CN114130407A - Cu2S/CuInS2/ZnIn2S4Preparation method and application of composite photocatalyst - Google Patents
Cu2S/CuInS2/ZnIn2S4Preparation method and application of composite photocatalyst Download PDFInfo
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- CN114130407A CN114130407A CN202111554694.XA CN202111554694A CN114130407A CN 114130407 A CN114130407 A CN 114130407A CN 202111554694 A CN202111554694 A CN 202111554694A CN 114130407 A CN114130407 A CN 114130407A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000005580 one pot reaction Methods 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052738 indium Inorganic materials 0.000 claims abstract description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 18
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004098 Tetracycline Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229960002180 tetracycline Drugs 0.000 claims description 4
- 229930101283 tetracycline Natural products 0.000 claims description 4
- 235000019364 tetracycline Nutrition 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003522 tetracyclines Chemical class 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 5
- 230000001360 synchronised effect Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000703 high-speed centrifugation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- -1 tetracycline hydrochloride Chemical class 0.000 description 1
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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
-
- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to Cu2S/CuInS2/ZnIn2S4A preparation method and application of a composite photocatalyst, belonging 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 provided2S/CuInS2/ZnIn2S4The preparation method of the composite photocatalyst and the application thereof, the method comprises the steps of adding raw materials into a hydrothermal reaction kettleAdding a copper source, a zinc source, an indium source and a sulfur source into an organic solvent capable of dissolving raw materials for dissolving, then controlling the temperature of a hydrothermal reaction kettle in a sealed state for carrying out one-step reaction, cooling and separating to obtain Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided. The invention can realize the synchronous in-situ reaction to form the p-type CuInS2And p-type Cu2S and n type ZnIn2S4The structure of the double p-n junction with a compact heterogeneous interface is formed, and the photocatalytic activity is obviously improved.
Description
Technical Field
The invention relates to Cu2S/CuInS2/ZnIn2S4A preparation method and application of a composite photocatalyst, belonging to the technical field of photocatalytic materials.
Background
As the energy crisis and the environmental pollution become two major problems which afflict human beings, the development of new energy which is pollution-free, renewable and green is a great challenge facing the development of the world at present. And the solar energy is the most ideal energy source in the future based on the advantages of environmental friendliness, abundant resources and the like. The photocatalyst material can effectively utilize solar energy to degrade organic tetracycline hydrochloride and the like in environmental pollution, and degrade organic pollutants in waste liquid in production and processing, such as the organic pollutants such as tetracycline hydrochloride and the like in the production waste liquid in medical enterprises, and the organic pollutants in the waste liquid or treatment liquid and the like formed in the middle and later treatment processes of plastic pipeline production and processing.
In the selection of the photocatalyst, particularly in a p-n junction heterogeneous photocatalyst, a strong built-in electric field can be generated due to the structural construction of a p-n junction, so that the photoinduced electrons on the conduction band of a p-type semiconductor are accelerated to be transferred to the conduction band of an n-type semiconductor; accordingly, photogenerated holes on the valence band of the n-type semiconductor can jump to the valence band of the p-type semiconductor, and finally high-efficiency separation of photogenerated carrier pairs is achieved. Thus, p-n junction photocatalysts generally have a high photocatalytic activity, such as CuInS2Belongs to a ternary direct band gap semiconductor compound of I-III-VI groups, has narrow energy band width (about 1.5eV), has the characteristics of strong visible light absorption, high photoconductivity, high stability and the like, is widely used for photocatalytic materials, and can be widely used for cuprous sulfide (Cu)2S), itThe forbidden band width is about 1.2eV, and the p-type narrow forbidden band semiconductor material is important. As a typical p-type narrow band gap semiconductor, the conduction band and valence band positions are further improved after the p-n junction is formed by constructing a complex. Therefore, the photo-generated electrons have strong reducibility. However, for a single component of Cu2S or CuInS2Is limited by the influence of carrier separation efficiency, leads to serious recombination of photogenerated holes and electrons and lower overall catalytic efficiency. Therefore, how to effectively regulate and control the carrying behavior of the two p-type semiconductor carriers and realize the efficient separation of photogenerated holes and electrons is a core problem to be solved for constructing the p-type photocatalyst with high activity. In order to solve the problem and improve the whole photocatalytic activity, the prior art discloses a photocatalyst of a zinc indium sulfide/copper indium sulfide two-dimensional heterojunction as disclosed in the prior document (publication No. CN109589991B), a preparation method and application thereof, 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; then mixing the copper source, the indium source and the sulfur source according to a certain molar ratio, adding the indium-zinc sulfide, mixing and reacting to form CuInS2And ZnIn2S4The two-dimensional heterojunction photocatalyst of (1). The treatment method adopts two components to form in sequence, so that the mixing of the two components improves the photocatalytic capacity to a certain extent, but the CuInS thereof2And ZnIn2S4Is formed step by step, which is equivalent to forming ZnIn firstly2S4(indium Zinc sulfide) followed by CuInS2The mixed two-dimensional heterostructure formed by steps is only the combination of two photocatalytic substances, still has single p-n type structural characteristics, has poor interface tightness and has poor degradation capability on organic pollutants, particularly tetracycline.
