CN112076739A - Composite material for efficiently degrading organic dye in wastewater and preparation method thereof - Google Patents
Composite material for efficiently degrading organic dye in wastewater and preparation method thereof Download PDFInfo
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- 238000004321 preservation Methods 0.000 claims description 2
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- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
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- 241000258149 Hemicentrotus Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- 238000007792 addition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
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- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a composite material for efficiently degrading organic dye in wastewater and a preparation method thereof, wherein the composite material is echinoid TiO2ZnO nanoparticles are uniformly loaded on the surface of the micron sphere, and TiO2And forms a heterojunction with ZnO. TiO of the invention2the/ZnO composite material can efficiently degrade organic dyes in wastewater, is non-toxic and environment-friendly, has large particles, is easy to separate from water, does not cause secondary pollution, and can be widely applied to treatment of organic dye wastewater.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a composite material for efficiently degrading organic dyes in wastewater and a preparation method thereof.
Background
Organic dyes are widely applied to the fields of leather, cosmetics, printing and dyeing and the like, and about 12 percent of the dyes are released into the environment in the production and use processes and easily enter water bodies. Most dyes are stable and difficult to be naturally degraded, and the ecological balance and the biological health are seriously influenced. The advanced oxidation technology is one of the important methods for treating organic dye wastewater, can generate strong oxidizing substances such as hydroxyl radicals and the like, and can degrade macromolecular organic substances which are difficult to biodegrade into small molecular substances or inorganic substances which are easy to biodegrade by destroying chromophoric groups through physical and chemical actions by utilizing the high chemical activity and non-selectivity of the strong oxidizing substances. At present, the advanced oxidation technology mainly comprises the following steps: fenton method, ozone oxidation method, wet oxidation method, ultrasonic oxidation method, photocatalytic oxidation method, supercritical water oxidation method, low temperature plasma technology, etc.
Compared with other advanced oxidation technologies, the photocatalysis technology is an efficient and safe environment-friendly environmental purification technology, and has the advantages of simple operation, low energy consumption and no secondary pollution. Various photocatalysts for contaminant degradation have been developed, such as TiO with good photocatalytic activity2、ZnO、CeO2、CdS、BiVO4And NiO, etc. TiO compared with other photocatalysts2It is attracting attention because of its non-toxicity, high chemical stability, low cost and strong light responsiveness. TiO 22Mainly comprises three crystal forms, namely anatase, rutile and brookite, wherein anatase phase TiO2The photocatalytic performance of (2) is optimal. TiO in general2The smaller the particle size of the nano particles, the larger the specific surface area, and the more active sites, the more favorable the photocatalytic reaction. But the particle size is too small, and the catalyst is not easy to separate from the water body. Therefore, researchers increase the specific surface area of the nano structure through three-dimensional layering, such as self-assembly structures like sea urchins, flowers and trees, and the like, so that better photocatalytic performance is obtained.
The recombination of photogenerated electrons and holes is an important factor limiting the photocatalytic performance (Journal of Environmental Chemical Engineering,7(3), (2019) 103096). Researchers throughA large number of experimental studies have found that TiO2With other semiconductors (e.g. ZnO, CdS, WO)3Etc.) coupling to construct a heterojunction structure is an effective method to hinder rapid charge recombination. Wherein, ZnO has valence band and conduction band ratio TiO2Is more negative in the valence and conduction bands, which contributes to ZnO/TiO2Separation of photogenerated electrons and holes in the heterojunction. And against CdS, WO3In other words, ZnO has the advantage of being non-toxic. Thus, the construction of TiO2The composite structure with ZnO improves the photocatalysis performance, and has important research value.
Disclosure of Invention
Based on the problems of the prior art, the invention aims to provide TiO for efficiently degrading organic dye in wastewater2the/ZnO composite material and the preparation method thereof solve the problems of poor degradation effect, complex technology, difficult separation from water and the like of the existing catalyst.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a composite material for efficiently degrading organic dye in wastewater is characterized in that: the composite material is sea urchin-shaped TiO2ZnO nanoparticles are uniformly loaded on the surface of the micron sphere, and TiO2And forms a heterojunction with ZnO. Wherein, the TiO is2The microspheres are anatase phases, and the ZnO nanoparticles are wurtzite crystal phases.
