CN114160177A - Visible light response ZnS/C3N4Photocatalyst and preparation method thereof - Google Patents
Visible light response ZnS/C3N4Photocatalyst and preparation method thereof Download PDFInfo
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/39—
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- B01J35/61—
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
Abstract
The invention relates to ZnS @ g-C3N4A heterojunction photocatalytic material and a preparation method thereof. The invention aims to solve the problems of narrow spectral response range, low solar energy utilization rate and fast electron hole recombination of the existing wide-bandgap semiconductor photocatalyst. ZnS @ g-C synthesized by the invention3N4The photocatalysis material is structurally characterized in that porous zinc sulfide (ZnS) microspheres assembled by 5-nanometer fine single crystals are deposited on g-C of a lamellar layer3N4The two forms a heterostructure with larger specific surface area; the preparation method of the composite material comprises the following steps: ultrasonic treatment of g-C3N4(ii) a Secondly, mixing and stirring; thirdly, heating;fourthly, washing and drying. The method adopts a solvent thermal synthesis method, is environment-friendly, has cheap and easily-obtained raw materials, low cost, simple synthesis route, easy large-scale industrial production, good stability of the obtained product, easy storage, good degradation effect on rhodamine B in a visible light region, and reusability. ZnS @ g-C synthesized by the invention3N4The heterojunction photocatalytic material improves the utilization rate of sunlight and can be applied to the field of sewage treatment.
Description
Technical Field
The invention relates to preparation of a visible light response semiconductor heterojunction photocatalyst, and belongs to the technical field of new materials.
Background
With the development of society and economic progress, environmental problems such as organic pollutants in water are becoming a serious challenge to human society. Among them, organic dye wastewater is highly toxic and difficult to degrade, which is a complex problem to be solved urgently. However, the traditional organic dye wastewater treatment methods such as flocculation, adsorption, ultrafiltration and the like have low efficiency and incomplete degradation. Therefore, there is a need to develop a novel method for degrading organic pollutants in water.
In recent years, a great deal of research finds that the semiconductor photocatalysis technology is more thorough and more environment-friendly compared with the traditional wastewater treatment method, and the degradation of organic pollutants in water by the photocatalysis technology gradually becomes a research hotspot. Wurtzite zinc sulfide is a II-VI metal sulfide group, has a band gap of about 3.8 eV, and belongs to a direct band gap semiconductor. In inorganic semiconductor photocatalysts, ZnS has the advantages of rich micro-morphology types, excellent transmission performance, good thermal stability, nontoxicity, lower cost and the like, so the ZnS is widely popular in the field of semiconductor photocatalysis. However, ZnS responds only to the ultraviolet absorption of electron-hole separation under ultraviolet light (λ < 340 nm), which accounts for only 3% -5% of sunlight. The inherent drawbacks of zinc sulfide, such as insufficient response to visible light and fast electron-hole recombination rate, limit its application in the field of photocatalysis. Research shows that an effective method for solving the problem of visible light response is to construct a heterostructure, wherein a narrow bandgap semiconductor can form a heterojunction with ZnS to improve photocatalytic performance, such as CdS/ZnS, CuS/ZnS, SnS2/ZnS and the like, and the heterostructure provides a new active site for photocatalytic reaction.
