CN1944519A - Nano zinc oxide/poly styrene composite material and its preparing method - Google Patents
Nano zinc oxide/poly styrene composite material and its preparing method Download PDFInfo
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Abstract
The present invention is nanometer zinc oxide/polystyrene composite material and its preparation process, and belongs to the field of nanometer material preparing and applying technology. The composite material consists of nanometer zinc oxide and polystyrene in the weight ratio of 1/15-10. It is prepared through dissolving polystyrene in the first solvent to obtain polystyrene solution; mixing water solution of urea, water solution of Zn(NO3)2, and the second solvent of methanol, ethanol, butanol or n-propanol to obtain basic zinc carbonate solution; dropping the polystyrene solution into the basic zinc carbonate solution via stirring, filtering, stoving to obtain solid matter; calcining to obtain the nanometer zinc oxide/polystyrene composite material. The composite material has visible light catalyzing performance. The preparation process is simple, low in cost and suitable for industrial production.
Description
Technical Field
The invention relates to a nano zinc oxide/polystyrene composite material, which has photocatalytic performance under a visible light source, and also provides a preparation method of the composite material, belonging to the technical field of nano material processing and application.
Background
Photocatalytic elimination and degradation of pollutants has been an active direction of research in the environmental field since the introduction of heterogeneous photocatalytic technology by Fujishima et al in 1972. The semiconductor material is used as a photocatalyst to degrade and remove organic matters in the environment, and the semiconductor material attracts attention at home and abroad in recent years. The reason is that the surface of the semiconductor oxide material is activated under the irradiation of light, and pollutants can be effectively oxidized and decomposed, heavy metal ions can be reduced, bacteria can be killed, and peculiar smell can be eliminated by utilizing the light energy. The photocatalysis technology can utilize solar energy to react at room temperature, so that the method is economic; the photocatalyst is nontoxic, harmless and noncorrosive, and can be used repeatedly; can completely mineralize organic pollutants into water and inorganic ions, has no secondary pollution, has incomparable charm compared with the traditional high-temperature and conventional catalytic technology and adsorption technology, and is a green environmental management technology with wide application prospect.
The nanometer ZnO is an important semiconductor material, has good performances of luminescence, photoelectric conversion, ultraviolet absorption and the like due to the larger energy gap width (similar to gallium nitride), is widely applied to field emission materials, gas sensors, ultraviolet-proof coatings, luminescent materials, photoelectric conversion materials, rubber, ceramics, coatings and daily chemical materials, and can be used for manufacturing luminescent electrodes, rubber additives, gas sensors, ultraviolet shielding materials, transformers and various optical devices. Besides, the nano zinc oxide has photocatalytic activity, and can degrade organic pollutants by taking sunlight as a light source, so that the nano zinc oxide plays an extremely important role in environmental pollution control. Because of its wide application prospect, it is praised as a modern functional material facing the 21 st century.
In recent years, research on photocatalysts mainly aims to find materials which are good in photoactivity, high in photocatalytic activity, wide in light absorption range, economical and low in cost, especially materials sensitive to sunlight or visible light, so that new products can be developed by means of photocatalysis, and the application range is expanded.
Disclosure of Invention
The invention aims to provide a nano zinc oxide/polystyrene composite material, which is formed by compounding nano zinc oxide and polystyrene, wherein the weight ratio of the nano zinc oxide to the polystyrene is 1: 15-10: 1. The composite material has the advantage of having photocatalytic performance under a visible light source.
Another object of the present invention is to provide a method for preparing nano zinc oxide/polystyrene composite material. The method is characterized in thatpolystyrene is dissolved in a first solvent to obtain a polystyrene solution, wherein the first solvent is any solvent capable of dissolving polystyrene; adding an aqueous solution of urea to Zn (NO)3)2Adding a second solvent into the aqueous solution of (1) to obtain a basic zinc carbonate solution, wherein the second solvent is one of methanol, ethanol, butanol or n-propanol; dripping the polystyrene solution into the basic zinc carbonate solution, uniformly stirring, filtering and drying to obtain a solid substance; calcining the solid substance to obtain the nano zinc oxide/polystyrene composite material. The method has the advantages of simple process, low cost, easy implementation and suitability for industrial production.
