WO2024216699A1 - 辐照催化电离脱毒系统及其用途和辐照催化电离脱毒方法 - Google Patents

辐照催化电离脱毒系统及其用途和辐照催化电离脱毒方法 Download PDF

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WO2024216699A1
WO2024216699A1 PCT/CN2023/095433 CN2023095433W WO2024216699A1 WO 2024216699 A1 WO2024216699 A1 WO 2024216699A1 CN 2023095433 W CN2023095433 W CN 2023095433W WO 2024216699 A1 WO2024216699 A1 WO 2024216699A1
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fewo
catalytic ionization
detoxification
ionization
active oxygen
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French (fr)
Inventor
杨庆利
马永超
刘萍
侯秀丹
朱英莲
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Qingdao Agricultural University
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Qingdao Agricultural University
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Definitions

  • the invention belongs to the technical field of radiation catalytic ionization equipment, and in particular relates to a radiation catalytic ionization detoxification system and a use thereof, and a radiation catalytic ionization detoxification method.
  • RCI Radiant catalytic ionization
  • ROS reactive oxygen species
  • Photocatalytic materials are crucial to radiation catalytic ionization technology. Different photocatalytic materials have different efficiencies in producing active oxygen. Currently, there are relatively few types of photocatalytic materials available, and the more common materials include TiO 2 , ZnO, and the like.
  • the present invention proposes a radiation catalytic ionization detoxification system, including a gas-liquid mixer for mixing air carrying active oxygen after radiation catalytic ionization with a liquid material to be detoxified and a reaction tube for circulating the mixed gas-liquid mixture.
  • the reaction tube includes several U-shaped tubes and connecting tubes for connecting the U-shaped tubes; the end of the straight tube section of the U-shaped tube is detachably connected to an air supply tube for filling the U-shaped tube with air carrying active oxygen after irradiation catalytic ionization; and several air supply holes are arranged on the wall of the air supply tube.
  • the air carrying active oxygen after irradiation catalytic ionization is provided by an irradiation catalytic ionization box;
  • the irradiation catalytic ionization box includes a box body, a plurality of mesh sheets arranged in the box body and a lamp tube for providing an irradiation light source;
  • the mesh is attached with a photocatalytic material that generates active oxygen after being irradiated with light.
  • a fixing frame for fixing the mesh and the lamp tube is also provided in the box;
  • the fixing frame is provided with fixing holes for fixing the lamp tube and fixing columns for fixing the mesh;
  • the mesh is provided with mounting holes for the lamp tube to pass through and fixing holes for the fixing columns to pass through.
  • the photocatalytic material is a FeWO 4 -rGO composite material.
  • the present invention also provides a method for preparing a FeWO 4 -rGO composite material. Specifically, the method comprises the following steps:
  • the molar ratio of Fe 3+ : ascorbic acid is: 5:0.2-5:1;
  • the above-mentioned irradiation catalytic ionization detoxification system can be used for water sterilization or edible oil aflatoxin removal.
  • the detoxification system of the present invention can be used for sterilizing water or removing aflatoxin from edible oil.
  • the irradiation catalytic ionization box in the system can provide the system with air containing active oxygen.
  • the use of a mesh with a photocatalytic material attached in the box not only increases the content of the photocatalytic material in the unit space, but also increases the area of illumination because the photocatalytic material is evenly attached to the surface of the mesh.
  • the system uses a U-tube as a reaction tube, and the length of the reaction tube can be freely designed according to the actual detoxification requirements. The installation is convenient and quick.
  • the system of the present invention uses an air supply pipe to continuously replenish new air carrying active oxygen after irradiation catalytic ionization.
  • the photocatalytic material- FeWO4 -rGO composite material used in the present invention has a simple material preparation method. Ascorbic acid used in the method can be used not only as a reducing agent, but also as a structure-directing agent to synthesize FeWO4 products. The surface charge is modified to construct FeWO4 -rGO nanoparticles with sufficient interface contact through electrostatic self-assembly. The composite photocatalyst provides a reasonable method.
  • the FeWO 4 -rGO composite material prepared by the method of the invention has strong photocatalytic performance.
  • FIG1 is a schematic diagram of the principle of the system described in Example 1;
  • FIG2 is a schematic diagram of the structure of the irradiation catalytic ionization box in the detoxification system of the present invention.
  • FIG3 is a schematic diagram of the structure of a mesh in a detoxification system of the present invention.
  • FIG4 is a schematic diagram of the structure of a reaction tube in a detoxification system of the present invention.
  • FIG5 is a schematic diagram of the structure of the air supply pipe in the detoxification system of the present invention and a partially enlarged schematic diagram;
  • FIG6 is a schematic diagram of the structure of a fixed frame in the detoxification system of the present invention.
  • FIG7 is an XRD pattern of the samples in Example 2, including (a) snowflake-shaped FeWO 4 , (b) FeWO 4 -rGO-U and (c) FeWO 4 -rGO;
  • FIG8 is the Raman spectra of the samples in Example 2, including (a) GO, (b) FeWO 4 and (c) FeWO 4 -rGO.
  • FIG9 is the UV-vis diffuse reflectance spectra of the samples in Example 2, including (a) FeWO 4 , (b) FeWO 4 -rGO-U and (c) FeWO 4 -rGO;
  • FIG10 is the N 2 adsorption and desorption isotherms of the samples in Example 2; wherein (a) snowflake-shaped FeWO 4 , (b) FeWO 4 -rGO-U and (c) FeWO 4 -rGO;
  • Figure 11 is the SEM and TEM images of the samples in Example 2; (a, b) SEM images of snowflake-shaped FeWO 4 , (c) FeWO 4 -rGO composite materials. (d) (e) HRTEM and (f) corresponding SAED of FeWO 4 -rGO composite materials;
  • FIG12 is a schematic reaction mechanism diagram of the photocatalytic redox reaction on the FeWO 4 -rGO composite photocatalyst under visible light irradiation;
  • Figure 13 is the SEM images of FeWO 4 generated under different temperature conditions; (a) 120°C, (b) 150°C, (c, d) 200°C;
  • Figure 14 shows the SEM images and XRD patterns of FeWO 4 generated under different time conditions; (a) 0h, (b) 2h, (c) 6h, (d) 9h and (e) 12h. (f) XRD patterns of the prepared samples after hydrothermal treatment at 180°C for different reaction times;
  • FIG15 is a schematic diagram of the L-ascorbic acid oxidation process
  • FIG16 is a schematic diagram of the formation of FeWO 4 having a snowflake-like structure
  • Figure 17 is a SEM image of FeWO 4 produced under different ascorbic acid dosage conditions, in which the molar ratio of Fe 3+ : ascorbic acid is different, including (a, b) 5:0.2, (c, d) 5:0.3 and (e, f) 5:1;
  • Figure 18 is a SEM image of FeWO 4 prepared from different raw materials, where (a, b) Fe(NO 3 ) 3 is used instead of FeCl 3 ; (c, d) 5 mmol FeCl 3 ⁇ 6H 2 O, 5 mmol Na 2 WO 4 ⁇ 2H 2 O, 0.5 mmol ascorbic acid and 0.1 mmol hexadecyltrimethylammonium bromide.
