CN110639555A - CdS/CdIn with visible light response2S4Preparation method and application of composite nano-structured photocatalyst - Google Patents
CdS/CdIn with visible light response2S4Preparation method and application of composite nano-structured photocatalyst 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
CdS/CdIn with visible light response2S4A preparation method of a composite nano-structured photocatalyst and application of the photocatalyst in degrading dye wastewater pollutants relate to a preparation method of a nano-particle photocatalyst and application thereof. The method solves the problems of high cost, difficult reutilization and low efficiency of the existing method for deeply purifying the dye wastewater pollutants. The method comprises the following steps: dissolving thiourea, indium nitrate and cadmium nitrate serving as raw materials in absolute ethyl alcohol respectively, and dissolving Cetyl Trimethyl Ammonium Bromide (CTAB) serving as a surfactant by ultrasonic to form a uniform mixed solution; secondly, putting the solution obtained in the step one into a reaction kettle with a polytetrafluoroethylene lining, and thenAnd thirdly, loading the product obtained by the one-step solvothermal method into a centrifuge tube for centrifugal washing for 3 ~ 6 times, removing supernatant, leaving precipitate, and drying to obtain the visible light catalytic material for photocatalytic degradation of dye wastewater pollutants.
Description
Technical Field
Visible light responding CdS/CdIn of the invention2S4Preparation of the composite nano-structured photocatalyst and application of the composite nano-structured photocatalyst in degradation of dye wastewater pollutants.
Background
In recent years, with the continuous development of economy and society, not only people's life is more convenient and faster, but also the environment is damaged, causing the problems of resource shortage, environmental pollution and the like. Fresh water resources are extremely precious in the world, and can be indirectly used in production and life of human beings, and are seriously deficient, and the fresh water resources in China also face serious examination. The total amount of the fresh water resources in China is about 28000 billion cubic meters, about six percent of the total amount of the global water resources and occupies the fourth world, but the per-capita fresh water resources are only 2200 cubic meters, are less than one fourth of the world standard and are positioned at the 121 th rank of the global fresh water resources. According to the investigation condition of the water conservancy monitoring department in China, the annual average precipitation in China is 62610 multiplied by 108The total amount of the river is 27243 multiplied by 10 in cubic meter and year8The annual average underground water resource of cubic meter is 8697 multiplied by 108Cubic meter, the water resource is very short for people all over the country.
With the rapid development of the dye textile industry, the dye brings bright and colorful colors to people's lives and generates great economic benefits, and simultaneously generates a great amount of dye wastewater harmful to the environment and discharges the dye wastewater into the environment water area, thereby causing the pollution of natural water areas. Some dyes produce significant color in the receiving water at concentrations below that which can contaminate large areas of water even with small amounts of dye. Dyes are mostly composed of harmful chemicals such as benzidine, metals, etc., so some dyes have carcinogenic and mutagenic effects. As such, in order to comply with the environmental regulations for wastewater discharge, these wastewaters must be treated before being discharged into the water body.
In recent years, photocatalytic decomposition of organic contaminants in the presence of semiconductor photocatalysts has proven to be one of the most promising contaminant purification methods. Among the various semiconductor photocatalysts, TiO2Wide bandgap semiconductor metal oxides such as ZnO have received much attention because of their low cost and high catalytic efficiency. However, they are not photocatalytically active under visible light irradiation. Therefore, the research on photocatalysts having visible light activity has been a hot research point in the field of photocatalysis. CdS and CdIn2S4Belongs to the field of transition metal sulfide with important application prospect in photoelectric conversion, catalysis and other fields. Nanostructured CdS has unique properties, unlike bulk materials. CdS nanoparticles have many applications as photocatalysts in light emitting diodes and solar cells, while CdS is considered the most common material for the fabrication of solar cells, electronics, optics and gas sensors. These materials are widely used as photocatalysts due to their interesting optical and electrical properties. Ternary metal sulfide CdIn2S4Belong to AB2X4Group compound semiconductor compound with narrow band gap (2.1 ~ 2.6.6 eV), strong absorption in visible light region, unique photoelectric characteristic and catalytic performance due to monomer CdS and CdIn2S4Under the irradiation of visible light, the photoinduced electron holes are easy to recombine, and the respective photocatalytic activity is reduced. If CdS and CdIn2S4The composite material is formed, so that the rapid migration and separation of photo-generated electrons on the surface of a reactant are facilitated, the recombination of the photo-generated electrons and holes can be effectively inhibited, and the photocatalysis efficiency is improved. Thus, CdS and CdIn were utilized2S4The CdS/CdIn with enhanced photocatalytic activity is prepared by the synergistic effect of the advantages2S4A composite nano photocatalyst.
