CN107469834B - Preparation method of ZnS/CuS nanosheet composite photocatalyst - Google Patents
Preparation method of ZnS/CuS nanosheet composite photocatalyst Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000002135 nanosheet Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 title abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 abstract description 9
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
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- 239000000203 mixture Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 2
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 abstract description 43
- 239000005083 Zinc sulfide Substances 0.000 abstract description 42
- 229910052984 zinc sulfide Inorganic materials 0.000 abstract description 42
- 238000000034 method Methods 0.000 abstract description 32
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 4
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- 150000002500 ions Chemical class 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- 238000001816 cooling Methods 0.000 description 4
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 231100000378 teratogenic Toxicity 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- 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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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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 belongs to the technical field of nano material preparation, and particularly relates to a preparation method of a ZnS/CuS nanosheet composite material. The method comprises the following steps: 1) weighing raw materials of copper nitrate trihydrate, zinc nitrate hexahydrate, thiourea and a surfactant according to a ratio, putting the raw materials into an acetonitrile aqueous solution for ultrasonic treatment, and stirring at a constant temperature to form a uniform copper-zinc mixed solution; 2) putting the solution into a hydrothermal reaction kettle, and reacting at a specified temperature and time; 3) and (3) after the reaction is finished and naturally cooled, removing the supernatant, washing the product with deionized water and absolute ethyl alcohol for three times respectively, and drying the product in an oven at 60 ℃ for 5 hours to obtain the product, namely the Cu: Zn = x: y composite nanosheet. When the copper sulfide (CuS)/zinc sulfide (ZnS) bimetallic sulfide is used as the photocatalyst, photo-generated carriers can be effectively separated, and the photocatalytic activity is effectively improved.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a preparation method of a ZnS/CuS nanosheet composite material.
Background
Contaminants in water include inorganic contaminants and organic contaminants. The inorganic pollutants mainly comprise heavy metal ions such as lead, chromium, diaphragm, mercury, copper and the like, and the heavy metal elements have the characteristics of difficult degradation, easy accumulation, irreversibility, high toxicity, slow metabolism and easy biological enrichment in the environment. Long-term drinking of water polluted by heavy metals can cause acute and chronic poisoning or canceration of the organism. The organic pollutants mainly comprise oxygen-consuming non-toxic organic matters (such as protein, fat, carbohydrate and the like) and toxic organic matters (such as phenolic compounds, organic pesticides, polycyclic aromatic hydrocarbons, dyes, food additives and the like), and the organic pollutants are teratogenic, mutagenic and carcinogenic substances.
A report of 2016 national drinking water source with high water quality shows that 98 water quality excesses exist in 24 provinces in water quality conditions of 1333 drinking water source places (995 surface water source places and 338 underground water source places) disclosed by 31 provincial environmental protection departments in 2016, the exceeding proportion of the underground water source is obviously higher than that of the surface water source, and the pollution duration is longer than that of the latter. If the prevention and treatment speed cannot keep up with the pollution speed, the pollution of the drinking water is difficult to be inhibited.
At present, chemical methods, physical and chemical methods, biotechnology and other methods are generally adopted to treat water pollutants.
The principle of the method is that heavy metal in an ionic state in wastewater is converted into water-insoluble precipitate through chemical reaction, and then the precipitate is separated from the waste liquid through filtration, wherein the removal of the heavy metal ions mainly adopts a chemical precipitation method, and the principle comprises an ammonia oxide precipitation method, a sulfide precipitation method, a calcium salt precipitation method, a ferrite coprecipitation method and the like. The method has the disadvantages that the treated waste liquid often cannot meet the discharge standard, and the generated precipitate is easy to cause secondary pollution if not treated properly. The removal of organic pollutants is usually a chemical degradation method, mainly utilizes a photocatalytic oxidation method, a wet oxidation method, a supercritical water oxidation method, an electrochemical oxidation method, an ozone oxidation method, an acoustochemical degradation method and the like to oxidize, decompose and convert the organic pollutants into nontoxic biodegradable substances, and the method is an effective method for treating persistent organic pollutants.
The physical and chemical methods mainly include adsorption, ion exchange and membrane separation. Adsorption is a common phenomenon existing in a solid-liquid interface, and the adsorbent which is loose and porous and has large specific surface area is used for adsorbing heavy metal ions and organic pollutants in sewage so as to achieve the aim of purifying water. The ion exchange method is to remove harmful ions in the wastewater by exchanging ions in the wastewater with exchange groups in an exchanger. The membrane separation method is to separate and concentrate by utilizing the selective permeability of a semipermeable membrane under the action of certain driving force, and common membrane separation methods comprise an electrodialysis method, a diffusion dialysis method, a reverse osmosis method, an ultrafiltration method and the like. The method has complex procedures and higher requirements on production technology, and is limited in popularization and application.
