CN111569905A - CuInS2/TiO2Composite photocatalyst and preparation method and application thereof - Google Patents
CuInS2/TiO2Composite photocatalyst and preparation method and application 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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 belongs to the technical field of preparation of environmental materials, and particularly relates to CuInS2/TiO2A composite photocatalyst and a preparation method and application thereof. The invention uses CuInS2Quantum dots and TiO2Load forming CuInS with Z-type heterojunction2/TiO2The composite photocatalyst is compared with pure TiO2The nano-rod has a higher light absorption range, the electron recombination efficiency is greatly reduced, and the degradation capability of the catalyst is greatly enhanced. Prepared CuInS2/TiO2The composite photocatalyst can efficiently degrade 2, 4-dichlorophenol wastewater, does not cause resource waste and additional pollution, is simple and convenient to operate, and isIs a green and environment-friendly high-efficiency treatment technology.
Description
Technical Field
The invention belongs to the technical field of preparation of environmental materials, and relates to CuInS2/TiO2A composite photocatalyst and a preparation method and application thereof.
Background
Phenols and compounds thereof are widely used in the fields of medicines, insecticides, herbicides, and the like. Due to the excessive use of the chlorophenols, certain pollution is caused to the environment. When entering water, soil and the like through a water circulation system, a large amount of residues are generated, which brings trouble to the survival of human beings. The 2, 4-dichlorophenol has the characteristics of stronger stability, volatility and strong irritation, has larger influence on the environment and even endangers the life of human beings. The effective removal of the residual 2, 4-dichlorophenol in the environment becomes a research hotspot of scientific researchers. The existing 2, 4-dichlorophenol processing method mainly comprises the following steps: natural enzyme method, activated carbon adsorption method and microorganism method. Compared with the pollution treatment technology, the photocatalytic oxidation method is efficient, green, energy-saving and environment-friendly, and has the characteristics of strong oxidizability and high efficiency, so that the photocatalytic oxidation method is widely concerned by researchers.
CuInS2The quantum dot has unique optical performance, is a direct band gap semiconductor, has band gap energy of 1.53eV, has an easily-regulated band gap structure, and has a band gap energy of up to 10 in a visible light region-5cm-1The light absorption coefficient of (a). However, the narrow band gap allows faster recombination of electron holes, and the low adsorption capacity further limits the CuInS2The practical application range. Titanium dioxide (TiO)2) TiO, which is believed to be the prototype of the photocatalyst2It is a most widely used photocatalyst due to its abundant reserves, high photocatalytic activity, and good biocompatibility, and has been used to decompose various organic pollutants. However, TiO alone2The nanoparticles have certain limitations in practical application processes because of their poor photocatalytic activity due to their wide band gap (anatase is about 3.2 eV) and high rate of recombination of photo-generated electron-hole pairs. At present, CuInS is not seen yet2Quantum dots and TiO2Research reports of relevant composite materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides CuInS2/TiO2The invention discloses a composite photocatalyst and a preparation method and application thereof, and the invention adopts a hydrothermal method to mix CuInS2Quantum dot photocatalyst and TiO2The nano-rod phase is compounded to form a Z-shaped heterojunction, and the prepared CuInS2/TiO2The composite photocatalyst can effectively treat phenols in wastewater, and particularly has an excellent degradation effect on 2, 4-dichlorophenol.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the invention provides CuInS2/TiO2Composite photocatalyst, CuInS in composite photocatalyst2The quantum dots are uniformly grown on the TiO2On nanorods, CuInS2Quantum dots and TiO2Z-shaped heterojunction, CuInS, is formed between the nanorods2Quantum dot accounts for CuInS2/TiO2The total mass of the composite photocatalyst is 10-40%. The degradation rate of the composite photocatalyst to 2, 4-dichlorophenol reaches 66.9% -86.6% within 120 min.
The invention also provides CuInS2/TiO2The preparation method of the composite photocatalyst comprises the following steps:
(1) taking TiO2Adding NaOH solution, stirring to obtain uniform solution, transferring to high-pressure reaction kettle, naturally cooling, stirring with dilute hydrochloric acid, soaking, washing to neutrality, oven drying, and calcining at high temperature to obtain TiO2A nanorod;
(2) copper chloride dihydrate (CuCl)2·2H2O) and ethylenediamine are mixed evenly and then indium chloride (InCl) is added3) Adding deionized water into the mixture, and then performing magnetic stirring reaction to obtain CuInS2A quantum dot precursor solution; adding the TiO prepared in the step (1)2The nano-rods are fully and uniformly stirred and then put into a high-pressure reaction kettle for reaction, and the CuInS is obtained after the reaction is naturally cooled, centrifuged, washed and dried2/TiO2A composite photocatalyst is provided.
