CN114130407B - Cu (copper) alloy 2 S/CuInS 2 /ZnIn 2 S 4 Preparation method and application of composite photocatalyst - Google Patents

Cu (copper) alloy 2 S/CuInS 2 /ZnIn 2 S 4 Preparation method and application of composite photocatalyst Download PDF

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CN114130407B
CN114130407B CN202111554694.XA CN202111554694A CN114130407B CN 114130407 B CN114130407 B CN 114130407B CN 202111554694 A CN202111554694 A CN 202111554694A CN 114130407 B CN114130407 B CN 114130407B
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陈卫
陈伟
黄剑
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Ad Co ltd
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Abstract

The invention relates to a Cu 2 S/CuInS 2 /ZnIn 2 S 4 A preparation method and application of a composite photocatalyst belong to the technical field of photocatalytic materials. In order to solve the problem of poor degradation of pollutants in the prior art, a Cu is provided 2 S/CuInS 2 /ZnIn 2 S 4 The preparation process and application of composite photocatalyst includes adding copper source, zinc source, indium source and sulfur source into organic solvent capable of dissolving material in hydrothermal reactor to dissolve, and further reaction in sealed state, cooling and separating to obtain Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst. The invention can realize synchronous in-situ reaction to form p-type CuInS 2 And p-type Cu 2 S and n type ZnIn 2 S 4 The composite construction structure of the structure is formed into a double p-n junction structure with a compact heterogeneous interface, and the photocatalytic activity is obviously improved.

Description

Cu (copper) alloy 2 S/CuInS 2 /ZnIn 2 S 4 Preparation method and application of composite photocatalyst
Technical Field
The invention relates to a Cu 2 S/CuInS 2 /ZnIn 2 S 4 A preparation method and application of a composite photocatalyst belong to the technical field of photocatalytic materials.
Background
With the energy crisis and environmental pollution becoming two major problems for human beings, the development of new energy sources that are pollution-free, renewable and green is a great challenge for the development of the world today. Solar energy is based on the advantages of environmental friendliness, abundant resources and the like, and is the most ideal energy source in the future. The photocatalyst material can effectively utilize solar energy to degrade organic matter tetracycline hydrochloride and the like in environmental pollution, and degrade organic pollutants in waste liquid in production and processing, such as degradation of organic pollutants in waste liquid in pharmaceutical enterprises, such as tetracycline hydrochloride and the like, and degradation of organic pollutants in waste liquid or treatment liquid and the like formed in post treatment in plastic pipeline production and processing.
In the selection of the photocatalyst, particularly in the p-n junction heterogeneous photocatalyst, a strong built-in electric field can be generated due to the structure construction of the p-n junction, so that the photo-generated electrons on the p-type semiconductor conduction band are accelerated to transfer to the conduction band of the n-type semiconductor; accordingly, the photo-generated holes on the valence band of the n-type semiconductor jump to the valence band of the p-type semiconductor, and finally the efficient separation of the photo-generated carrier pairs is realized. Thus, p-n junction photocatalysts generally have higher photocatalytic activity, such as CuInS 2 Belongs to I-III-VI ternary direct band gap semiconductor compounds, has narrower energy band width (about 1.5 eV), has the characteristics of strong visible light absorption, high photoconductivity, high stability and the like, and is widely used for photocatalytic materials, such as cuprous sulfide (Cu) 2 S), the forbidden band width of which is about 1.2eV, is an important p-type narrow forbidden band semiconductor material. As a typical p-type narrow bandgap semiconductor, its conduction and valence band positions are further raised after it forms a p-n junction at the time of building up the complex. Therefore, the photo-generated electrons have strong reducibility. However, for single component Cu 2 S or CuInS 2 Is influenced by carrier separation efficiency, so that the recombination of photo-generated holes and electrons is serious, and the overall catalytic efficiency is low. Therefore, how to effectively regulate the lyophobic behavior of the two p-type semiconductor carriers and realize the efficient separation of the photo-generated holes and electrons is a core problem to be solved in constructing the p-type photocatalyst with high activity. In order to solve the problem and improve the overall photocatalytic activity, a zinc-indium-sulfur/copper-indium-sulfur two-dimensional heterojunction photocatalyst disclosed in the prior art (publication No. CN 109589991B), a preparation method and application thereof, are disclosed, wherein a zinc source, an indium source and a sulfur source compound are firstly reacted according to a molar ratio to generate indium-zinc sulfide; mixing a copper source, an indium source and a sulfur source in a certain molar ratio, adding the indium zinc sulfide, mixing and reacting to form CuInS 2 And ZnIn 2 S 4 Is provided. The treatment method adopts two components to form successively so as to mix and improve the photocatalytic capability to a certain extent, however, the CuInS 2 And ZnIn 2 S 4 Is formed stepwise, corresponding to the formation of ZnIn 2 S 4 (indium zinc sulfide) and then CuInS is formed 2 The two-dimensional heterostructure formed by the steps is only a combination of two photocatalytic substances, the formed p-n type heterostructure has single p-n type structure characteristics, the interface compactness is poor, and the degradation capability to organic pollutants, particularly to tetracycline is poor.
