WO2022105831A1 - 一种消减黄曲霉毒素的绿色方法 - Google Patents

一种消减黄曲霉毒素的绿色方法 Download PDF

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WO2022105831A1
WO2022105831A1 PCT/CN2021/131472 CN2021131472W WO2022105831A1 WO 2022105831 A1 WO2022105831 A1 WO 2022105831A1 CN 2021131472 W CN2021131472 W CN 2021131472W WO 2022105831 A1 WO2022105831 A1 WO 2022105831A1
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aflatoxin
composite
composite film
film
substrate
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English (en)
French (fr)
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李培武
毛劲
张奇
张文
张良晓
李慧
喻理
程玲
杨祥龙
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中国农业科学院油料作物研究所
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
    • A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
    • A23L5/273—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption using adsorption or absorption agents, resins, synthetic polymers, or ion exchangers
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
    • A23D9/06—Preservation of finished products
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J27/24—Nitrogen compounds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils

Definitions

  • the invention belongs to the technical field of food harmful pollutant control, and in particular relates to a green method for reducing aflatoxin.
  • Edible vegetable oils such as peanut oil and corn oil are rich in unsaturated fatty acids, which have good fatty acid composition and are easy to digest and absorb by the human body.
  • Peanut oil is also rich in a variety of functional nutrients such as sterols, wheat germ phenol, vitamin E, choline, phospholipids, etc., which are favored by consumers.
  • the media reported a number of incidents of aflatoxin exceeding the standard in edible vegetable oils, mainly because individuals or enterprises in the process of purchasing peanuts, due to lax checks or restrictions on post-harvest storage conditions, used toxin-contaminated peanuts and corn. Raw material processing, resulting in excessive aflatoxin in edible oil.
  • Aflatoxin has strong carcinogenic and teratogenic properties, and is classified as a class I carcinogen by the International Organization for Cancer.
  • aflatoxin detoxification and attenuation mainly include chemical, physical and biological methods.
  • Chemical methods usually use strong oxidants to destroy aflatoxin structure, but at the same time, it may also affect the flavor or nutrients in food or oil; physical methods include Washing or adsorption, but the molecular structure of the toxin has not changed, and its existence in the environment may cause secondary pollution; biological methods have the characteristics of high efficiency and high selectivity, but need more objective theoretical data support in large-scale application and safety evaluation. Therefore, from the perspective of high-quality development, new, energy-saving and green aflatoxin reduction technologies are urgently needed for current industrial development.
  • the purpose of the present invention is to provide a green reduction method of aflatoxin. It is used for the reduction of aflatoxin, and has the characteristics of green, high efficiency and safety, and does not affect the nutritional functional components in the sample that have a similar benzene ring structure to aflatoxin, such as phenolic substances containing a benzene ring structure.
  • the method of reducing aflatoxin is to fully contact the aflatoxin-containing sample with the composite film used to reduce aflatoxin.
  • the composite film for reducing aflatoxin includes a substrate and a gC 3 N 4 /WO 3 composite material on the substrate, gC 3 N 4 is a lamellar structure, and WO 3 nanoparticles It is uniformly dispersed on the surface of the lamella gC 3 N 4 , and tightly combined to form a composite semiconductor photocatalytic material.
  • the mass ratio of WO 3 in the gC 3 N 4 /WO 3 composite material is 5-20%; the WO 3 nanoparticles are uniform in size, about 10 nm in size, and the gC 3 N 4 sheet size is 100-200 nm.
  • the substrate is ITO glass or fluorine-doped SnO 2 conductive glass FTO.
  • the wavelength of the xenon lamp light source is 420-700 nm.
  • the method for contacting the aflatoxin-containing sample with the composite film is as follows: fix the composite film on the production line, and during the production process, the sample slowly flows through the composite film to contact the composite film; or fix the composite film on the rotating
  • the blade of the paddle mixer is put into the container for storing the sample, and it is stirred and contacted, and the operation is convenient.
  • the sample is edible vegetable oil, including peanut oil, corn oil, etc. which are susceptible to aflatoxin contamination.
  • the above-mentioned composite film for reducing aflatoxin comprising a substrate and a gC 3 N 4 /WO 3 composite material on the substrate, the gC 3 N 4 is a lamellar structure, and the WO 3 nanoparticles are uniformly dispersed in the lamellar gC 3
  • the N4 surface which is tightly bound, forms a composite semiconductor photocatalytic material.