The concentration of the NaOH solution in the step (1) is 8-12 mol/L, and TiO is2The dosage ratio of the NaOH solution to the NaOH solution is1.0g:50mL。
The pH value of the dilute hydrochloric acid in the step (1) is 2.5-3.5.
In the step (1), the reaction temperature in the high-pressure reaction kettle is 140-160 ℃, and the reaction time is 22-26 h.
The high-temperature calcination in the step (1) is carried out at the temperature of 450-550 ℃ for 2-3 h.
The dosage ratio of the copper chloride dihydrate, the ethylenediamine, the indium chloride and the L-cysteine in the step (2) is 0.017g to 20-30 mL to 0.022g to 0.024 g.
The volume ratio of the ethylenediamine to the deionized water in the step (2) is 1: 1-1.5.
The TiO in the step (2)2The dosage ratio of the nano rod to the copper chloride dihydrate is 0.017g: 0.036-0.46 g.
The temperature of the high-pressure reaction kettle in the step (2) is 160-200 ℃, and the reaction time is 10-14 h.
The invention also provides CuInS2/TiO2The application of the composite photocatalyst is to remove 2, 4-dichlorophenol in wastewater.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses narrow band gap CuInS2Quantum dots and wide band gap TiO2The direct Z-shaped CuInS is successfully constructed by the nano-rod through a hydrothermal method2/TiO2A composite photocatalyst is provided. CuInS2The quantum dot has very high light absorption coefficient and can widen TiO2The absorption range of light is widened, the utilization rate of light is improved, the separation of photogenerated carriers can be promoted by a transfer channel of the photogenerated carriers in the Z-type heterojunction, the activity loss caused by the recombination of the photogenerated carriers is effectively prevented, the photocatalytic activity is enhanced, and the problem of CuInS is solved2The electron hole recombination rate of the quantum dots is high; the invention uses semiconductor material as photocatalyst, simulates sunlight as excitation, realizes catalysis or conversion effect through the interface interaction with pollutant molecules, and enables ambient oxygen and water molecules to be excited into substances with strong oxidizing property, such as oxygen free radicals with strong oxidizing power, thereby achieving the purpose of degrading harmful organic substances in the environmentPrepared CuInS2/TiO2Photocatalyst is compared with pure CuInS2The quantum dot photocatalyst has more excellent photocatalytic activity and can efficiently degrade 2, 4-dichlorophenol wastewater. The preparation method of the invention does not cause resource waste and additional pollution, is simple and convenient to operate, and is an environment-friendly high-efficiency treatment technology.
Drawings
FIG. 1 is CuInS prepared in example 22/TiO2A UV-Vis diagram of the composite photocatalyst;
FIG. 2 is CuInS prepared in example 22/TiO2XRD pattern of the composite photocatalyst;
FIG. 3 is an Electron Spin Resonance (ESR) diagram of the CuInS2/TiO2 composite photocatalyst prepared in example 2.
Detailed Description
In order to further understand the present invention, the following further describes the present invention with reference to specific embodiments, and the technical solutions in the embodiments of the present invention are clearly and completely described. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products, and all of them are commercially available. Titanium dioxide (TiO) used in the present invention2) Sodium hydroxide (NaOH), hydrochloric acid (HCl), absolute ethyl alcohol (C)2H5OH), L-cysteine (C)3H7NO2S), ethylenediamine (C)2H8N2) Copper chloride dihydrate (CuCl)2·2H2O) are all analytically pure and purchased from national pharmaceutical chemical reagent company Limited; indium chloride (InCl)3) And purchased from Shanghai Michelin Biochemical technology, Inc.
Photocatalytic activity evaluation of the photocatalyst prepared in the present invention: in DW-01 model photochemical reaction instrumentFrom Yangzhou university city science and technology Co., Ltd.), simulating sunlight irradiation, adding 100mL2, 4-dichlorophenol simulated wastewater into a reactor, measuring the initial value, adding the prepared photocatalyst, magnetically stirring, starting an aeration device, introducing air to keep the catalyst in a suspension or floating state, sampling and analyzing at 15min intervals in the illumination process, centrifuging, taking supernatant liquid, and placing the supernatant liquid in a spectrophotometer lambdamaxAbsorbance at 285nm, and by the formula: ƞ = [ (1-C)t/C0)]x100% to calculate the degradation rate, where C0Absorbance of 2, 4-dichlorophenol solution to reach adsorption equilibrium, CtAbsorbance of 2, 4-dichlorophenol solution measured for sampling at regular time.