FromWangFirst synthesized by et al, g-C3N4Has been favored by researchers (Wang X. C.; Maeda K.; Thomas A.; Takanabe K.; Xin G.; Carlsson J. M.; Domen K.; Antonietti M., A metal-free polymeric photocatalyst for hydrogen production from water under visible light, Nature Materials, 8(2009), 76-80) The non-metal semiconductor with narrow forbidden band has two-dimensional lamellar structure and larger surface area, and g-C is formed by delocalized p-p conjugation3N4Has high electron mobility. Furthermore, g-C3N4Has a narrow band gap of 2.7 eV, and has good response performance to visible light. Based on the above advantages, in recent years with respect to g-C3N4The reports of/ZnS photocatalysts are of interest. In the year 2014, the method has the advantages that,Shiby reaction at g-C3N4Deposition of spherical ZnS on a substrate, two-dimensional g-C was found3N4The two-dimensional structure of (A) can effectively reduce the agglomeration phenomenon of ZnSShi Y.; Jiang S.; Zhou K.;Wang B.; Wang B.; Gui Z.; Hu Y.; Richard K. K. Y., Facile preparation of ZnS/g-C 3 N 4 nanohybrids for enhanced optical properties, RSC Advances, 4 (2014), 2609-2613). In the year 2014, the method has the advantages that,Wangregulating the appearance of ZnS by using a template agent to mix nano cage-shaped ZnS with g-C3N4Phase recombination, finding that the regulation and control of the micro-morphology have obvious influence on the migration of electrons and the separation of electron holes (Wang J.; Guo P.; Guo Q.; Jönsson P. G.; Zhao Z., Fabrication of novel g-C 3 N 4 /nanocage ZnS composites with enhanced photocatalytic activities under visible light irradiation, CrystEngComm, 16(2014), 4485-4492). In the year 2015, the number of the main raw materials,Wangpreparation of ZnS/g-C by reflux hydrothermal process3N4The photocatalytic efficiency is limited by the composite material, product size and agglomeration problems (Wang Q.; Shi Y.; Du Z.; He J.; Zhong J.; Zhao L.; She H.; Liu G.; Su B., Synthesis of Rod- Like g-C 3 N 4 /ZnS Composites with Superior Photocatalytic Activity for the Degradation of Methyl Orange. European Journal of Inorganic Chemistry, 24 (2015), 4108-4115). In the year of 2019, the method has the advantages that,Wangpreparation of ZnS/g-C by thermal polycondensation3N4A heterojunction. Due to g-C3N4Accelerates the electron rotationThe photoluminescence intensity of the heterojunction is obviously reduced, but the agglomeration and the low specific surface area of the product limit the photocatalytic effect thereof (1)Wang Q.; Xu P.; Zhang G.; Hu L.; Wang P., Visible-light responsive g-C 3 N 4 coupled with ZnS nanoparticles via a rapid microwave route: Characterization and enhanced photocatalytic activity, Applied Surface Science, 488(2019), 360-369). Recently, Mukherjee Biswanath (Mukherjee Biswanath., Experimental Investigation with DFT Analysis Towards a Promising Recyclable Photocatalyst from g-C3N4/ZnS Nanocomposite, ChemistrySelect, 5(2020), 9736- 9744) High crystallinity g-C by in situ synthesis3N4The method is matched with ZnS microspheres, the obtained heterojunction can degrade rhodamine B by 95% under ultraviolet irradiation, and researches show that the improvement of ZnS performance is attributed to the reduction of carrier recombination of the heterojunction under ultraviolet light, namely at g-C3N4the/ZnS interface is capable of more efficient charge separation and transport, but the photocatalytic process under visible light is not involved here. The above work demonstrates ZnS/g-C3N4The research value and application potential of the composite material in the field of photocatalysis, however, the ZnS/g-C which is not easy to agglomerate and responds to visible light so far3N4The visible light semiconductor photocatalytic material with less reports, high degradation rate and good stability of the photocatalyst composite material still needs further research and development.
Disclosure of Invention
The invention aims to provide a preparation method of a visible light response ZnS @ g-C3N4 semiconductor photocatalyst.
The material of the invention is a semiconductor heterojunction, and is structurally characterized in that:
1) porous microsphere assembled by fine single crystal with nano zinc sulfide (ZnS) structure of 5 nm and deposited on g-C of lamella3N4The two forms a heterostructure with larger specific surface area;
2）g-C3N4the lamellar structure provides a growth platform for ZnS, and can be effectiveAnd the agglomeration phenomenon of ZnS is reduced.
The preparation method is characterized in that:
1) ultrasonic treatment: g to C3N4Dissolving in appropriate amount of glycol solution, and performing ultrasonic treatment for 25-35 min;
2) mixing and stirring: mixing thiourea and zinc acetate dihydrate with a certain molar ratio with the solution obtained in the step 1), and stirring at room temperature for 25-35 minutes;
3) heating: putting the mixture obtained in the step 2) into a 100 ml stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 80 percent, putting the reaction kettle into a 150-DEG C and 200-DEG C drying oven, and reacting for 10-14 hours under the action of autogenous pressure. Turning off the power supply of the oven, and naturally cooling to room temperature to obtain light yellow precipitate;
4) washing and drying: washing the precipitate obtained in the step 3) with distilled water for 3-5 times, and then drying in a vacuum drying oven at 60-90 ℃ for 8-12h to obtain ZnS @ g-C3N4A heterojunction photocatalyst;
the invention provides a ZnS @ g-C3N4 photocatalyst and a preparation method thereof, and the photocatalyst has the advantages that:
1) ZnS @ g-C of the present invention3N4The photocatalyst is obtained under the solvothermal condition, has the characteristics of small size, good appearance uniformity, large specific surface area, many reaction sites and the like, and is easier to adsorb pollutants;
2) the invention takes thiourea and zinc acetate with low cost as raw materials, adopts a solvothermal method for synthesis, has environment-friendly synthetic route, is simple and easy to implement, has low cost, and is easy for large-scale industrial production;
3) ZnS @ g-C prepared by the invention3N4The visible light degradation agent has good response to visible light, can realize effective degradation of MB and Rh.B dyes under visible light, and can be applied to the field of sewage treatment.
