared by the invention has chemical stability, high reaction activity and piezoelectricity, and has excellent application value in the field of piezoelectric-photocatalysis.
Description
Technical Field
The invention relates to the technical field of nano materials and piezoelectricity-photocatalysis, in particular to a preparation method of a copper-doped zinc oxide nano rod and application of the material in removing water pollutants through piezoelectricity-photocatalysis.
Background
Due to the rapid development of industry and the large use of fossil fuels, environmental pollution and energy shortage seriously threaten the sustainable development of the current society. Among various solutions, semiconductor-based photocatalytic technologies have good application prospects because of the advantages of green process, convenience in implementation and the like. The photocatalytic reaction efficiency greatly depends on the separation and migration rate of the photo-generated charges, but the photo-generated charges can be rapidly recombined on the bulk and the surface of the photocatalyst, which results in low charge separation efficiency and low photocatalytic efficiency, thereby limiting the practical application of the photocatalyst. Therefore, various strategies (such as constructing heterojunctions, modifying metals or metal oxides, and forming surface defects) have been proposed to promote surface charge separation, enhance photocatalytic activity, and among them, polarization field engineering has been demonstrated as a method that can effectively improve photogenerated charge separation and enhance photocatalytic performance.
Zinc oxide (ZnO) has been widely used in catalysis, the paint industry, ceramic bodies, piezoresistors, fertilizers, and cosmetics as an important semiconductor material. In the field of photocatalysis, zinc oxide semiconductors have become a popular choice for environmental processing due to their unique properties, such as direct wide band gap in the near ultraviolet spectral region, extremely strong oxidation capability, good photocatalytic performance, and large free exciton binding energy (exciton emission process can last at room temperature or even higher).
The performance of zinc oxide catalyst for degrading pollutants needs to be improved, the prior art mixes a solution containing zinc salt and copper salt with an inorganic alkaline aqueous solution, controls the pH value to be 10.5-11.5, then places the mixture in a closed container for hydrothermal reaction, separates solid and liquid after the reaction is finished, collects the solid, washes the solid with water, dries the solid, and calcines the solid under the protection of protective gas to obtain the mesoporous nano rod-shaped catalyst of copper oxide doped with zinc oxide, and the catalyst needs to be driven by hydrogen peroxide when degrading pollutants. The zinc oxide catalyst prepared by the prior art needs to be calcined, and no zinc oxide or doped zinc oxide catalyst prepared without calcination is available at present.
Disclosure of Invention
The invention aims to provide a nano material capable of responding to visible light and external pressure simultaneously, which can quickly and effectively degrade pollutants in a water body through the piezoelectric-photocatalytic synergistic effect. The catalytic performance of the nano material prepared by the invention is researched by taking bisphenol A as a target organic pollutant. The copper-doped zinc oxide nanorod disclosed by the invention can improve the degradation performance by utilizing the piezoelectric effect in cooperation with photocatalysis. Under the combined action of illumination and ultrasonic vibration, the material is excited by light to generate photo-generated charges, and a polarization electric field is generated under the ultrasonic action to promote the migration and separation of the photo-generated charges, so that the photocatalytic performance is effectively enhanced. The material is in a one-dimensional nanorod shape, can provide a fast channel for electron migration, and promotes charge separation. The nano material prepared by the invention has chemical stability, high reaction activity and piezoelectricity, and has excellent application value in the field of piezoelectric-photocatalysis.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
a copper-doped zinc oxide nanorod is prepared by mixing water-soluble zinc salt, water-soluble copper salt, polyvinylpyrrolidone, hexamethylenetetramine and water, and performing hydrothermal reaction to obtain a copper-doped zinc oxide nanorod; specifically, zinc nitrate hexahydrate, copper nitrate trihydrate and an aqueous solution of polyvinylpyrrolidone (PVP) are mixed, hexamethylenetetramine is added, and then the copper-doped zinc oxide nanorod is prepared by a hydrothermal method.
In the present invention, the molar amount of copper in the water-soluble copper salt is 1 to 10%, preferably 3 to 7%, more preferably 4 to 6%, for example 5%, of the molar amount of zinc in the water-soluble zinc salt.
In the invention, the mass ratio of the water-soluble zinc salt, the polyvinylpyrrolidone and the hexamethylenetetramine is (6-12) to (5-10) to (3-6), preferably (6-7) to (5-6) to (3-4), such as 6: 5: 3.