The above-mentioned preparation method will now be described in detail. A preparation method of a nano zinc oxide/polystyrene composite material is characterized by comprising the following specific operation steps:
(1) preparation of a polystyrene solution
Dissolving 0.1-6 g of polystyrene in a first solvent to obtain 5-150 mL of polystyrene solution, wherein the concentration of the solution is 20-40 g/L, and the first solvent is any solvent capable of dissolving polystyrene;
(2) preparation of basic Zinc carbonate solution
100mL0.2mol/L urea water solution is added to 50mL0.2mol/L Zn (NO)3)2Stirring the mixture evenly in water solution at room temperature, continuing stirring the mixture for 6 hours at 95 ℃, cooling the mixture to room temperature, adding 50mL of a second solvent into the mixed solution, and stirring the mixture evenly to obtain 200mL of basic zinc carbonate solution, wherein the second solvent is lower alcohol R-OH, and R ═ C1～C4；
(3) Preparation of solid substances
Dropwise adding the polystyrene solution obtained in the step (1) into the basic zinc carbonate solution obtained in the step (2), stirring uniformly to obtain a basic zinc carbonate-polystyrene solution, and filtering and drying the basic zinc carbonate-polystyrene solution to obtain 0.810-6.698 g of solid substances;
(4) calcining the solid material to obtain the product
And (3) calcining the solid substance obtained in the step (3) at the temperature of 200-500 ℃ for 2-5 hours to obtain 0.569-4.905 g of product, namely the nano zinc oxide/polystyrene composite material.
In the product, the weight ratio of the nano zinc oxide to the polystyrene is 1: 15-10: 1 in the nano zinc oxide/polystyrene composite material.
The reaction of the chemical reaction related to step (2) is simply represented by:
the reaction of the chemical reaction related to the step (4) is simply represented by:
the above production method is further characterized in that the first solvent is one of butanone, acetone, cyclohexanone, toluene, or nitrobenzene.
The above production method is further characterized in that the second solvent is methanol or ethanol.
The above production method is further characterized in that the first solvent is one of butanone, acetone, cyclohexanone, toluene, or nitrobenzene, and the second solvent is methanol or ethanol.
Another object of the present invention is to provide a method for using the composite material of the present invention as a photocatalyst. A method for photocatalytic degradation of sewage by using a nano zinc oxide/polystyrene composite material as a photocatalyst is characterized in that under a visible light source, the composite material can be used for photocatalytic degradation of sewage containing methyl orange, Sudan red, phenol, catechol and other pollutants, the adding amount of the composite material is 30-100 mg per 25mL of sewage, and the pollutant concentration of the sewage is 1-100 mg/L.
The application method of the nano zinc oxide/polystyrene composite material as the photocatalyst is further characterized in that the visible light source is a sun, a fluorescent lamp, a halogen lamp, a mercury xenon lamp, a metal halide lamp, a light-emitting diode or organic matter combustion flame.
The nano zinc oxide/polystyrene composite material has the advantage that the composite material has photocatalytic performance under the irradiation of a visible light source. The preparation method of the composite material has the advantages of simple process, low cost, easy implementation and suitability for industrial production.
Drawings
Fig. 1 TEM (micrograph of microstructure) of nano zinc oxide.
FIG. 2 TEM (micrograph of microstructure) of nano-zinc oxide in the nano-zinc oxide/polystyrene composite.
By comparison, the particle size of the nano zinc oxide in fig. 2 is significantly smaller than that of the nano zinc oxide in fig. 1.
