CN108187694B - CuInS2Quantum dot/rGO composite photocatalytic material and application thereof - Google Patents
CuInS2Quantum dot/rGO composite photocatalytic material and application thereof Download PDFInfo
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- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 29
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 28
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 27
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- 238000001816 cooling Methods 0.000 claims description 19
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- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 16
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- 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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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- 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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- C09K11/621—Chalcogenides
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to a method for utilizing CuInS2A quantum dot supported reduced graphene oxide (rGO) composite photocatalyst and application thereof belong to the technical field of preparation of environmental protection materials. CuInS2The semiconductor material is used as a photocatalyst, is excited under visible light, realizes special catalysis or conversion through an interface interaction effect with pollutant molecules, and enables surrounding oxygen and water molecules to be excited into substances with strong oxidizing property such as oxygen free radicals and hydroxyl free radicals with strong oxidizing property, thereby achieving the purpose of degrading harmful organic substances in the environment.
Description
Technical Field
The invention relates to a method for utilizing CuInS2A quantum dot supported reduced graphene oxide (rGO) composite photocatalyst and application thereof belong to the technical field of preparation of environmental protection materials.
Background
Antibiotics are widely used for the treatment of diseases of human and animals in large quantities and are added to animal feed in sub-therapeutic doses to prevent animal diseases and promote their growth, but most antibiotics cannot be completely absorbed by the body, about 90% of the antibiotics are discharged into the environment in the form of raw or metabolic substances through feces and urine of patients and livestock and poultry and cause pollution to soil and water bodies through different ways.
Quantum dots, which may also be referred to as nanocrystals, are nanoparticles composed of group II-VI or III-V elements. The particle size of the quantum dot is generally between 1-10 nm, and because electrons and holes are limited by quanta, a continuous energy band structure is changed into a discrete energy level structure with molecular characteristics, and the quantum dot can emit fluorescence after being excited. Based on quantum effect, the quantum dots have wide application prospect in the fields of solar cells, luminescent devices, optical biomarkers and the like. Scientists have invented many different methods to fabricate quantum dots and expect this nanomaterial to have great potential for application in nanoelectronics (nanoelectronics) in the twenty-first century. Due to the photo-corrosion phenomenon of the quantum dots, the photocatalytic performance of the quantum dots is seriously inhibited, and the stability of the quantum dots is greatly reduced. Graphene carbon materialBecause of its large specific surface area, strong conductivity and toughness, researchers have applied it to modified semiconductor materials to improve its photocatalytic activity. Therefore, the content of the invention mainly lies in that graphene oxide (rGO) is reduced by loading a high-quality carbon material carrier, so that CuInS is greatly improved2The stability of the tetracycline hydrochloride is improved, and the photocatalytic activity of the tetracycline hydrochloride is improved, and the tetracycline hydrochloride is applied to the research of photocatalytic degradation of tetracycline hydrochloride wastewater.
Disclosure of Invention
The invention takes an oil bath method and a hydrothermal method as technical means to prepare the CuInS2Quantum dot supported rGO (CuInS)2the/rGO) composite photocatalyst realizes reduction of Graphite Oxide (GO) into reduced graphene oxide (rGO) during reaction.
The invention is carried out according to the following steps:
(1)CuInS2the preparation of (1):
in (Ac)3Mixing (indium acetate), CuI (cuprous iodide) and dodecanethiol (DDT) in a three-neck flask, putting the three-neck flask into an oil bath pot, continuously heating under the atmosphere of argon gas protection, immediately immersing the three-neck flask into cold water for cooling treatment after a reactant solution turns black, washing the obtained sample with toluene/methanol for 3 times, and freeze-drying the washed sample with a freeze dryer to obtain a solid CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
the CuInS prepared in the step (1) is added2Dissolving in methanol, adding GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying in a drying oven to obtain CuInS2a/rGO composite photocatalyst.
Wherein the molar ratio of the indium acetate, the cuprous iodide and the dodecanethiol in the step (1) is 1: 1: 4.
Wherein the oil bath heating temperature in the step (1) is 180-230 ℃, the cold water temperature is 20 ℃, and the cooling time is 3-15 min.
Wherein said GO powder in step (2) is obtained byThe graphite oxide prepared by the improved Hummers method has the mass of CuInS220-100 wt% of the mass of (A).
CuInS obtained according to the preparation method described above2the/rGO composite photocatalyst is applied to degrading tetracycline hydrochloride in antibiotic wastewater.