Biotechnology includes phytoremediation technology and microbial remediation technology. The plant repairing technology is to utilize plant and its coexisting microbe system of natural growth or genetic engineering to accumulate some pollutant in excess and eliminate pollutant in environment. Phytoremediation modes include plant extraction, plant degradation, plant stabilization, plant volatilization, and the like. The microbial repairing technology is to utilize naturally occurring or artificially cultured functional microbe group to absorb or degrade toxic pollutant in proper environment condition. The technology shows the advantages of high efficiency, low cost, no secondary pollution and the like in the aspect of treating heavy metal pollution and organic pollutants, and becomes one of the hotspots of research in the technical field of environmental bioremediation.
Among the above treatment methods, the photocatalytic oxidation method has the advantages of high treatment effect, short reaction time, simple and convenient operation, difficult secondary pollution and the like, and particularly has special application value in the fields of heavy metal pollution and organic polluted wastewater which have strong pollution and low concentration and are difficult to effectively treat by other treatment methods. Commonly used photocatalysts include titanium dioxide (TiO)2) Zinc oxide (ZnO), tin oxide (SnO)2) Zirconium dioxide (ZrO)2) And various oxide sulfide semiconductors such as cadmium sulfide (CdS), wherein titanium dioxide is the most red nanometer photocatalyst material in the world due to its strong oxidizing ability, stable chemical properties and non-toxicity, but because of its high band gap energy and low solar energy utilization rate, it is difficult to realize photocatalytic degradation under visible light conditions. Cadmium sulfide (CdS) and zinc oxide (ZnO) have also been used more often in the early daysHowever, since both of them are unstable in chemical properties, and are photo-dissolved at the same time as being photo-catalyzed, and the dissolved harmful metal ions have a certain biological toxicity, developed countries have rarely used them as a domestic photo-catalytic material at present, and development of inexpensive and efficient nano-photocatalysts is an important aspect of adsorption research at present.
Disclosure of Invention
The invention aims to overcome the problems and provides a preparation method of a ZnS/CuS nanosheet composite material. The method takes the nano CuS/ZnS nano composite sheet as a photocatalyst and takes the rhodamine B which is difficult to degrade and has low cost as a treating agent, thereby improving the application of the inorganic composite nano material in the field of photodegradation.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a preparation method of a ZnS/CuS nanosheet composite material comprises the following steps:
1) weighing raw materials of copper nitrate trihydrate, zinc nitrate hexahydrate, thiourea and a surfactant according to a proportion, then placing the raw materials into an acetonitrile aqueous solution for ultrasonic treatment, and stirring at a constant temperature to form a uniform copper-zinc mixed solution; the mass ratio of the copper nitrate trihydrate, the zinc nitrate hexahydrate and the thiourea is 0.1-3 g: 0.1-4 g: 0.2 to 5 g. The volume ratio of the mass of the thiourea to the acetonitrile solution is 0.2-5 g: 50-200 mL; the concentration of the acetonitrile solution was 50 wt%.
2) Putting the solution into a hydrothermal reaction kettle, and reacting at a specified temperature and time;
3) and (3) after the reaction is finished and naturally cooled, removing the supernatant, washing the product with deionized water and absolute ethyl alcohol for three times respectively, and drying the product in an oven at 60 ℃ for 5 hours to obtain the product, namely the Cu: Zn = x: y composite nanosheet.
The surfactant is any one or a mixture of several of sodium dodecyl sulfate, polyethylene glycol with Mw =10000, polyethylene glycol with Mw =20000, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone with Mw =58000 and cetyl trimethyl ammonium bromide.
The constant-temperature stirring condition in the step 1) is as follows: the temperature is 25-35 ℃, the stirring intensity is 100-400 r/min, and the stirring time is 30-150 min.
The ultrasonic conditions are as follows: the strength is 50-99 Hz, the temperature is 20-50 ℃, and the time is 5-20 min;
the hydrothermal reaction conditions in the step 2) are as follows: the temperature is 150-250 ℃, and the time is 4-10 h.
The positive effects of the invention are as follows:
copper sulfide (s)/zinc sulfide (ZnS) bimetallic sulfide enables efficient separation of photogenerated carriers, and as a photocatalyst, it can improve light absorption efficiency and photocatalytic activity.