  • the mass ratio of WO 3 in the composite WO 3 /gC 3 N 4 is 5-20wt%, preferably 5-15wt%, more preferably 10%, and the WO3 nanoparticles are uniform in size, about 10 nm in size,
  • the gC 3 N 4 sheet size is 100-200 nm.
  • the substrate is ITO glass or fluorine-doped SnO 2 conductive glass FTO.
  • carbon nitride is prepared by high-temperature pyrolysis, peeled at high temperature, and post-processed to obtain carbon nitride nanosheets;
  • the high temperature pyrolysis method described in step 1) prepares carbon nitride as follows: urea and dicyandiamide are dissolved in distilled water at 50 to 60°C in a mass ratio of 1:2 to 3, and placed in an oven for recrystallization , After the crystallization is evenly ground, put it into a crucible, cover it, and then place it in a tube furnace or muffle furnace, heat it up to 550-560 °C, and keep it for 3-4 hours;
  • the high-temperature peeling temperature is 580-600° C. for 2-3 hours.
  • the post-treatment is as follows: grinding, washing three times with dilute nitric acid and ethanol solution respectively, and drying to obtain carbon nitride powder.
  • the hydrothermal time in step 2) is 24-30h.
  • the post-processing is as follows: centrifugation to obtain a yellow solid substance, washing three times with ethanol and distilled water respectively, and drying for subsequent use;
  • Step 3) is: weighing 1.0-2.0 g of the composite photocatalytic material, dissolving it in 20-30 mL of distilled water, ultrasonically dispersing, adding 3-5 mL of dimethylformamide or methanol, and fully grinding to a uniform and viscous suspension, Then, the suspension was dropped on the ITO glass sheet by natural casting to form a film, and under the protection of inert gas N 2 , it was calcined and sintered at 300-350 °C to make the composite membrane bond more tightly, and the aflatoxin-reduced composite film was made.
  • a composite film composed of gC3N4 nanosheets, WO3 nanoparticles and ITO glass is used for aflatoxins including aflatoxin B1, aflatoxin B2, aflatoxin M1, aflatoxin M2, etc. It has excellent selective adsorption and visible light catalytic performance, specifically: on the one hand, it is based on the ⁇ - ⁇ stacking effect of the ring aromatic conjugated structure in the graphitic carbon nitride and the benzene ring in the aflatoxin structure, and on the other hand, the yellow In the structure of aspergillus, the oxygen lone pair of electrons on the lactone ring forms a coordination bond with the 5d empty orbital of the tungsten atom.
  • the synergistic adsorption properties of the two materials are mainly used to achieve excellent selective adsorption and removal of aflatoxin, achieving high selectivity.
  • the purpose of adsorption is to enable the composite film to adsorb aflatoxins without affecting the nutritional functional components in the sample system that are similar to the benzene ring structure of aflatoxin, such as phenolic substances containing benzene ring structures.
  • the composite film also has excellent visible light catalytic activity.
  • the two semiconductor catalysts of carbon nitride and tungsten oxide form a Z-type semiconductor composite material, which has strong reducing ability and oxidizing ability.
  • the composite film based on the above principle has excellent selective adsorption and photocatalytic properties, and can safely and efficiently reduce aflatoxin in the sample.
  • the present invention first uses selective adsorption to remove aflatoxin to achieve "reduction”, and then exposes the composite film to sunlight or xenon light source, based on the composite film.
  • Excellent visible light catalytic activity, carbon nitride and tungsten oxide form a Z - type semiconductor composite material, which has strong reducing and oxidizing ability, and gradually degrades toxins. As a result, this green and efficient technology can be safely used to deplete aflatoxins in samples.
  • the composite film prepared by the invention has good aflatoxin reduction performance.
  • 10% WO 3 /gC 3 N 4 (the mass ratio of WO 3 : gC 3 N 4 is 10%) is composited
  • the reduction rate of aflatoxin is 92.2%, and the composite membrane can be reused. It has the advantages of good economy, energy saving, green efficiency, and no secondary pollution. It is expected to be used in samples such as peanut oil and corn oil.
  • the control and removal of AFB 1 toxins provides a new path for ensuring the safety of consumption and industrial development of edible vegetable oils such as peanut oil.