Disclosure of Invention
The present invention has been made in view of the above problems occurring in the prior art, and provides a Cu2S/CuIn S2/ZnIn2S4The preparation method and the application of the composite photocatalyst solve the problem of how to realize that the formed composite photocatalyst has the structural characteristic of double p-n type and has high catalytic degradation activity.
The inventionOne of the objects of is achieved by the following technical solution, a Cu2S/CuInS2/ZnIn2S4The preparation method of the composite photocatalyst is characterized by comprising the following steps:
adding raw materials of a copper source, a zinc source, an indium source and a sulfur source into an organic solvent capable of dissolving the raw materials in a hydrothermal reaction kettle for dissolving, then carrying out one-step reaction on the hydrothermal reaction kettle in a sealed state at a controlled temperature of 110-160 ℃, and after the reaction is finished, cooling and separating to obtain Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided.
Directly and integrally adding four components of a copper source, a zinc source, an indium source and a sulfur source into an organic solvent capable of dissolving raw materials, wherein the organic solvent capable of dissolving the raw materials is an organic solvent capable of dissolving the raw materials of the copper source, the zinc source, the indium source and the sulfur source, then carrying out a one-step solvothermal method for reaction, and carrying out the reaction in a sealed state, namely, in the reaction process, a system can be carried out under a certain positive pressure condition, in the sealed state, the solvent in the system can form saturated vapor pressure, and in the reaction process, a p-type CuInS can be formed by synchronous in-situ reaction2And p-type Cu2S and n type ZnIn2S4Compositely constructing a structural system to form Cu with a double p-n junction having a compact heterogeneous interface2S/CuInS2/ZnIn2S4The composite photocatalyst is equivalent to a double p-n junction system which is beneficial to constructing a p-n junction structure (p-p-n) with a compact heterogeneous interface, and the formed composite photocatalyst can fully play the synergistic effect of two components by utilizing the structural construction of the composite system and effectively promote the separation of photogenerated 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 method can not form the heterogeneous interface characteristic of a double p-n junction system, and has the advantages of operation and compact interface. Therefore, the process of the invention is more beneficial to the mass preparation of the high-activity Cu2S/CuInS2/ZnIn2S4Composite photocatalyst and high photocatalytic activityAnd (4) sex.
In the above Cu2S/CuInS2/ZnIn2S4In the preparation method of the composite photocatalyst, preferably, the copper source: a zinc source: indium source: the molar ratio of the sulfur source is x: 1: 2-5: 8-12, wherein x is 0<x is less than or equal to 3. By further controlling the dosage proportion of each component, p-type CuInS can be more effectively and synchronously formed in the reaction process2P-type Cu2S and n type ZnIn2S4The composite catalyst has a compact heterogeneous interface, so that the formed composite catalyst has better catalytic activity. More preferably, x is 0.15<x≤0.5。
In the above Cu2S/CuInS2/ZnIn2S4In 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 0.3 MPa. The system forms a certain positive pressure condition in the reaction process, the reaction is more favorably carried out at the required high temperature, and because the system is in a sealed state, the solvent can not be directly volatilized, but saturated vapor pressure is carried out in the hydrothermal reaction kettle, so that a three-phase system (Cu) can be better ensured to be formed in the reaction process2S/CuInS2/ZnIn2S4) Thereby realizing the effect of high photocatalytic activity.