4) The product has good stability in air and water, is easy to store, can be repeatedly utilized, and is convenient for industrial popularization and application.
FIG. 1 ZnS @ g-C obtained in example 13N4A phase structure diagram of the photocatalyst by X-ray diffraction (XRD);
FIG. 2 ZnS @ g-C obtained in example 13N4Microscopic morphology of the photocatalyst under a Transmission Electron Microscope (TEM);
FIG. 3 ZnS @ g-C obtained in example 13N4Degradation curve of the photocatalyst to Rh.B under the irradiation of visible light;
FIG. 4 ZnS @ g-C obtained in example 13N4Degradation cycle test chart of photocatalyst on Rh.B under irradiation of visible light.
FIG. 5 ZnS @ g-C obtained in example 13N4The photocatalytic reaction mechanism of the photocatalyst.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the examples.
EXAMPLE 1 preparation of ZnS @ g-C3N4
g-C3N4 (16.2 mg, 0.17 mmol) and ethylene glycol (80 mL) were mixed and sonicated for 30 minutes, then thiourea (190.3 mg, 2.5 mmol) and zinc acetate (219.5 mg, 1 mmol) were added to the above solution in an amount of 2.5:1, stirred with a magnetic stirrer for 30 minutes at 450 rpm, the resulting mixture was charged into a 100 mL stainless steel reaction vessel with a Teflon liner, filled to 80%, sealed, placed in a 180 ℃ oven, and heated under autogenous pressure for 12 hours. Turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain light yellow precipitate; washing the obtained precipitate with distilled water for 3 times, then washing with anhydrous ethanol for 3 times, centrifuging, placing the product into a vacuum oven, drying at 80 ℃ for 10 hours, turning off the power supply of the oven, and naturally cooling to room temperature to obtain the product. The obtained sample is light yellow powder after being ground, and is characterized by XRD (XD-3, China), and diffraction data of the sample show that zinc sulfide is a hexagonal wurtzite phase (PDF card NO. 80-0007), and the figure is shown in figure 1; the microstructure of the material is characterized by a transmission electron microscope (JEOL JEM-2100F, JAPAN), and the composition of the ZnS @ g-C3N4 heterostructure is shown in FIG. 2.
EXAMPLE 2 preparation of ZnS @ g-C3N4
g-C3N4 (16.2 mg, 0.17 mmol) and ethylene glycol (80 mL) were mixed and sonicated for 30 minutes, then thiourea (190.3 mg, 2.5 mmol) and zinc acetate (219.5 mg, 1 mmol) were added to the above solution in an amount of 2.5:1, stirred with a magnetic stirrer for 30 minutes at 450 rpm, the resulting mixture was charged into a 100 mL stainless steel reaction vessel with a Teflon liner, filled to 80%, sealed, placed in a 180 ℃ oven, and heated under autogenous pressure for 12 hours. Turning off the power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain light yellow precipitate; washing the obtained precipitate with distilled water for 3 times, then washing with anhydrous ethanol for 3 times, centrifuging, placing the product into a vacuum oven, drying at 80 ℃ for 10 hours, turning off the power supply of the oven, and naturally cooling to room temperature to obtain the product. The obtained sample is ground into light yellow powder, and is characterized by XRD (XD-3, China), and diffraction data of the light yellow powder show that zinc sulfide is a hexagonal wurtzite phase (PDF card NO. 80-0007) and is the same as the sample in the example 1; the microstructure of the material is characterized by a transmission electron microscope (JEOL JEM-2100F, JAPAN), and the composition of the ZnS @ g-C3N4 heterostructure is shown in FIG. 2.
EXAMPLE 3 determination of the photocatalytic Properties of ZnS @ g-C3N4
The photocatalytic performance of the photocatalyst under visible light is characterized by the degradation rate of Methylene Blue (MB) and rhodamine B (Rh.B). Fig. 3 is a graph of the degradation of rh.b by this catalyst under visible light. The milled catalyst (30 mg) was added to Rh.B solution (10mg/L, 50 ml). The suspension was then stirred with a magnetic stirrer away from light for 30 minutes to reach adsorption-desorption equilibrium. The suspension was irradiated with xenon visible light (300 watts) for 120 minutes. In this process, the sample was centrifuged every 10 minutes to measure absorbance. In contrast to other proportions of ZnS @ g-C3N4, the catalyst exhibited the highest catalytic efficiency (96%) when the recombination rate of g-C3N4 was 15%.