In the invention, the hydrothermal reaction is carried out for 5-8 h at 80-100 ℃, preferably 6 h at 90 ℃.
The invention discloses a method for removing organic pollutants in water, which comprises the steps of putting the copper-doped zinc oxide nano rod into water containing the organic pollutants, and carrying out illumination and/or ultrasonic treatment to finish the removal of the organic pollutants in the water. Preferably, the organic contaminant is bisphenol a; the illumination is visible light illumination.
The invention has the advantages that:
1. the copper-doped zinc oxide nanorod disclosed by the invention is simple in preparation method and regular in shape, particularly does not need calcination, and overcomes the technical bias that the preparation of zinc oxide or a doped zinc oxide catalyst needs calcination in the prior art; the raw materials are commonly and easily obtained; the shape of the one-dimensional nanorod can provide a fast channel for electron migration; the doping of copper element can improve the light absorption capacity of the zinc oxide semiconductor, thereby improving the photocatalysis effect;
2. the copper-doped zinc oxide nanorod disclosed by the invention has the advantages that the piezoelectricity is adjusted, and the radial piezoelectricity is enhanced, so that the separation and migration of internal photo-generated charges are promoted; under the combined action of visible light and ultrasound, the catalyst shows remarkable performance improvement;
3. after the copper-doped zinc oxide nanorod disclosed by the invention is circulated for multiple times, the catalytic performance of the catalyst is not obviously reduced, and the structural morphology does not change, which shows that the structure is stable and the property is stable.
Drawings
FIG. 1 is a scanning electron micrograph of copper-doped zinc oxide nanorods;
FIG. 2 is a transmission electron micrograph of copper-doped zinc oxide nanorods;
FIG. 3 shows the results of photocatalytic degradation experiments of bisphenol A in water with different catalysts;
FIG. 4 shows the results of the piezo-electric catalytic degradation experiments of bisphenol A in water with different catalysts;
FIG. 5 is a graph showing the degradation effect of copper-doped zinc oxide nanorods on bisphenol A under different conditions;
FIG. 6 is a kinetic fit curve of a piezo-photocatalytic degradation experiment of bisphenol A in water;
FIG. 7 is a diagram showing the cyclic degradation of copper-doped zinc oxide nanorods to bisphenol A;
FIG. 8 is SEM images of 1% Cu-ZnO and 10% Cu-ZnO with different doping amounts.
Detailed Description
In the catalyst of the present invention, when stress is applied to the unit cell, the centers of positive and negative ions move in opposite directions, resulting in dipole polarization (ion charge) and a built-in electric field (piezoelectric field). When the dipole moments are superimposed in the entire cell, a potential distributed in the direction of the stress, i.e., a piezoelectric potential, is generated.
The method comprises the steps of uniformly stirring the zinc nitrate hexahydrate and the aqueous solution of polyvinylpyrrolidone (PVP), adding hexamethylenetetramine, and preparing the zinc oxide nanorod by a hydrothermal method for comparison. Specifically, 0.6-1.2 g of zinc nitrate hexahydrate and 0.5-1.0 g of PVP are weighed and dissolved in 40-80 mL of deionized water, 0.3-0.6 g of hexamethylenetetramine is added after uniform stirring, and stirring is continued for 30-60 min. Then transferring the uniformly stirred solution into a reaction kettle inner container with the capacity of 50 mL, sealing, and placing in a place of 90-180 DEG C o And C, reacting for 6-9 h in a blast oven. And cooling to room temperature, respectively centrifugally cleaning for several times by using deionized water and absolute ethyl alcohol, and drying to obtain the zinc oxide nano rod.
The preparation method of the copper-doped zinc oxide nanorod comprises the following steps: firstly, 0.6-1.2 g of zinc nitrate hexahydrate, 25-50 mg of copper nitrate trihydrate and 0.5-1.0 g of PVP are weighed and dissolved in 40-80 mL of deionized water, after the mixture is uniformly stirred, 0.3-0.6 g of hexamethylenetetramine is added, and the mixture is continuously stirred for 30-60 min. Then transferring the uniformly stirred solution into a reaction kettle inner container with the capacity of 50 mL, sealing, and placing in a place of 90-180 DEG C o And C, reacting for 6-9 h in a blast oven. And cooling to room temperature, respectively centrifugally cleaning for several times by using deionized water and absolute ethyl alcohol, and drying to obtain the copper-doped zinc oxide nano rod.
