WO2023108950A1 - PREPARATION METHOD FOR Z-SCHEME α-FE2O3/ZNIN2S4 COMPOSITE PHOTOCATALYST AND USE THEREOF - Google Patents

PREPARATION METHOD FOR Z-SCHEME α-FE2O3/ZNIN2S4 COMPOSITE PHOTOCATALYST AND USE THEREOF Download PDF

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WO2023108950A1
WO2023108950A1 PCT/CN2022/083570 CN2022083570W WO2023108950A1 WO 2023108950 A1 WO2023108950 A1 WO 2023108950A1 CN 2022083570 W CN2022083570 W CN 2022083570W WO 2023108950 A1 WO2023108950 A1 WO 2023108950A1
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znin
composite photocatalyst
source
type
temperature
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French (fr)
Chinese (zh)
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陈伟
陈卫
黄剑
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公元股份有限公司
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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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • 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
    • 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
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2101/40—Organic compounds containing sulfur
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the invention relates to a preparation method and application of a Z-type ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, belonging to the technical field of photocatalytic materials.
  • iron oxide Fe 2 O 3
  • Fe 2 O 3 As a low-cost, stable and environmentally friendly narrow-bandgap semiconductor photocatalytic material, has a bandgap of 2.1-2.2eV, has visible light response and Strong photogenerated hole oxidation ability has attracted extensive attention in the fields of photocatalytic degradation of organic pollutants and water splitting. Degradation, or the degradation of organic matter in waste liquid formed during the processing of plastic pipes.
  • the high recombination rate of photogenerated carriers in Fe 2 O 3 leads to low photoelectric conversion efficiency of Fe 2 O 3 , which greatly limits its practical application.
  • ZnIn 2 S 4 belongs to the ternary semiconductor metal sulfide of AB m C n group, ZnIn 2 S 4 has a suitable band gap (2.1 ⁇ 2.5eV), but in the actual photocatalysis, it also faces the problem of photogenerated electrons and holes.
  • the ⁇ -Fe 2 O 3 is first prepared by a multi-step method, and then combined with ZnIn 2 S 4 to form a corresponding photocatalyst.
  • the specific surface effect of the formed ⁇ -Fe 2 O 3 is not good, which is not conducive to the improvement of catalytic activity. .
  • the present invention aims at the above existing problems in the prior art, and provides a preparation method and application of a Z-type ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst. Has high photocatalytic activity.
  • One of the objectives of the present invention is achieved through the following technical solutions, a method for preparing a Z-type ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, characterized in that the method comprises the following steps:
  • the iron source, zinc source, indium source and sulfur source are all added to the amine solvent containing oxygen atoms that can dissolve the raw materials, and then the hydrothermal reaction kettle is in a sealed state, and the temperature is raised to control the temperature at 120 Under the condition of °C ⁇ 180°C, high-temperature reaction is carried out, and after the reaction is completed, cooling and separation are carried out to obtain the corresponding Z-type ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst.
  • the Fe 2 O 3 formed by the in-situ reaction synchronously during the high-temperature reaction process It is an ⁇ -type characteristic, and the ⁇ -Fe 2 O 3 formed has a huge specific surface area, and the surface effect is remarkable, and the ⁇ -Fe 2 O 3 particles formed are small, and the volume percentage of the surface is large, and the bonding state and electrons on the surface
  • the state of the particle is different from that of the inside of the particle, and the coordination of the surface atoms is different, which leads to an increase in the overall activity of the surface, which makes the overall surface catalytic activity better; and in the sealed state, the system can maintain a certain positive pressure during the reaction process, so that the solvent is in the air.
  • O 3 and reduced ZnIn 2 S 4 composite system has the characteristics of direct Z-type heterojunction, which can make the obtained ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst in the process of photocatalysis, when The direct Z-type ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst absorbs light to generate carriers, the photogenerated holes are enriched in the valence band of ⁇ -Fe 2 O 3 at the deep valence band level, and the photogenerated electrons transfer to the conduction band of ZnIn 2 S 4 with strong reducing power, so as to maintain the strong oxidation of photogenerated holes and the strong reduc
  • the molar ratio of the iron source: zinc source: indium source: sulfur source is x: 1: 2-4 : 8 to 10, where the value of x is 0 ⁇ x ⁇ 2.
  • the dosage ratio of each raw material it is possible to make better use of raw materials, especially the control of the dosage of iron source, which can better ensure that the final product has high catalytic activity and has a good photocatalytic effect on ceftiofur sodium Degradation activity.
  • the value of x is 0.25 ⁇ x ⁇ 1.0.
  • the system pressure of the hydrothermal reactor is kept at a positive pressure, and the positive pressure is controlled At ⁇ 0.3MPa.
  • the temperature can be higher than the boiling point of the amine solvent used, the reaction can be better heated to high temperature conditions, especially the reaction temperature can be raised to above 160 ° C for the reaction, and because The system is sealed, and the solvent will not volatilize directly, but the saturated vapor pressure is carried out in the hydrothermal reactor, which is more conducive to promoting the reaction to form a photocomposite catalyst with high catalytic activity.
  • the above-mentioned iron source, zinc source and indium source can be organic or inorganic, but because the organic salt is quite expensive higher. Inorganic sources of iron, zinc and indium are generally preferred. Even if the reaction is guaranteed, the processing cost can be well reduced.
  • 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 both of indium nitrate, indium sulfate and indium chloride; thioacetamide and/or thiourea.
  • the amine solvent containing oxygen atoms is selected from dimethylformamide and/or dimethylacetamide .
  • the temperature of the high-temperature reaction is 160°C to 180°C.
  • the ⁇ -Fe 2 O 3 system can be better formed and the activity of the photocatalyst can be improved.
  • the time for the high-temperature reaction is 6-18 hours.
  • the second purpose of the present invention is achieved through the following technical scheme, the application of a Z-type ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, using Z-type ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite Photocatalytic degradation of ceftiofur sodium.
  • the composite photocatalyst obtained by the above method has a huge specific surface area and significant surface effect, and the formed ⁇ -Fe 2 O 3 particles are fine, which makes the overall surface catalytic activity better, and can effectively treat organic pollutants such as Degradation properties of ceftiofuran.
  • the present invention has the following advantages:
  • the present invention forms a composite system of ⁇ -Fe 2 O 3 and ZnIn 2 S 4 through synchronous in-situ reaction in a sealed state to construct a direct Z-type heterojunction.
  • the composite photocatalyst absorbs light to generate carriers, the photogenerated holes are enriched in the valence band of ⁇ -Fe 2 O 3 with deep valence band energy level, and the photogenerated electrons are transferred to the conduction band of ZnIn 2 S 4 with strong reducing force , maintaining the strong oxidative properties of the photogenerated holes and the strong reductive properties of the photogenerated electrons, thereby achieving the performance of high photocatalytic activity.
  • Fig. 1 is the X-ray diffraction spectrum of the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -0.25 composite photocatalyst and the photocatalyst Fe 2 O 3 and ZnIn 2 S 4 obtained in Example 1 of the present invention.
  • Fig. 2 is the ultraviolet-visible light diffuse reflectance spectrum of the ⁇ -Fe 2 O 3 /ZnIn 2 S 44 -0.25 composite photocatalyst and the photocatalyst Fe 2 O 3 and ZnIn 2 S 4 obtained in Example 2 of the present invention.
  • Figure 3 shows the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 and ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -2 composite photocatalysts prepared in Example 3 of the present invention, and the single-component photocatalyst Fe Photocatalytic degradation activity of 2 O 3 and ZnIn 2 S 4 on ceftiofur sodium.
  • Fig. 4 is a comparison chart of the photocatalytic degradation activity of ceftiofur sodium prepared by the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared in Example 3 of the present invention when different capture agents are added.
  • Fig. 5 is a photocatalytic photocurrent comparison diagram of the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared in Example 3 of the present invention and the single-component photocatalyst Fe 2 O 3 .
  • the solid target product obtained is dried at 60°C , that is, ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst. According to the amount of ferric nitrate added, the prepared product was named ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -0.25.
  • Fig. 1 is an X-ray diffraction pattern corresponding to the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -0.25 composite photocatalyst obtained in this example, and the Fe 2 O 3 and ZnIn 2 S 4 photocatalysts.
  • Fe 2 O 3 and ZnIn 2 S 4 photocatalysts corresponding to single components are prepared here using the same heat treatment parameters as those used in the above examples to prepare ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -0.25 composite photocatalysts, the difference is that in In raw material selection, a single iron source (ferric nitrate), or corresponding ZnIn 2 S 4 raw material zinc source (zinc nitrate), indium source (indium nitrate) and sulfur source (thioacetamide) is used to obtain the corresponding single-component catalyst of light.
  • the diffraction peak of Fe 2 O 3 obtained by the heat treatment parameter method of the present invention is the diffraction of ⁇ -Fe 2 O 3 , that is, Fe 2 O 3 in Figure 1 corresponds to the ⁇ -Fe 2 O 3 photocatalyst.
  • Fe 2 O 3 /ZnIn 2 S 4 -0.25 in FIG. 1 corresponds to the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst of this embodiment.
  • the solid target product obtained is dried at 60°C to obtain ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst.
  • the prepared product was named ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -0.5 composite photocatalyst.
  • Fig. 2 is an ultraviolet-visible diffuse reflectance spectrum corresponding to the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -0.5 composite photocatalyst obtained in this example, and the Fe 2 O 3 and ZnIn 2 S 4 photocatalysts.
  • the same heat treatment parameters were used to prepare the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -0.5 composite photocatalyst in the above-mentioned Example 2.
  • the difference Be that in raw material selection, single iron source (ferric nitrate) that adopts, or corresponding ZnIn 2 S Raw material zinc source (zinc nitrate), indium source (indium nitrate) and sulfur source (thioacetamide), obtain corresponding One-component photocatalyst.
  • the absorption edge of ZnIn 2 S 4 is around 530nm in wavelength, and the absorption edge of pure Fe 2 O 3 (that is, showing ⁇ -Fe 2 O 3 diffraction) is around 620nm, which is similar to that of pure ZnIn 2 S 4 , Fe 2 O 3 has a better absorption effect on light, so the present invention forms Fe 2 O 3 with ⁇ -Fe 2 O 3 diffraction through the method of the present invention to improve the absorption of ZnIn 2 S 4 to visible light, And compared with pure ZnIn 2 S 4 , the absorption edge of the composite ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -0.5 photocatalyst of the present invention is slightly red-shifted, and the absorption range of the covered spectrum is larger, indicating that through the present invention The method can effectively obtain ⁇ -Fe 2 O 3 products, and it shows that the modification of ZnIn 2 S 4 by ⁇ -Fe 2 O 3 helps to improve its optical properties
  • the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst After natural cooling, high-speed centrifugation, washing with water, and drying at 60°C, the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst.
  • the products prepared by the method in this example are named ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst and ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -2 composite photocatalyst.
  • the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst obtained in this example was used as a photocatalyst for degrading ceftiofur sodium.
  • Figure 3 shows the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 and ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -2 composite photocatalysts prepared in Example 3, and the corresponding Fe 2 O 3 , ZnIn 2 S 4 photocatalyst photocatalytic degradation of ceftiofur sodium activity diagram, where the single-component Fe 2 O 3 , ZnIn 2 S 4 photocatalyst was prepared using the same heat treatment parameters as in this example, the difference is the choice of raw materials Corresponding raw materials, adopt the corresponding raw material iron nitrate corresponding to single-component Fe2O3 , or the raw material zinc source (zinc nitrate), indium source (indium nitrate) and sulfur source ( thioacetamide ) corresponding to ZnIn2S4 .
  • the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 composite material obtained in this example has better photocatalytic activity for ceftiofur sodium and high degradation ability, but the photocatalytic property does not increase with ⁇ - As the content of Fe 2 O 3 increases, it can be seen from Figure 3 that ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 has the best degradation effect on ceftiofur sodium. After 6 hours of degradation, cephalosporin The concentration of sodium thiofurate drops to about 40%, which is mainly due to the fact that the appropriate component ratio helps to build a tight heterogeneous interface between the two, accelerates the carrier separation, and thus obtains a highly active composite component. Therefore, for When selecting the molar dosage of raw materials, it is best to make the ratio of the molar dosage of the iron source to the molar dosage of the zinc source 0.25-1.0:1.0.
  • Fig. 4 is an activity diagram of the photocatalytic degradation of ceftiofur sodium by the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared in this example when a trapping agent is added.
  • p-benzoquinone (BQ), ammonium oxalate (AO) and tert-butanol (TBA) were added as scavengers for superoxide anion radicals, photogenerated holes and hydroxyl radicals, respectively.
  • Fig. 5 is the transient photocurrent data of the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared in Example 3. It can be seen from Figure 5 that compared to pure Fe 2 O 3 (the transient photocurrent corresponds to below 0.050 ⁇ A in the figure), the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 - The composite photocatalyst of 1 has a higher transient photocurrent, which not only shows that the photoelectric response of the ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared by the method of the present invention is good; The enhanced current response also reflects accelerated charge generation and transfer kinetics. Under the same experimental conditions, it was shown that the heterostructure of ⁇ -Fe 2 O 3 /ZnIn 2 S 4 -1 could accelerate the charge transfer separation faster and further promote the photocatalytic degradation rate.