  • the present patent provides a radiation catalytic ionization detoxification system, which includes a gas-liquid mixer 1 for mixing air carrying active oxygen after radiation catalytic ionization with a liquid material to be detoxified and a reaction tube 4 for circulating the mixed gas-liquid mixture.
  • RCI Radiant catalytic ionization
  • ROS reactive oxygen species
  • photocatalytic materials can use gC3N4 and/or FeWO4 -rGO composite materials, TiO2 , Bi2WO6 , Upconversion nanoparticles@ TiO2 , Ag-AgCl/ ⁇ - Fe2O3 , etc.
  • the gas-liquid mixer 1 is a device for fully mixing gas and liquid. During the mixing process, the gas in the liquid is broken into small bubbles or micron or nanometer bubbles, thereby increasing the contact area between the gas and the liquid, and effectively improving the redox reaction between the active oxygen in the gas and the object to be treated in the liquid.
  • the liquid material to be detoxified can be edible oil contaminated with aflatoxin (it can also be zearalenone, vomitoxin, etc.), beverages, soy milk, milk, etc., or it can be sewage to be sterilized.
  • aflatoxin it can also be zearalenone, vomitoxin, etc.
  • beverages soy milk, milk, etc., or it can be sewage to be sterilized.
  • the detoxification system of the present invention performs detoxification in a manner that the photocatalytic material does not contact the liquid to be treated. Firstly, secondary contamination of the liquid by the photocatalytic material can be avoided. Secondly, the risk of quality reduction caused by direct exposure of the liquid to light can be avoided (for example, light can change the acid value, peroxide value, unsaturated fatty acids, etc. of peanut oil).
  • the active oxygen continuously performs redox reaction.
  • the oxidizing capacity of the gas gradually decreases.
  • the amount of active oxygen in the active oxygen-containing air filled into the liquid material is sufficient, there is no need to add new active oxygen into the reaction tube 4.
  • the active oxygen-containing air filled into the liquid material is not enough to treat the liquid material to be detoxified, based on the above technical solution, it is necessary to continuously fill the air carrying the active oxygen ionized by irradiation catalysis during the circulation of the gas-liquid mixture in the reaction tube 4.
  • the present invention provides a specific implementation case of a reaction tube 4, as shown in Figure 4,
  • the reaction tube 4 includes a plurality of U-shaped tubes 4-1 and connecting tubes 4-2 for connecting the U-shaped tubes 4-1; the connecting tubes 4-2 can be connected between the U-shaped tubes 4-1 by threaded connection.
  • This method can freely design the length of the reaction tube according to the actual detoxification requirements, and the installation is convenient and quick.
  • the present invention designs the end of the straight tube section of the U-shaped tube 4-1 as an open structure that can be opened or closed at any time.
  • the opening When it is necessary to supplement the active oxygen gas, the opening is opened, and the air supply pipe 4-3 is inserted into the straight tube section from the opening, and the air carrying active oxygen after catalytic ionization by radiation is filled into the U-shaped tube 4-1 by the air supply pipe 4-3; the air supply pipe 4-3 is detachably connected to the end of the straight tube section of the U-shaped tube 4-1; when air supply is not needed, the end of the straight tube section of the U-shaped tube 4-1 is sealed with an end plug (not shown in the figure).
  • a plurality of air supply holes 4-31 are provided on the wall of the air supply pipe 4-3.
  • a plurality of fins 4-32 are provided on the gas supply pipe 4-3.
  • the provision of the plurality of fins 4-32 can not only break the newly added gas into small bubbles, but also effectively improve the mixing degree of the gas and the liquid.
  • the amount of active oxygen carried in the air is crucial to the detoxification effect.
  • the present invention provides a specific implementation case.
  • the air carrying active oxygen after irradiation catalytic ionization is provided by an irradiation catalytic ionization box 2;
  • the irradiation catalytic ionization box 2 includes a box body 2-1, a plurality of mesh sheets 2-2 arranged in the box body 2-1, and a lamp tube 2-3 for providing an irradiation light source; a photocatalytic material that generates active oxygen after light irradiation is attached to the mesh sheets 2-2.
  • the several meshes 2-2 with photocatalytic materials attached thereto can stimulate more active oxygen under the irradiation of the lamp tube 2-3.
  • the box body 2-1 is open at both ends, one end for air intake and the other end for air exhaust.
  • the active oxygen is driven by a fan (not shown in the figure) from the box body 2 to enter the gas-liquid mixer 1 to mix with the liquid material to be treated.
  • the mesh 2-2 can be made of a light-transmitting material, and the surface of the mesh 2-2 is attached with a photocatalytic material.
  • the irradiated catalytic ionization box 2 of the present invention uses a mesh 2-2 with photocatalytic materials attached thereto, instead of arranging the photocatalytic materials on a flat plate.
  • This not only increases the content of the photocatalytic materials in the unit space, but also increases the photocatalytic materials.
  • the mesh 2-2 is uniformly attached to the surface of the mesh, and the area of illumination is increased.
  • the mesh structure of the mesh 2-2 is more loaded with photocatalytic materials, while meeting the needs of gas circulation, facilitating the circulation of air through the mesh and taking away the active oxygen generated by the irradiation of the photocatalytic material on the mesh, thereby providing sufficient active oxygen for the system.
  • the mesh 2-2 uses a light-transmitting acrylic plate, PC or PVC hard plate with air holes, on which the photocatalytic material is attached.
  • a fixing frame 2-4 for fixing the mesh 2-2 and the lamp 2-3 is also provided in the box 2-1;
  • the fixing frame 2-4 is provided with fixing holes 2-41 for fixing the lamp 2-3 and fixing posts 2-42 for fixing the mesh 2-2;
  • the mesh 2-2 is provided with mounting holes 2-21 for the lamp 2-3 to pass through and fixing holes 2-22 for the fixing posts 2-42 to pass through.