In the above Cu2S/CuInS2/ZnIn2S4In 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 is quite expensive. Therefore, inorganic sources of copper, zinc and indium are preferred. 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 selected from one or more of indium nitrate and indium chloride; the sulfur source is selected from one or more of sodium sulfide, thiourea and thioacetamide.
In the above Cu2S/CuInS2/ZnIn2S4In the preparation method of the composite photocatalyst, the solvent at least contains the solvent with the boiling point higher than 105 ℃, so that the reaction can be effectively ensured to be carried out at relatively high temperature, and the Cu formed in the reaction process can be better realized2S、CuInS2And ZnIn2S4Three products and a system formed by synchronous original reaction also have tighter heterogeneous interface characteristics. Preferably, the organic solvent capable of dissolving the raw materials is selected from alcohol solvents and/or amine solvents. The alcohol solvent is selected from one or more of 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 raw materials can be fully dissolved and dispersed in a solvent system, the full reaction is better ensured, and the yield effect of the product is improved.
In the above Cu2S/CuInS2/ZnIn2S4In the preparation method of the composite photocatalyst, the one-step reaction time is 12-36 hours preferably. The reaction can be fully carried out by time control, and the yield and quality of the product are improved.
In the above Cu2S/CuInS2/ZnIn2S4Application of the composite photocatalyst, preferably, the Cu2S/CuInS2/ZnIn2S4The composite photocatalyst is used for degrading tetracycline or tetracycline hydrochloride.
In summary, compared with the prior art, the invention has the following advantages:
the method adopts a one-step solvothermal method, ensures that a reaction system keeps a certain positive pressure in the reaction process under a sealed state in the reaction process, and can effectively realize synchronous in-situ reaction to form p-type CuInS2And p-type Cu2S and n type ZnIn2S4The Cu of the double p-n junction with the compact heterogeneous interface is formed2S/CuInS2/ZnIn2S4Composite photocatalyst, and the composite photocatalyst formed therebyThe structure construction of the compound can fully play the synergistic effect of the two components, and effectively promote the separation of photon-generated carriers by utilizing the construction of the p-n junction, thereby obviously improving the photocatalytic activity.
Drawings
FIG. 1 shows Cu obtained in example 1 of the present invention2S/CuInS2/ZnIn2S4Composite photocatalyst and single CuInS2And ZnIn2S4Analysis of the X-ray diffraction spectrum of (1).
FIG. 2 shows Cu prepared in an example of the present invention2S/CuInS2/ZnIn2S4-0.15 composite photocatalyst and single CuInS2And ZnIn2S4The activity of the catalyst for photocatalytic degradation of tetracycline hydrochloride is compared with that of the catalyst.
Detailed Description
The technical solutions of the present invention will be further specifically described below with reference to specific examples and drawings, but the present invention is not limited to these examples.
Example 1
Adding appropriate amount of copper sulfate, 1mmol of zinc acetate, 2mmol of indium chloride and 8mmol of thiourea into 30mL of dimethylformamide according to the molar amount of the raw materials, stirring, fully mixing, uniformly dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, carrying out one-step reaction for 24 hours in a sealed state by heating, raising the temperature and controlling the temperature at 160 ℃, controlling the system to be carried out under positive pressure in the reaction process and keeping the system pressure at less than or equal to 0.3MPa, after the reaction is finished, naturally cooling, carrying out high-speed centrifugation, washing with water, and drying at room temperature to obtain the corresponding product Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided.
In this example, the product was named Cu according to the amount of copper sulfate added2S/CuInS2/ZnIn2S4x-Cu to be used for analytical explanation in this example2S/CuInS2/ZnIn2S4The compound photocatalyst samples are corresponding according to the following names, and the adding molar weight of copper sulfate is respectively usedIn amounts of 0.2mmol, 0.3mmol, 0.4mmol and 0.5 mmol. That is, the samples are respectively Cu2S/CuInS2/ZnIn2S4-0.2、Cu2S/CuInS2/ZnIn2S4-0.3、Cu2S/CuInS2/ZnIn2S4-0.4 and Cu2S/CuInS2/ZnIn2S4-0.5 represents.