  • Fig. 1 is the composite material electron diffraction XRD pattern developed by example 1;
  • Fig. 2 is the composite material transmission electron microscope TEM spectrum of example 1 development
  • Fig. 3 is the composite material filter membrane atomic force microscope AFM spectrum of example 1 development
  • Fig. 4 is the performance of AFB 1 in the composite filter membrane of example 2 to reduce peanut oil;
  • Fig. 5 is the effect diagram of AFB 1 in the repeated utilization of the composite filter membrane of example 2 to reduce the peanut oil;
  • Figure 6 is the effect of composite membrane on total phenolic content in peanut oil.
  • Figure 7 is the hydroxyl radical spectrum (a) and the electron transport mechanism (b) of the Z-type system tested by the composite filter membrane ESR;
  • the solution was placed in a reaction kettle, hydrothermally heated at 200 °C for 24 h, separated and centrifuged to obtain a yellow solid material, washed three times with ethanol and distilled water, respectively, and dried at 60 °C to obtain a composite material (composite material WO 3 /gC 3 N 4 in WO The mass ratio of 3 is 5%, 10%, 15%, 20%).
  • Fig. 1 is the electron diffraction XRD pattern of the 10% WO 3 /gC 3 N 4 composite material developed in Example 1;
  • Fig. 2 is the transmission electron microscope TEM pattern of the composite material developed in Example 1 with different magnifications; wherein the lamellae are gC 3 N 4 , the length is 100-200 nm, and the WO 3 is granular and the size is about 10 nm;
  • FIG. 3 is the AFM spectrum of the composite filter membrane developed in Example 1. The film thickness was uniform, about 25 nm.
  • Example 2 Prepare 200mL of peanut oil containing 5.6, 11.2, 16.8 and 22.4ppb AFB 1 , and let the peanut oil flow on the composite filter membrane developed in Example 1 at a flow rate of 50mL/min. The surface was washed three times with methanol, the composite membrane was recovered, and the above operations were repeated. The content of AFB 1 in peanut oil was tested by liquid chromatography, and the reduction rate was calculated.
  • Figure 4 shows the effect of 10% WO 3 /gC 3 N 4 composite film on reducing AFB 1 peanut oil with different initial concentrations. After one reduction, the composite film can reduce toxins by more than 80%, indicating that it can effectively reduce aflatoxin in peanut oil.
  • Figure 5 shows the repeated use performance evaluation of the 10%WO 3 /gC 3 N 4 composite film. It can be seen from the figure that the composite filter repeatedly reduced peanut oil with an initial concentration of 16.8ppb, and the reduction rate was all about 92%, indicating that the composite filter The film has stable performance and can be reused.
  • the composite membranes developed with different mass ratios of WO 3 and gC 3 N have the effect of reducing AFB 1 in peanut oil at one time as shown in Table 1. It can be seen from the results that 10% WO 3 /gC 3 N 4 has the best effect (the initial concentration of AFB 1 is 16.8ppb) .
  • the composite membrane can not only efficiently remove aflatoxins, but also degrade toxins by sunlight catalysis. This technology has the advantages of green, energy saving and economy, and is expected to become a technology for the prevention and control of aflatoxins in edible vegetable oils such as peanut oil. one.
  • Table 1 The photocatalytic performance of the composites with different mass ratios for the reduction of peanut oil with an initial concentration of 16.8ppb AFB 1
  • Example 3 Effect of composite film on total phenolics in peanut oil
  • the total phenolic content in peanut oil was tested by the Folin phenol method to evaluate the effect of filtration reduction process on the total phenolic content in peanut oil. The results are shown in Figure 6. After 4 rounds of repeated filtration, there was no obvious change in the total phenolic content in peanut oil, indicating that the film can not only effectively remove AFB 1 in peanut oil, but also ensure that the functional active components containing benzene ring aromatic groups in peanut oil are not lost.
  • the method has the characteristics of green, low energy consumption, high efficiency and safety.
  • these phenolic substances contain benzene ring structure and may also form ⁇ - ⁇ stacking with the ring aromatic conjugated structure in carbon nitride, the combination is not tight compared with the adsorption synergy between the composite film and AFB 1 .
  • the peanut oil continuously flows in the composite film or is stirred and shaken, and these phenolic substances can be well preserved in the sample.
  • the electron spin resonance ESR method was used to determine the oxygen radicals, especially the hydroxyl radicals generated by the composite films, to confirm that the photocatalytic electron transfer mechanism of the composite films was a Z-type system.