Disclosure of Invention
The invention aims to solve the problems of high cost, difficult reutilization and low efficiency of the existing deep purification of dye wastewater pollutants, and provides visible light response CdS/CdIn2S4Preparation of composite nano-structure photocatalyst and preparation method thereofThe application of the compound in the degradation of dye wastewater pollutants.
CdS/CdIn of the invention2S4A method for preparing a composite nanostructured photocatalyst, characterized in that the method comprises the steps of:
dissolving a certain amount of thiourea in 30 ~ 50 mL of absolute ethyl alcohol to be marked as I, dissolving indium nitrate in 20 ~ 30mL of absolute ethyl alcohol, performing ultrasonic dissolution and mixing to form a uniform solution II, dissolving cadmium nitrate in 20 ~ 30mL of absolute ethyl alcohol to be marked as solution III, then sequentially adding the solution III and a certain amount of CTAB into the solution II, uniformly mixing, adding the solution I, and stirring to obtain a solution A;
secondly, placing the solution A obtained in the first step into a reaction kettle by adopting a solvothermal method, and reacting for a certain time at a certain temperature to obtain a solution B;
thirdly, the solution obtained in the second step is filled into a centrifugal tube, high-speed centrifugation is carried out for 3 ~ 6 times, and then supernatant is removed, thus obtaining CdS/CdIn2S4A composite nanostructured photocatalyst;
further, in the step one, the ultrasonic power is 60 ~ 100W;
further, the centrifugation rate in step three was 2000 ~ 7000 r/min.
CdS/CdIn prepared by the method2S4The application of the composite nano-structured photocatalyst in the degradation of dye wastewater.
The invention can realize the degradation of pollutants in dye wastewater, and the degradation efficiency is 98.6%.
The principle of the invention is as follows:
CdS/CdIn in invention2S4The working principle of the composite nano-structure photocatalyst in the degradation of pollutants in dye wastewater is as follows: when light with enough energy is irradiated on the CdS/CdIn2S4On the photocatalyst, electrons are transferred from the Valence Band (VB) to the Conduction Band (CB). CdIn2S4The energy level of CdS is very close to that of the former, but the conduction band of the former is more negative than that of the latter, and electrons can be led from CdIn2S4VB of (a) to its CB and thus to the CB of CdS, while the photogenerated holes remain anyhow in CdIn2S4And simultaneously under the action of illumination, holes on VB of CdS are transferred to CdIn2S4On VB of (c). Thus, the photo-generated electrons and holes are distributed in CdIn2S4And CdS, the recombination probability of the CdS and the CdS is greatly reduced, and the photocatalytic efficiency is greatly improved. CdS/CdIn2S4When the composite nano structure photocatalytically degrades Methylene Blue (MB) solution, electrons transferred to a CdS conduction band meet oxygen in the air, the oxygen is reduced into oxygen free radicals, and finally the MB solution is catalytically degraded into non-toxic carbon dioxide and water. This indicates that the CdS/CdIn we prepared2S4The composite nano photocatalyst has higher visible light catalytic activity, and the degradation efficiency of the composite nano photocatalyst is 98.6% in dye wastewater treatment application represented by MB solution.
The invention has the beneficial effects that:
the method comprises the steps of dissolving thiourea, indium nitrate and cadmium nitrate serving as raw materials in absolute ethyl alcohol respectively, taking CTAB as a surfactant, and synthesizing CdS/CdIn with a nano structure by a solvothermal method2S4A composite photocatalyst is provided. Thus, the CdS/CdIn of the present invention can be utilized2S4The composite nano-structured photocatalyst degrades dye wastewater.