Indium acetate (in (Ac) used in the present invention3) Copper iodide (CuI), dodecanethiol (DDT), methanol, toluene and graphite are analytically pure and purchased from pharmaceutical chemicals, Inc
Tetracycline hydrochloride antibiotics were used as standard and purchased from Shanghai Shunbo bioengineering, Inc.
The invention has the beneficial effects that:
the invention realizes the use of CuInS2the/rGO nano composite material is used as a photocatalyst for degrading antibiotic wastewater. CuInS2The semiconductor material is used as a photocatalyst, is excited under visible light, realizes special catalysis or conversion through an interface interaction effect with pollutant molecules, and enables surrounding oxygen and water molecules to be excited into substances with strong oxidizing property such as oxygen free radicals and hydroxyl free radicals with strong oxidizing property, thereby achieving the purpose of degrading harmful organic substances in the environment.
Drawings
FIG. 1 is CuInS2XRD pattern of/rGO composite photocatalyst.
FIG. 2 is CuInS2TEM image of/rGO composite photocatalyst.
Detailed Description
The invention is further illustrated by the following examples.
The difference of the implementation conditions can cause different lattice changes and interface effects of the doped composite photocatalytic material, thereby causing the difference of the degradation rate. The method is researched, and the optimal process parameters in the implementation process of the method are respectively as follows: in (Ac)3The dosage is 0.438g, CuI is 0.285g, dodecanethiol is 7.5mL, the optimal addition of rGO is 0.4g, and CuInS2The optimum oil bath temperature isCooling at 210 deg.C for 5min to obtain CuInS2The optimal hydrothermal synthesis condition of the/CNTs composite photocatalyst is heating for 1h at 200 ℃, and the optimal degradation effect can reach 94.12%.
Photocatalytic activity evaluation of the photocatalyst prepared in the present invention: irradiating with visible light lamp in DW-01 type photochemical reactor (purchased from technologies, Inc. of city, Yangzhou university), adding 100mL tetracycline hydrochloride analog wastewater into the reactor, measuring its initial value, adding the prepared photocatalyst, magnetically stirring, starting an aeration device, introducing air to keep the catalyst in suspension or floating state, sampling and analyzing at an interval of 10min during the irradiation process, centrifuging, collecting supernatant, and subjecting to lambda-fluorescencemaxAbsorbance was measured with a spectrophotometer at 357nm and by the formula: dr ═ 1-Ai/A0]The degradation rate is calculated by multiplying 100%. Wherein A is0Absorbance of the tetracycline solution to equilibrium for adsorption, AiThe absorbance of the tetracycline solution was determined for the timed samples.
Example 1:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 5mL of dodecanethiol (DDT) are mixed in a three-neck flask, the mixture is placed in an oil bath pot to be heated to 210 ℃, the heating is continuously carried out under the atmosphere of argon protection gas, the three-neck flask is immediately immersed in cold water at 20 ℃ for cooling treatment for 5min after reactant solution becomes black, the obtained samples are respectively washed for 3 times by toluene/methanol, and the solid obtained after the freeze-drying treatment of a freeze-dryer for 24h is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving in methanol, adding 0.4g GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying at 70 deg.C to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride antibiotic reaches 63.08% within 60 min.
Example 2:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 7.5mL of dodecanethiol (DDT) are mixed in a three-neck flask, the mixture is placed in an oil bath pot to be heated to 210 ℃, the heating is continuously carried out under the argon protective gas atmosphere, after the reactant solution turns black, the three-neck flask is immediately immersed in cold water at 20 ℃ to be cooled for 5min, the obtained samples are respectively washed for 3 times by toluene/methanol, and the solid obtained after the freeze-drying treatment is carried out for 24h by a freeze-dryer is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving in methanol, adding 0.4g GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying at 70 deg.C to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride antibiotic reaches 94.12% within 60 min.
Example 3:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 10mL of dodecanethiol (DDT) are mixed in a three-neck flask, the mixture is put into an oil bath pot to be heated to 210 ℃, the heating is continuously carried out under the atmosphere of argon protection gas, the three-neck flask is immediately immersed into cold water at 20 ℃ to be cooled for 5min after reactant solution turns black, the obtained samples are respectively washed for 3 times by toluene/methanol, and the solid obtained after the freeze-drying treatment is carried out for 24h by a freeze-dryer is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving in methanol, adding 0.4g GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying at 70 deg.C to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride antibiotic reaches 87.31% within 60 min.