  • DMPO dimethyl-1-pyrroline N-oxide
  • the measurement was carried out by A200S-9.5/12 electron paramagnetic resonance spectrometer of Bruker, Germany, under the condition of microwave frequency 9.8GHz, power 2.2mW, The field strength is 3500G, and the xenon lamp is used as the light source during the test, and the wavelength is 420-700nm.
  • the results of ESR testing of hydroxyl radicals are shown in Figure 7a.
  • the DMPO-OH spectrum consists of a quartet peak with a peak height of 1:2:2:1, which verifies the existence of hydroxyl radicals and proves that WO 3 /gC 3 N 4 receives light After excitation, hydroxyl radicals can be generated. As shown in Fig .
  • the valence bands of WO3 and gC3N4 are 3.2V and 1.4V, respectively, if the two form a heterojunction, the photogenerated holes pass from WO3 to gC3N4 , which cannot directly generate hydroxyl groups Free radicals, because gC 3 N 4 valence band is more positive than OH - / ⁇ OH (+2.4V vs NHE), it is difficult to oxidize H 2 O or OH - to generate hydroxyl groups. Therefore, WO 3 and gC 3 N 4 can be inferred to be Z-type systems.
  • the electrons on the conduction band of WO 3 recombine with the holes on the valence band of gC 3 N 4 , while the holes of WO 3 remain in its valence band.
  • the electron transport of the composite material is a Z-type system, which can utilize the strong oxidation and reduction ability, has excellent photocatalytic activity, and efficiently reduces aflatoxin.

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Abstract

消减黄曲霉毒素的绿色方法，将含黄曲霉毒素的样品充分接触用于消减黄曲霉毒素的复合薄膜，复合薄膜先选择性吸附脱除样品中黄曲霉毒素，然后将复合薄膜置于太阳光或氙灯光源下照射，逐步降解黄曲霉毒素，所述用于消减黄曲霉毒素的复合薄膜包括基底和基底上的g-C 3N 4/WO 3复合材料，g-C 3N 4为片层结构，WO 3纳米颗粒均匀分散在片层g-C 3N 4表面，结合紧密，形成复合半导体光催化材料。

Description

一种消减黄曲霉毒素的绿色方法 技术领域
本发明属于食品有害污染物控制技术领域，具体涉及一种消减黄曲霉毒素的绿色方法。
背景技术