  • the mesh 2-2, the lamp 2-3 and the fixing frame 2-4 can be assembled outside the box 2-1 in advance, and after assembly, they can be inserted into the box 2-1, and the fixing frame 2-4 can be fixed in the box 2-1 (the four legs of the fixing frame 2-4 are fixed to the inner wall of the box 2-1).
  • FIG3 only shows one implementation of the position and number of the mounting hole 2-21 and the fixing hole 2-22. When in use, the position and number of the mounting hole 2-21 and the fixing hole 2-22 can be freely set as needed.
  • the structure of the fixing frame 2-4 is shown in Figure 6. Because the box 2-1 is ventilated when in use, in order to increase the stability of the mesh 2-2 and the lamp tube 2-3, as shown in Figure 2, a fixing frame is added on the other side of the mesh (the left side in the figure). The fixing column is replaced by a circular hole in the middle of this fixing frame. The circular hole is used for inserting the fixing column 2-42, which will not be repeated here.
  • lamp tube 2-3 is not particularly limited, as long as it can irradiate the catalytic semiconductor material to produce active oxygen, such as an ordinary fluorescent lamp tube or a lamp tube that produces light of a special wavelength, such as a 300-watt xenon lamp and an optical cutoff filter used in Example 3.
  • this example provides a photocatalytic material that can be used in the system - FeWO 4 -rGO composite material
  • the FeWO 4 -rGO composite material is prepared by the following method:
  • FeWO 4 -rGO-U FeWO 4 -rGO-U is a mixture of FeWO 4 and rGO directly ground and mixed
  • FeWO 4 -rGO prepared by the above method were tested for comparison.
  • the optical properties of the material can be characterized by UV-vis DRS spectroscopy, and the snowflake-shaped FeWO 4 shows strong absorption in the visible light region.
  • the absorption of visible light in the region between 500 and 800 nm is enhanced.
  • the expansion of the light absorption range can achieve more efficient use of the solar spectrum and enhanced photocatalytic activity.
  • the background absorption of the FeWO 4 -rGO composite material in the visible light region is significantly enhanced.
  • the N 2 adsorption-desorption isotherms of the prepared products are shown in Fig. 10.
  • the specific surface areas of FeWO 4 -rGO, FeWO 4 -rGO-U and pure snowflake-like FeWO 4 are 49.18, 47.03 and 45.80 cm 3 g -1 , respectively, with no significant difference in the values.
  • FIG 11 (d) The TEM of the FeWO 4 -rGO composite is shown in Figure 11 (d).
  • the FeWO 4 assembly is deposited on the surface of the rGO sheet.
  • the sample shows some wrinkles at the edges of both the rGO sheet and the interlayer sheet, providing more adsorption active sites.
  • Figure 11 (e) shows clear lattice fringes with a spacing of 0.22 nm, which corresponds to the (020) plane of FeWO 4 .
  • SAED selected area electron diffraction
  • surface charge modification provides a reasonable method for constructing FeWO 4 -rGO nanocomposite photocatalysts with sufficient interfacial contacts via electrostatic self-assembly compared with FeWO 4 -GO-U composites. All of the above factors contribute to improving the separation efficiency of electron-hole pairs, thereby significantly improving the photoactivity of FeWO 4 -rGO composites.
  • Figure 13 shows the effect of temperature on the morphology of FeWO 4 samples. Irregular shapes were observed at 120°C ( Figure 13 (a)). After the temperature was increased to 150°C, although the morphology of the product was similar to that of the sample hydrothermally treated at 120°C, the average size of the product was smaller. When the temperature was increased to 180°C ( Figure 11 (a) and (b)), the prepared sample consisted of snowflakes with perfect uniformity. When the temperature was 200°C, although the sample maintained a snowflake-like structure, the surface of the nanorods became smoother ( Figure 13 (c) and (d)). This result also shows that the final morphology depends on the formation temperature of the FeWO 4 crystals.
  • Figure 14 (e) shows the XRD patterns of FeWO 4 samples prepared at different hydrothermal times. The crystalline phase is enhanced with increasing hydrothermal time. All XRD patterns can be easily identified as FeWO 4 .
  • the shape evolution process of the snowflake-like microstructure is shown in Figures 15 and 16.
  • DHA and DGA strongly prefer to coordinate with Fe 2+ cations and form complexes. Therefore, the concentration of free Fe 2+ cations decreases.
  • the slow formation rate of FeWO 4 will lead to the separation of nucleation and growth steps.
  • WO 4 2- reacts with the complex to form FeWO 4 nuclei.
  • DHA and DGA in the reaction system are absorbed by the surface of FeWO 4 nuclei.
  • the FeWO 4 nuclei tend to aggregate.
  • the nanoparticles prefer to grow into nanorods by directional attachment. With the extension of the hydrothermal treatment time, the snowflake-like microstructure is formed.
  • the formation of hierarchical snowflake-like microstructure is the result of ascorbic acid-induced reduction, formation and aggregation of nanoparticles, followed by the growth of nanorods and their subsequent self-assembly.
  • FeWO4 has amine functional groups. Under the action of electrostatic attraction, FeWO4 is anchored on the surface of negatively charged rGO nanosheets.
  • Figure 17 shows the SEM images of samples prepared in the presence of different amounts of ascorbic acid (0.2 to 1 mmol) in the reaction system.
  • ascorbic acid was added, disordered tiny particles were the main products ( Figure 17 (a) (b)).
  • Figure 17 (c) (d) After increasing the amount of ascorbic acid (0.3 mmol), some particle aggregates were formed ( Figure 17 (c) (d)).
  • Figure 11 (a) (b) the prepared sample consisted of snowflakes with perfect uniformity and monodispersity
  • Aflatoxin (AFB 1 ) degradation test the steps are as follows:
  • Example 2 500 mg of the flower-like FeWO 4 -rGO composite material prepared in Example 2 was coated on a glass substrate, and then added to 100 mL of corn oil containing AFB 1 (concentration 16.8 ppb) and magnetically stirred at 500 rpm. Then it was placed in the dark and stirred for 30 min to reach adsorption-desorption equilibrium. A 300-watt xenon lamp was used to irradiate the suspension. 5 mL of corn oil was collected at 0 min, 15 min, 30 min, 45 min, 60 min, and 75 min irradiation times. The concentration of AFB1 in peanut oil was tested by liquid chromatography, and the results are shown in Table 1. The control group was the snowflake-like FeWO 4 and FeWO 4 -rGO-U prepared in the comparative example.
  • AFB 1 concentration 16.8 ppb
  • N0 and Nt in the formula are the number of colonies counted on the control group and sample plates respectively.
  • the snowflake-shaped FeWO 4 -rGO prepared in the present application has excellent photocatalytic killing performance against Escherichia coli.