Example 1
(1) With anatase TiO2The powder was used as raw material and 1.0g TiO was weighed2Adding the powder into 50ml of NaOH solution (10 mol/L), stirring to obtain a uniform solution, transferring the uniform solution to a high-pressure reaction kettle, reacting at 150 ℃ for 22 hours, naturally cooling, stirring and soaking with dilute hydrochloric acid with the pH of 2.5 for 8 hours, washing with deionized water for multiple times until the solution is nearly neutral, drying at 60 ℃, calcining at 550 ℃ for 2 hours, and raising the temperature at the rate of 5 ℃/min to obtain anatase TiO2A nanorod;
(2) 0.017g of copper chloride dihydrate (CuCl)2·2H2O) and 25mL of ethylenediamine were placed in a small beaker, and 0.022g of indium chloride (InCl) was added after all were dissolved3) And 0.024g of L-cysteine, adding 25mL of deionized water, magnetically stirring, and carrying out auxiliary reaction for 30min to obtain CuInS2A quantum dot precursor solution; 0.46g of TiO prepared in step (1) was added2The nano rods are fully and uniformly stirred and then are placed into a high-pressure reaction kettle, and are heated for 10 hours at the temperature of 200 ℃; after natural cooling, taking the reaction product, centrifuging, washing, and drying in an oven at 60 ℃; obtaining CuInS2/TiO2Composite photocatalyst (5 CISQ/TiO)2) Wherein, CuInS2The quantum dots account for 5% of the total mass of the composite photocatalyst.
The CuInS prepared in this example was used2/TiO2Placing the composite photocatalyst into a photochemical reactor to perform a photocatalytic degradation test, and measuring the photocatalyst pairsThe degradation rate of the 2, 4-dichlorophenol antibiotic reaches 66.7 percent within 120 min.
Example 2
(1) With anatase TiO2The powder was used as raw material and 1.0g TiO was weighed2Adding the powder into 50ml of NaOH solution (10 mol/L), stirring to obtain a uniform solution, transferring the uniform solution into a high-pressure reaction kettle, reacting at 150 ℃ for 24 hours, naturally cooling, stirring and soaking with dilute hydrochloric acid with the pH value of 3 for 6 hours, washing with deionized water for multiple times until the solution is nearly neutral, drying at 60 ℃, calcining at 500 ℃ for 2 hours, and heating at the rate of 5 ℃/min to obtain anatase TiO2A nanorod;
(2) 0.017g of copper chloride dihydrate (CuCl)2·2H2O) and 20mL of ethylenediamine were placed in a small beaker, and 0.022g of indium chloride (InCl) was added after all were dissolved3) And 0.024g of L-cysteine, adding 20mL of deionized water, magnetically stirring, and carrying out auxiliary reaction for 30min to obtain CuInS2A quantum dot precursor solution; 0.218g of TiO prepared in step (1) was added2The nano rods are fully and uniformly stirred and then are placed into a high-pressure reaction kettle, and are heated for 12 hours at the temperature of 180 ℃; after natural cooling, taking the reaction product, centrifuging, washing, and drying in an oven at 60 ℃; obtaining CuInS2/TiO2Composite photocatalyst (10 CISQ/TiO)2) Wherein, CuInS2The quantum dots account for 10% of the total mass of the composite photocatalyst.
The CuInS prepared in this example was used2/TiO2The composite photocatalyst is put into a photochemical reactor for a photocatalytic degradation test, and the degradation rate of the photocatalyst to the 2, 4-dichlorophenol antibiotic is measured to reach 86.6 percent within 120 min.
FIG. 1 is CuInS prepared in this example2/TiO2UV-Vis diagram of the composite photocatalyst, and CuInS prepared from the diagram can be seen2/TiO2The photoresponse capability of the composite photocatalyst is compared with that of TiO2The monomer has great enhancement, CuInS2Is a black full spectrum absorption, TiO2Monomer can only absorb ultraviolet light, CuInS2Contribute to broadening TiO2Light absorption range of (1). Thus, the prepared CuInS2/TiO2The composite photocatalyst has higher visibilityLight trapping ability and photocatalytic activity.