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Abstract

The present invention relates to a preparation method for a Z-scheme α-Fe2O3/ZnIn2S4 composite photocatalyst and a use thereof, in the technical field of photocatalytic materials, In order to solve the existing problem of poor activity, a preparation method for a Z-scheme α-Fe2O3/ZnIn2S4 composite photocatalyst is provided. The method comprises: in a hydrothermal reaction kettle, adding an iron source, a zinc source, an indium source and a sulfur source into an amine solvent containing oxygen atoms and capable of dissolving the raw materials; then, keeping the hydrothermal reaction kettle in a sealed state, raising the temperature and controlling the temperature to carry out a high-temperature reaction under temperature conditions of 120°C to 180°C; and performing cooling and separation after the reaction is completed, so as to obtain the Z-scheme α-Fe2O3/ZnIn2S4 composite photocatalyst. The composite catalyst can maintain the strong oxidizing property of photo-generated holes and the strong reduction of photo-generated electrons, thereby achieving high photocatalytic activity performance.

Description

一种Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法和应用 A Z-type α-Fe 2O 3/ZnIn 2S 4 Preparation method and application of composite photocatalyst 技术领域technical field

本发明涉及一种Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法和应用，属于光催化材料技术领域。 The invention relates to a preparation method and application of a Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, belonging to the technical field of photocatalytic materials.