A small amount of the obtained composite photocatalyst was sampled and analyzed, and the analysis result is shown in FIG. 1, which is Cu of the composite photocatalyst obtained in this example2S/CuInS2/ZnIn2S4X samples (x represents the molar amount of copper sulfate added), and CuInS2As shown in FIG. 1, the X-ray diffraction spectrum of the sample shows that the diffraction peak of the composite photocatalyst of the invention simultaneously shows Cu2S、CuInS2And ZnIn2S4The diffraction peaks show that the three substances can be effectively formed by the one-step reaction, and no diffraction peak of other impurities is detected in a spectrogram, so that the composite photocatalyst obtained by the method has certain high-purity characteristics, wherein the obtained Cu has the characteristics of high purity2S/CuInS2/ZnIn2S4Cu in the sample2S belongs to Cu of type 00-009-0328 in JCPDS standard library2S。
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 amount of the raw materials, stirring, fully mixing, uniformly dissolving, transferring to a 50mL hydrothermal reaction kettle, heating, raising the temperature, controlling the temperature at 160 ℃ to perform one-step reaction for 30h, controlling the system to perform under positive pressure in the reaction process, keeping the system pressure less than or equal to 0.3MPa, after the reaction is finished, naturally cooling, performing high-speed centrifugation, washing with water, and drying at room temperature to obtain the corresponding product Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided.
Taking a certain amount of analysis product Cu2S/CuInS2/ZnIn2S4The composite photocatalyst is used as a sample for degrading tetracycline hydrochloride, namely the Cu of the invention is added into a solution system containing tetracycline hydrochloride2S/CuInS2/ZnIn2S4And degrading the composite photocatalyst. Analysis of the degradation Activity Performance shows that Cu is taken2S/CuInS2/ZnIn2S4The compound photocatalyst sample is corresponding to the name of Cu2S/CuInS2/ZnIn2S40.15 sample, i.e. the amount of copper source (copper chloride) added in this example is 0.15 mmol.
The test conditions for degradation performance were as follows: using visible light as a light source, 10mg of photocatalyst was first dispersed in 40mL of a solution having an initial concentration of 50mg L-1After dark treatment, the tetracycline hydrochloride solution is subjected to photocatalytic test. CuInS in one component2Or ZnIn2S4As a control, the Cu obtained by the present invention can be seen from FIG. 22S/CuInS2/ZnIn2S4The composite photocatalyst has the performance of high-efficiency photocatalytic degradation of tetracycline hydrochloride activity, and the composite catalyst formed by the one-step reaction constructs the junction color of double p-n junctions, so that the separation of photon-generated carriers is remarkably accelerated, and the photocatalytic activity of the photocatalyst is 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 amount of the raw materials, stirring, fully mixing, uniformly dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, heating, raising the temperature, controlling the temperature at 140 ℃ and carrying out a one-step reaction for 36h, controlling the system to be carried out under positive pressure in the reaction process, keeping the system pressure less than or equal to 0.3MPa, after the reaction is finished, naturally cooling, carrying out high-speed centrifugation and water washing, and drying at room temperature to obtain the corresponding product Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided.
The obtained product Cu2S/CuInS2/ZnIn2S4The X-ray diffraction analysis of the composite photocatalyst showed that the compound photocatalyst was substantially the same as the X-ray diffraction analysis of the composite photocatalyst in example 1, indicating that the diffraction peaks of the composite photocatalyst appeared in the presence of Cu simultaneously2S、CuInS2And ZnIn2S4The diffraction peaks show that the three substances can be effectively formed by the one-step reaction, and the diffraction peaks of other impurities are not detected in the spectrogram, so that the product has high purity and quality.
Meanwhile, the product Cu obtained in the embodiment is adopted2S/CuInS2/ZnIn2S4The composite photocatalyst is used for carrying out degradation performance test on tetracycline hydrochloride, and the result shows that the composite photocatalyst basically reaches the level equivalent to the degradation activity of tetracycline hydrochloride in the example 2, and shows that the composite photocatalyst also has high photocatalytic degradation activity.