The application takes the nano CuS/ZnS nano composite sheet as a photocatalyst and takes the rhodamine B which is difficult to degrade and has low cost as a treating agent, thereby improving the application of the inorganic composite nano material in the field of photodegradation.
Drawings
FIG. 1 shows characteristic diffraction peaks of CuS and ZnS phases detected in an XRD spectrum of a CuS/ZnS nanosheet composite material with a CuS/ZnS molar ratio of 1: 1.
FIG. 2 is an EDX spectrum of a CuS/ZnS nanosheet composite material (CuS/ZnS molar ratio 1: 2)
The elements such as Cu, Zn and S are detected in the map, which shows that the synthesized nanosheet composite material consists of the three elements, and the CuS/ZnS composite material can be synthesized by a hydrothermal synthesis method.
FIG. 3a is an SEM image of a CuS/ZnS nanosheet composite (CuS/ZnS molar ratio 1: 2) with a scale bar of 1 μm.
FIG. 3b is an SEM image of a CuS/ZnS nanosheet composite (CuS/ZnS molar ratio 1: 2) with a scale bar of 200 nm.
FIG. 4a is an SEM image of a CuS/ZnS nanosheet composite (CuS/ZnS molar ratio 1: 4) with a scale bar of 1 μm;
FIG. 4b is an SEM image of a CuS/ZnS nanosheet composite (CuS/ZnS molar ratio 1: 4) with a scale bar of 200 nm;
FIG. 5a is an SEM image of a CuS/ZnS (CuS/ZnS molar ratio 3: 1) nanosheet composite, with a scale bar of 1 μm;
FIG. 5b is an SEM image of a CuS/ZnS (CuS/ZnS molar ratio 3: 1) nanosheet composite, with a scale bar of 200 nm;
FIG. 6a is an SEM image of a CuS/ZnS (CuS/ZnS molar ratio 4: 1) nanosheet composite, with a scale bar of 1 μm;
FIG. 6b is an SEM image of a CuS/ZnS (CuS/ZnS molar ratio 4: 1) nanosheet composite, with a scale bar of 200 nm.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to specific embodiments for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples.
Example 1:
weighing 0.322g of copper nitrate trihydrate, 0.7934g of zinc nitrate hexahydrate, 0.6976g of thiourea and 0.1g of polyvinylpyrrolidone (Mw = 58000) and adding the mixture into an acetonitrile mixed solution with the volume of 160mL and the mass fraction of 50wt%, carrying out ultrasonic treatment for 5min, stirring the mixture at the stirring speed of 500r/min for 60min at normal temperature to form a copper-zinc mixed solution, putting the copper-zinc mixed solution into a polytetrafluoroethylene high-temperature reaction kettle, carrying out hydrothermal reaction for 6h at 200 ℃, removing supernatant after natural cooling, washing the mixture three times with deionized water and absolute ethyl alcohol respectively, and drying the mixture in an oven at 60 ℃ for 5h to obtain the composite nanosheet with the CuS/ZnS molar ratio of 1: 2.
Example 2:
0.1932g of copper nitrate trihydrate, 0.9520g of zinc nitrate hexahydrate, 0.6976g of thiourea and 0.1g of polyethylene glycol 20000 are weighed and added into an acetonitrile mixed solution with the volume of 140mL and the mass fraction of 50wt%, ultrasonic treatment is carried out for 5min, the mixture is stirred at the stirring speed of 500r/min for 60min at normal temperature to form a copper-zinc mixed solution, the copper-zinc mixed solution is filled into a polytetrafluoroethylene high-temperature reaction kettle, hydrothermal reaction is carried out for 5h at 200 ℃, after natural cooling, supernatant is removed, the copper-zinc mixed solution is washed with deionized water and absolute ethyl alcohol for three times respectively, and drying is carried out in an oven at 60 ℃ for 5h, so that the obtained product is the composite nanosheet with the CuS/ZnS molar ratio of 1: 4.