背景技术Background technique

半导体光催化技术技术作为高效、绿色的具有广阔应用前景的水处理技术，日益受到人们的重视。在众多半导体光催化材料中，氧化铁(Fe 2O 3)，作为一种低成本、性能稳定且环境友好的窄带隙半导体光催化材料，其禁带宽度为2.1-2.2eV，具有可见光响应以及较强的光生空穴氧化能力，在光催化降解有机污染物、水分解等领域受到广泛关注，如对于废液中的有机污染物的光催化降解，医药领域的废液中的有机污染物的降解，或塑料管道的加工处理过程中形成的废液等中的有机物降解处理。然而，Fe 2O 3的光生载流子复合率高，导致Fe 2O 3光电转化效率低，极大限制了其实际应用。所以，通常是使Fe 2O 3与其它半导体复合使用构建组分协同的Z型Fe 2O 3基复合催化剂以维持其高矿化能力并优化其活性。复合如ZnIn 2S 4属于AB mC n族的三元半导体金属硫化物，ZnIn 2S 4具有合适的带隙(2.1～2.5eV)，但在实际光催化中同样面临光生电子和空穴的高复合，且现有的通常都是先制成Fe 2O 3材料，再与另一半导体光催化材料的原料进行混合后高温反应，制成相应的复合材料，如现有的相关专利文献(公开号：CN110369858A)中有通过将铁源六水氯化铁溶于乙二醇中，并将一定量的氢氧化钠水溶液滴加到上述含氯化铁的乙二醇溶液中，混合均匀，在一定温度下干燥一定时间，制得γ-Fe 2O 3，然后，将γ-Fe 2O 3与一定量的氯化锌、三氯化铟和硫代乙酰胺在水热反应釜中加入甘油和乙 二醇的混合溶剂反应，得到γ-Fe 2O 3/ZnIn 2S 4光催化剂。通过多步法先制备γ-Fe 2O 3，再与ZnIn 2S 4复合形成相应的光催化剂，但是，其形成的γ-Fe 2O 3的比表面效应不佳，不利于催化活性的提升。 As an efficient and green water treatment technology with broad application prospects, semiconductor photocatalysis technology has been paid more and more attention by people. Among many semiconductor photocatalytic materials, iron oxide (Fe 2 O 3 ), as a low-cost, stable and environmentally friendly narrow-bandgap semiconductor photocatalytic material, has a bandgap of 2.1-2.2eV, has visible light response and Strong photogenerated hole oxidation ability has attracted extensive attention in the fields of photocatalytic degradation of organic pollutants and water splitting. Degradation, or the degradation of organic matter in waste liquid formed during the processing of plastic pipes. However, the high recombination rate of photogenerated carriers in Fe 2 O 3 leads to low photoelectric conversion efficiency of Fe 2 O 3 , which greatly limits its practical application. Therefore, it is usually to combine Fe 2 O 3 with other semiconductors to use a Z-type Fe 2 O 3 -based composite catalyst with synergistic components to maintain its high mineralization ability and optimize its activity. Composite such as ZnIn 2 S 4 belongs to the ternary semiconductor metal sulfide of AB m C n group, ZnIn 2 S 4 has a suitable band gap (2.1 ~ 2.5eV), but in the actual photocatalysis, it also faces the problem of photogenerated electrons and holes. High recombination, and the existing Fe 2 O 3 material is usually made first, then mixed with another semiconductor photocatalytic material and then reacted at high temperature to make a corresponding composite material, such as the existing related patent documents ( Publication No.: CN110369858A) has by dissolving iron source ferric chloride hexahydrate in ethylene glycol, and adding a certain amount of aqueous sodium hydroxide solution dropwise in the above-mentioned ethylene glycol solution containing ferric chloride, mixing evenly, Dry at a certain temperature for a certain period of time to obtain γ-Fe 2 O 3 , then add γ-Fe 2 O 3 and a certain amount of zinc chloride, indium trichloride and thioacetamide into the hydrothermal reaction kettle The mixed solvent reaction of glycerin and ethylene glycol yields γ-Fe 2 O 3 /ZnIn 2 S 4 photocatalyst. The γ-Fe 2 O 3 is first prepared by a multi-step method, and then combined with ZnIn 2 S 4 to form a corresponding photocatalyst. However, the specific surface effect of the formed γ-Fe 2 O 3 is not good, which is not conducive to the improvement of catalytic activity. .

发明内容Contents of the invention

本发明针对以上现有技术中存在的问题，提供一种Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法和应用，解决的问题是实现提升比表面和使光复合催化剂具有高光催化活性。 The present invention aims at the above existing problems in the prior art, and provides a preparation method and application of a Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst. Has high photocatalytic activity.

本发明的目的之一是通过以下技术方案得以实现的，一种Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法，其特征在于，该方法包括以下步骤： One of the objectives of the present invention is achieved through the following technical solutions, a method for preparing a Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, characterized in that the method comprises the following steps:

在水热反应釜中，将铁源、锌源、铟源和硫源均加入能溶解原料的含有氧原子的胺类溶剂中，然后使水热反应釜在密封状态下，升温控制温度在120℃～180℃条件下进行高温反应，反应结束后，进行冷却和分离，得到相应的Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂。 In the hydrothermal reaction kettle, the iron source, zinc source, indium source and sulfur source are all added to the amine solvent containing oxygen atoms that can dissolve the raw materials, and then the hydrothermal reaction kettle is in a sealed state, and the temperature is raised to control the temperature at 120 Under the condition of ℃～180℃, high-temperature reaction is carried out, and after the reaction is completed, cooling and separation are carried out to obtain the corresponding Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst.

通过直接将铁源、锌源、铟源和硫代乙酰胺都加入胺类溶剂，并在密封状态下进行高温反应，能够使在高温反应的过程中，同步原位反应形成的Fe 2O 3为α型的特性，实现形成的α-Fe 2O 3具有巨大的比表面，表面效应显著，且形成α-Fe 2O 3粒子细小，表面所占的体积百分数大，表面的键态和电子态与颗粒内部不同，表面原子配位不同等导致表面的整体活性增加，使整体表面催化活性更佳；且在密封状态下，能够使反应过程中体系保持一定的正压条件下，使溶剂在高温下形成饱和蒸汽压，部分溶剂能提供氧原子供反应过程中形成α-Fe 2O 3，利于反应的高效进行；同时，通过在密封状态下同步原位反应形成的氧化型α-Fe 2O 3和还原型ZnIn 2S 4复合体系的构建具有直接Z型异质结的特性，能够使得到的α-Fe 2O 3/ZnIn 2S 4复合光催化剂在进行光催化的过程中，当直接 Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂吸光产生载流子，光生空穴富集在深价带能级的α-Fe 2O 3的价带上，而光生电子转移到强还原力的ZnIn 2S 4的导带上，从而维持光生空穴的强氧化性和光生电子的强还原性，从而实现高光催化能力的效果，且本方法直接一步法反应完成，操作更简单，更易于批量产业化生产。 By directly adding the iron source, zinc source, indium source and thioacetamide into the amine solvent, and performing high-temperature reaction in a sealed state, it is possible to make the Fe 2 O 3 formed by the in-situ reaction synchronously during the high-temperature reaction process It is an α-type characteristic, and the α-Fe 2 O 3 formed has a huge specific surface area, and the surface effect is remarkable, and the α-Fe 2 O 3 particles formed are small, and the volume percentage of the surface is large, and the bonding state and electrons on the surface The state of the particle is different from that of the inside of the particle, and the coordination of the surface atoms is different, which leads to an increase in the overall activity of the surface, which makes the overall surface catalytic activity better; and in the sealed state, the system can maintain a certain positive pressure during the reaction process, so that the solvent is in the air. Saturated vapor pressure is formed at high temperature, and part of the solvent can provide oxygen atoms for the formation of α-Fe 2 O 3 in the reaction process, which is conducive to the efficient progress of the reaction; at the same time, the oxidized α-Fe 2 formed by synchronous in-situ reaction in a sealed state The construction of O 3 and reduced ZnIn 2 S 4 composite system has the characteristics of direct Z-type heterojunction, which can make the obtained α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst in the process of photocatalysis, when The direct Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst absorbs light to generate carriers, the photogenerated holes are enriched in the valence band of α-Fe 2 O 3 at the deep valence band level, and the photogenerated electrons transfer to the conduction band of ZnIn 2 S 4 with strong reducing power, so as to maintain the strong oxidation of photogenerated holes and the strong reducibility of photogenerated electrons, thereby achieving the effect of high photocatalytic ability, and this method directly completes the reaction in one step, and the operation is more efficient. Simple and easier for mass industrial production.