Disclosure of Invention
The present invention is directed to solving the above problems occurring in the prior art and provides a Cu 2 S/CuIn S 2 /ZnIn 2 S 4 The preparation method and application of the composite photocatalyst solve the problem of how to realize that the formed composite photocatalyst has double p-n type structural characteristics and has high catalytic degradation activity.
One of the purposes of the invention is achieved by the following technical proposal, a Cu 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps:
adding a copper source, a zinc source, an indium source and a sulfur source serving as raw materials into an organic solvent capable of dissolving the raw materials in a hydrothermal reaction kettle, then enabling the hydrothermal reaction kettle to perform one-step reaction under the condition of controlling the temperature to be 110-160 ℃ in a sealed state, and cooling and separating after the reaction is finished to obtain Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst.
The method comprises directly adding copper source, zinc source, indium source and sulfur source into organic solvent capable of dissolving raw materials, wherein the organic solvent capable of dissolving raw materials is organic solvent capable of dissolving copper source, zinc source, indium source and sulfur source, performing one-step solvothermal reaction, and making the reaction proceed under sealed condition, which is equivalent to that in the reaction process, the system can be kept under certain positive pressure condition, and under sealed condition, the method comprises the steps ofThe solvent in the system can form saturated vapor pressure, and the p-type CuInS can be formed by synchronous in-situ reaction in the reaction process 2 And p-type Cu 2 S and n type ZnIn 2 S 4 Composite building of structural systems to form Cu with double p-n junctions with tight heterogeneous interfaces 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst is equivalent to a double p-n junction system which is favorable for constructing a p-n junction structure (p-p-n) with a compact heterogeneous interface, and the formed composite photocatalyst can fully exert the synergistic effect of two components by utilizing the structure construction of the composite system and effectively promote the separation of photon-generated carriers by utilizing the construction of the p-n junction, thereby realizing high-efficiency visible light photocatalytic activity. Compared with the traditional composite photocatalyst obtained by multi-step reaction, the heterogeneous interface characteristic of a double p-n junction system cannot be formed, and the method has the advantage of compact interface in operation. Therefore, the process of the invention is more beneficial to the mass preparation of high-activity Cu 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst has high photocatalytic activity.
The Cu is as above 2 S/CuInS 2 /ZnIn 2 S 4 In the preparation method of the composite photocatalyst, preferably, the copper source: zinc source: indium source: the molar ratio of the sulfur source is x:1:2 to 5:8 to 12, wherein x has a value of 0<x is less than or equal to 3. By further controlling the dosage proportion of each component, the p-type CuInS can be formed more effectively and synchronously in the reaction process 2 P-type Cu 2 S and n type ZnIn 2 S 4 And the composite structure system has the characteristic of a tighter heterogeneous interface, so that the formed composite catalyst has better catalytic activity. As a further preference, the value of x is 0.15<x≤0.5。
The Cu is as above 2 S/CuInS 2 /ZnIn 2 S 4 In the preparation method of the composite photocatalyst, preferably, in the one-step reaction process, the system pressure of the hydrothermal reaction kettle is kept at positive pressure, and the positive pressure is controlled to be less than or equal to 0.3MPa. The system forms a certain positive pressure condition in the reaction process, is more favorable for the reaction to be carried out at the required high temperature, and is formed byIn the sealed state, the solvent is not volatilized directly, but saturated vapor pressure is carried out in the hydrothermal reaction kettle, so that a three-phase system (Cu) is better ensured to be formed in the reaction process 2 S/CuInS 2 /ZnIn 2 S 4 ) Thereby achieving the effect of high photocatalytic activity.