Example 3:
0.7248g of copper nitrate trihydrate, 0.2974g of zinc nitrate hexahydrate, 0.6976g of thiourea and 0.1g of sodium dodecyl benzene sulfonate are weighed and added into 150mL of acetonitrile mixed solution with the mass fraction of 60wt%, the mixture is subjected to ultrasonic treatment for 5min and stirred at the stirring speed of 500r/min for 60min at normal temperature to form a copper-zinc mixed solution, the copper-zinc mixed solution is put into a polytetrafluoroethylene high-temperature reaction kettle and subjected to hydrothermal reaction for 8h at 190 ℃, after natural cooling, a supernatant is removed, the copper-zinc mixed solution is washed with deionized water and absolute ethyl alcohol for three times respectively and dried in an oven for 5h at 60 ℃, and the obtained product is the composite nanosheet with the CuS/ZnS molar ratio of 3: 1.
Example 4:
0.9664g of copper nitrate trihydrate, 0.2974g of zinc nitrate hexahydrate, 0.6976g of thiourea, 0.1g of sodium dodecyl benzene sulfonate and 0.05g of hexadecyl trimethyl ammonium bromide are weighed and added into 160mL of acetonitrile mixed solution with the mass fraction of 45wt%, ultrasonic treatment is carried out for 5min, the mixture is stirred at the normal temperature of 500r/min for 60min to form copper-zinc mixed solution, the copper-zinc mixed solution is put into a polytetrafluoroethylene high-temperature reaction kettle, hydrothermal reaction is carried out for 8h at 190 ℃, supernatant is removed after natural cooling, deionized water and absolute ethyl alcohol are respectively washed for three times, and the copper-zinc mixed solution is dried in an oven at 60 ℃ for 5h to obtain the composite nanosheet with the CuS/ZnS molar ratio of 4: 1.
Respectively weighing 0.15g of the nanosheet composite materials prepared in the above examples and having the CuS/ZnS molar ratios of 1:2, 1:4, 3:1 and 4:1, using the nanosheet composite materials as a rhodamine B solution with a degradation volume of 100mL and a concentration of 20mg/L in a visible light region (400W xenon lamp), and measuring the degradation rates of the nanosheet composite materials with the CuS/ZnS molar ratios of 1:2, 1:4, 3:1 and 4:1 to the rhodamine B solution after 2 hours of irradiation with 20 muL of hydrogen peroxide: 97.2%, 78.3%, 80.0% and 86.5%. The degradation rate of ZnS and CuS on the rhodamine B solution under the same condition is 70.1 percent and 73.4 percent respectively. This shows that the photocatalytic activity of the CuS/ZnS nanosheet composite material is higher than that of the CuS and CuS when the ZnS and CuS are used independently.
Claims (1)
1. A preparation method of a ZnS/CuS nanosheet composite material is characterized by comprising the following steps:
1) weighing raw materials of copper nitrate trihydrate, zinc nitrate hexahydrate, thiourea and a surfactant according to a proportion, and putting the raw materials into an acetonitrile water solution for ultrasonic treatment, wherein the ultrasonic treatment conditions are as follows: the strength is 50-99 Hz, the temperature is 20-50 ℃, and the time is 5-20 min; and then stirring at constant temperature to form a uniform copper-zinc mixed solution, wherein the mass ratio of the copper nitrate trihydrate, the zinc nitrate hexahydrate and the thiourea is 0.1-3 g: 0.1-4 g: 0.2-5 g, wherein the volume ratio of the mass of the thiourea to the acetonitrile solution is 0.2-5 g: 50-200 mL; the concentration of the acetonitrile solution is 50wt%, and the constant-temperature stirring conditions are as follows: the temperature is 25-35 ℃, the stirring intensity is 100-400 r/min, and the stirring time is 30-150 min; the surfactant is any one or a mixture of several of sodium dodecyl sulfate, polyethylene glycol with Mw of 10000, polyethylene glycol with Mw of 20000, sodium dodecyl benzene sulfonate and polyvinylpyrrolidone with Mw of 58000;
2) putting the solution into a hydrothermal reaction kettle, and reacting at a specified temperature and time under the hydrothermal reaction conditions of: the temperature is 190-250 ℃, and the time is 4-10 h;
3) and (3) after the reaction is finished and naturally cooled, removing the supernatant, washing the reactant with deionized water and absolute ethyl alcohol for three times respectively, and drying the reactant in an oven at 60 ℃ for 5 hours to obtain the product, namely the Cu: Zn ═ x: y composite nanosheet.
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| CN110739103B (en) * | 2018-10-17 | 2020-11-03 | 嘉兴学院 | Preparation method of CuS/ZnS composite conductive film |
| CN109368686B (en) * | 2018-10-18 | 2021-05-21 | 温州大学新材料与产业技术研究院 | Method for preparing ZnS/CuS heterostructure through hydrothermal synthesis and ZnS/CuS heterostructure |
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