在上述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法中，作为优选，所述铁源：锌源：铟源：硫源的摩尔比为x：1：2～4：8～10，其中x的取值为0<x≤2。通过控制各原料的用量比例，能够使更好的利用原料，尤其是对铁源的用量控制，能够更好的保证最终形成的产物具有高催化活性，对头孢噻呋钠具有很好的光催化降解活性。作为进一步的优选，所述x的取值为0.25≤x≤1.0。 In the preparation method of the above-mentioned Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, preferably, the molar ratio of the iron source: zinc source: indium source: sulfur source is x: 1: 2-4 : 8 to 10, where the value of x is 0<x≤2. By controlling the dosage ratio of each raw material, it is possible to make better use of raw materials, especially the control of the dosage of iron source, which can better ensure that the final product has high catalytic activity and has a good photocatalytic effect on ceftiofur sodium Degradation activity. As a further preference, the value of x is 0.25≤x≤1.0.

在上述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法中，作为优选，所述高温反应过程中，使水热反应釜的体系压力保持正压，且正压压力控制在≤0.3MPa。通过使体系在正压力条件下，使能高于所用的胺类溶剂的沸点温度，能够使反应更好的升温到高温条件下，尤其是能使反应温度升到160℃以上进行反应，且由于体系是密封状态的，溶剂也不会直接挥发，而是在水热反应釜内进行了饱和的蒸汽压，实现更有利于促进反应形成高催化活性的光复合催化剂。 In the preparation method of the above-mentioned Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, as a preference, during the high-temperature reaction process, the system pressure of the hydrothermal reactor is kept at a positive pressure, and the positive pressure is controlled At ≤0.3MPa. By making the system under positive pressure conditions, the temperature can be higher than the boiling point of the amine solvent used, the reaction can be better heated to high temperature conditions, especially the reaction temperature can be raised to above 160 ° C for the reaction, and because The system is sealed, and the solvent will not volatilize directly, but the saturated vapor pressure is carried out in the hydrothermal reactor, which is more conducive to promoting the reaction to form a photocomposite catalyst with high catalytic activity.

在上述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法中，上述的铁源、锌源和铟源可以是有机的，也可以是无机的，但是由于有机盐相当价格较高。一般最好采用无机的铁源、锌源和铟源。即使保证反应的进行，又能够很好的降解加工成本。作为优选，所述锌源选自硝酸锌、氯化锌和乙酸锌中的一种或几种；所述铟源选自硝酸铟、硫酸铟和氯化铟中的一种或两种；所述硫代乙酰胺和/或硫脲。 In the preparation method of the above-mentioned Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, the above-mentioned iron source, zinc source and indium source can be organic or inorganic, but because the organic salt is quite expensive higher. Inorganic sources of iron, zinc and indium are generally preferred. Even if the reaction is guaranteed, the processing cost can be well reduced. Preferably, 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 both of indium nitrate, indium sulfate and indium chloride; thioacetamide and/or thiourea.

在上述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法中，作 为优选，所述含氧原子的胺类溶剂选自二甲基甲酰胺和/或二甲基乙酰胺。 In the preparation method of the above-mentioned Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, as a preference, the amine solvent containing oxygen atoms is selected from dimethylformamide and/or dimethylacetamide .

在上述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法中，作为优选，所述高温反应的温度为160℃～180℃。在高温下能够更好的形成α-Fe 2O 3体系，提高光催化剂的活性能力。作为进一步的优选，所述高温反应的时间为6～18h。 In the preparation method of the above-mentioned Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, preferably, the temperature of the high-temperature reaction is 160°C to 180°C. At high temperature, the α-Fe 2 O 3 system can be better formed and the activity of the photocatalyst can be improved. As a further preference, the time for the high-temperature reaction is 6-18 hours.

本发明的目的之二是通过以下技术方案来实现，一种Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的应用，采用Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂降解头孢噻呋钠。通过上述方法得到的复合光催化剂，由于具有巨大的比表面，且表面效应显著，形成的α-Fe 2O 3粒子细小，使整体的表面催化活性更佳，能够实现有效的对有机污染物如头孢噻呋喃的降解性能。 The second purpose of the present invention is achieved through the following technical scheme, the application of a Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, using Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite Photocatalytic degradation of ceftiofur sodium. The composite photocatalyst obtained by the above method has a huge specific surface area and significant surface effect, and the formed α-Fe 2 O 3 particles are fine, which makes the overall surface catalytic activity better, and can effectively treat organic pollutants such as Degradation properties of ceftiofuran.

综上所述，与现有技术相比，本发明具有以下优点：In summary, compared with the prior art, the present invention has the following advantages:

本发明通过在密封状态下同步原位反应形成α-Fe 2O 3和ZnIn 2S 4复合体系构建具有直接Z型异质结的特性，当直接Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂吸光产生载流子，光生空穴富集在深价带能级的α-Fe 2O 3的价带上，而光生电子转移到强还原力的ZnIn 2S 4的导带上，维持了光生空穴的强氧化性和光生电子的强还原性，从而实现高光催化活性的性能。 The present invention forms a composite system of α-Fe 2 O 3 and ZnIn 2 S 4 through synchronous in-situ reaction in a sealed state to construct a direct Z-type heterojunction. When the direct Z-type α-Fe 2 O 3 /ZnIn 2 S 4 The composite photocatalyst absorbs light to generate carriers, the photogenerated holes are enriched in the valence band of α-Fe 2 O 3 with deep valence band energy level, and the photogenerated electrons are transferred to the conduction band of ZnIn 2 S 4 with strong reducing force , maintaining the strong oxidative properties of the photogenerated holes and the strong reductive properties of the photogenerated electrons, thereby achieving the performance of high photocatalytic activity.

附图说明Description of drawings

图1是本发明实施例1得到的α-Fe 2O 3/ZnIn 2S 4-0.25复合光催化剂和光催化剂Fe 2O 3以及ZnIn 2S 4的X射线衍射谱图。 Fig. 1 is the X-ray diffraction spectrum of the α-Fe 2 O 3 /ZnIn 2 S 4 -0.25 composite photocatalyst and the photocatalyst Fe 2 O 3 and ZnIn 2 S 4 obtained in Example 1 of the present invention.

图2是本发明实施例2得到的α-Fe 2O 3/ZnIn 2S 44-0.25复合光催化剂和光催化剂Fe 2O 3以及ZnIn 2S 4的紫外-可见光漫反射谱图。 Fig. 2 is the ultraviolet-visible light diffuse reflectance spectrum of the α-Fe 2 O 3 /ZnIn 2 S 44 -0.25 composite photocatalyst and the photocatalyst Fe 2 O 3 and ZnIn 2 S 4 obtained in Example 2 of the present invention.

图3是本发明实施例3制备得到的α-Fe 2O 3/ZnIn 2S 4-1和α-Fe 2O 3/ZnIn 2S 4-2复合光催化剂，以及单组份的光催化剂Fe 2O 3和ZnIn 2S 4对头孢噻呋钠的光催化降解活性图。 Figure 3 shows the α-Fe 2 O 3 /ZnIn 2 S 4 -1 and α-Fe 2 O 3 /ZnIn 2 S 4 -2 composite photocatalysts prepared in Example 3 of the present invention, and the single-component photocatalyst Fe Photocatalytic degradation activity of 2 O 3 and ZnIn 2 S 4 on ceftiofur sodium.

图4是本发明实施例3中制备得到的α-Fe 2O 3/ZnIn 2S 4-1复合光催化剂在添加不同捕获剂时对头孢噻呋钠的光催化降解活性对比图。 Fig. 4 is a comparison chart of the photocatalytic degradation activity of ceftiofur sodium prepared by the α-Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared in Example 3 of the present invention when different capture agents are added.