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Abstract

本发明公开了一种辐照催化电离脱毒系统，包括用于将携带辐照催化电离后的活性氧的空气与待脱毒处理的液体物料进行气液混合的气液混合器和用于混合后的气液混合物流通的反应管。本发明的脱毒系统可以用于水体除菌或食用油除黄曲霉毒素，系统中的辐照催化电离箱可以为系统提供含活性氧的空气，箱体中使用附着有光催化材料的网片，不但增大了单位空间内光催化材料的含量，而且由于光催化材料均匀的附着在网片的表面，增大了光照的面积。系统中使用U型管作为反应管，可以根据实际的脱毒要求，自由的设计反应管的长度，安装方便、快捷，为了系统的脱毒效率，本发明的系统使用补气管不断补充新的携带辐照催化电离后的活性氧的空气。

Description

辐照催化电离脱毒系统及其用途和辐照催化电离脱毒方法 技术领域
本发明属于辐照催化电离设备技术领域，具体涉及一种辐照催化电离脱毒系统及其用途和辐照催化电离脱毒方法。
背景技术
辐照催化电离后的活性氧是通过辐照催化电离技术获得的，辐照催化电离(Radiant Catalytic Ionization，RCI)是一种新兴杀菌脱毒技术，可在有人、动物和植物的环境中无限制地使用，因为它不会产生潜在的危险副产品，如臭氧、甲醛或一氧化碳等。该技术的核心是光催化效应，即借助光催化材料吸收光能产生电子(e–)和空穴(h+)对，转化为强氧化能力的活性氧(Reactive oxygen species，ROS)，参与有机物的氧化还原反应。现有技术中使用该技术进行脱毒、杀菌时，均是在实验室条件下进行，实验时，液体需要直接接触光催化材料，这就带来了一定的食品安全风险。同时，目前还没有合适的设备来完成生产条件下的大量的液体物料的脱毒、杀菌等处理。
光催化材料对辐照催化电离技术来说至关重要，不同的光催化材料产生活性氧的效率不相同，目前，可用的光催化材料种类也比较少，比较常规的材料有TiO2、ZnO等。
发明内容
针对现有技术中存在的问题，本发明提出一种辐照催化电离脱毒系统，包括用于将携带辐照催化电离后的活性氧的空气与待脱毒处理的液体物料进行气液混合的气液混合器和用于混合后的气液混合物流通的反应管。
在上述方案的基础上，所述反应管包括若干个U型管和用于连接U型管的连接管；所述U型管的直管段的端部可拆卸连接有用于向U型管充入携带辐照催化电离后的活性氧的空气的补气管；所述补气管的壁上设置有若干个补气孔。
在上述方案的基础上，所述补气管上还设置有若干个翅片。
在上述方案的基础上，所述携带辐照催化电离后的活性氧的空气由辐照催化电离箱提供；所述辐照催化电离箱包括箱体、设置于箱体内的若干个网片和用于提供辐照光源的灯管；所 述网片上附着有光辐照后产生活性氧的光催化材料。
在上述方案的基础上，所述箱体内还设置有用于固定网片和灯管的固定架；所述固定架上设置用于固定灯管的固定孔和用于固定网片的固定柱；所述网片上设置有用于灯管穿过的安装孔和用于固定柱穿过的固定孔。
在上述方案的基础上，所述光催化材料为FeWO4-rGO复合材料。
本发明还提供了一种制备FeWO4-rGO复合材料的方法，具体的，方法包含如下步骤：
(1)FeWO4的制备
首先将5mmol FeCl3·6H2O和5mmol Na2WO4·2H2O分别溶解在25mL蒸馏水中。然后，在连续搅拌下向FeCl3溶液中加入抗坏血酸以完全溶解。接着，将Na2WO4溶液缓慢加入上述混合物中。进一步搅拌30min后，将混合物加入100mL高压釜中(高压釜只作为反应容器)，并在150-200℃下保持9h以上。然后将高压釜自然冷却至室温。通过离心收集所得沉淀物，用蒸馏水和无水乙醇洗涤数次，并在80℃空气中干燥6h。
其中：Fe3+：抗坏血酸的摩尔比为：5:0.2-5:1；
(2)FeWO4-rGO复合材料的制备
首先将2g FeWO4加入300mL乙醇中并超声(超声条件300W)处理30min。将2mL APTES加入FeWO4悬浮液中后，将混合物在70℃下加热4h。随后，收集粉末，用乙醇洗涤数次，然后在80℃下干燥过夜。之后，将1g APTES改性FeWO4加入60mL蒸馏水中并超声(超声条件300W)处理15min，然后加入0.05g rGO。搅拌60min后，将所得悬浮液转移到高压釜中，并在180℃下保持12h。收集所得产物，用水洗涤并在80℃下干燥过夜，得到FeWO4-rGO。
上述的辐照催化电离脱毒系统可以用于水体除菌或食用油除黄曲霉毒素。
本发明还提供一种辐照催化电离脱毒方法，使用上述的系统，包括辐照催化电离得到活性氧的步骤、将携带辐照催化电离后的活性氧的空气与待脱毒处理的液体物料进行气液混合的步骤和活性氧对液体物料中的菌或黄曲霉毒素进行脱毒的步骤。
本发明的脱毒系统可以用于水体除菌或食用油除黄曲霉毒素，系统中的辐照催化电离箱可以为系统提供含活性氧的空气，箱体中使用附着有光催化材料的网片，不但增大了单位空间内光催化材料的含量，而且由于光催化材料均匀的附着在网片的表面，增大了光照的面积。系统中使用U型管作为反应管，可以根据实际的脱毒要求，自由的设计反应管的长度，安装方便、快捷，为了系统的脱毒效率，本发明的系统使用补气管不断补充新的携带辐照催化电离后的活性氧的空气。同时，本发明的同中使用的光催化材料-FeWO4-rGO复合材料，材料的制备方法简单，方法中使用抗坏血酸不仅可以作为还原剂，而且可以作为结构导向剂来合成FeWO4产物，表面电荷修饰为通过静电自组装构建具有足够界面接触的FeWO4-rGO纳米 复合光催化剂提供了一种合理的方法。本发明方法制备的FeWO4-rGO复合材料的光催化性能强。
附图说明
图1为实施例1中所述的系统的原理示意图；
图2为本发明脱毒系统中辐照催化电离箱的结构示意图；
图3为本发明脱毒系统中网片的结构示意图；
图4为本发明脱毒系统中反应管的结构示意图；
图5为本发明脱毒系统中补气管的结构示意图及局部放大示意图；
图6为本发明脱毒系统中固定架的结构示意图；