FIG. 2 is a CuInS prepared in this example2/TiO2XRD pattern of the composite photocatalyst; the CuInS is clearly shown in FIG. 22Quantum dot, TiO2And the prepared CuInS2/TiO2The characteristic peak and peak intensity of the composite photocatalyst are high, and the crystallinity and purity of the synthesized photocatalyst are proved to be good.
FIG. 3 is CuInS prepared in this example2/TiO2The Electron Spin Resonance (ESR) diagram of the composite photocatalyst shows that CuInS is shown in FIG. 32/TiO2The composite photocatalyst generates superoxide radical under the condition of illumination. Combined with empirical formula Eg=EVB-ECBCuInS can be calculated2The band gap value, valence band position and conduction band position of the quantum dot are 1.66eV, 1.24eV and 0.42eV, respectively. Similarly, calculate TiO2E of the nanorodsg、EVBAnd ECBRespectively 3.21eV, 2.90eV, and 0.31 eV. According to the conventional mechanism of photon-generated carrier transfer, CuInS2Quantum dots and TiO2There is a tendency for type II heterojunctions, CuInS, to form between nanorods2Photon-generated electron transfer in quantum dot conduction band to TiO2The conducting band of the nano-rod. At the same time, TiO2Photo-generated holes in nanorods migrate to CuInS2The valence band of the quantum dots. However, TiO2The conduction band position of the nano rod is less than O at-0.31 eV2/·O2 -The potential of-0.33 eV, theoretically could not generate superoxide radical, and the results of spin-trapping ESR detection confirm that O is generated during the photocatalytic reaction2 -Free radicals exist and the strength is high. Thus, the CuInS prepared by the invention2/TiO2The composite photocatalyst is not consistent with the traditional photon-generated carrier transfer mechanism. The present invention proposes another possible mechanism, since CuInS2Conduction band ratio O of quantum dots2/·O2 -The reduction potential of (-0.33 eV) is more negative, so the electron generated is in CuInS2Quantum dot conduction band is easy to be O2Reduction to O2 -Free radicals, not transferred to TiO2In the conduction band of the nano-rod. In the same way, TiO2Valence band ratio H of the nanorods2Oxidation potential correction of O/. OH (+ 2.72 eV), TiO2Holes in the valence band of the nanorods are prone to H2O is oxidized into OH free radical, and the test result shows that the Z-type transfer mode is more consistent with the experimental test result. Thus verifying the CuInS prepared by the invention2/TiO2The composite photocatalyst has the characteristic of Z-shaped heterojunction; compared with the traditional heterojunction, the transfer channel of the photogenerated carriers in the Z-type heterojunction can promote the separation of the photogenerated carriers and effectively prevent the activity loss caused by the recombination of the photogenerated carriers. Enhance photocatalytic activity.
Example 3
(1) Take 1.0g TiO2Adding the powder into 50mL of NaOH solution (8 mol/L), stirring to obtain a uniform solution, transferring the uniform solution into a 100mL high-pressure reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 24 hours, naturally cooling, and stirring and soaking by using dilute hydrochloric acid with the pH value of 3.5; washing with deionized water for several times until the temperature is close to neutral, drying at 60 ℃, calcining at 450 ℃ for 3h in a reaction kettle at the heating rate of 5 ℃/min to obtain TiO2A nanorod;
(2) 0.017g of copper chloride dihydrate (CuCl)2·2H2O) and 30mL of ethylenediamine were placed in a small beaker, and 0.022g of indium chloride (InCl) was added after all were dissolved3) And 0.024g of L-cysteine, adding 45mL of deionized water, magnetically stirring, and carrying out auxiliary reaction for 30min to obtain CuInS2A quantum dot precursor solution; 0.097g of TiO2Adding the nano-rod into the CuInS prepared above2Fully and uniformly stirring the quantum dot precursor solution, and then putting the quantum dot precursor solution into a high-pressure reaction kettle to heat for 14 hours at the temperature of 160 ℃; after natural cooling, taking the reaction product core, washing, and drying in a 60 ℃ oven to obtain CuInS2CuInS with quantum dots accounting for 20% of total mass of composite photocatalyst2/TiO2Composite photocatalyst (20 CISQ/TiO)2）。
The CuInS prepared in this example was used2/TiO2The composite photocatalyst is put into a photochemical reactor for a photocatalytic degradation test, and the degradation rate of the photocatalyst to the 2, 4-dichlorophenol antibiotic is measured to reach 72.2 percent within 120 min.