The invention is synthesized by a one-step solvent thermal method, and has the advantages of simple preparation method, low cost and wide source of raw materials and simple operation. Since thiourea, indium nitrate and cadmium nitrate are taken as raw materials to be dissolved in absolute ethyl alcohol respectively, CTAB is taken as a surfactant, CdS/CdIn with a nano structure is synthesized by a solvothermal method2S4A composite photocatalyst is provided. Produced CdS/CdIn2S4The composite nano-structure photocatalyst has good photocatalytic performance, so that the composite nano-structure photocatalyst has good degradation capability, and the degradation efficiency is 98.6%. The above shows CdS/CdIn2S4The composite nano-structure photocatalyst has good practicability and wide application prospect.
CdS/CdIn prepared by the method2S4The photocatalyst with the composite nano structure has uniform size and dispersibility, the synthesis method is simple, the raw materials are cheap and easy to obtain, the cost is low, and the photocatalyst is preparedThe product is nontoxic, has good photocatalytic performance, and has a degradation function on environmental dye wastewater pollutants. Has wide application prospect in the fields of environmental monitoring and treatment and material chemistry.
Drawings
FIG. 1 is CdS/CdIn prepared in example 12S4SEM images of the composite nanostructured photocatalyst;
FIG. 2 is CdS/CdIn prepared in example 12S4An XRD spectrum of the composite nanostructured photocatalyst;
FIG. 3 is CdS/CdIn prepared in example 12S4An ultraviolet-visible diffuse reflectance spectrum of the composite nanostructured photocatalyst;
FIG. 4 shows CdS/CdIn prepared under the action of visible light in example 12S4A time-dependent change curve of the absorption spectrum of a Methylene Blue (MB) solution degraded by the composite nano-structure photocatalyst;
FIG. 5 shows CdS/CdIn prepared under the action of visible light in example 12S4A composite nanostructured photocatalyst recycling efficiency map.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: CdS/CdIn in this embodiment2S4A method for preparing a composite nanostructured photocatalyst, characterized in that the method comprises the steps of:
dissolving a certain amount of thiourea in 10 ~ 50 mL of absolute ethyl alcohol to be marked as I, dissolving indium nitrate in 10 ~ 30mL of absolute ethyl alcohol, performing ultrasonic dissolution and mixing to form a uniform solution II, dissolving cadmium nitrate in 10 ~ 30mL of absolute ethyl alcohol to be marked as solution III, then sequentially adding the solution III and a certain amount of CTAB into the solution II, uniformly mixing, adding the solution I, and stirring to obtain a solution A;
secondly, placing the solution A obtained in the first step into a reaction kettle by adopting a solvothermal method, and reacting for a certain time at a certain temperature to obtain a solution B;
thirdly, the solution obtained in the second step is filled into a centrifugal tube, high-speed centrifugation is carried out for 3 ~ 6 times, and then supernatant is removed, thus obtaining CdS/CdIn2S4A composite nanostructured photocatalyst;
second embodiment, the difference between the first embodiment and the second embodiment is that the ultrasonic power in the first step is 60 ~ 100W.
Third embodiment this embodiment is different from the first or second embodiment in that the mixed solution in the first step is stirred at room temperature for 1 ~ 3 h, and the rest is the same as the first or second embodiment.
Fourth embodiment the present embodiment is different from the first to third embodiments in that the molar mass ratio of cadmium nitrate to thiourea in the first step (1 ~ 3) is 1.
Fifth embodiment this embodiment is different from the first to fourth embodiments in that the molar mass ratio of cadmium nitrate, indium nitrate and thiourea in the first step is (1 ~ 6) to (1 ~ 3) to (4 ~ 9) and the others are the same as in the first to fourth embodiments.
Sixth embodiment this embodiment differs from one of the first to fifth embodiments in that the molar mass of cetyltrimethylammonium bromide in step one is 0.1 ~ 0.5.5 mmol.
Seventh embodiment mode this embodiment is different from one of the first to sixth embodiment modes in that the reaction is heated at 180 ℃ for 6 ~ 20 h in the second step.
Eighth embodiment the present embodiment is different from the first to seventh embodiments in that the centrifugation rate in the second step is 2000 ~ 7000 r/min.