图7为实施例2中样品的XRD图谱，其中(a)雪花状FeWO4、(b)FeWO4-rGO-U和(c)FeWO4-rGO；
图8为实施例2中样品的拉曼光谱，其中(a)GO、(b)FeWO4和(c)FeWO4-rGO。
图9为实施例2中样品的UV-vis漫反射光谱，其中(a)FeWO4、(b)FeWO4-rGO-U和(c)FeWO4-rGO；
图10为实施例2中样品的N2吸附和解吸等温线；其中(a)雪花状FeWO4，(b)FeWO4-rGO-U和(c)FeWO4-rGO；
图11为实施例2中样品的扫描电镜和透视电镜图；(a，b)雪花状FeWO4，(c)FeWO4-rGO复合材料的SEM图像。(d)(e)HRTEM和(f)FeWO4-rGO复合材料的相应SAED；
图12为可见光照射下FeWO4-rGO复合光催化剂上的光催化氧化还原反应的示意反应机理图；
图13为不同温度条件下生成的FeWO4的SEM图；其中(a)120℃，(b)150℃，(c，d)200℃；
图14为不同时间条件下生成的FeWO4的SEM图和XRD图；(a)0h，(b)2h，(c)6h，(d)9h和(e)12h。(f)制备的样品在180℃水热处理不同反应时间后的XRD图谱；
图15为L-抗坏血酸氧化过程示意图；
图16为具有雪花状结构的FeWO4的形成示意图；
图17为不同抗坏血酸用量条件下生成的FeWO4的SEM图，图中：Fe3+：抗坏血酸的摩尔比不同，其中(a，b)5:0.2，(c，d)5:0.3和(e，f)5:1；
图18为不同原料制备的FeWO4的SEM图，其中(a，b)使用Fe(NO3)3代替FeCl3； (c、d)5mmol FeCl3·6H2O、5mmol Na2WO4·2H2O、0.5mmol抗坏血酸和0.1mmol的十六烷基三甲基溴化铵。
具体实施方式
在本发明中所使用的术语，除非有另外说明，一般具有本领域普通技术人员通常理解的含义。
下面结合具体实施例，并参照数据进一步详细的描述本发明。以下实施例只是为了举例说明本发明，而非以任何方式限制本发明的范围。
实施例1
如图1所示，本专利提供一种辐照催化电离脱毒系统，该系统包括用于将携带辐照催化电离后的活性氧的空气与待脱毒处理的液体物料进行气液混合的气液混合器1和用于混合后的气液混合物流通的反应管4。
辐照催化电离后的活性氧是通过辐照催化电离技术获得的，辐照催化电离(Radiant Catalytic Ionization，RCI)是一种新兴杀菌脱毒技术，可在有人、动物和植物的环境中无限制地使用，因为它不会产生潜在的危险副产品，如臭氧、甲醛或一氧化碳等。该技术的核心是光催化效应，即借助光催化材料吸收光能产生电子(e–)和空穴(h+)对，转化为强氧化能力的活性氧(Reactive oxygen species，ROS)，参与有机物的氧化还原反应。光催化材料目前已经有很多，比如：光催化材料可以使用g-C3N4和/或FeWO4-rGO复合材料，还可以使用TiO2、Bi2WO6、Upconversion nanoparticles@TiO2、Ag-AgCl/α-Fe2O3等。
气液混合器1是用于将气体和液体进行充分混合的装置，混合过程中将气体在液体中破碎成小气泡或者微米、纳米类型的气泡，从而增大了气体与液体的接触面积，有效的提高气体中活性氧与液体中的待处理物进行充分的氧化还原反应。
待脱毒处理的液体物料可以是黄曲霉毒素污染的食用油(还可以是玉米赤霉烯酮、呕吐毒素等)、饮料、豆浆、牛奶等，也可以是待杀菌的污水。
本发明的脱毒系统采用光催化材料与待处理液体不接触的方式来进行脱毒处理，首先可以避免光催化材料对液体的二次污染，其次可以避免液体直接被光线照射后引起的品质降低风险(比如光照会改变花生油的酸价、过氧化值、不饱和脂肪酸等)。
携带活性氧的空气与待脱毒处理的液体物料在反应管4内流通的过程中由活性氧不断发挥氧化还原反应，但是随着空气中活性氧的不断消耗，气体的氧化能力逐渐降低，为了解决 这一问题，需要在气液混合物在反应管4内流通的过程中不断充入携带辐照催化电离后的活性氧的空气，进而达到快速处理的效果。当液体物料中充入的含活性氧空气中活性氧的量够的情况下，无需在反应管4中再加入新的活性氧，但是如果当液体物料中充入的含活性氧空气不足以处理待脱毒处理的液体物料时，基于上述的技术方案，需要在气液混合物在反应管4内流通的过程中不断充入携带辐照催化电离后的活性氧的空气。
作为一个具体的实施方案，本发明提供一个反应管4的具体实施案例，如图4所示，所述反应管4包括若干个U型管4-1和用于连接U型管4-1的连接管4-2；连接管4-2可以通过螺纹连接的方式连接在U型管4-1之间，这种方式可以根据实际的脱毒要求，自由的设计反应管的长度，安装方便、快捷。
混合物料在反应管4中流通的过程中，空气中活性氧的不断消耗，气体的氧化能力逐渐降低，因此，为了提高脱毒效率，需要保持混合物料中活性氧的含量，为此，需要不断补充新的携带辐照催化电离后的活性氧的空气。作为一个具体的实施方案，如图4所示，本发明将U型管4-1的直管段的端部设计为可以随时打开或者关闭的开口结构，当需要补充活性氧气体时，打开开口，从开口处向直管段内插入补气管4-3，由补气管4-3向U型管4-1充入携带辐照催化电离后的活性氧的空气；补气管4-3与U型管4-1的直管段的端部可拆卸连接；当不需要补气时，U型管4-1的直管段的端部用封端堵头(图中不再示出)封堵即可。所述补气管4-3的壁上设置有若干个补气孔4-31。
为了提高新补入的气体与液体之间的混合程度，如图5所示，在所述补气管4-3上设置有若干个翅片4-32。若干个翅片4-32的设置不但可以将新补入的气体打碎成小气泡，同时，还可以有效提高气体与液体的混合程度。
对于本发明的脱毒系统来说，空气中携带的活性氧的多少对脱毒效果至关重要，为了提高空气中携带的活性氧的浓度，本发明提供一个具体的实施案例，如图2所示，所述携带辐照催化电离后的活性氧的空气由辐照催化电离箱2提供；所述辐照催化电离箱2包括箱体2-1、设置于箱体2-1内的若干个网片2-2和用于提供辐照光源的灯管2-3；所述网片2-2上附着有光辐照后产生活性氧的光催化材料。