图5是本发明实施例3中制备得到的α-Fe 2O 3/ZnIn 2S 4-1复合光催化剂和单组份的光催化剂Fe 2O 3的光催化光电流对比图。 Fig. 5 is a photocatalytic photocurrent comparison diagram of the α-Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared in Example 3 of the present invention and the single-component photocatalyst Fe 2 O 3 .

具体实施方式Detailed ways

下面通过具体实施例和附图，对本发明的技术方案作进一步具体的说明，但是本发明并不限于这些实施例。The technical solution of the present invention will be further specifically described below through specific embodiments and accompanying drawings, but the present invention is not limited to these embodiments.

实施例1Example 1

在一洁净容器中，分别将0.25mmol的硝酸铁，1mmol的硝酸锌，2mmol的硝酸铟以及8mmol的硫代乙酰胺溶解于75mL的二甲基甲酰胺中形成混合液，然后，再将混合液转移至100mL的水热反应釜，控制水热反应釜在密封状态下，升温控制温度于180℃的条件下进行反应10小时，反应过程中由于水热反应釜是密封状态，随着温度的升高和反应的进行，体系压力呈正压，且反应过程中还控制体系的压力在≤0.3MPa，反应结束，待自然冷却后，经高速离心、水洗，得到的固体目标产物在60℃下干燥，即得α-Fe 2O 3/ZnIn 2S 4复合光催化剂。根据硝酸铁的加入量不同，将制备产物命名为α-Fe 2O 3/ZnIn 2S 4-0.25。 In a clean container, dissolve 0.25mmol of ferric nitrate, 1mmol of zinc nitrate, 2mmol of indium nitrate and 8mmol of thioacetamide in 75mL of dimethylformamide to form a mixed solution, and then, the mixed solution Transfer to a 100mL hydrothermal reaction kettle, control the hydrothermal reaction kettle in a sealed state, raise the temperature and control the temperature to react for 10 hours under the condition of 180°C, during the reaction process, since the hydrothermal reaction kettle is in a sealed state, as the temperature rises, During the reaction, the pressure of the system is positive, and the pressure of the system is also controlled at ≤0.3MPa during the reaction. After the reaction is completed, after natural cooling, high-speed centrifugation and water washing, the solid target product obtained is dried at 60°C , that is, α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst. According to the amount of ferric nitrate added, the prepared product was named α-Fe 2 O 3 /ZnIn 2 S 4 -0.25.

图1是对应本实施例中得到的α-Fe 2O 3/ZnIn 2S 4-0.25复合光催化剂，以及Fe 2O 3和ZnIn 2S 4光催化剂的X射线衍射图谱。对应于单组分的Fe 2O 3和ZnIn 2S 4光催化剂这里采用与上述实施例中制备α-Fe 2O 3/ZnIn 2S 4-0.25复合光催化剂相同的热处理参数制备，区别在于在原料选择上，单一采用铁源(硝酸铁)，或对应ZnIn 2S 4的原料锌源(硝酸锌)、铟源(硝酸铟)和硫源(硫代乙酰胺)，得到相应的单组份光催化剂。从图1可知，通过本发明的热处理参数方法获得的Fe 2O 3的衍射峰为α-Fe 2O 3的衍射，即图1中Fe 2O 3 对应于α-Fe 2O 3光催化剂。在图1中的Fe 2O 3/ZnIn 2S 4-0.25对应于本实施例的α-Fe 2O 3/ZnIn 2S 4复合光催化剂。从图中可看出Fe 2O 3/ZnIn 2S 4-0.25样品中所有的XRD图谱显示ZnIn 2S 4的衍射峰，在Fe 2O 3/ZnIn 2S 4-0.25复合材料的XRD图谱中没有观察到Fe 2O 3的特征衍射峰，这可能由于复合体系中Fe 2O 3的含量较低，也表明本发明制备的Fe 2O 3在ZnIn 2S 4中均匀的分散，且粒径较小，不易观察到，但是对应于单组分的Fe 2O 3的衍射峰显示出α-Fe 2O 3的衍射，说明本发明的热处理方法得到α-Fe 2O 3的衍射的效果。 Fig. 1 is an X-ray diffraction pattern corresponding to the α-Fe 2 O 3 /ZnIn 2 S 4 -0.25 composite photocatalyst obtained in this example, and the Fe 2 O 3 and ZnIn 2 S 4 photocatalysts. Fe 2 O 3 and ZnIn 2 S 4 photocatalysts corresponding to single components are prepared here using the same heat treatment parameters as those used in the above examples to prepare α-Fe 2 O 3 /ZnIn 2 S 4 -0.25 composite photocatalysts, the difference is that in In raw material selection, a single iron source (ferric nitrate), or corresponding ZnIn 2 S 4 raw material zinc source (zinc nitrate), indium source (indium nitrate) and sulfur source (thioacetamide) is used to obtain the corresponding single-component catalyst of light. It can be seen from Figure 1 that the diffraction peak of Fe 2 O 3 obtained by the heat treatment parameter method of the present invention is the diffraction of α-Fe 2 O 3 , that is, Fe 2 O 3 in Figure 1 corresponds to the α-Fe 2 O 3 photocatalyst. Fe 2 O 3 /ZnIn 2 S 4 -0.25 in FIG. 1 corresponds to the α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst of this embodiment. It can be seen from the figure that all the XRD patterns in the Fe 2 O 3 /ZnIn 2 S 4 -0.25 sample show the diffraction peak of ZnIn 2 S 4 , in the XRD pattern of the Fe 2 O 3 /ZnIn 2 S 4 -0.25 composite material The characteristic diffraction peak of Fe2O3 is not observed, which may be due to the low content of Fe2O3 in the composite system , which also shows that the Fe2O3 prepared by the present invention is uniformly dispersed in ZnIn2S4 , and the particle size It is small and difficult to observe, but the diffraction peak corresponding to the single-component Fe 2 O 3 shows the diffraction of α-Fe 2 O 3 , indicating that the heat treatment method of the present invention obtains the diffraction effect of α-Fe 2 O 3 .

实施例2Example 2

在一洁净容器中，分别将0.5mmol的硝酸铁，1mmol的硝酸锌，2mmol的硝酸铟以及8mmol的硫代乙酰胺溶解于75mL的二甲基甲酰胺中形成混合液，然后，再将混合液转移至100mL的水热反应釜，控制水热反应釜在密封状态下，升温控制温度于170℃的条件下进行反应12小时，反应过程中由于水热反应釜是密封状态，随着温度的升高和反应的进行，体系压力呈正压，且反应过程中还控制体系的压力在≤0.3MPa，待自然冷却后，经高速离心、水洗，得到的固体目标产物在60℃下干燥，即得α-Fe 2O 3/ZnIn 2S 4复合光催化剂。根据硝酸铁的加入量不同，将制备产物命名为α-Fe 2O 3/ZnIn 2S 4-0.5复合光催化剂。 In a clean container, dissolve 0.5mmol of ferric nitrate, 1mmol of zinc nitrate, 2mmol of indium nitrate and 8mmol of thioacetamide in 75mL of dimethylformamide to form a mixed solution, and then dissolve the mixed solution Transfer to a 100mL hydrothermal reaction kettle, control the hydrothermal reaction kettle in a sealed state, raise the temperature and control the temperature to react for 12 hours under the condition of 170°C, during the reaction process, since the hydrothermal reaction kettle is in a sealed state, as the temperature rises, When the reaction is carried out, the pressure of the system is positive, and the pressure of the system is also controlled at ≤0.3MPa during the reaction process. After natural cooling, high-speed centrifugation and water washing, the solid target product obtained is dried at 60°C to obtain α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst. According to the different addition amount of ferric nitrate, the prepared product was named α-Fe 2 O 3 /ZnIn 2 S 4 -0.5 composite photocatalyst.