Example 4
(1) Anatase TiO2The powder was used as raw material and 1.0g TiO was weighed2Adding the powder into 50mL of NaOH solution (12 mol/L), stirring to obtain a uniform solution, transferring the mixed solution into a 100mL high-pressure reaction kettle, and reacting at 140 ℃ for 26 h; after natural cooling, stirring and soaking the mixture by using dilute hydrochloric acid with the pH value of 3, then washing the mixture by using deionized water for multiple times until the mixture is nearly neutral, drying the mixture at the temperature of 60 ℃, putting the dried mixture into a reaction kettle, calcining the mixture for 2.5 hours at the temperature of 500 ℃, and heating the mixture at the rate of 5 ℃/min to prepare TiO2A nanorod;
(2) 0.017g of copper chloride dihydrate (CuCl)2·2H2O) and 20mL of ethylenediamine were placed in a small beaker, and 0.022g of indium chloride (InCl) was added after all were dissolved3) And 0.024g of L-cysteine, adding 30mL of deionized water, magnetically stirring, and carrying out auxiliary reaction for 30min to obtain CuInS2A quantum dot precursor solution; 0.036g of TiO2Adding the nano-rod into the CuInS prepared above2Fully and uniformly stirring the quantum dot precursor solution, putting the solution into a high-pressure reaction kettle, and heating the solution at the temperature of 180 ℃ for 12 hours; after natural cooling, taking the reaction product, centrifuging, washing, and drying in an oven at 60 ℃; obtaining CuInS2CuInS with quantum dots accounting for 40% of total mass of composite photocatalyst2/TiO2Composite photocatalyst (40 CISQ/TiO)2）。
The CuInS prepared in this example was used2/TiO2The composite photocatalyst is put into a photochemical reactor for a photocatalytic degradation test, and the degradation rate of the photocatalyst to the 2, 4-dichlorophenol antibiotic is measured to reach 69.5 percent within 120 min.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be made by those skilled in the art without inventive work within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (10)
1. CuInS2/TiO2The composite photocatalyst is characterized in that CuInS2The quantum dots are uniformly grown on the TiO2On nanorods, CuInS2Quantum dots and TiO2Z-shaped heterojunction, CuInS, is formed between the nanorods2Quantum dot accounts for CuInS2/TiO2The total mass of the composite photocatalyst is 10-40%.
2. CuInS2/TiO2The preparation method of the composite photocatalyst is characterized by comprising the following steps:
(1) taking TiO2Adding NaOH solution, stirring to obtain uniform solution, performing hydrothermal reaction in a high-pressure reaction kettle, naturally cooling, stirring and soaking with dilute hydrochloric acid, washing to neutrality, drying, and calcining at high temperature to obtain TiO2A nanorod;
(2) copper chloride dihydrate (CuCl)2·2H2O) and ethylenediamine are evenly mixed, then indium chloride and L-cysteine are added, deionized water is added, and then the mixture is magnetically stirred to react to obtain CuInS2A quantum dot precursor solution; adding the TiO prepared in the step (1)2The nano-rods are fully and uniformly stirred and then put into a high-pressure reaction kettle for reaction, and the CuInS is obtained after the reaction is naturally cooled, centrifuged, washed and dried2/TiO2A composite photocatalyst is provided.
3. The preparation method according to claim 2, wherein the concentration of the NaOH solution in the step (1) is 8-12 mol/L, and TiO is used2The amount of NaOH solution was 1.0 g/50 mL.
4. The method according to claim 2, wherein the pH of the dilute hydrochloric acid in the step (1) is 2.5 to 3.5; the reaction temperature in the high-pressure reaction kettle is 140-160 ℃, and the reaction time is 22-26 h.
5. The preparation method of claim 2, wherein the high-temperature calcination in step (1) is carried out at a temperature of 450 to 550 ℃ for 2 to 3 hours.
6. The method according to claim 2, wherein the copper chloride dihydrate, the ethylenediamine, the indium chloride and the L-cysteine in the step (2) are used in a ratio of 0.017g: 20-30 mL:0.022g:0.024 g.
7. The preparation method according to claim 2, wherein in the step (2), the volume ratio of the ethylenediamine to the deionized water is 1: 1-1.5.
8. The method according to claim 2, wherein the TiO in the step (2)2The dosage ratio of the nano rod to the copper chloride dihydrate is 0.017g: 0.036-0.46 g.
9. The preparation method according to claim 2, wherein the temperature of the high-pressure reaction kettle in the step (2) is 160-200 ℃, and the reaction time is 10-14 h.
10. The CuInS of claim 12/TiO2The application of the composite photocatalyst in removing 2, 4-dichlorophenol in wastewater.
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