Example 4
Adding 0.4mmol of copper nitrate, 1mmol of zinc chloride, 2.4mmol of indium chloride and 10mmol of thioacetamide into a mixed solvent of 20mL of dimethylformamide and 10mL of ethanol according to the molar amount of the raw materials, stirring, fully mixing, uniformly dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, heating, raising the temperature, controlling the temperature at 135 ℃ to perform one-step reaction for 32 hours, controlling the system to perform under positive pressure in the reaction process, keeping the system pressure less than or equal to 0.3MPa, after the reaction is finished, naturally cooling, performing high-speed centrifugation, washing with water, and drying at room temperature to obtain the corresponding product Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided.
The obtained product Cu2S/CuInS2/ZnIn2S4The X-ray diffraction analysis of the composite photocatalyst was carried out, and the results were the same as those of example 1 for Cu2S/CuInS2/ZnIn2S4The X diffraction analysis results of the composite photocatalyst are substantially consistent, and the results show that the diffraction peaks of the composite photocatalyst obtained by the invention simultaneously appear Cu2S、CuInS2And ZnIn2S4The diffraction peaks show that the three substances can be effectively formed by the one-step reaction, and the three substances are not detected in the spectrogramThe diffraction peak of the impurity has higher purity and quality of the product.
Meanwhile, the product Cu obtained in the embodiment is adopted2S/CuInS2/ZnIn2S4The composite photocatalyst is used for carrying out degradation performance test on tetracycline hydrochloride, and the result shows that the composite photocatalyst basically reaches the level equivalent to the degradation activity of tetracycline hydrochloride in the example 2, and shows that the composite photocatalyst also 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 amount of the raw materials, stirring, fully mixing, uniformly dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, heating, raising the temperature, controlling the temperature at 110 ℃ to perform one-step reaction for 36 hours, controlling the system to perform under positive pressure in the reaction process, keeping the system pressure less than or equal to 0.3MPa, after the reaction is finished, naturally cooling, performing high-speed centrifugation, washing with water, and drying at room temperature to obtain the corresponding product Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided.
The obtained product Cu2S/CuInS2/ZnIn2S4The X-ray diffraction analysis of the composite photocatalyst was carried out, and the results were the same as those of example 1 for Cu2S/CuInS2/ZnIn2S4The X-ray diffraction analysis results of the composite photocatalyst are substantially consistent, which indicates that the diffraction peaks of the composite photocatalyst obtained in the embodiment simultaneously appear Cu2S、CuInS2And ZnIn2S4The diffraction peaks show that the three substances can be effectively formed by the one-step reaction, and the diffraction peaks of other impurities are not detected in the spectrogram, so that the product has high purity and quality.
Meanwhile, the product Cu obtained in the embodiment is adopted2S/CuInS2/ZnIn2S4The compound photocatalyst is used for carrying out degradation performance test on tetracycline hydrochloride, and the result shows that the compound photocatalyst also basically reaches the level equivalent to the degradation activity of tetracycline hydrochloride in the example 2, and shows that the compound photocatalyst also has high degradation activityPhotocatalytic 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 glycol solvent according to the molar dosage of the raw materials, stirring, fully mixing and dissolving the mixture uniformly, transferring the mixture to a hydrothermal reaction kettle with the volume of 50mL, heating and raising the temperature to perform one-step reaction for 32 hours at the temperature of 110 ℃, controlling the system to perform under positive pressure in the reaction process, keeping the system pressure less than or equal to 0.3MPa, after the reaction is finished, naturally cooling, performing high-speed centrifugation, washing with water, and drying at room temperature to obtain the corresponding product Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided.
The obtained product Cu2S/CuInS2/ZnIn2S4The X-ray diffraction analysis of the composite photocatalyst was carried out, and the results were the same as those of example 1 for Cu2S/CuInS2/ZnIn2S4The X-ray diffraction analysis results of the composite photocatalyst are substantially consistent, which indicates that the diffraction peaks of the composite photocatalyst obtained in the embodiment simultaneously appear Cu2S、CuInS2And ZnIn2S4The diffraction peaks show that the three substances can be effectively formed by the one-step reaction, and the diffraction peaks of other impurities are not detected in the spectrogram, so that the product has high purity and quality.