FIG. 3 shows UV-Vis (ultraviolet-visible light) absorption spectra of nano zinc oxide (a) and nano zinc oxide/polyvinyl chloride composite material (b). As can be seen from the figure, the light absorption range of the nano zinc oxide/polyvinyl chloride composite material is widened, and the absorption of visible light is obviously higher than that of the nano zinc oxide.
FIG. 4 shows the ESR (electron spin resonance) spectrum of nano zinc oxide.
Figure 5 ESR spectrum of calcined polystyrene.
FIG. 6 is the ESR spectrum of the nano zinc oxide/polystyrene composite material.
Fig. 4, fig. 5 and fig. 6 show that the ESR response of the nano zinc oxide/polystyrene composite material is obviously enhanced compared with the ESR response of pure nano zinc oxide or pure polystyrene.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
(1) dissolving 2g of polystyrene in 50mL of first solvent and acetone to obtain 50mL of polystyrene solution, wherein the concentration of the solution is 40 g/L;
(2) 100mL0.2mol/L urea water solution is added to 50mL0.2mol/L Zn (NO)3)2Stirring the mixed solution at room temperature for 6 hours at 95 ℃ in the aqueous solution, cooling to room temperature, adding 50mL of a second solvent and methanol into the mixed solution, and stirring the mixture uniformly to obtain 200mL of basic zinc carbonate solution;
(3) dropwise adding a polystyrene solution into the basic zinc carbonate solution, stirring uniformly to obtain a basic zinc carbonate-polystyrene solution, filtering and drying the basic zinc carbonate-polystyrene solution to obtain 2.706g of a solid substance;
(4) the solid matter is calcined in air at 200 deg.c for 5 hr to obtain 1.878 g of nanometer zinc oxide/polystyrene composite material.
Example 2:
(1) dissolving 6g of polystyrene in 150mL of first solvent and acetone to obtain 150mL of polystyrene solution, wherein the concentration of the solution is 40 g/L;
(2) 100mL0.2mol/L urea water solution is added to 50mL0.2mol/L Zn (NO)3)2Stirring in water solution at room temperature to obtain uniform solution, and mixing the solutionStirring for 6 hours at 95 ℃, cooling to room temperature, adding 50mL of second solvent and ethanol into the mixed solution, and stirring uniformly to obtain 200mL of basic zinc carbonate solution;
(3) dropwise adding a polystyrene solution into the basic zinc carbonate solution, stirring uniformly to obtain a basic zinc carbonate-polystyrene solution, filtering and drying the basic zinc carbonate-polystyrene solution to obtain 6.698g of a solid substance;
(4) the solid matter was calcined in air at 300 ℃ for 4 hours to obtain 4.905g of product, nano zinc oxide/polystyrene composite.
Example 3:
(1) dissolving 5g of polystyrene in 125mL of first solvent and butanone to obtain 125mL of polystyrene solution, wherein the concentration of the solution is 40 g/L;
(2) 100mL0.2mol/L urea water solution is added to 50mL0.2mol/L Zn (NO)3)2Stirring the mixed solution at room temperature for 6 hours at 95 ℃ in the aqueous solution, cooling to room temperature, adding 50mL of a second solvent and ethanol into the mixed solution, and stirring the mixture uniformly to obtain 200mL of basic zinc carbonate solution;
(3) dropwise adding a polystyrene solution into the basic zinc carbonate solution, stirring uniformly to obtain a basic zinc carbonate-polystyrene solution, filtering and drying the basic zinc carbonate-polystyrene solution to obtain 5.701g of a solid substance;
(4) the solid matter was calcined in air at 400 ℃ for 3 hours to obtain 4.151g of product, nano zinc oxide/polystyrene composite.