The specific implementation method nine: CdS/CdIn in this embodiment2S4The application of the composite nano-structured photocatalyst in the degradation of dye wastewater.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
dissolving 5 mmol of thiourea in 20 mL of absolute ethyl alcohol to be marked as I, dissolving 2 mmol of indium nitrate in 15 mL of absolute ethyl alcohol, performing ultrasonic dissolution and mixing to form a uniform solution II, dissolving 2 mmol of cadmium nitrate in 15 mL of absolute ethyl alcohol, marking the solution as solution III, sequentially adding the solution III and 0.25 mmol of CTAB into the solution II, uniformly mixing, adding the solution I, and stirring to obtain a solution A;
secondly, placing the solution A obtained in the first step into a reaction kettle by adopting a solvothermal method, and reacting for 10 hours at 180 ℃ to obtain a solution B;
thirdly, the solution obtained in the second step is put into a centrifuge tube and is centrifuged at 6000 r/min for 3 times at a high speed, the supernatant is removed, and precipitate is left, and CdS/CdIn is obtained after washing and drying2S4A composite nanocatalyst;
fourthly, adding 0.06 g of CdS/CdIn2S4The composite nano photocatalyst is put into 50 mL (10 mg/L) of methylene blue solution, and the degradation condition of the MB solution is observed by illuminating the composite nano photocatalyst at different times.
FIG. 1 shows CdS/CdIn prepared in this example2S4Scanning electron microscope image of composite nanostructured photocatalyst, shown in FIG. 1, of prepared CdS/CdIn2S4The particle size of the composite nano particles is about 50 ~ 80 nm, the size is relatively uniform, and the dispersibility is good.
FIG. 2 CdS/CdIn prepared in this example2S4The XRD spectrum of the composite nano-structured photocatalyst can be seen in CdS/CdIn2S4CdS and CdIn on the graph of the composite catalyst2S4No impurity peak was detected, indicating that it had a higher purity.
FIG. 3 CdS/CdIn prepared in this example2S4Ultraviolet-visible diffuse reflectance spectrum of the composite nanostructured photocatalyst. It can be clearly seen that the absorption wavelengths of these samples range from UV to visibleThe absorption range of visible light is relatively large. And CdS/CdIn2S4The composite nanocatalyst shows strong light absorption capacity almost in the whole visible light region, which is probably due to CdS and CdIn2S4Synergistic effect in complex system.
FIG. 4 this example is CdS/CdIn under the action of visible light2S4The absorption spectrum of the MB solution degraded by the photocatalyst changes along with the time curve chart, and the concentration of the MB solution is gradually reduced along with the extension of the illumination time.
FIG. 5 CdS/CdIn in this example under visible light2S4The recycling efficiency chart of the photocatalyst for degrading the MB solution shows that the degradation efficiency is still 90.5% after five times of recycling, which indicates that the photocatalyst has good recycling efficiency.
CdS/CdIn prepared in this example2S4The composite nano-structure photocatalyst has better degradation capability, and the degradation efficiency is 98.6% under the irradiation of visible light for 60 min.
Example 2:
dissolving 8 mmol of thiourea in 40 mL of absolute ethyl alcohol and recording as a first solution, dissolving 3 mmol of indium nitrate in 20 mL of absolute ethyl alcohol, dissolving and mixing by ultrasonic to form a uniform solution, dissolving 4 mmol of cadmium nitrate in 20 mL of absolute ethyl alcohol, marking the solution as a third solution, then sequentially adding the third solution and 0.35 mmol of CTAB into the second solution, uniformly mixing, adding the first solution, and stirring to obtain a solution A;
secondly, placing the solution A obtained in the first step into a reaction kettle by adopting a solvothermal method, and reacting for 15 hours at 180 ℃ to obtain a solution B;
thirdly, the solution obtained in the second step is filled into a centrifugal tube, high-speed centrifugation is carried out for 3 times at 7000 r/min, supernatant is removed, sediment is left, and CdS/CdIn is obtained after washing and drying2S4A composite nanomaterial;
fourthly, adding 0.04 g CdS/CdIn2S4The nano composite material is put into 50 mL (10 mg/L) of methylene blue solution, and the methylene blue solution is illuminated at different times to observe the degradation condition of the methylene blue wastewater.