本发明的辐照催化电离箱2内设置的若干个附着有光催化材料的网片2-2在灯管2-3的照射下，可以激发出更多的活性氧，箱体2-1两端开口，一端进气、一端出气，活性氧由风机(图中不再示出)带动从箱体2进入到气液混合器1内与待处理液体物料进行混合。具体的，网片2-2可以使用透光材料的网片，网片2-2的表面附着上光催化材料。与现有的催化电离设备相比，本发明的辐照催化电离箱2使用附着有光催化材料的网片2-2，而不是将光催化材料设置在平板上，这样不但增大了单位空间内光催化材料的含量，而且由于光催化材料 均匀的附着在网片的表面，同时增大了光照的面积。同时，网片2-2的网状结构在满足气体流通的需要，便于流通的空气从网片上穿过并带走网片上的光催化材料被辐照产生的活性氧的前提下，更多的负载了光催化材料，从而为系统提供足够的活性氧。作为一个具体的实施案例，所述的网片2-2使用布设有透气孔的透光亚克力板、PC或PVC硬质板，在上面附着有光催化材料。
作为一个具体的应用方案，如图2所示，所述箱体2-1内还设置有用于固定网片2-2和灯管2-3的固定架2-4；所述固定架2-4上设置用于固定灯管2-3的固定孔2-41和用于固定网片2-2的固定柱2-42；如图3所示，所述网片2-2上设置有用于灯管2-3穿过的安装孔2-21和用于固定柱2-42穿过的固定孔2-22。通过这种方式，可以提前在箱体2-1外将网片2-2、灯管2-3和固定架2-4进行组装，组装后插入到箱体2-1内，并将固定架2-4固定在箱体2-1内(固定架2-4的四个脚与箱体2-1的内壁固定)。图3中仅给出了一个安装孔2-21和固定孔2-22位置和数量的一个实施方式，使用时，可以根据需要自由设置安装孔2-21和固定孔2-22位置和数量。
固定架2-4的结构如图6所示，因为箱体2-1内在使用时是通风的，为了增加网片2-2和灯管2-3的稳定性，如图2所示，在如干个网片的另一侧(图中的左侧)增加一个固定架，这个固定架中间由圆孔代替固定柱，圆孔用于固定柱2-42插入，在此不再赘述。
灯管2-3的具体类型不进行特别的限定，只要能够辐照催化半导体材料产生活性氧即可，比如普通的日光灯管或者产生特殊波长光的灯管，比如在实施例3中使用了300瓦氙灯及光学截止滤光器。
使用时，打开辐照催化电离箱2内的灯管2-3进行辐照催化，使用泵将料液箱3内的待处理物料泵入气液混合器1内，同时，使用风机将辐照催化电离箱2产生的活性氧充入到气液混合器1内与液体物料进行混合，混合后的物料由泵泵入反应管4内进行脱毒。在反应管4内，气体的氧化能力逐渐降低，因此，为了提高脱毒效率，使用补气管4-3向反应管4内进行补气。
实施例2
基于实施例1中的脱毒系统，本实施例提供一种可用于系统的光催化材料-FeWO4-rGO复合材料，所述FeWO4-rGO复合材料由以下方法制备而成：
(1)FeWO4的制备
首先将5mmol FeCl3·6H2O和5mmol Na2WO4·2H2O分别溶解在25mL蒸馏水中。然后，在连续搅拌下向FeCl3溶液中加入0.5mmol抗坏血酸以完全溶解。接着，将Na2WO4溶液缓慢加入上述混合物中。进一步搅拌30min后，将混合物加入100mL高压釜中(本实施例中 的高压釜只作为反应容器)，并在180℃下保持12h。然后将高压釜自然冷却至室温。通过离心收集所得沉淀物，用蒸馏水和无水乙醇洗涤数次，并在80℃空气中干燥6h。
(2)FeWO4-rGO复合材料的制备
首先将2g FeWO4加入300mL乙醇中并超声(超声条件300W)处理30min。将2mL APTES加入FeWO4悬浮液中后，将混合物在70℃下加热4h。随后，收集粉末，用乙醇洗涤数次，然后在80℃下干燥过夜。之后，将1g APTES改性FeWO4加入60mL蒸馏水中并超声(超声条件300W)处理15min，然后加入0.05g rGO。搅拌60min后，将所得悬浮液转移到高压釜中，并在180℃下保持12h。收集所得产物，用水洗涤并在80℃下干燥过夜，得到FeWO4-rGO。
实施例3
为了对比电荷改性方法的优越性，分别对步骤(1)制备的雪花状FeWO4、FeWO4-rGO-U(FeWO4-rGO-U为直接将FeWO4与rGO研磨混合后的混合物)和上述方法制备的FeWO4-rGO进行对比测试。
(1)XRD测试
结果如图7所示。所有产物衍射峰都可以归纳到FeWO4的标准卡片(JCPDS No.46-1446)。此外，没有观察到rGO的衍射峰。
(2)拉曼光谱测试
结果如图8所示，通过拉曼分析进一步确定复合物中含有rGO。如图8中(a)所示，在1596和1346cm-1附近观察到两个主峰，这应该归因于GO的G带和D带。如图8中(b)所示，93，132，215，179，349，683和875cm-1处的峰对应于FeWO4的拉曼光谱。对于FeWO4-rGO复合材料，除了归属于FeWO4的峰外，rGO的G带和D带分别位于1598和1345cm-1处。这清楚地表明在制备的rGO-FeWO4复合材料中存在rGO。
(3)UV-vis漫反射
结果如图9所示，材料的光学性质可以通过UV-vis DRS光谱进行表征，雪花状FeWO4在可见光区域显示出较强的吸收。通过添加rGO，可以清楚地观察到在500和800nm之间的区域中可见光的吸收增强。光吸收范围的扩展可以实现对太阳光谱的更有效利用和增强的光催化活性。此外，FeWO4-rGO复合材料在可见光区域的背景吸收显著增强。
(4)N2吸附和解吸
制备的产物的N2吸附-解吸等温线如图10所示。FeWO4-rGO、FeWO4-rGO-U和纯雪花状FeWO4的比表面积分别为49.18、47.03和45.80cm3g-1，数值无明显差别。
(5)SEM和TEM测试