图2是对应本实施例中得到的α-Fe 2O 3/ZnIn 2S 4-0.5复合光催化剂，以及Fe 2O 3、ZnIn 2S 4光催化剂的紫外-可见漫反射光谱图。对应图2中的Fe 2O 3和ZnIn 2S 4光催化剂这里采用与上述实施例2中制备α-Fe 2O 3/ZnIn 2S 4-0.5复合光催化剂相同的热处理参数制备方法得到，区别在于在原料选择上，单一采用的铁源(硝酸铁)，或对应ZnIn 2S 4的原料锌源(硝酸锌)、铟源(硝酸铟)和硫源(硫代乙酰胺)，得到相应的单组分光催化剂。从图2中可以看出，ZnIn 2S 4的吸收边缘在波长530nm左右，纯的Fe 2O 3(即显示α-Fe 2O 3衍射)的吸收边缘在620nm左右，与纯的ZnIn 2S 4相比，Fe 2O 3对 光具有更好的吸收作用，所以，本发明通过本发明方法形成具有α-Fe 2O 3衍射的Fe 2O 3来提高ZnIn 2S 4对可见光的吸收，且与较纯的ZnIn 2S 4相比，本发明复合的α-Fe 2O 3/ZnIn 2S 4-0.5光催化剂的吸收边缘略微红移，覆盖光谱的吸收范围越大，表明通过本发明的方法能够有效的得到α-Fe 2O 3产物，且说明通过α-Fe 2O 3改性ZnIn 2S 4有助于提升其光学性能，这有助于产生更多的光生载流子，从而更有利于光催化降解反应。 Fig. 2 is an ultraviolet-visible diffuse reflectance spectrum corresponding to the α-Fe 2 O 3 /ZnIn 2 S 4 -0.5 composite photocatalyst obtained in this example, and the Fe 2 O 3 and ZnIn 2 S 4 photocatalysts. Corresponding to the Fe 2 O 3 and ZnIn 2 S 4 photocatalysts in Figure 2, the same heat treatment parameters were used to prepare the α-Fe 2 O 3 /ZnIn 2 S 4 -0.5 composite photocatalyst in the above-mentioned Example 2. The difference Be that in raw material selection, single iron source (ferric nitrate) that adopts, or corresponding ZnIn 2 S Raw material zinc source (zinc nitrate), indium source (indium nitrate) and sulfur source (thioacetamide), obtain corresponding One-component photocatalyst. It can be seen from Figure 2 that the absorption edge of ZnIn 2 S 4 is around 530nm in wavelength, and the absorption edge of pure Fe 2 O 3 (that is, showing α-Fe 2 O 3 diffraction) is around 620nm, which is similar to that of pure ZnIn 2 S 4 , Fe 2 O 3 has a better absorption effect on light, so the present invention forms Fe 2 O 3 with α-Fe 2 O 3 diffraction through the method of the present invention to improve the absorption of ZnIn 2 S 4 to visible light, And compared with pure ZnIn 2 S 4 , the absorption edge of the composite α-Fe 2 O 3 /ZnIn 2 S 4 -0.5 photocatalyst of the present invention is slightly red-shifted, and the absorption range of the covered spectrum is larger, indicating that through the present invention The method can effectively obtain α-Fe 2 O 3 products, and it shows that the modification of ZnIn 2 S 4 by α-Fe 2 O 3 helps to improve its optical properties, which helps to generate more photogenerated carriers, This is more conducive to the photocatalytic degradation reaction.

实施例3Example 3

在一洁净容器中，分别将1mmol或者2mmol的硝酸铁，1mmol的硝酸锌，2mmol的硝酸铟以及8mmol的硫代乙酰胺溶解于80mL的二甲基甲酰胺中形成混合液，然后，再将混合液转移至100mL的水热反应釜，控制水热反应釜在密封状态下，升温控制温度于180℃的条件下进行反应14小时，反应过程中由于水热反应釜是密封状态，随着温度的升高和反应的进行，体系压力呈正压，且反应过程中还控制体系的压力在≤0.3MPa，待自然冷却后，经高速离心、水洗，60℃下干燥，即得α-Fe 2O 3/ZnIn 2S 4复合光催化剂。根据硝酸铁的加入量(1mmol或者2mmol)不同，将本实施例方法制备得到的产物分别命名为α-Fe 2O 3/ZnIn 2S 4-1复合光催化剂和α-Fe 2O 3/ZnIn 2S 4-2复合光催化剂。 In a clean container, dissolve 1mmol or 2mmol of ferric nitrate, 1mmol of zinc nitrate, 2mmol of indium nitrate and 8mmol of thioacetamide in 80mL of dimethylformamide to form a mixed solution, and then mix the Transfer the liquid to a 100mL hydrothermal reactor, control the hydrothermal reactor in a sealed state, raise the temperature and control the temperature to react for 14 hours under the condition of 180°C, during the reaction process, because the hydrothermal reactor is in a sealed state, as the temperature increases During the rise and reaction, the pressure of the system is positive, and the pressure of the system is also controlled at ≤0.3MPa during the reaction process. After natural cooling, high-speed centrifugation, washing with water, and drying at 60°C, the α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst. Depending on the amount of ferric nitrate (1mmol or 2mmol), the products prepared by the method in this example are named α-Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst and α-Fe 2 O 3 /ZnIn 2 S 4 -2 composite photocatalyst.

利用本实施例得到的α-Fe 2O 3/ZnIn 2S 4复合光催化剂应用于降解头孢噻呋钠的光催化剂。 The α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst obtained in this example was used as a photocatalyst for degrading ceftiofur sodium.

具体为：取本实施例制备得到的α-Fe 2O 3/ZnIn 2S 4-2复合光催化剂样品20mg分散于40mL浓度为30mg L -1的头孢噻呋钠溶液中，放置搅拌器上于暗处搅拌30分钟至α-Fe 2O 3/ZnIn 2S 4-2复合光催化剂样品与头孢噻呋钠溶液达到完全充分吸附，直至饱和状态。用针管取样2mL后，开启装有420nm截止滤光片的350W氙灯作为光催化的可见光源。此时搅拌器处于工作状态不断进行搅拌。之后每隔1小时取一次样，共取出六组样品后在离心机上 离心，将清液抽出后将样品编号保存。将取出的清液样品做紫外可见吸收光谱的测试分析。 Specifically: Take 20 mg of the α-Fe 2 O 3 /ZnIn 2 S 4 -2 composite photocatalyst sample prepared in this example and disperse it in 40 mL of ceftiofur sodium solution with a concentration of 30 mg L -1 , place it on a stirrer Stir in the dark for 30 minutes until the α-Fe 2 O 3 /ZnIn 2 S 4 -2 composite photocatalyst sample and the ceftiofur sodium solution are fully adsorbed until saturated. After sampling 2mL with a needle tube, turn on a 350W xenon lamp equipped with a 420nm cut-off filter as a visible light source for photocatalysis. At this moment, the stirrer is in the working state to continuously stir. After that, samples were taken every 1 hour. A total of six groups of samples were taken out and centrifuged on a centrifuge. The supernatant was drawn out and the sample number was saved. The taken out serum samples were tested and analyzed by UV-Vis absorption spectrum.