Example 4:
(1) dissolving 0.25g of polystyrene in 7.5mL of a first solvent, namely butanone, to obtain 7.5mL of polystyrene solution, wherein the concentration of the solution is 33.33 g/L;
(2) 100mL0.2mol/L urea water solution is added to 50mL0.2mol/L Zn (NO)3)2Stirring the mixed solution at room temperature for 6 hours at 95 ℃ in the aqueous solution, cooling to room temperature, adding 50mL of second solvent and butanol into the mixed solution, and stirring the mixture uniformly to obtain 200mL of basic zinc carbonate solution;
(3) dropwise adding a polystyrene solution into the basic zinc carbonate solution, stirring uniformly to obtain a basic zinc carbonate-polystyrene solution, filtering and drying the basic zinc carbonate-polystyrene solution to obtain 0.970g of a solid substance;
(4) the solid matter is calcined in air at 300 deg.c for 2 hr to obtain 0.685g of composite nanometer zinc oxide/polystyrene material.
Example 5:
(1) dissolving 0.5g of polystyrene in 15mL of first solvent and toluene to obtain 15mL of polystyrene solution, wherein the concentration of the solution is 33.33 g/L;
(2) 100mL0.2mol/L urea water solution is added to 50mL0.2mol/L Zn (NO)3)2Stirring the mixed solutionat room temperature for 6 hours at 95 ℃ in the aqueous solution, cooling to room temperature, adding 50mL of a second solvent and methanol into the mixed solution, and stirring the mixture uniformly to obtain 200mL of basic zinc carbonate solution;
(3) dropwise adding a polystyrene solution into the basic zinc carbonate solution, stirring uniformly to obtain a basic zinc carbonate-polystyrene solution, filtering and drying the basic zinc carbonate-polystyrene solution to obtain 1.211g of a solid substance;
(4) calcining the solid substance in air at 500 ℃ for 2 hours to obtain 0.857g of product, namely the nano zinc oxide/polystyrene composite material.
Example 6:
(1) dissolving 0.1g of polystyrene in 5mL of cyclohexanone, a first solvent to obtain 5mL of polystyrene solution, wherein the concentration of the solution is 20 g/L;
(2) 100mL0.2mol/L urea water solution is added to 50mL0.2mol/L Zn (NO)3)2Stirring the mixed solution at room temperature for 6 hours at 95 ℃ in the aqueous solution, cooling to room temperature, adding 50mL of a second solvent and methanol into the mixed solution, and stirring the mixture uniformly to obtain 200mL of basic zinc carbonate solution;
(3) dropwise adding a polystyrene solution into the basic zinc carbonate solution, stirring uniformly to obtain a basic zinc carbonate-polystyrene solution, filtering and drying the basic zinc carbonate-polystyrene solution to obtain 0.810g of a solid substance;
(4) calcining the solid substance in air at 300 ℃ for 4 hours to obtain 0.569g of product, namely the nano zinc oxide/polystyrene composite material.
The embodiment of the method for degrading sewage by photocatalysis by using the nano zinc oxide/polystyrenecomposite material as the photocatalyst comprises the following steps:
example 7:
(1) adding 0.12g of the composite material into 50mL of 10mg/L methyl orange solution, and uniformly stirring;
(2) using a 15W fluorescent lamp for common illumination to illuminate, wherein the distance between the fluorescent lamp and the liquid level is 10cm, and using a spectrophotometer to measure the concentration of methyl orange in a reaction system;
(3) after 11 hours, the degradation rate of methyl orange was 50%.
Example 8:
(1) adding 0.20g of the composite material into 50mL of 100mg/L methyl orange solution, and uniformly stirring;
(2) illuminating by a 15W common illuminating fluorescent lamp, wherein the distance between the fluorescent lamp and the liquid level is 10cm, and measuring the concentration of methyl orange in a reaction system by using a spectrophotometer;
(3) after 11 hours of experiment, the degradation rate of methyl orange was 35%.
Claims (7)
1. The nano zinc oxide/polystyrene composite material is characterized by being formed by compounding nano zinc oxide and polystyrene, wherein the weight ratio of the nano zinc oxide to the polystyrene is 1: 15-10: 1.