花生油、玉米油等食用植物油富含不饱和脂肪酸，脂肪酸组成良好，易于人体消化吸收。花生油还富含多种功能性营养物质如甾醇、麦胚酚、维生素E、胆碱、磷脂等，深受广大消费者青睐。但是近年来，媒体报道了多起食用植物油中黄曲霉毒素超标的事件，主要由于个人或企业在收购花生过程中，由于把关不严或收后贮存条件限制，用被毒素污染后的花生、玉米原料加工，导致食用油中黄曲霉毒素超标。黄曲霉毒素具有强致癌致畸性，被国际癌症组织定为Ⅰ类致癌物质。国内外也发生过多起因黄曲霉毒素超标而导致的人畜中毒恶性事件，它已成为制约消费安全和产业发展的重要因素。因此，如何安全、高效地除去黄曲霉毒素，保障消费者生命健康和消费安全成为目前关注的热点，也是各国研究学者感兴趣的难点。
目前，黄曲霉毒素脱毒和减毒主要包括化学、物理和生物等方法，化学法通常用强氧化剂破坏黄曲霉毒素结构，但同时也可能会影响食品或油脂中风味或营养物质；物理法有水洗或吸附，但毒素分子结构尚未改变，存在于环境中可能造成二次污染；生物法具有高效、高选择性等特点，但在大规模应用和安全性评价方面需要更客观的理论数据支撑。因此，从高质量发展角度，新型、节能、绿色的黄曲霉毒素消减技术是目前产业发展亟需。
发明内容
本发明的目的旨在提供一种黄曲霉毒素的绿色消减方法。其用于黄曲霉毒素的消减，具有绿色、高效和安全的特点，且不影响样品中具有和黄曲霉毒素苯环结构类似的营养功能成分如含苯环结构的酚类物质。
消减黄曲霉毒素的方法，将含黄曲霉毒素的样品充分接触用于消减黄曲霉毒素的复合薄膜，复合薄膜先选择性吸附脱除样品中黄曲霉毒素，然后将复合薄膜置于太阳光或氙灯光源下照射，逐步降解黄曲霉毒素，所述用于消减黄曲霉毒素的复合薄膜包括基底和基底上的g-C 3N 4/WO 3复合材料，g-C 3N 4为片层结构，WO 3纳米颗粒均匀分散在片层g-C 3N 4表面，结合紧密，形成复合半导体光催化材料。
按上述方案，g-C 3N 4/WO 3复合材料中WO 3的质量比例为5～20％；WO 3纳米颗粒 尺寸均一，大小为10nm左右，g-C 3N 4片层大小为100～200nm。
按上述方案，所述的基底为ITO玻璃或掺杂氟的SnO 2导电玻璃FTO。
按上述方案，氙灯光源波长为420～700nm。
按上述方案，所述的含黄曲霉毒素的样品接触复合薄膜方法为：将复合薄膜固定于生产流水线，生产过程中样品缓缓流过复合薄膜，与复合薄膜接触；或将复合薄膜固定在旋桨式搅拌机的叶片，放入存放样品的容器，搅拌接触，操作方便。
按上述方案，所述的样品为食用植物油，包括易受黄曲霉毒素污染的花生油、玉米油等。
提供上述一种用于消减黄曲霉毒素的复合薄膜，包括基底和基底上的g-C 3N 4/WO 3复合材料，g-C 3N 4为片层结构，WO 3纳米颗粒均匀分散在片层g-C 3N 4表面，结合紧密，形成复合半导体光催化材料。
按上述方案，复合材料WO 3/g-C 3N 4中WO 3的质量比例为5～20wt％，优选为5～15wt％，更优选为10％，WO 3纳米颗粒尺寸均一，大小为10nm左右，g-C 3N 4片层大小为100～200nm。
按上述方案，所述的基底为ITO玻璃或掺杂氟的SnO 2导电玻璃FTO。
提供上述一种可选择性吸附且利用可见光催化消减黄曲霉毒素的复合薄膜材料的制备方法：
1)首先通过高温热解法制备氮化碳，高温剥离，后处理得到氮化碳纳米片；
2)将氮化碳纳米片分散于水中搅拌后超声分散，然后加入一定量钨酸钠，搅拌溶解，加酸，将钨酸钠转化为沉淀，离心取黄色沉淀物，清洗，然后加入酸，调整pH值为1.2～1.5，置于反应釜，在180～200℃水热反应，制备WO 3/g-C 3N 4复合材料；
3)复合材料加水分散，加入有机溶剂，充分研磨至均一、粘稠的悬浮体，然后将悬浮体滴在基底上自然流延成膜，在惰性气体保护下，煅烧固定烧结，使复合材料与基底结合更紧密，制成消减黄曲霉毒素复合薄膜。
按上述方案，步骤1)所述的高温热解法制备氮化碳为：将尿素和二氰二胺按质量比为1：2～3溶于50～60℃蒸馏水中，置于烘箱重结晶，结晶研磨均匀后，放入坩埚，加盖，然后置于管式炉或马弗炉，升温至550～560℃，保持3～4h；
所述的高温剥离温度为580～600℃，保持2～3h。
所述的后处理为：研磨，并分别用稀硝酸和乙醇溶液清洗三次，烘干，制得氮化碳粉末。
步骤2)所述的水热时间为24～30h。所述的后处理为：离心得到黄色固体物质，分别用乙醇和蒸馏水洗涤三次，在烘干备用；