The preparation method of the composite material comprises the following steps:
step 1, mixing and uniformly stirring deionized water, diethylene glycol, titanium potassium oxalate and urea, then transferring the mixture to a reaction kettle for hydrothermal reaction at 190 ℃ for 10-12h, centrifuging, washing and drying the obtained product, then placing the product in a muffle furnace, heating to 500-550 ℃, and carrying out heat preservation and calcination for 1-2 h to obtain echinoid TiO2Micro-balls;
Further, in the step 1, the dosage ratio of the deionized water, the diethylene glycol, the potassium titanium oxalate and the urea is 20 mL: 50-70 mL: 0.6-1.0 g: 2.2-2.6 g.
Further, in step 2, the concentration of the aqueous solution of hexamethylenetetramine is 0.05mol/L, and the aqueous solution of zinc nitrate, hexamethylenetetramine, deionized water and sea urchin-like TiO are added2The dosage ratio of the micro-spheres is 40 mg: 5-15 mL: 50-70 mL: 0.1-0.3 g.
Further, in the step 1, the temperature rise rate is 5-10 ℃/min.
In step 2 of the preparation method of the present invention, hexamethylenetetramine functions to hydrolyze at a high temperature to generate hydroxyl, and then reacts with zinc ions to form zinc hydroxide, and finally ZnO is formed.
Compared with the prior art, the invention has the beneficial effects that:
1. TiO of the invention2the/ZnO composite material can efficiently degrade organic dyes in wastewater, is non-toxic and environment-friendly, has large particles, is easy to separate from water, does not cause secondary pollution, can be widely applied to the treatment of organic dye wastewater, overcomes the defects of high degradation cost, complex degradation process and the like of the existing catalyst, and has important social benefits and good application prospects.
2. The composite material prepared by the invention is sea urchin-shaped TiO2ZnO nanoparticles are uniformly loaded on the surface of the microspheres, the particles are large, the specific surface area is large, the external burr-shaped appearance can provide more active sites for photodegradable organic dyes, and meanwhile, TiO nanoparticles are uniformly loaded on the surface of the microspheres2And ZnO form a heterojunction, thereby prolonging the service life of a photon-generated carrier and reducing the recombination of the photon-generated carrier, so that the composite material has excellent photocatalytic performance.
3. According to the invention, a large number of experiments are carried out to screen suitable raw materials and suitable preparation parameters, and a simple two-step hydrothermal method is adopted to mix ZnO and TiO2Compounding to prepare sea urchin-shaped TiO2The micron spheres are attached with ZnO nanoparticles on the surfaces, and the method is simple and easy to implement.
Drawings
FIG. 1 shows TiO obtained in example 1 of the present invention2SEM picture (FIG. 1(a)), EDS picture (FIG. 1(b)) and EDS element general spectrum (FIG. 1(c)) of/ZnO composite material;
FIG. 2 shows TiO obtained in example 1 of the present invention2XPS diagram of/ZnO composite material, wherein FIG. 2(a) is XPS spectrum of composite material, FIG. 2(b-d) is position of Ti2p, O1s, Zn2p peak with high resolution;
FIG. 3 shows TiO obtained in example 1 of the present invention2ZnO composite material and pure urchin-shaped TiO2XRD pattern of microspheres;
FIG. 4 shows TiO in example 1 of the present invention2/ZnO composite material (TZ) and TiO2ZnO mixture (PMTZ) and pure echinoid TiO2The degradation effect of the microspheres on the organic dye (methyl orange) changes along with the illumination time.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. The following disclosure is merely exemplary and illustrative of the inventive concept, and those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
The experimental reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