图3为实施例3中制备得到的α-Fe 2O 3/ZnIn 2S 4-1和α-Fe 2O 3/ZnIn 2S 4-2复合光催化剂，以及对应的Fe 2O 3、ZnIn 2S 4光催化剂的光催化降解头孢噻呋钠的活性图，这里单组份的Fe 2O 3、ZnIn 2S 4光催化剂采用与本实施例相同的热处理参数条件制备得到，区别是原料选择对应的原料，采用相应的对应单组份Fe 2O 3的原料硝酸铁，或者对应ZnIn 2S 4的原料锌源(硝酸锌)、铟源(硝酸铟)和硫源(硫代乙酰胺)。通过测试分析，从图3中可以看出，纯的Fe 2O 3对头孢噻呋钠的催化降解作用是非常低的，经可见光照射6小时后头孢噻呋钠的浓度仍然有95％以上，这说明Fe 2O 3的光催化活性并不好。相比而言，本实施例得到的α-Fe 2O 3/ZnIn 2S 4复合材料对头孢噻呋钠具有更好的光催化活性，降解能力高，但是光催化性并不是随着α-Fe 2O 3的含量增加而增加的，由图3可看出，对头孢噻呋钠降解作用最好的是α-Fe 2O 3/ZnIn 2S 4-1，在降解6小时后，头孢噻呋钠的浓度下降到40％左右，这主要由于合适的组分配比有助于两者间构建紧密的异质界面，加速载流子分离，从而获得高活性的复合组分，因此，对于原料的摩尔用量选择时，最好使铁源的摩尔用量与锌源的摩尔用量之比为0.25-1.0：1.0。 Figure 3 shows the α-Fe 2 O 3 /ZnIn 2 S 4 -1 and α-Fe 2 O 3 /ZnIn 2 S 4 -2 composite photocatalysts prepared in Example 3, and the corresponding Fe 2 O 3 , ZnIn 2 S 4 photocatalyst photocatalytic degradation of ceftiofur sodium activity diagram, where the single-component Fe 2 O 3 , ZnIn 2 S 4 photocatalyst was prepared using the same heat treatment parameters as in this example, the difference is the choice of raw materials Corresponding raw materials, adopt the corresponding raw material iron nitrate corresponding to single-component Fe2O3 , or the raw material zinc source (zinc nitrate), indium source (indium nitrate) and sulfur source ( thioacetamide ) corresponding to ZnIn2S4 . Through test analysis, it can be seen from Fig. 3 that pure Fe 2 O 3 has a very low catalytic degradation effect on ceftiofur sodium, and the concentration of ceftiofur sodium still has more than 95% after 6 hours of visible light irradiation, This shows that the photocatalytic activity of Fe 2 O 3 is not good. In comparison, the α-Fe 2 O 3 /ZnIn 2 S 4 composite material obtained in this example has better photocatalytic activity for ceftiofur sodium and high degradation ability, but the photocatalytic property does not increase with α- As the content of Fe 2 O 3 increases, it can be seen from Figure 3 that α-Fe 2 O 3 /ZnIn 2 S 4 -1 has the best degradation effect on ceftiofur sodium. After 6 hours of degradation, cephalosporin The concentration of sodium thiofurate drops to about 40%, which is mainly due to the fact that the appropriate component ratio helps to build a tight heterogeneous interface between the two, accelerates the carrier separation, and thus obtains a highly active composite component. Therefore, for When selecting the molar dosage of raw materials, it is best to make the ratio of the molar dosage of the iron source to the molar dosage of the zinc source 0.25-1.0:1.0.

为了进一步说明本发明α-Fe 2O 3/ZnIn 2S 4复合光催化剂的性能，通过加入相应的捕获剂进行测试。图4是本实施例制备得到的α-Fe 2O 3/ZnIn 2S 4-1复合光催化剂在添加捕获剂时复合光催化剂光催化降解头孢噻呋钠的活性图。在该测试中分别添加对苯醌(BQ)、草酸铵(AO)和叔丁醇(TBA)作为超氧负离子自由基、光生空穴和羟基自由基的捕获剂。从图4中可以看出，加了BQ后，α-Fe 2O 3/ZnIn 2S 4-1复合催化剂光催化降解头孢噻呋钠的活性明显降低，这说明在降解头孢噻呋钠过程中超氧负离子自由基其 主导作用，也进一步说明了本发明α-Fe 2O 3/ZnIn 2S 4复合光催化剂复合体系中载流子遵循直接Z型机制。该方式有利于复合体系拥有高效载流子分离效率；同时，仍能维持本α-Fe 2O 3/ZnIn 2S 4-1复合催化剂体系的强氧化还原能力。 In order to further illustrate the performance of the α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst of the present invention, a test is carried out by adding corresponding capture agents. Fig. 4 is an activity diagram of the photocatalytic degradation of ceftiofur sodium by the α-Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared in this example when a trapping agent is added. In this test, p-benzoquinone (BQ), ammonium oxalate (AO) and tert-butanol (TBA) were added as scavengers for superoxide anion radicals, photogenerated holes and hydroxyl radicals, respectively. It can be seen from Figure 4 that after the addition of BQ, the photocatalytic activity of the α-Fe 2 O 3 /ZnIn 2 S 4 -1 composite catalyst in the degradation of ceftiofur sodium was significantly reduced, which indicated that in the process of degrading ceftiofur sodium, super The dominant role of oxyanion radicals also further illustrates that the carriers in the α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst composite system of the present invention follow the direct Z-type mechanism. This method is beneficial for the composite system to have high carrier separation efficiency; at the same time, it can still maintain the strong redox ability of the α-Fe 2 O 3 /ZnIn 2 S 4 -1 composite catalyst system.

图5是本实施例3制备得到的α-Fe 2O 3/ZnIn 2S 4-1复合光催化剂的瞬态光电流数据。从图5中可以看出，相比于纯的Fe 2O 3(瞬态光电流对应在图中的0.050μA以下)，本发明实施例得到的α-Fe 2O 3/ZnIn 2S 4-1的复合光催化剂具有更高的瞬态光电流，这不仅能说明本发明方法制备得到的α-Fe 2O 3/ZnIn 2S 4-1复合光催化剂的光电响应好；另一方面，显著增强的电流响应也反映了加速的电荷产生和转移动力学。在相同的实验条件下，表明α-Fe 2O 3/ZnIn 2S 4-1的异质结构能更快地加速电荷转移分离，进一步促进光催化降解速率。 Fig. 5 is the transient photocurrent data of the α-Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared in Example 3. It can be seen from Figure 5 that compared to pure Fe 2 O 3 (the transient photocurrent corresponds to below 0.050μA in the figure), the α-Fe 2 O 3 /ZnIn 2 S 4 - The composite photocatalyst of 1 has a higher transient photocurrent, which not only shows that the photoelectric response of the α-Fe 2 O 3 /ZnIn 2 S 4 -1 composite photocatalyst prepared by the method of the present invention is good; The enhanced current response also reflects accelerated charge generation and transfer kinetics. Under the same experimental conditions, it was shown that the heterostructure of α-Fe 2 O 3 /ZnIn 2 S 4 -1 could accelerate the charge transfer separation faster and further promote the photocatalytic degradation rate.

实施例4Example 4

在一洁净容器中，分别将0.75mmol的硫酸铁，1mmol的乙酸锌，3mmol的硝酸铟以及10mmol的硫代乙酰胺溶解于75mL的二甲基乙酰胺中形成混合液，然后，再将混合液转移至100mL的水热反应釜，控制水热反应釜在密封状态下，升温控制温度于160℃的条件下进行反应16小时，反应过程中由于水热反应釜是密封状态，随着温度的升高和反应的进行，体系压力呈正压，且反应过程中还控制体系的压力在≤0.3MPa，待自然冷却后，经高速离心、水洗，得到的固体目标产物在60℃下干燥，即得α-Fe 2O 3/ZnIn 2S 4复合光催化剂。 In a clean container, dissolve 0.75mmol of ferric sulfate, 1mmol of zinc acetate, 3mmol of indium nitrate and 10mmol of thioacetamide in 75mL of dimethylacetamide to form a mixed solution, and then dissolve the mixed solution Transfer to a 100mL hydrothermal reaction kettle, control the hydrothermal reaction kettle in a sealed state, raise the temperature and control the temperature to react for 16 hours under the condition of 160°C, during the reaction process, since the hydrothermal reaction kettle is in a sealed state, as the temperature rises, When the reaction is carried out, the pressure of the system is positive, and the pressure of the system is also controlled at ≤0.3MPa during the reaction process. After natural cooling, high-speed centrifugation and water washing, the solid target product obtained is dried at 60°C to obtain α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst.