Meanwhile, the product Cu obtained in the embodiment is adopted2S/CuInS2/ZnIn2S4The composite photocatalyst is used for carrying out degradation performance test on tetracycline hydrochloride, and the result shows that the composite photocatalyst basically reaches the level equivalent to the degradation activity of tetracycline hydrochloride in the example 2, and shows that the composite photocatalyst also 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 amount of the raw materials, stirring, fully mixing, uniformly dissolving, transferring to a hydrothermal reaction kettle with the volume of 50mL, heating, raising the temperature, and controlling the temperature at 120 DEG CPerforming one-step reaction for 30h, controlling the system to perform under positive pressure in the reaction process, keeping the system pressure less than or equal to 0.3MPa, after the reaction is finished, naturally cooling, performing high-speed centrifugation, washing with water, and drying at room temperature to obtain the corresponding product Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided.
The obtained product Cu2S/CuInS2/ZnIn2S4The X-ray diffraction analysis of the composite photocatalyst was carried out, and the results were the same as those of example 1 for Cu2S/CuInS2/ZnIn2S4The X-ray diffraction analysis results of the composite photocatalyst are substantially consistent, which indicates that the diffraction peaks of the composite photocatalyst obtained in the embodiment simultaneously appear Cu2S、CuInS2And ZnIn2S4The diffraction peaks show that the three substances can be effectively formed by the one-step reaction, and the diffraction peaks of other impurities are not detected in the spectrogram, so that the product has high purity and quality.
Meanwhile, the product Cu obtained in the embodiment is adopted2S/CuInS2/ZnIn2S4The composite photocatalyst is used for carrying out degradation performance test on tetracycline hydrochloride, and the result shows that the composite photocatalyst basically reaches the level equivalent to the degradation activity of tetracycline hydrochloride in the example 2, and shows that the composite photocatalyst also has high photocatalytic degradation activity.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended 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 (10)
1. Cu2S/CuInS2/ZnIn2S4Composite lightA method for preparing a catalyst, comprising the steps of:
adding raw materials of a copper source, a zinc source, an indium source and a sulfur source into an organic solvent capable of dissolving the raw materials in a hydrothermal reaction kettle for dissolving, then carrying out one-step reaction on the hydrothermal reaction kettle in a sealed state at a controlled temperature of 110-160 ℃, and after the reaction is finished, cooling and separating to obtain Cu2S/CuInS2/ZnIn2S4A composite photocatalyst is provided.
2. Cu according to claim 12S/CuInS2/ZnIn2S4The preparation method of the composite photocatalyst is characterized in that the copper source: a zinc source: indium source: the molar ratio of the sulfur source is x: 1: 2-5: 8-12, wherein x is 0<x≤3。
3. Cu according to claim 22S/CuInS2/ZnIn2S4The preparation method of the composite photocatalyst is characterized in that the value of x is 0.15<x≤0.5。
4. Cu according to claim 22S/CuInS2/ZnIn2S4The 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 0.3 MPa.
5. Cu according to claim 12S/CuInS2/ZnIn2S4The preparation method of the composite photocatalyst is characterized in that 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 selected from one or more of indium nitrate and indium chloride; the sulfur source is selected from one or more of sodium sulfide, thiourea and thioacetamide.
6. According to the claimsSolution of 1 of Cu2S/CuInS2/ZnIn2S4The preparation method of the composite photocatalyst is characterized in that the organic solvent capable of dissolving the raw materials is selected from an alcohol solvent and/or an amine solvent.
7. Cu according to claim 62S/CuInS2/ZnIn2S4The preparation method of the composite photocatalyst is characterized in that the alcohol solvent is selected from one or more of methanol, ethanol, ethylene glycol, propylene glycol and propanol; the amine solvent is selected from dimethylformamide and/or dimethylacetamide.
8. Cu according to claim 72S/CuInS2/ZnIn2S4The preparation method of the composite photocatalyst is characterized in that the organic solvent capable of dissolving the raw materials is selected from ethylene glycol, dimethylformamide or a mixed solvent of the ethylene glycol and the dimethylformamide.
9. Cu according to any of claims 1 to 82S/CuInS2/ZnIn2S4The preparation method of the composite photocatalyst is characterized in that the one-step reaction time is 12-36 hours.
10. Cu2S/CuInS2/ZnIn2S4The application of the composite photocatalyst is characterized in that Cu is adopted2S/CuInS2/ZnIn2S4The composite photocatalyst degrades tetracycline or tetracycline hydrochloride.
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