This example preparation of CdS/CdIn2S4The composite nano-structured photocatalyst can realize the degradation of pollutants in dye wastewater, and the degradation efficiency reaches 95.1 percent when the photocatalyst is irradiated by visible light for 60 min.
Example 3:
dissolving 4 mmol of thiourea in 30mL of absolute ethyl alcohol to be marked as a first step, dissolving 1.5 mmol of indium nitrate in 25 mL of absolute ethyl alcohol to be ultrasonically dissolved and mixed to form a uniform solution, dissolving 5 mmol of cadmium nitrate in 20 mL of absolute ethyl alcohol to be marked as a solution (c), then sequentially adding the solution (c) and 0.20 mmol of CTAB into the solution (c), uniformly mixing, adding the solution (a) and stirring to obtain a solution A;
secondly, placing the solution A obtained in the first step into a reaction kettle by adopting a solvothermal method, and reacting at 180 ℃ for 18 hours to obtain a solution B;
thirdly, the solution obtained in the second step is filled into a centrifugal tube, high-speed centrifugation is carried out for 3 times at 5000 r/min, supernatant liquid is removed, sediment is left, and CdS/CdIn is obtained after washing and drying2S4A composite nano photocatalyst;
fourthly, adding 0.08 g of CdS/CdIn2S4And (3) putting the composite nano material into 50 mL (10 mg/L) of methylene blue solution, and illuminating the composite nano material at different times to observe the degradation condition of the methylene blue wastewater.
This example preparation of CdS/CdIn2S4The composite nano-structured photocatalyst can realize the degradation of pollutants in dye wastewater, and the degradation efficiency reaches 96.5 percent when the photocatalyst is irradiated by visible light for 60 min.
Claims (9)
1. CdS/CdIn2S4A method for preparing a composite nanostructured photocatalyst, characterized in that the method comprises the steps of:
dissolving a certain amount of thiourea in 10 ~ 50 mL of absolute ethyl alcohol to be marked as I, dissolving indium nitrate in 10 ~ 30mL of absolute ethyl alcohol, performing ultrasonic dissolution and mixing to form a uniform solution II, dissolving cadmium nitrate in 10 ~ 30mL of absolute ethyl alcohol to be marked as solution III, then sequentially adding the solution III and a certain amount of CTAB into the solution II, uniformly mixing, adding the solution I, and stirring to obtain a solution A;
secondly, placing the solution A obtained in the first step into a reaction kettle by adopting a solvothermal method, and reacting for a certain time at a certain temperature to obtain a solution B;
thirdly, the solution B is filled into a centrifuge tube, high-speed centrifugation is carried out for 3 ~ 6 times, and then supernatant is removed, thus obtaining CdS/CdIn2S4A composite nanostructured photocatalyst.
2. CdS/CdIn according to claim 12S4The preparation method of the composite nano-structure photocatalyst is characterized in that in the first step, the ultrasonic power is 60 ~ 100W.
3. CdS/CdIn according to claim 12S4The preparation method of the composite nano-structure photocatalyst is characterized in that the mixed solution in the first step is stirred at room temperature for 1 ~ 3 hours.
4. CdS/CdIn according to claim 12S4The preparation method of the composite nano-structure photocatalyst is characterized in that in the first step, the molar mass ratio of the cadmium nitrate to the thiourea (1 ~ 3) is 1.
5. CdS/CdIn according to claim 12S4The preparation method of the composite nano-structure photocatalyst is characterized in that in the first step, the molar mass ratio of cadmium nitrate to indium nitrate to thiourea is (1 ~ 6) (1 ~ 3) (4 ~ 9).
6. CdS/CdIn according to claim 12S4The preparation method of the composite nano-structure photocatalyst is characterized in that in the first step, the CTAB molar mass is 0.1 ~ 0.5.5 mmol.
7. CdS/CdIn according to claim 12S4The preparation method of the composite nano-structure photocatalyst is characterized in that in the second step, the heating reaction is carried out for 8 ~ 20 hours at 180 ℃.
8. CdS/CdIn according to claim 12S4The preparation method of the composite nano-structure photocatalyst is characterized in that the centrifugation rate in the step is 2000 ~ 7000 r/min.
9. CdS/CdIn prepared according to the method of claim 12S4The application of the composite nano-structured photocatalyst in the degradation of dye wastewater pollutants.
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