The Cu is as above 2 S/CuInS 2 /ZnIn 2 S 4 In the preparation method of the composite photocatalyst, the copper source, the zinc source and the indium source can be organic or inorganic, but the organic salt has relatively high price. Therefore, an inorganic copper source, zinc source and indium source are preferably used. Preferably, the copper source is selected from one or more of copper sulfate, copper chloride and copper nitrate; the zinc source is selected from one or more of zinc nitrate, zinc chloride and zinc acetate; the indium source is one or more selected from indium nitrate and indium chloride; the sulfur source is selected from one or more of sodium sulfide, thiourea and thioacetamide.
The Cu is as above 2 S/CuInS 2 /ZnIn 2 S 4 In the preparation method of the composite photocatalyst, the solvent at least contains a solvent with a boiling point of more than 105 ℃, so that the reaction can be effectively ensured to be carried out at a relatively high temperature, thereby being beneficial to better realizing Cu formation in the reaction process 2 S、CuInS 2 And ZnIn 2 S 4 The three products are synchronous, and a system formed by the original reaction also has more compact heterogeneous interface characteristics. Preferably, the organic solvent capable of dissolving the raw material is selected from alcohol solvents and/or amine solvents. The alcohol solvent is one or more selected from methanol, ethanol, ethylene glycol, propylene glycol and propanol; the amine solvent is selected from dimethylformamide and/or dimethylacetamide. Preferably, the solvent is selected from ethylene glycol, dimethylformamide or a mixed solvent thereof. The method can fully dissolve and disperse the raw materials in a solvent system, ensures the reaction to be full better, and improves the yield effect of the product.
The Cu is as above 2 S/CuInS 2 /ZnIn 2 S 4 In the method for producing a composite photocatalyst, preferably, the oneThe reaction time of the step method is 12-36 hours. The reaction can be fully carried out by time control, and the yield and quality of the product are improved.
The Cu is as above 2 S/CuInS 2 /ZnIn 2 S 4 Application of composite photocatalyst, preferably, the Cu 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst is used for degrading tetracycline or tetracycline hydrochloride.
In summary, compared with the prior art, the invention has the following advantages:
the invention adopts a one-step solvothermal method, and ensures that the reaction system maintains a certain positive pressure in the reaction process under a sealed state in the reaction process, thereby effectively realizing synchronous in-situ reaction to form p-type CuInS 2 And p-type Cu 2 S and n type ZnIn 2 S 4 To form Cu with double p-n junction of compact heterogeneous interface 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst is constructed by utilizing the structure of a compound, so that the synergistic effect of two components can be fully exerted, the separation of photo-generated carriers is effectively promoted by utilizing the construction of a p-n junction, and the photo-catalytic activity is remarkably improved.
Drawings
FIG. 1 shows Cu obtained in example 1 of the present invention 2 S/CuInS 2 /ZnIn 2 S 4 Composite photocatalyst and single CuInS 2 And ZnIn 2 S 4 Is analyzed by X-ray diffraction pattern.
FIG. 2 shows Cu obtained by the method of the present invention 2 S/CuInS 2 /ZnIn 2 S 4 -0.15 composite photocatalyst and single CuInS 2 And ZnIn 2 S 4 Activity comparison graph of photocatalytic degradation of tetracycline hydrochloride by the catalyst.
Detailed Description
The technical scheme of the present invention will be further specifically described by means of specific examples and drawings, but the present invention is not limited to these examples.
Example 1
According to the respective originsAdding a proper amount of copper sulfate, 1mmol of zinc acetate, 2mmol of indium chloride and 8mmol of thiourea into 30mL of dimethylformamide, stirring, fully mixing, uniformly dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, carrying out one-step reaction for 24h under the condition that the hydrothermal reaction kettle is sealed and the heating temperature is controlled to 160 ℃, controlling the system to be under positive pressure in the reaction process, keeping the pressure of the system to be less than or equal to 0.3MPa, naturally cooling after the reaction is finished, centrifuging at high speed, washing with water, and drying at room temperature to obtain the corresponding product Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst.
In this example, the product was designated Cu depending on the amount of copper sulfate added 2 S/CuInS 2 /ZnIn 2 S 4 X, in this example, cu is taken for analysis 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst samples were prepared in the following names, with the molar amounts of copper sulfate added being 0.2mmol, 0.3mmol, 0.4mmol and 0.5mmol, respectively. Namely, the samples are respectively treated with Cu 2 S/CuInS 2 /ZnIn 2 S 4 -0.2、Cu 2 S/CuInS 2 /ZnIn 2 S 4 -0.3、Cu 2 S/CuInS 2 /ZnIn 2 S 4 -0.4 and Cu 2 S/CuInS 2 /ZnIn 2 S 4 -0.5.