Example 4:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 7.5mL of dodecanethiol (DDT) are mixed in a three-neck flask, the mixture is placed in an oil bath pot to be heated to 180 ℃, the heating is continuously carried out under the argon protective gas atmosphere, after the reactant solution becomes black, the three-neck flask is immediately immersed in cold water at 20 ℃ to be cooled for 5min, the obtained sample is respectively washed with toluene/methanol for 3 times, and the solid obtained after the freeze-drying treatment is carried out for 24h by a freeze-dryer is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving in methanol, adding 0.4g GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying at 70 deg.C to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride antibiotic reaches 64.50% within 60 min.
Example 5:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 7.5mL of dodecanethiol (DDT)Putting the three-neck flask into an oil bath pot, heating the three-neck flask to 230 ℃, continuously heating the three-neck flask in the atmosphere of argon protection gas, immediately soaking the three-neck flask into cold water at the temperature of 20 ℃ after a reactant solution turns black, cooling the three-neck flask for 5min, washing the obtained sample for 3 times by using methylbenzene/methanol respectively, and freeze-drying the washed sample by using a freeze dryer for 24h to obtain a solid which is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving in methanol, adding 0.4g GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying at 70 deg.C to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the tetracycline hydrochloride antibiotic reaches 79.73% within 60 min.
Example 6:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 7.5mL of dodecanethiol (DDT) are mixed in a three-neck flask, the mixture is placed in an oil bath pot to be heated to 210 ℃, the heating is continuously carried out under the argon protective gas atmosphere, after the reactant solution turns black, the three-neck flask is immediately immersed in cold water at 20 ℃ to be cooled for 3min, the obtained sample is respectively washed with toluene/methanol for 3 times, and the solid obtained after the freeze-drying treatment is carried out for 24h by a freeze-dryer is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving in methanol, adding 0.4g GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying at 70 deg.C to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the tetracycline hydrochloride antibiotic reaches 69.91% within 60 min.
Example 7:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 7.5mL of dodecanethiol (DDT) are mixed in a three-neck flask, the mixture is placed in an oil bath pot to be heated to 210 ℃, the heating is continuously carried out under the argon protective gas atmosphere, after the reactant solution turns black, the three-neck flask is immediately immersed in cold water at 20 ℃ to be cooled for 10min, the obtained samples are respectively washed for 3 times by toluene/methanol, and the solid obtained after the freeze-drying treatment is carried out for 24h by a freeze-dryer is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving the precursor in methanol, adding 0.4g of GO powder, pouring the system into a high-pressure reaction kettle, heating the system in an oven at 200 ℃, continuously reacting for 1h, taking out the system, naturally cooling, centrifuging the solution, washing the solution for 3 times by using deionized water and methanol respectively, and drying the solution in a drying oven at 70 ℃ to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the tetracycline hydrochloride antibiotic reaches 81.59% within 60 min.
Example 8:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 7.5mL of dodecanethiol (DDT) are mixed in a three-neck flask, the mixture is placed in an oil bath pot to be heated to 210 ℃, the heating is continuously carried out under the argon protective gas atmosphere, after the reactant solution turns black, the three-neck flask is immediately immersed in cold water at 20 ℃ to be cooled for 15min, the obtained samples are respectively washed for 3 times by toluene/methanol, and the solid obtained after the freeze-drying treatment is carried out for 24h by a freeze-dryer is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving in methanol, adding 0.4g GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying at 70 deg.C to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the tetracycline hydrochloride antibiotic reaches 75.03% within 60 min.
Example 9:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 7.5mL of dodecanethiol (DDT) are mixed in a three-neck flask, the mixture is placed in an oil bath pot to be heated to 210 ℃, the heating is continuously carried out under the argon protective gas atmosphere, after the reactant solution turns black, the three-neck flask is immediately immersed in cold water at 20 ℃ to be cooled for 5min, the obtained samples are respectively washed for 3 times by toluene/methanol, and the solid obtained after the freeze-drying treatment is carried out for 24h by a freeze-dryer is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving in methanol, adding 0.16g of GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1h, taking out, cooling naturally, centrifuging, washing with deionized water and methanol for 3 times, and drying in a drying oven at 70 deg.C to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the tetracycline hydrochloride antibiotic reaches 71.19% within 60 min.