Piezoelectric synergistic photocatalytic degradation experiment: the nano material is put into a water solution containing bisphenol A, and after the nano material is adsorbed for one hour in a dark place, the organic pollutants in water are removed by the combined action of ultrasonic and simulated solar light sources.
Zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ∙6H 2 O) from Sigma-Aldrich. Hexamethylenetetramine (C) 6 H 12 N 4 ) Copper nitrate trihydrate (Cu (NO) 3 ) 2 ∙3H 2 O) and vanadium pentoxide (V) 2 O 5 ) Purchased from national drug group chemical agents limited. Polyvinylpyrrolidone (PVP, M) w = 40000) and bisphenol a (C) 15 H 16 O 2 ) Purchased from TCI. The raw materials adopted by the invention are all existing products, and the specific preparation operation and the test method are conventional technologies, such as stirring is a conventional mixing method in the field.
Example one
The preparation method of the zinc oxide nano rod comprises the following specific steps: weighing 0.6 g of zinc nitrate hexahydrate and 0.5 g of PVP, dissolving in 40 mL of deionized water, stirring for 3 min, adding 0.3 g of hexamethylenetetramine, stirring for 30 min, placing the solution into a reaction kettle, and stirring at 90 DEG o C, reacting for 6 hours; and cooling to room temperature, respectively centrifugally cleaning for 3 times by using deionized water and absolute ethyl alcohol, and drying to obtain the zinc oxide nano rod.
Example two
The preparation method of the copper-doped zinc oxide nanorod comprises the following specific steps: weighing 0.6 g of zinc nitrate hexahydrate, 25 mg of copper nitrate trihydrate and 0.5 g of PVP, dissolving in 40 mL of deionized water, stirring for 3 min, adding 0.3 g of hexamethylenetetramine, continuously stirring for 30 min, then placing the solution into a reaction kettle, and stirring at 90 DEG for o C, reacting for 6 hours, cooling to room temperature, respectively centrifugally cleaning for 3 times by using deionized water and absolute ethyl alcohol, and drying to obtain the copper-doped zinc oxide nano rod, wherein the copper-doped zinc oxide nano rod is 5% of Cu-ZnO, and the molar weight of copper is 5% of that of zinc.
FIG. 1 is a scanning electron microscope image of the copper-doped zinc oxide nanorod, and FIG. 2 is a transmission electron microscope image of the copper-doped zinc oxide nanorod, which shows that the copper-doped zinc oxide nanorod has a regular and uniform one-dimensional nanorod morphology and is of a solid structure.
Comparative example 1
Weighing 0.6 g of zinc nitrate hexahydrate, 9 mg of vanadium pentoxide and 0.5 g of PVP, dissolving in 40 mL of deionized water, stirring for 3 min, adding 0.3 g of hexamethylenetetramine, stirring for 30 min, placing the solution into a reaction kettle, and stirring at 90 DEG for o C, reacting for 6 hours; cooling to room temperature, respectively centrifugally cleaning with deionized water and anhydrous ethanol for 3 times, and drying to obtain vanadium doped productA zinc oxide heteroxide nanorod and 5% of V-ZnO.
EXAMPLE III photocatalytic degradation experiment of bisphenol A in water.
25 mg of the catalyst 5% Cu-ZnO obtained in example II were weighed out and added to 50 ml of an aqueous solution containing bisphenol A (10 mg/L) respectively. Adsorbing for 1 hour in dark to reach adsorption equilibrium. Beginning the photocatalytic degradation experiment after balancing, using a 300W xenon lamp as a simulated solar light source, taking 1 ml every 30 minutes, filtering with a filter head, injecting into a high performance liquid sample bottle, and using a high performance liquid chromatograph to perform the photocatalytic degradation experiment on deionized water: methanol = 30: 70, recording the peak area of bisphenol A at about 6 min, and recording the concentration of initial bisphenol A as 100 percent to obtain the photocatalytic degradation curve of bisphenol A.
25 mg of the catalyst obtained in example one and comparative example one was weighed out and subjected to the same photocatalytic degradation test of bisphenol A in water, respectively. The results are shown in FIG. 3.
Example four experiments on the piezoelectric catalytic degradation of bisphenol a in water.