The composite photocatalyst obtained in small amounts was taken as a sample for analysis, and the analysis results are shown in FIG. 1, which shows Cu of the composite photocatalyst obtained in this example 2 S/CuInS 2 /ZnIn 2 S 4 -x sample (x represents the molar amount of copper sulphate added), and CuInS 2 As can be seen from FIG. 1, the diffraction peaks of the composite photocatalyst of the present invention are simultaneously present with Cu in the x-ray diffraction pattern of the sample 2 S、CuInS 2 And ZnIn 2 S 4 The diffraction peaks of the above are shown to be effective in forming three substances by a one-step reaction, and no diffraction peaks of other impurities are detected in the spectrogram, thus showing that the composite light obtained by the method of the present inventionThe catalyst has a certain high purity characteristic, wherein the obtained Cu 2 S/CuInS 2 /ZnIn 2 S 4 Cu in sample 2 S is Cu of the type 00-009-0328 in JCPDS standard library 2 S。
Example 2
Adding 0.15mmol of copper chloride, 1mmol of zinc acetate, 2.15mmol of indium nitrate and 8mmol of thiourea into a mixed solvent of 20mL of dimethylformamide and 10mL of ethanol according to the molar dosage of each raw material, stirring, fully and uniformly mixing, dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, heating to control the temperature to be 160 ℃ for one-step reaction for 30h, controlling the system to be under positive pressure in the reaction process, keeping the pressure of the system to be less than or equal to 0.3MPa, after the reaction is finished, naturally cooling, centrifuging at a high speed, washing with water, and drying at room temperature to obtain the corresponding product Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst.
Taking a certain amount of analysis product Cu 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst is used as a sample to degrade tetracycline hydrochloride, namely, the Cu of the invention is added into a solution system containing the tetracycline hydrochloride 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst is degraded. Analysis of degradation Activity Performance shows that Cu is taken 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst samples correspond to the following names, namely Cu 2 S/CuInS 2 /ZnIn 2 S 4 A sample of 0.15, i.e. in this example 0.15mmol of copper source (copper chloride) was added.
The test conditions for degradation performance were as follows: using visible light as light source, firstly dispersing 10mg of photocatalyst in 40mL of initial concentration of 50mg L -1 In the tetracycline hydrochloride solution, after the treatment in the dark, the photocatalysis test is carried out. CuInS in one component 2 Or ZnIn 2 S 4 As a comparison, the Cu obtained by the present invention can be seen from FIG. 2 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst has high-efficiency lightThe performance of catalyzing and degrading the activity of the tetracycline hydrochloride is just because the composite catalyst formed by the one-step reaction constructs the junction color of the double p-n junction, the separation of the photon-generated carriers is obviously accelerated, and the photocatalysis activity of the photon-generated carriers is further improved.
Example 3
Adding 3mmol of copper sulfate, 1mmol of zinc acetate, 5mmol of indium chloride and 12mmol of thiourea into 30mL of dimethylformamide according to the molar dosage of each raw material, stirring, fully mixing, uniformly dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, carrying out one-step reaction for 36h at the temperature of 140 ℃ under the condition of heating and heating control, controlling the system to be under positive pressure in the reaction process, keeping the pressure of the system to be less than or equal to 0.3MPa, naturally cooling after the reaction is finished, centrifuging at high speed, washing with water, and drying at room temperature to obtain the corresponding product Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst.
The obtained product Cu 2 S/CuInS 2 /ZnIn 2 S 4 The X-ray diffraction analysis of the composite photocatalyst showed that the result was substantially identical to the X-ray diffraction analysis result of the composite photocatalyst in example 1, indicating that the diffraction peak of the composite photocatalyst was simultaneously present with Cu 2 S、CuInS 2 And ZnIn 2 S 4 The diffraction peaks of the three-phase reaction are proved to be capable of effectively forming three substances through a one-step reaction, diffraction peaks of other impurities are not detected in a spectrogram, and the product purity and quality are high.
Meanwhile, cu, a product obtained in this example 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst has the degradation performance test on tetracycline hydrochloride, and the result shows that the composite photocatalyst also basically reaches the level equivalent to the degradation activity on tetracycline hydrochloride in the example 2, and has high photocatalytic degradation activity.