This example prepares TiO for efficient degradation of organic dyes in wastewater as follows2The ZnO composite material:
step 1, adding 20mL of deionized water, 60mL of diethylene glycol, 0.8g of potassium titanium oxalate and 2.4g of urea into a 100mL beaker, uniformly stirring by magnetic force, then transferring the mixture into a reaction kettle for hydrothermal reaction at 180 ℃ for 12 hours, sequentially washing the obtained product by centrifugation, deionized water and absolute ethyl alcohol, drying the product at 60 ℃ overnight, then placing the product in a muffle furnace, and raising the temperature at 5 ℃/minHeating to 500 deg.C at a certain rate, and calcining for 1 hr to obtain sea urchin-shaped TiO2Micro-balls;
FIG. 1 shows TiO obtained in this example2SEM picture (FIG. 1(a)), EDS picture (FIG. 1(b)) and EDS element summary spectrum (FIG. 1(c)) of/ZnO composite material. As shown in FIG. 1(a), the prepared TiO2The sea urchin sphere is about 1.5 mu m in diameter, and a plurality of burrs are distributed on the outer part of the sea urchin sphere, so that more active sites can be provided for photodegradation of organic dyes, and the degradation rate is improved. From FIG. 1(b) TiO2The element distribution of the/ZnO composite material shows that Zn is uniformly distributed in TiO2Surface, this example demonstrates the successful synthesis of TiO2/ZnO composite, TiO2Forming a heterojunction with ZnO, thereby increasing the lifetime of the photogenerated carriers and reducing the recombination of the photogenerated carriers. The elemental summary spectrum of FIG. 1(c) gives the Zn, Ti and O contents in the composite material, and it can be seen that the composite material is TiO2Mainly comprises the following steps.
FIG. 2 shows TiO obtained in this example2XPS plot of the/ZnO composite. The XPS spectrum of the composite material shown in fig. 2(a) shows characteristic peaks of C1s, Ti2p, O1s and Zn2p, which further indicates that the composite material contains Ti, Zn and O elements, and the presence of C element is due to contamination of C element in the XPS test system, thereby indicating that the example has successfully prepared TiO2A/ZnO composite material. FIG. 2(b-d) shows the positions of the peaks of Ti2p, O1s, and Zn2p with high resolution. FIG. 2(b) shows TiO2Respectively located at 458.6eV (Ti2 p)3/2) And 464.3eV (Ti2 p)1/2). FIG. 2(c) shows two characteristic peaks of ZnO, respectively located at 1022.7eV (Zn2 p)3/2) And 1045.9eV (Zn 2)p1/2). FIG. 2(d) shows the characteristic peak of O at 530.1eV for TiO2Or lattice oxygen in ZnO.
FIG. 3 shows TiO obtained in this example2the/ZnO composite material (TZ in the figure) and the urchin-shaped TiO obtained in the step 12XRD pattern of microspheres. The elongated spike appearing at 25.3 ° in the graph corresponds to anatase TiO2The peak appearing at 31.9 degrees is the (100) plane of the wurtzite crystalline phase ZnO. Pure TiO2And TiO2the/ZnO composite material detects the following crystal faces: 25.3 ° (101), 37.8 ° (004), 48.0 ° (200), 54.0 ° (105), 55.1 ° (211), with anatase TiO2The standard card (JCPDS card No. 73-1764) is consistent with that of the present example, which shows that TiO is obtained in this example2TiO in/ZnO composite material2Has good anatase crystalline phase. At the same time, 31.9 ° (100), 34.7 ° (002) crystallographic planes were also detected in the composite material, which is consistent with the standard card for wurtzite crystalline phase ZnO { JCPDS card No.36-1451}, wherein the 36.2 ° (101) and 56.4 ° (110) crystallographic planes of wurtzite crystalline phase ZnO coincide with the 37.8 ° and 55.1 ° crystallographic phases of anatase in the figure.
This example also prepared TiO for comparison of degradation efficiency2A mixture of/ZnO and/or PMTZ, prepared by mixing 16.4mg of Hemicentrotus TiO2Grinding the micro-spheres and 3.6mg of ZnO nano-particles for 10min to ensure that the micro-spheres and the ZnO nano-particles are physically and uniformly mixed to obtain the nano-particles.