25 mg of the copper-doped zinc oxide nanorods (5% Cu-ZnO) obtained in example II were weighed out and added to 50 ml of an aqueous solution containing bisphenol A (10 mg/L). Adsorbing for 1 hour in dark to reach adsorption equilibrium. Starting a piezoelectric degradation experiment after balancing, taking 1 ml of the piezoelectric degradation experiment every 30 minutes by using a 150W (40 kHz) ultrasonic cleaner as an ultrasonic source, filtering the piezoelectric degradation experiment by using a filter head, injecting the piezoelectric degradation experiment into a high performance liquid sample bottle, and performing a high performance liquid chromatograph on the sample bottle with deionized water: methanol = 30: 70, recording the peak area of bisphenol A at about 6 min, and recording the concentration of initial bisphenol A as 100% to obtain the piezoelectric catalytic degradation curve of bisphenol A.
25 mg of the catalyst obtained in example one and comparative example one was weighed out and subjected to the same experiment for the piezoelectric catalytic degradation of bisphenol A in water. The results are shown in FIG. 4.
Example five piezoelectric-photocatalytic degradation experiments of bisphenol a in water with copper-doped zinc oxide nanorods.
25 mg of the copper-doped zinc oxide nanorods (5% Cu-ZnO) obtained in example II were weighed out and added to 50 ml of an aqueous solution containing bisphenol A (10 mg/L). Adsorbing for 1 hour in dark to reach adsorption equilibrium. Starting a piezoelectric-photodegradation experiment after balancing, taking 1 ml every 30 minutes by using a 300W xenon lamp as a simulated solar light source and a 150W (40 kHz) ultrasonic cleaner as an ultrasonic source, filtering by using a filter head, injecting into a high performance liquid sample bottle, and performing a high performance liquid chromatograph on deionized water: an absorption curve of the test sample at an ultraviolet wavelength of 290 nm in a mobile phase of methanol = 30: 70, a peak appearance area of bisphenol a at about 6 min was recorded, and a concentration of initial bisphenol a was recorded as 100%, to obtain a piezoelectric-photocatalytic degradation curve of bisphenol a. FIG. 5 is a graph showing the degradation curve of copper-doped zinc oxide nanorods to bisphenol A in water under different conditions. Under the combined action of ultrasound and illumination, the degradation effect of the copper-doped zinc oxide nano rod is obviously improved, and the removal rate of bisphenol A in water reaches 97 percent when the piezoelectric-photocatalytic degradation is carried out for 120 minutes, which is far higher than that of a single zinc oxide nano rod.
25 mg of the catalyst obtained in the first embodiment and the first comparative example are weighed and respectively subjected to the same piezoelectric-photocatalytic degradation experiment of bisphenol A in water, a conventional method is adopted for dynamic fitting, and a dynamic fitting curve in figure 6 shows that the piezoelectric-photocatalytic degradation rate of Cu-ZnO is the fastest, and the piezoelectric-photocatalytic degradation rate of V-ZnO is the slowest; piezoelectric-photocatalytic rate of Cu-ZnO nanorod (0.0281 min) -1 ) Is the V-ZnO photocatalysis rate (0.0126 min) -1 ) 2.2 times of the total weight of the powder. The results of the piezoelectric-photocatalytic reaction are well combined with the conclusions of the photocatalytic reaction and the piezoelectric reaction, and 5% of Cu-ZnO improves the photocatalytic activity and the piezoelectric property, so that the highest piezoelectric-photocatalytic activity is shown.
Earlier experiments show that the composite catalyst is obtained by preparing the zinc oxide nano rod and performing hydrothermal reaction on the zinc oxide nano rod and the copper nitrate trihydrate, and the effect of piezoelectric-photocatalytic degradation of bisphenol A is not as good as that of a single zinc oxide nano rod.
Example six copper doped zinc oxide nanorods were tested for cyclic degradation of bisphenol a in water.
Centrifugation was used to collect the copper dope of example fiveThe zinc oxide heteroxide nano-rod is added, and then the collected catalyst is placed in 60 o And C, drying in an oven for 12 hours. The dried catalyst was again placed in 50 mL of an aqueous solution of bisphenol A (10 mg/L) and stirred away from light until adsorption equilibrium was reached. Starting a piezoelectric-photodegradation experiment after balancing, taking 1 ml every 30 minutes by using a 300W xenon lamp as a simulated solar light source and a 150W ultrasonic cleaner as an ultrasonic source, filtering by using a filter head, injecting into a high performance liquid sample bottle, and performing a high performance liquid chromatograph on deionized water: methanol = 30: 70, measuring the absorption curve of the sample under 290 nm ultraviolet wavelength in the mobile phase, recording the bisphenol A peak area about 6 min, and obtaining the residual concentration of the bisphenol A in the corresponding water sample by referring to the standard curve. Three cycles were followed and the degradation curve of bisphenol A was recorded.