Example 4
According to the molar amount of each raw material, 0.4mmol of copper nitrate, 1mmol of zinc chloride, 2.4mmol of indium chloride and 10mmol of thioacetamide are added into a mixed solvent of 20mL of dimethylformamide and 10mL of ethanol, and stirredFully and uniformly mixing and dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, heating to control the temperature to be 135 ℃ for one-step reaction for 32h, controlling the system to be under positive pressure in the reaction process, keeping the pressure of the system to be less than or equal to 0.3MPa, naturally cooling after the reaction, centrifuging at high speed, washing with water, and drying at room temperature to obtain the corresponding product Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst.
The obtained product Cu 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst was subjected to X-ray diffraction analysis, and the results were the same as in example 1 regarding Cu 2 S/CuInS 2 /ZnIn 2 S 4 The X-ray diffraction analysis results of the composite photocatalyst are substantially consistent, which shows that the diffraction peak of the composite photocatalyst obtained by the invention simultaneously shows Cu 2 S、CuInS 2 And ZnIn 2 S 4 The diffraction peaks of the three-phase reaction are proved to be capable of effectively forming three substances through a one-step reaction, diffraction peaks of other impurities are not detected in a spectrogram, and the product purity and quality are high.
Meanwhile, cu, a product obtained in this example 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst has the degradation performance test on tetracycline hydrochloride, and the result shows that the composite photocatalyst also basically reaches the level equivalent to the degradation activity on tetracycline hydrochloride in the example 2, and has high photocatalytic degradation activity.
Example 5
Adding 1mmol of copper chloride, 1mmol of zinc nitrate, 3mmol of indium chloride and 10mmol of thioacetamide into a mixed solvent of 25mL of dimethylacetamide and 5mL of propanol according to the molar dosage of each raw material, stirring, fully and uniformly mixing, dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, carrying out one-step reaction for 36h under the condition of heating and heating control temperature of 110 ℃, controlling the system to be under positive pressure in the reaction process, keeping the pressure of the system to be less than or equal to 0.3MPa, naturally cooling after the reaction, centrifuging at high speed, washing with water, and drying at room temperature to obtain the corresponding product Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst.
The obtained product Cu 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst was subjected to X-ray diffraction analysis, and the results were the same as in example 1 regarding Cu 2 S/CuInS 2 /ZnIn 2 S 4 The X-ray diffraction analysis results of the composite photocatalyst are substantially consistent, which shows that the diffraction peak of the composite photocatalyst obtained in the embodiment simultaneously shows Cu 2 S、CuInS 2 And ZnIn 2 S 4 The diffraction peaks of the three-phase reaction are proved to be capable of effectively forming three substances through a one-step reaction, diffraction peaks of other impurities are not detected in a spectrogram, and the product purity and quality are high.
Meanwhile, cu, a product obtained in this example 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst has the degradation performance test on tetracycline hydrochloride, and the result shows that the composite photocatalyst also basically reaches the level equivalent to the degradation activity on tetracycline hydrochloride in the example 2, and has high photocatalytic degradation activity.
Example 6
Adding 0.5mmol of copper sulfate, 1mmol of zinc acetate, 2.5mmol of indium chloride and 10mmol of thiourea into 30mL of ethylene glycol solvent according to the molar dosage of each raw material, stirring, fully mixing, uniformly dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, heating, controlling the temperature to be 110 ℃, performing one-step reaction for 32h, controlling the system to be under positive pressure in the reaction process, keeping the pressure of the system to be less than or equal to 0.3MPa, naturally cooling after the reaction is finished, centrifuging at a high speed, washing with water, and drying at room temperature to obtain the corresponding product Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst.
The obtained product Cu 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst was subjected to X-ray diffraction analysis, and the results were the same as in example 1 regarding Cu 2 S/CuInS 2 /ZnIn 2 S 4 The X-ray diffraction analysis results of the composite photocatalyst are substantially consistent, which shows that the diffraction peaks of the composite photocatalyst obtained in the embodiment are simultaneouslyAppear to be Cu 2 S、CuInS 2 And ZnIn 2 S 4 The diffraction peaks of the three-phase reaction are proved to be capable of effectively forming three substances through a one-step reaction, diffraction peaks of other impurities are not detected in a spectrogram, and the product purity and quality are high.