实施例5Example 5

在一洁净容器中，分别将1.2mmol的硫酸铁，1mmol的乙酸锌，4mmol的氯化铟以及9mmol的硫代乙酰胺溶解于75mL的二甲基乙酰胺中形成混合液，然后，再将混合液转移至100mL的水热反应釜，控制水热反应釜在密封状态下，升温控制温度于180℃ 的条件下进行反应8小时，反应过程中由于水热反应釜是密封状态，随着温度的升高和反应的进行，体系压力呈正压，且反应过程中还控制体系的压力在≤0.3MPa，待自然冷却后，经高速离心、水洗，得到的固体目标产物在60℃下干燥，即得α-Fe 2O 3/ZnIn 2S 4复合光催化剂。 In a clean container, dissolve 1.2mmol of ferric sulfate, 1mmol of zinc acetate, 4mmol of indium chloride and 9mmol of thioacetamide in 75mL of dimethylacetamide to form a mixed solution, and then mix the The liquid was transferred to a 100mL hydrothermal reaction kettle, and the hydrothermal reaction kettle was controlled to be in a sealed state, and the temperature was raised and the temperature was controlled at 180°C to react for 8 hours. During the reaction process, the hydrothermal reaction kettle was in a sealed state. During the rise and reaction, the pressure of the system is positive, and the pressure of the system is also controlled at ≤0.3MPa during the reaction process. After natural cooling, high-speed centrifugation and water washing, the solid target product obtained is dried at 60°C, namely The α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst was obtained.

实施例6Example 6

在一洁净容器中，分别将1.5mmol的硫酸铁，1mmol的氯化锌，3.5mmol的氯化铟以及10mmol的硫代乙酰胺溶解于70mL的二甲基乙酰胺中形成混合液，然后，再将混合液转移至100mL的水热反应釜，控制水热反应釜在密封状态下，升温控制温度于160℃的条件下进行反应18小时，反应过程中由于水热反应釜是密封状态，随着温度的升高和反应的进行，体系压力呈正压，且反应过程中还控制体系的压力在≤0.3MPa，待自然冷却后，经高速离心、水洗，得到的固体目标产物在60℃下干燥，即得α-Fe 2O 3/ZnIn 2S 4复合光催化剂。 In a clean container, dissolve 1.5mmol of ferric sulfate, 1mmol of zinc chloride, 3.5mmol of indium chloride and 10mmol of thioacetamide in 70mL of dimethylacetamide to form a mixed solution, and then Transfer the mixed solution to a 100mL hydrothermal reaction kettle, control the hydrothermal reaction kettle in a sealed state, raise the temperature and control the temperature to react for 18 hours under the condition of 160°C, during the reaction process, because the hydrothermal reaction kettle is in a sealed state, along with With the increase of temperature and the progress of the reaction, the pressure of the system is positive, and the pressure of the system is also controlled at ≤0.3MPa during the reaction process. After natural cooling, high-speed centrifugation and water washing, the solid target product obtained is dried at 60°C , that is, α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst.

本发明中所描述的具体实施例仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。The specific embodiments described in the present invention are only to illustrate the spirit of the present invention. Those skilled in the art to which the present invention belongs can make various modifications or supplements to the described specific embodiments or adopt similar methods to replace them, but they will not deviate from the spirit of the present invention or go beyond the definition of the appended claims range.

尽管对本发明已作出了详细的说明并引证了一些具体实施例，但是对本领域熟练技术人员来说，只要不离开本发明的精神和范围可作各种变化或修正是显然的。Although the present invention has been described in detail and some specific examples have been cited, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Claims (8)

一种Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法，其特征在于，该方法包括以下步骤： A method for preparing a Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst, characterized in that the method comprises the following steps: 在水热反应釜中，将铁源、锌源、铟源和硫源均加入能溶解原料的含氧原子的胺类溶剂中，再使水热反应釜在密封状态下，升温控制温度在120℃～180℃条件下进行高温反应，反应结束后，进行冷却和分离，得到相应的Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂。 In the hydrothermal reaction kettle, the iron source, zinc source, indium source and sulfur source are all added to the amine solvent containing oxygen atoms that can dissolve the raw materials, and then the hydrothermal reaction kettle is in a sealed state, and the temperature is raised to control the temperature at 120 Under the condition of ℃～180℃, high-temperature reaction is carried out, and after the reaction is completed, cooling and separation are carried out to obtain the corresponding Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst. 根据权利要求1所述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法，其特征在于，所述铁源：锌源：铟源：硫源的摩尔比为x：1：2～4：8～10，其中x的取值为0<x≤2。 According to the preparation method of the Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst of claim 1, it is characterized in that the molar ratio of the iron source: zinc source: indium source: sulfur source is x:1 : 2~4: 8~10, where the value of x is 0<x≤2. 根据权利要求2所述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法，其特征在于，所述x的取值为0.25≤x≤1.0。 The preparation method of the Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst according to claim 2, characterized in that the value of x is 0.25≤x≤1.0. 根据权利要求1所述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法，其特征在于，所述高温反应过程中，使水热反应釜的体系压力保持正压，且正压压力控制在≤0.3MPa。 According to the preparation method of the Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst of claim 1, it is characterized in that, in the process of the high temperature reaction, the system pressure of the hydrothermal reactor is maintained at a positive pressure, and The positive pressure is controlled at ≤0.3MPa. 根据权利要求1所述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法，其特征在于，所述铁源选自硫酸铁、氯化铁和硝酸铁中的一种或几种；所述锌源选自硝酸锌、氯化锌和乙酸锌中的一种或几种；所述铟源选自硝酸铟、硫酸铟和氯化铟中的一种或两种；所述硫代乙酰胺和/或硫脲。 According to the preparation method of Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst according to claim 1, it is characterized in that, the iron source is selected from one of ferric sulfate, ferric chloride and ferric nitrate or several; 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 both of indium nitrate, indium sulfate and indium chloride; the thioacetamide and/or thiourea. 根据权利要求1-5任意一项所述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法，其特征在于，所述含氧原子的胺类溶剂选自二甲基甲酰胺和/或二甲基乙酰胺。 According to the preparation method of the Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst according to any one of claims 1-5, it is characterized in that the amine solvent containing oxygen atoms is selected from dimethyl formaldehyde amide and/or dimethylacetamide. 根据权利要求1-5任意一项所述Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的制备方法，其特征在于，所述高温反应的温度为160℃～180℃。 The method for preparing Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst according to any one of claims 1-5, characterized in that the temperature of the high temperature reaction is 160°C-180°C. 一种Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂的应用，其特征在于，采用Z型α-Fe 2O 3/ZnIn 2S 4复合光催化剂降解头孢噻呋钠。 The application of a Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst is characterized in that the Z-type α-Fe 2 O 3 /ZnIn 2 S 4 composite photocatalyst is used to degrade ceftiofur sodium.
PCT/CN2022/083570 2021-12-17 2022-03-29 PREPARATION METHOD FOR Z-SCHEME α-FE2O3/ZNIN2S4 COMPOSITE PHOTOCATALYST AND USE THEREOF WO2023108950A1 (en)

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