结果如图11所示，用SEM和TEM研究了雪花状FeWO4和FeWO4-rGO复合材料的形貌和结构。如图11中(a)所示，FeWO4由直径约为1μm的均匀雪花状微晶组成。高倍SEM显示，每个具有近似六重对称性的雪花状FeWO4由在特定方向上组装的纳米棒组成(图11中b)。至于FeWO4-rGO复合材料(图11中c-d)，FeWO4被rGO纳米片包裹，这意味着FeWO4和rGO之间有可能充分接触和有效的界面相互作用。FeWO4-rGO复合材料的TEM如图11中(d)所示。FeWO4组件沉积在rGO片的表面上。样品在rGO片和夹层片的边缘都显示出一些褶皱，提供了更多的吸附活性位点。图11中(e)显示了间距为0.22nm的明确的晶格条纹，其对应于FeWO4的(020)平面。此外，选区电子衍射(SAED)显示出明确的环，这证实了样品具有多晶性质。
如图12所示，在可见光照射下，价带(VB)中的电子被激发到导带(CB)，在VB中留下空穴，并在FeWO4中产生电子-空穴对。然后，光生电子(e-)从FeWO4微结构转移到rGO片上，并进一步与O2反应产生高活性的自由基(O2·-)。FeWO4的VB中的空穴与水反应形成活性OH·。这些自由基能够攻击真菌毒素，通过光催化氧化还原反应消减真菌毒素。另一方面，与FeWO4-GO-U复合材料相比，表面电荷修饰为通过静电自组装构建具有足够界面接触的FeWO4-rGO纳米复合光催化剂提供了一种合理的方法。上述所有因素都有助于提高电子-空穴对的分离效率，从而显著提高FeWO4-rGO复合材料的光活性。
不同温度条件下，生成的FeWO4的形态变化
首先将5mmol FeCl3·6H2O和5mmol Na2WO4·2H2O分别溶解在25mL蒸馏水中。然后，在连续搅拌下向FeCl3溶液中加入0.5mmol抗坏血酸以完全溶解。接着，将Na2WO4溶液缓慢加入上述混合物中。进一步搅拌30min后，将混合物加入100mL高压釜中，并在一定温度下下保持12h。然后将高压釜自然冷却至室温。通过离心收集所得沉淀物，用蒸馏水和无水乙醇洗涤数次，并在80℃空气中干燥6h。
结果如图13所示，图13显示出温度对FeWO4样品形貌的影响。在120℃下观察到不规则形状(图13中(a))。温度升高到150℃后，尽管产物的形态与120℃水热处理的样品相似，但产物的平均尺寸更小。当温度升高到180℃时(图11中(a)和(b))，所制备的样品由具有完美均匀性的雪花组成。当温度为200℃时，尽管样品保持雪花状结构，但纳米棒的表面变得更光滑(图13中(c)和(d))。这一结果还表明，最终形态取决于FeWO4晶体的形成温度。
不同时间条件下，生成的FeWO4的形态变化
首先将5mmol FeCl3·6H2O和5mmol Na2WO4·2H2O分别溶解在25mL蒸馏水中。然后，在连续搅拌下向FeCl3溶液中加入0.5mmol抗坏血酸以完全溶解。接着，将Na2WO4溶液缓 慢加入上述混合物中。进一步搅拌30min后，将混合物加入100mL高压釜中，并在180℃下保持一定时间。然后将高压釜自然冷却至室温。通过离心收集所得沉淀物，用蒸馏水和无水乙醇洗涤数次，并在80℃空气中干燥6h。
为了理解雪花状FeWO4的生长机制，在不同水热时间制备材料的SEM如图14所示。当反应时间低于2h，产物由大的卵形颗粒组成(图14中(a)和(b))。图14中(c)显示了样品反应6h的图像，表明形成了板状聚集体。这些聚集体是由许多纳米颗粒和纳米棒形成的。随着这一过程的继续，9h后出现雪花状的FeWO4结构，显示出六边形对称性(图14中(d))。应该注意的是，纳米棒以自组装的形式从聚集体的中心向外延伸。随着反应的继续，不规则颗粒消失，形成了更长的纳米棒，这表明更长的纳米棒是以较小颗粒为代价生长的。12h后，FeWO4雪花表面的纳米颗粒沿其轴线生长，形成纳米棒(图14中(e))。这些图像清楚地展示了所获得的产品从纳米颗粒构建的聚集体到雪花状结构的形状演变过程。图14中(f)显示了在不同水热时间下制备的FeWO4样品的XRD图谱。结晶相随着水热时间的增加而增强。所有XRD图谱都可以很容易地鉴定为FeWO4。
基于上述分析，雪花状微观结构的形状演变过程如图15和16所示。在这个过程中，DHA和DGA中的含氧基团(如-OH和C＝O)强烈倾向于与Fe2+阳离子配位并形成络合物。因此，游离Fe2+阳离子的浓度降低。FeWO4的缓慢形成速率将导致成核和生长步骤的分离。然后WO4 2-与配合物反应形成FeWO4核。反应体系中的DHA和DGA被FeWO4核表面吸收。同时，由于晶核表面能的降低以及DHA和DGA之间的氢相互作用，FeWO4晶核倾向于聚集。此外，由于FeWO4的高本征各向异性性质，纳米颗粒更喜欢通过定向附着生长成纳米棒。随着水热处理时间的延长，形成了雪花状的微观结构。我们可以得出结论，分级雪花状微结构的形成是抗坏血酸诱导的纳米颗粒的还原、形成和聚集，然后是纳米棒的生长及其随后的自组装的结果。根据已报道的文献，经APTES修饰后，FeWO4具有胺官能团。在静电吸引的作用下，FeWO4锚定在带负电荷的rGO纳米片表面。
不同量的抗坏血酸对产物形貌的影响
首先将5mmol FeCl3·6H2O和5mmol Na2WO4·2H2O分别溶解在25mL蒸馏水中。然后，在连续搅拌下向FeCl3溶液中加入一定量的抗坏血酸以完全溶解。接着，将Na2WO4溶液缓慢加入上述混合物中。进一步搅拌30min后，将混合物加入100mL高压釜中，并在180℃下保持12h。然后将高压釜自然冷却至室温。通过离心收集所得沉淀物，用蒸馏水和无水乙醇洗涤数次，并在80℃空气中干燥6h。
研究不同量的抗坏血酸对产物形貌的影响，结果如图17所示。图17显示了在反应体系中存在不同量的抗坏血酸(0.2至1mmol)的情况下制备的样品的SEM图像。当加入0.2mmol 抗坏血酸时，无序的微小颗粒是主要的产物(图第17中(a)(b))。在增加抗坏血酸的量(0.3mmol)后，形成了一些颗粒聚集体(图17中(c)(d))。进一步将抗坏血酸的量增加到0.5mmol，所制备的样品由具有完美均匀性和单分散性的雪花组成(图11中(a)(b))。当抗坏血酸的用量高达1mmol时，产物呈现球形，由纳米棒组成(图17中(e)(f))。因此，新型FeWO4纳米结构的成功制备表明，在本系统中，抗坏血酸不仅可以作为还原剂，而且可以作为结构导向剂合成FeWO4产物。