The TiO obtained in this example2/ZnO composite material and echinoid TiO2Micro-sphere, TiO2Pure TiO is researched by taking methyl orange as a target dye pollutant by taking a ZnO mixture (PMTZ) as a photocatalyst2、TiO2/ZnO mixture and TiO2The degradation effect of the/ZnO composite material is measured by adopting an ultraviolet visible spectrophotometer to measure the change of the dye concentration before and after ultraviolet irradiation: preparing 20mg/L methyl orange aqueous solution in a 50mL beaker, then weighing 20mg of photocatalyst, mixing the photocatalyst into the methyl orange aqueous solution, magnetically stirring for 1h under dark condition before illumination to achieve the adsorption-desorption balance of the organic dye and the photocatalyst, and then using a xenon lamp light source provided with an ultraviolet filter with the central wavelength of 365nm as an ultraviolet light source to irradiate the solution for 4h while continuously stirring the solution. Every otherA1 mL sample was taken at 0.5h and the photocatalyst was filtered off, and then the change in dye concentration was measured using an ultraviolet-visible spectrophotometer.
FIG. 4 is TiO2/ZnO composite Material, TiO2ZnO mixture and pure echinoid TiO2The degradation effect of the microspheres on the organic dye (methyl orange) changes along with the illumination time, and the result shows that the TiO is added2/ZnO composite Material, TiO2ZnO mixture and pure echinoid TiO2The concentrations of the methyl orange solution with the microspheres as the photocatalyst after 4 hours of illumination are respectively 0.769mg/L, 5.484mg/L and 6.009mg/L, and the degradation rates of the methyl orange solution with the microspheres as the photocatalyst are respectively 96.2%, 72.6% and 69.9% according to calculation. It can be seen that this example successfully produced TiO2the/ZnO composite material has higher degradation effect on methyl orange due to the sea urchin-shaped appearance of the composite material providing more active sites for photocatalytic reaction, and compared with simple physical mixing, ZnO and TiO in the composite material2The formed heterojunction can prolong the service life of a photon-generated carrier and reduce the recombination of the photon-generated carrier, thereby synergistically promoting the degradation effect.
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A composite material for efficiently degrading organic dye in wastewater is characterized in that: the composite material is sea urchin-shaped TiO2ZnO nanoparticles are uniformly loaded on the surface of the micron sphere, and TiO2And forms a heterojunction with ZnO.
2. The composite material of claim 1, wherein: the TiO is2The microspheres are anatase phases, and the ZnO nanoparticles are wurtzite crystal phases.
3. A method for preparing a composite material according to claim 1 or 2, comprising the steps of:
step 1, mixing and uniformly stirring deionized water, diethylene glycol, titanium potassium oxalate and urea, then transferring the mixture to a reaction kettle for hydrothermal reaction at 190 ℃ for 10-12h, centrifuging, washing and drying the obtained product, then placing the product in a muffle furnace, heating to 500-550 ℃, and carrying out heat preservation and calcination for 1-2 h to obtain echinoid TiO2Micro-balls;
step 2, mixing and uniformly stirring zinc nitrate, a hexamethylenetetramine aqueous solution and deionized water, and then adding the echinoid TiO prepared in the step 12The micro-balls are continuously stirred evenly and then transferred into a reaction kettle to react for 2 to 3 hours at the temperature of between 90 and 100 ℃, and the obtained product is centrifuged, washed and dried to obtain TiO for efficiently degrading organic dye in wastewater2A/ZnO composite material.
4. The production method according to claim 3, characterized in that: in the step 1, the dosage ratio of deionized water, diethylene glycol, potassium titanium oxalate and urea is 20 mL: 50-70 mL: 0.6-1.0 g: 2.2-2.6 g.
5. The production method according to claim 3, characterized in that: in step 2, the concentration of the aqueous solution of the hexamethylenetetramine is 0.05mol/L, and the aqueous solution of the zinc nitrate and the hexamethylenetetramine, the deionized water and the echinoid TiO are added2The dosage ratio of the micro-spheres is 40 mg: 5-15 mL: 50-70 mL: 0.1-0.3 g.
6. The production method according to claim 3, characterized in that: in the step 1, the heating rate is 5-10 ℃/min.
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