Meanwhile, cu, a product obtained in this example 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst has the degradation performance test on tetracycline hydrochloride, and the result shows that the composite photocatalyst also basically reaches the level equivalent to the degradation activity on tetracycline hydrochloride in the example 2, and has high photocatalytic degradation activity.
Example 7
Adding 0.3mmol of copper sulfate, 1mmol of zinc acetate, 2.3mmol of indium nitrate and 8mmol of thiourea into a mixed solvent of 20mL of ethylene glycol and 10mL of dimethylformamide according to the molar dosage of each raw material, stirring, fully and uniformly mixing, dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, heating to control the temperature to perform one-step reaction for 30h at 120 ℃, controlling the system to be under positive pressure in the reaction process, keeping the pressure of the system to be less than or equal to 0.3MPa, after the reaction is finished, naturally cooling, centrifuging at a high speed, washing with water, and drying at room temperature to obtain a corresponding product Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst.
The obtained product Cu 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst was subjected to X-ray diffraction analysis, and the results were the same as in example 1 regarding Cu 2 S/CuInS 2 /ZnIn 2 S 4 The X-ray diffraction analysis results of the composite photocatalyst are substantially consistent, which shows that the diffraction peak of the composite photocatalyst obtained in the embodiment simultaneously shows Cu 2 S、CuInS 2 And ZnIn 2 S 4 The diffraction peaks of the three-phase reaction are proved to be capable of effectively forming three substances through a one-step reaction, diffraction peaks of other impurities are not detected in a spectrogram, and the product purity and quality are high.
Meanwhile, cu, a product obtained in this example 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst has the degradation performance test on tetracycline hydrochloride, and the result shows that the composite photocatalyst also basically reaches the level equivalent to the degradation activity on tetracycline hydrochloride in the example 2, and has high photocatalytic degradation activity.
The specific embodiments described herein are offered by way of illustration only. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (11)

1. Cu (copper) alloy 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps:
adding a copper source, a zinc source, an indium source and a sulfur source serving as raw materials into an organic solvent capable of dissolving the raw materials in a hydrothermal reaction kettle, then enabling the hydrothermal reaction kettle to perform one-step reaction under the condition of controlling the temperature to be 110-160 ℃ in a sealed state, and cooling and separating after the reaction is finished to obtain Cu 2 S/CuInS 2 /ZnIn 2 S 4 A composite photocatalyst.
2. Cu according to claim 1 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the copper source is as follows: zinc source: indium source: the molar ratio of the sulfur source is x:1:2 to 5:8 to 12, wherein x has a value of 0<x≤3。
3. Cu according to claim 2 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the x is takenA value of 0.15<x≤0.5。
4. Cu according to claim 2 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that in the one-step reaction process, the system pressure of the hydrothermal reaction kettle is kept at positive pressure, and the positive pressure is controlled to be less than or equal to 0.3MPa.
5. Cu according to claim 1 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the copper source is one or more selected from copper sulfate, copper chloride and copper nitrate; the zinc source is selected from one or more of zinc nitrate, zinc chloride and zinc acetate; the indium source is one or more selected from indium nitrate and indium chloride; the sulfur source is selected from one or more of sodium sulfide, thiourea and thioacetamide.
6. Cu according to claim 1 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the organic solvent capable of dissolving the raw materials is selected from alcohol solvents and/or amine solvents.
7. The Cu of claim 6 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the alcohol solvent is one or more selected from methanol, ethanol, ethylene glycol, propylene glycol and propanol; the amine solvent is selected from dimethylformamide and/or dimethylacetamide.
8. Cu according to claim 7 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the organic solvent capable of dissolving the raw materials is selected from glycol, dimethylformamide or a mixed solvent thereof.
9. Cu according to any one of claims 1 to 8 2 S/CuInS 2 /ZnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the reaction time of the one-step method is 12-36 hours.
10. Cu (copper) alloy 2 S/CuInS 2 /ZnIn 2 S 4 The use of a composite photocatalyst characterized by Cu obtained by the process of any one of claims 1 to 9 2 S/CuInS 2 /ZnIn 2 S 4 The composite photocatalyst degrades tetracycline.
11. Cu (copper) alloy 2 S/CuInS 2 /ZnIn 2 S 4 The use of a composite photocatalyst characterized by Cu obtained by the process of any one of claims 1 to 9 2 S/CuInS 2 /ZnIn 2 S 4 The compound photocatalyst degrades tetracycline hydrochloride.
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