Example 4 testing of the photocatalytic stability of ZnS @ g-C3N4
The photocatalytic stability performance of the photocatalyst is characterized by the cyclic use of degraded MB and rh.b. FIG. 4 shows that 30 mg of the catalyst obtained in example 1 was added to Rh.B solution (10mg/L, 50 ml) after grinding. The suspension was then stirred with a magnetic stirrer away from light for 30 minutes to reach adsorption-desorption equilibrium. The suspension was irradiated with xenon visible light (300 watts) for 120 minutes. In this process, the sample was centrifuged every 10 minutes to measure absorbance. After the reaction is finished, the residual ZnS @ g-C3N4 is centrifugally collected, washed with distilled water and absolute ethyl alcohol three times respectively, dried in a vacuum oven at 80 ℃ for 12 hours, and the obtained ZnS @ g-C3N4 sample is ground and then subjected to photocatalytic test again for 4 times of circulating test. FIG. 4 shows the results of cycling tests of ZnS @ g-C3N4, with MB still having 81% photocatalytic efficiency after 4 cycles.
Claims (5)
1. A ZnS @ g-C3N4 visible light response photocatalyst is structurally characterized in that:
1) porous microspheres assembled by fine single crystals with zinc sulfide (ZnS) of 5 nanometers and deposited on g-C with lamellar structure3N4The two forms a heterostructure with larger specific surface area;
2）g-C3N4the lamellar structure provides a growth platform for ZnS, and can effectively reduce the agglomeration phenomenon of ZnS.
2. The method of claim 1 wherein ZnS @ g-C3N4The preparation method of the visible light response photocatalytic material comprises the following steps:
1) ultrasonic treatment: g to C3N4Dissolving in a proper amount of glycol solution, and carrying out ultrasonic treatment for 30 minutes;
2) mixing and stirring: mixing thiourea and zinc acetate dihydrate in a certain molar ratio with the solution obtained in the step 1), and then stirring for 30 minutes at room temperature;
3) heating: putting the mixture obtained in the step 2) into a 100 ml stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle with the filling degree of 80 percent, putting the reaction kettle into a 180 ℃ oven, and reacting for 12 hours under the action of autogenous pressure; turning off a power supply of the oven, gradually cooling to room temperature, and opening the reaction kettle to obtain light yellow precipitate;
4) washing and drying: washing the precipitate obtained in step 3) with distilled water for 3 timesThen drying the mixture for 10 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain ZnS @ g-C3N4A photocatalyst.
3. The method of claim 2 wherein said ZnS @ g-C3N4The preparation method of the visible light response photocatalytic material is characterized in that the step 2) is to mix thiourea (190.3 mg, 2.5 mmol) and zinc acetate (219.5 mg, 1 mmol) according to the mass ratio of 2.5:1, and 80ml of glycol and g-C are added3N4(16.2 mg, 0.17 mmol) was mixed in the solution, followed by stirring at room temperature for 30 minutes.
1) Ultrasonic treatment: g to C3N4Dissolving in a proper amount of glycol solution, and carrying out ultrasonic treatment for 30 minutes;
2) mixing and stirring: mixing thiourea and zinc acetate dihydrate in a certain molar ratio with the solution obtained in the step 1), and then stirring for 30 minutes at room temperature;
3) heating: putting the mixture obtained in the step 2) into a 100 ml stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing, putting the reaction kettle into a 180 ℃ oven, and reacting for 12 hours under the action of autogenous pressure.
4) Washing and drying: washing the precipitate obtained in the step 3) with distilled water for 3 times, and then drying at room temperature for 10 hours to obtain ZnS @ g-C3N4A photocatalyst.
4. The method of claim 2 wherein said ZnS @ g-C3N4The preparation method of the visible light response photocatalytic material is characterized in that the step 3) is to transfer the mixture obtained in the step 2) into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, the filling degree is 80%, the mixture reacts in an oven at 180 ℃ for 12 hours, the power supply of the oven is turned off, and the mixture is gradually cooled to room temperature to obtain a light yellow precipitate.
5. The method of claim 2 wherein said ZnS @ g-C3N4The preparation method of the photocatalytic material is characterized in that the step 4) is to wash the precipitate obtained in the step 3) with distilled water for 3 times, and then to wash the precipitate with distilled water for 3 timesDrying at 80 deg.C for 10 hr in vacuum drying oven.
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