不同原料对FeWO4的影响
分别在实施例2中的步骤(1)不变的情况下A仅将FeCl3·6H2O替换为等摩尔的Fe(NO3)3·9H2O和B仅在加入抗坏血酸的同时加入0.1mmol的十六烷基三甲基溴化铵。
结果如图18所示，FeWO4产物的形态和尺寸依赖于所用的铁前体盐。铁前体盐的阴离子决定了FeWO4的最终结构。在类似的条件下，仅用Fe(NO3)3代替FeCl3，就无法获得由纳米棒组装的均匀雪花状结构。相应的SEM如图18中(a)(b)所示。除了铁前体盐，我们发现CTAB的存在也会影响最终产物的形态，如图18(c)(d)所示。在CTAB存在的情况下，最终产物也可以由纳米棒组成，但雪花状的有组织结构根本不存在。因此，CTAB还可以提供对产品形态的额外控制。
黄曲霉毒素(AFB1)降解试验，步骤如下：
将500mg实施例2制备的花状FeWO4-rGO复合材料涂覆在玻璃基板上，然后加入到100mL含有AFB1的玉米油(浓度16.8ppb)中，500rpm磁力搅拌。然后置于黑暗中搅拌30min，以达到吸附-解吸平衡。采用300瓦氙灯照射悬浮液。分别于0min、15min、30min、45min、60min、75min照射时间收集5mL玉米油。液相色谱测试花生油中AFB1的浓度，结果如表1所示。对照组为对比例制备的雪花状FeWO4和FeWO4-rGO-U。
表1
由表1可知，与雪花状FeWO4和FeWO4-rGO-U相比，花状FeWO4-rGO对玉米油AFB1具有优异的光催化降解性能。
应用例2
将大肠杆菌菌液与制备的材料混合，用光学截止滤光器(λ＞420nm)，使用300瓦氙灯照射进行抗菌性能评估实验。取不同照射时间间隔(0min，5min，10min，15min，20min， 25min)的菌悬液在LB琼脂平板上涂布，37℃恒温箱中培养4h，观察菌落生长情况。同时对菌液进行稀释，进行平板计数，测定存活的细菌数，计算杀菌效率。
杀菌效率(％)＝(N0-Nt)/N0×100％
注：公式中N0和Nt分别为对照组和样品平板计数的菌落数
试验结果如表2所示。
表2
由表2可知，与雪花状FeWO4和FeWO4-rGO-U相比，本申请制备的雪花状FeWO4-rGO对大肠杆菌具有优异的光催化杀灭性能。
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。

Claims (10)

  1. 一种辐照催化电离脱毒系统，其特征在于，包括用于将携带辐照催化电离后的活性氧的空气与待脱毒处理的液体物料进行气液混合的气液混合器(1)和用于混合后的气液混合物流通的反应管(4)。
  2. 根据权利要求1所述的辐照催化电离脱毒系统，其特征在于，所述反应管(1)包括若干个U型管(4-1)和用于连接U型管(4-1)的连接管(4-2)；所述U型管(4-1)的直管段的端部可拆卸连接有用于向U型管(4-1)充入携带辐照催化电离后的活性氧的空气的补气管(4-3)；所述补气管(4-3)的壁上设置有若干个补气孔(4-31)。
  3. 根据权利要求2所述的辐照催化电离脱毒系统，其特征在于，所述补气管(4-3)上还设置有若干个翅片(4-32)。
  4. 根据权利要求1所述的辐照催化电离脱毒系统，其特征在于，所述携带辐照催化电离后的活性氧的空气由辐照催化电离箱(2)提供；所述辐照催化电离箱(2)包括箱体(2-1)、设置于箱体(2-1)内的若干个网片(2-2)和用于提供辐照光源的灯管(2-3)；所述网片(2-2)上附着有光辐照后产生活性氧的光催化材料。
  5. 根据权利要求4所述的辐照催化电离脱毒系统，其特征在于，所述箱体(2-1)内还设置有用于固定网片(2-2)和灯管(2-3)的固定架(2-4)；所述固定架(2-4)上设置用于固定灯管(2-3)的固定孔(2-41)和用于固定网片(2-2)的固定柱(2-42)；所述网片(2-2)上设置有用于灯管(2-3)穿过的安装孔(2-21)和用于固定柱(2-42)穿过的固定孔(2-22)。
  6. 根据权利要求4所述的辐照催化电离脱毒系统，其特征在于，所述光催化材料为FeWO4-rGO复合材料。
  7. 根据权利要求6所述的辐照催化电离脱毒系统，其特征在于，所述FeWO4-rGO复合材料由以下方法制备而成：
    将FeWO4加入乙醇中并超声处理；将APTES加入FeWO4悬浮液中后，将混合物在70℃下加热4h；随后，收集粉末，用乙醇洗涤后干燥；之后，将APTES改性FeWO4加入蒸馏水中并超声，然后加入rGO；搅拌60min后，将所得悬浮液在180℃下保持12h；最后收集所得产物，用水洗涤并在80℃下干燥，得到FeWO4-rGO。
  8. 根据权利要求8所述的辐照催化电离脱毒系统，其特征在于，所述FeWO4由以下方法制备而成：
    首先将FeCl3·6H2O和Na2WO4·2H2O分别溶解在蒸馏水中；然后，在连续搅拌下向FeCl3溶液中加入抗坏血酸以完全溶解；接着，将Na2WO4溶液缓慢加入上述混合物中；进一步搅拌后，将混合物在高温下保持一段时间；然后自然冷却至室温；通过离心收集所得沉淀物，洗涤后干燥。
  9. 权利要求1-8任一项所述的辐照催化电离脱毒系统在水体除菌或食用油除黄曲霉毒素中的应用。
  10. 一种辐照催化电离脱毒方法，其特征在于，使用权利要求1-8任一项所述的系统，包括辐照催化电离得到活性氧的步骤、将携带辐照催化电离后的活性氧的空气与待脱毒处理的液体物料进行气液混合的步骤和活性氧对液体物料中的菌或黄曲霉毒素进行脱毒的步骤。
PCT/CN2023/095433 2023-04-21 2023-05-22 辐照催化电离脱毒系统及其用途和辐照催化电离脱毒方法 Ceased WO2024216699A1 (zh)

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