2. The preparation method of the nano zinc oxide/polystyrene composite material as claimed in claim 1, which is characterized by comprising the following specific operation steps:
(1) preparation of a polystyrene solution
Dissolving 0.1-6 g of polystyrene in a first solvent to obtain 5-150 mL of polystyrene solution, wherein the concentration of the solution is 20-40 g/L, and the first solvent is any solvent capable of dissolving polystyrene;
(2) preparation of basic Zinc carbonate solution
100mL0.2mol/L of ureaThe aqueous solution was added to 50mL of 0.2mol/L Zn (NO)3)2Stirring the mixture evenly in water solution at room temperature, continuing stirring the mixture for 6 hours at 95 ℃, cooling the mixture to room temperature, adding 50mL of a second solvent into the mixed solution, and stirring the mixture evenly to obtain 200mL of basic zinc carbonate solution, wherein the second solvent is lower alcohol R-OH, and R ═ C1～C4；
(3) Preparation of solid substances
Dropwise adding the polystyrene solution obtained in the step (1) into the basic zinc carbonate solution obtained in the step (2), stirring uniformly to obtain a basic zinc carbonate-polystyrene solution, and filtering and drying the basic zinc carbonate-polystyrene solution to obtain 0.810-6.698 g of solid substances;
(4) calcining the solid material to obtain the product
And (3) calcining the solid substance obtained in the step (3) at the temperature of 200-500 ℃ for 2-5 hours to obtain 0.569-4.905 g of product, namely the nano zinc oxide/polystyrene composite material.
3. The method for preparing nano zinc oxide/polystyrene composite material according to claim 2, wherein the first solvent is one of butanone, acetone, cyclohexanone, toluene or nitrobenzene.
4. The method for preparing nano zinc oxide/polystyrene composite material according to claim 2, wherein the second solvent is methanol or ethanol.
5. The method for preparing nano zinc oxide/polystyrene composite material according to claim 2, wherein the first solvent is one of butanone, acetone, cyclohexanone, toluene or nitrobenzene, and the second solvent is methanol or ethanol.
6. The method for photocatalytic degradation of sewage by using the nano zinc oxide/polystyrene composite material as the photocatalyst in claim 1, wherein the composite material is used for photocatalytic degradation of sewage containing pollutants such as methyl orange, Sudan red, phenol and catechol under a visible light source, the addition amount of the composite material is 30-100 mg per 25mL of sewage, and the concentration of the pollutants in the sewage is 1-100 mg/L.
7. The method for photocatalytic degradation of sewage by using the nano zinc oxide/polystyrene composite material as the photocatalyst according to claim 6, wherein the visible light source is a sun, a fluorescent lamp, a halogen lamp, a mercury xenon lamp, a metal halide lamp, a light emitting diode or an organic matter combustion flame.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338192B (en) * | 2008-06-23 | 2011-03-16 | 苏州大学 | Nanometer modified high molecular fluorescent material and method for preparing same |
| CN106179498A (en) * | 2016-07-12 | 2016-12-07 | 天津工业大学 | Polystyrene catalysis bead and slurry photocatalytic reactor |
| CN110193380A (en) * | 2019-05-24 | 2019-09-03 | 武汉工程大学 | It is a kind of using waste polystyrene as catalysis material of aggregate and its preparation method and application |
-
2006
- 2006-06-21 CN CNB2006100279301A patent/CN100560647C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338192B (en) * | 2008-06-23 | 2011-03-16 | 苏州大学 | Nanometer modified high molecular fluorescent material and method for preparing same |
| CN106179498A (en) * | 2016-07-12 | 2016-12-07 | 天津工业大学 | Polystyrene catalysis bead and slurry photocatalytic reactor |
| CN110193380A (en) * | 2019-05-24 | 2019-09-03 | 武汉工程大学 | It is a kind of using waste polystyrene as catalysis material of aggregate and its preparation method and application |
| CN110193380B (en) * | 2019-05-24 | 2022-05-10 | 武汉工程大学 | Photocatalytic material with waste polystyrene as aggregate and preparation method and application thereof |
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