Figure 7 is a cyclic degradation diagram of copper doped zinc oxide nanorods. It can be seen from the figure that the performance of the catalyst is stable, and the better catalytic performance is still maintained in three times of cyclic degradation. This shows that the copper-doped zinc oxide nanorod has good stability and strong practical application potential.
Comparative example No. two
The same test method as that of example five is adopted to test the piezoelectric-photocatalytic degradation effect of the 5% V-ZnO catalyst of comparative example one, and when the piezoelectric-photocatalytic degradation is carried out for 120 minutes, the residual rate of the bisphenol A in the water is 24.8%, which is not the same as that of the single zinc oxide nano rod.
EXAMPLE seven
On the basis of the second embodiment, Cu (NO) is added in a changing way 3 ) 2 ∙3H 2 The amount of O was adjusted to adjust the doping ratio, and 1% Cu-ZnO and 10% Cu-ZnO were prepared, and the SEM images are respectively shown in FIG. 8. By adopting the same test method as that of the fifth example, the piezoelectric-photocatalytic degradation performance is not as good as that of 5% Cu-ZnO.
Example eight
In the fifth experiment of the embodiment, the initial concentration of the bisphenol A is adjusted to be 5 mg/L, and the removal rate of the bisphenol A in water reaches more than 90 percent when the piezoelectric-photocatalytic degradation is carried out for 60 minutes; when the piezoelectric-photodegradation is carried out for 90 minutes, the removal rate of bisphenol A in water reaches more than 96 percent; bisphenol A was completely removed from the water at 120 minutes of piezo-photodegradation.
The invention discloses a piezoelectric and visible light coordinated catalytic degradation nano material for organic pollutants, a preparation method thereof and effective removal of organic pollutants (such as bisphenol A) in a water body. Copper element is doped into the zinc oxide crystal by a simple hydrothermal method to obtain the copper-doped zinc oxide nano rod. The invention synthesizes copper-doped zinc oxide nano-rods, introduces copper element into the zinc oxide to adjust the piezoelectricity of the zinc oxide and improve the light absorption capacity, thereby improving the catalytic performance of the zinc oxide. The purpose of quickly and effectively degrading organic pollutants in water is achieved by adding ultrasound to assist photocatalysis, and the organic pollutants can be recycled and the cost is reduced.
Claims (10)
1. A preparation method of a copper-doped zinc oxide nanorod is characterized in that water-soluble zinc salt, water-soluble copper salt, polyvinylpyrrolidone, hexamethylenetetramine and water are mixed and then subjected to hydrothermal reaction to obtain the copper-doped zinc oxide nanorod.
2. The method for preparing the copper-doped zinc oxide nanorod according to claim 1, characterized in that zinc nitrate hexahydrate, copper nitrate trihydrate, polyvinylpyrrolidone and water are mixed, then hexamethylenetetramine is added, and then the copper-doped zinc oxide nanorod is prepared by a hydrothermal method.
3. The method for preparing the copper-doped zinc oxide nanorod according to claim 1, wherein the molar amount of copper in the water-soluble copper salt is 1-10% of the molar amount of zinc in the water-soluble zinc salt.
4. The method for preparing copper-doped zinc oxide nanorods according to claim 1, characterized in that the mass ratio of the water-soluble zinc salt, the polyvinylpyrrolidone and the hexamethylenetetramine is (6-12) to (5-10) to (3-6).
5. The method for preparing the copper-doped zinc oxide nanorod according to claim 1, wherein the hydrothermal reaction is carried out at 80-100 ℃ for 5-8 h.
6. The copper-doped zinc oxide nanorod prepared by the method according to claim 1.
7. The use of the copper-doped zinc oxide nanorods of claim 6 to remove organic contaminants.
8. Use according to claim 7, wherein the removal method is a photocatalyst and/or a piezo-electric catalysis.
9. A method for removing organic pollutants in water, which is characterized in that the copper-doped zinc oxide nanorod of claim 6 is placed in water containing the organic pollutants and is subjected to illumination and/or ultrasonic treatment to complete the removal of the organic pollutants in the water.
10. The method of removing organic contaminants from a body of water of claim 9, wherein the organic contaminants are bisphenol a; the illumination is visible illumination.
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