Example 10:
(1)CuInS2the preparation of (1):
0.438g of In (Ac) was weighed3(indium acetate), 0.285g of CuI (cuprous iodide) and 7.5mL of dodecanethiol (DDT) are mixed in a three-neck flask, the mixture is placed in an oil bath pot to be heated to 210 ℃, the heating is continuously carried out under the argon protective gas atmosphere, after the reactant solution turns black, the three-neck flask is immediately immersed in cold water at 20 ℃ to be cooled for 5min, the obtained samples are respectively washed for 3 times by toluene/methanol, and the solid obtained after the freeze-drying treatment is carried out for 24h by a freeze-dryer is CuInS2。
(2)CuInS2Preparation of rGO composite photocatalyst:
0.8g of CuInS prepared in the step (1)2Dissolving in methanol, adding 0.8g of GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying at 70 deg.C to obtain CuInS2a/rGO composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to the tetracycline hydrochloride antibiotic reaches 88.41% within 60 min.
FIG. 1 is CuInS2XRD pattern of/rGO composite photocatalyst, and CuInS is clearly shown in the pattern2Characteristic peak of (a); FIG. 2 shows CDs @ In2S3TEM image of/CNFs composite photocatalyst, from which CuInS can be seen2The shape of/rGO is that quantum dots are loaded on lamellar reduced graphene oxide.
Claims (8)
1. CuInS2The quantum dot/rGO composite photocatalytic material comprises the preparation step of CuInS2The preparation steps are characterized in that: the prepared CuInS2Dissolving in methanol, adding GO powder, pouring the system into a high-pressure reaction kettle, heating in an oven at 200 deg.C, reacting for 1 hr, taking out, naturally cooling, centrifuging, washing with deionized water and methanol for 3 times, and oven drying in a drying oven to obtain CuInS2a/rGO composite photocatalyst; by controlling CuInS2Indium acetate, cuprous iodide and twelve in the preparation step of (1)Molar ratio of mercaptan, heating temperature of oil bath, temperature and time of cold water, and CuInS occupied by graphite oxide2The best degradation effect is obtained.
2. A CuInS according to claim 12The quantum dot/rGO composite photocatalytic material is characterized in that: the mass of the graphite oxide is CuInS220-100 wt% of the mass of (A).
3. A CuInS according to claim 22The quantum dot/rGO composite photocatalytic material is characterized in that: the mass of the graphite oxide is CuInS250 wt% of the mass of (A).
4. A CuInS according to claim 12The quantum dot/rGO composite photocatalytic material is characterized in that the CuInS2The preparation steps are as follows: in (Ac)3Mixing (indium acetate), CuI (cuprous iodide) and dodecanethiol (DDT) in a three-neck flask, putting the three-neck flask into an oil bath pot, continuously heating under the atmosphere of argon gas protection, immediately immersing the three-neck flask into cold water for cooling treatment after a reactant solution turns black, washing the obtained sample with toluene/methanol for 3 times, and freeze-drying the washed sample with a freeze dryer to obtain a solid CuInS2。
5. A CuInS as claimed in claim 42The quantum dot/rGO composite photocatalytic material is characterized in that the oil bath heating temperature is 180-230 ℃, the cold water temperature is 20 ℃, and the cooling time is 3-15 min.
6. A CuInS as claimed in claim 52The quantum dot/rGO composite photocatalytic material is characterized in that the oil bath heating temperature is 210 ℃, the cold water temperature is 20 ℃, and the cooling time is 5 min.
7. A CuInS as claimed in claim 42The quantum dot/rGO composite photocatalytic material is characterized in that the indium acetate and the iodized methylene areThe molar ratio of copper to dodecanethiol is 1: 1: 4.
8. a CuInS according to claim 12The application of the quantum dot/rGO composite photocatalytic material in degrading tetracycline hydrochloride in antibiotic wastewater under visible light.
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| CN104609397A (en) * | 2014-12-09 | 2015-05-13 | 尹争艳 | Preparation method for reduced graphene-CuInS2 composite material |
| CN107201226A (en) * | 2016-03-17 | 2017-09-26 | 上海科技大学 | CuInS2Quantum dot, CuInS2/ ZnS quantum dot and its preparation and application |
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| CN104609397A (en) * | 2014-12-09 | 2015-05-13 | 尹争艳 | Preparation method for reduced graphene-CuInS2 composite material |
| CN107201226A (en) * | 2016-03-17 | 2017-09-26 | 上海科技大学 | CuInS2Quantum dot, CuInS2/ ZnS quantum dot and its preparation and application |
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| CuInS2/石墨烯混合物的合成及其在太阳能电池中的应用;华健等;《安徽大学学报（自然科学版）》;20150131;第39卷(第1期);83-91 * |
| Reduced graphene oxide conjugated with CuInS2/ZnS nanocrystals with low toxicity for enhanced photothermal and photodynamic cancer therapies;Qiang Wu，et al.;《Carbon》;20160621;第108卷;21-37 * |
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