步骤3)为:称取1.0～2.0g复合光催化材料，溶于20～30mL蒸馏水中，超声分散，加入3～5mL二甲基甲酰胺或甲醇，充分研磨至均一、粘稠的悬浮体，然后将悬浮体滴在ITO玻璃片上自然流延成膜，在惰性气体N 2保护下，300～350℃煅烧固定烧结，使复合滤膜结合更紧密，制成消减黄曲霉毒素复合薄膜。
本发明中使用由g-C 3N 4纳米片、WO 3纳米颗粒和ITO玻璃组成的复合薄膜，用于黄曲霉毒素包括黄曲霉毒素B1、黄曲霉毒素B2、黄曲霉毒素M1、黄曲霉毒素M2等的消减，具有优异的选择性吸附和可见光催化性能，具体地：一方面基于石墨型氮化碳中环芳香族共轭结构与黄曲霉毒素结构中苯环的π-π堆积效应，另外一方面黄曲霉毒素结构中内酯环上氧孤对电子与钨原子5d空轨道形成配位键，主要利用两个材料协同吸附性能，可实现优异的选择性吸附脱除黄曲霉毒素的能力，达到高选择性吸附目的；使复合薄膜在吸附黄曲霉毒素的同时，不影响样品体系中具有和黄曲霉毒素苯环结构类似的营养功能成分，如含苯环结构的酚类物质等。此外，复合薄膜也具备优良的可见光催化活性，氮化碳和氧化钨两种半导体催化剂形成了Z型半导体复合材料，具备强的还原能力和氧化能力，在可见光激发下，产生大量活性基团如羟基自由基和超氧自由基，将黄曲霉毒素逐步消减，最终矿化为CO 2和H 2O，避免毒素进入环境或食物链，发生二次污染。因此，基于上述原理的复合薄膜具备优异的选择性吸附和光催化性能，能安全、高效消减样品中黄曲霉毒素。
简言之，本发明通过可见光催化和选择性吸附技术的结合，首先利用选择性吸附将黄曲霉毒素脱除，达到“减”，然后将复合薄膜置于太阳光或氙灯光源照射，基于复合薄膜优良的可见光催化活性，氮化碳和氧化钨形成了Z型半导体复合材料，具备强的还原能力和氧化能力，将毒素逐步降解，其终产物为CO 2和H 2O，达到“消”，由此实现了这一绿色、高效的技术安全用于消减样品中黄曲霉毒素。
本发明制备的复合薄膜具备良好的消减中黄曲霉毒素的性能，当AFB 1初始浓度为16.8ppb，10％WO 3/g-C 3N 4(WO 3：g-C 3N 4质量比为10％)复合滤膜的一次过滤后，黄曲霉毒素消减率为92.2％，并且复合薄膜能重复利用，具备良好的经济节能、绿色高效、无二次污染等优势，有望用于样品如花生油、玉米油等中AFB 1毒素控制与脱除，为保障花生油等食用植物油消费安全和产业发展提供新的路径。
附图说明
图1是实例1研制的复合材料电子衍射XRD图谱；
图2是实例1研制的复合材料透射电镜TEM图谱；
图3是实例1研制的复合材料滤膜原子力显微镜AFM图谱；
图4是实例2复合滤膜消减花生油中AFB 1性能；
图5是实例2复合滤膜重复利用消减花生油中AFB 1效果图；
图6是复合滤膜对花生油中总酚含量的影响。
图7是复合滤膜ESR测试羟基自由基图谱(a)和Z型体系电子传递机制(b)；
具体实施方式
实例1：复合滤膜的研制
将5.0g尿素和10.0g二氰二胺溶于50℃蒸馏水，置于烘箱重结晶，结晶研磨均匀后，放入坩埚，加盖，然后置于管式炉或马弗炉，以5°/min加热速度升温至550℃，保持3h，再升温至580℃，保持2h，进行高温剥离，得黄色粉末，研磨，并分别用稀硝酸和乙醇溶液清洗三次，烘干得氮化碳粉末。将1.0g氮化碳分散于100mL蒸馏水搅拌后超声分散，然后加入一定量钨酸钠，搅拌溶解，加入盐酸溶液，调整pH值为1.2，离心取沉淀物，用乙醇和蒸馏水清洗，然后加入硝酸溶液，置于反应釜，在200℃水热24h，分离离心得到黄色固体物质，分别用乙醇和蒸馏水洗涤三次，在60℃烘干备用得复合材料(复合材料WO 3/g-C 3N 4中WO 3的质量比例为5％,10％,15％,20％)。
称取2.0g复合光催化材料，溶于20mL蒸馏水中，超声均匀分散30min，加入5mL二甲基甲酰胺，充分研磨至均一、粘稠的悬浮体，然后将悬浮体浇注在ITO玻璃片(20cm×20cm)上自然流延成膜，在惰性气体N 2保护下，300℃煅烧固定烧结，使材料结合更紧密，制成消减黄曲霉毒素复合薄膜。
图1是实例1研制的10％WO 3/g-C 3N 4复合材料电子衍射XRD图谱；
图2是实例1研制的复合材料不同放大倍数的透射电镜TEM图谱；其中片层状为g-C 3N 4，长度为100～200nm，WO 3为颗粒状，大小为10nm左右；
图3是实例1研制的复合材料滤膜原子力显微镜AFM图谱。膜厚度均一，大约25nm。
实例2：花生油中AFB 1消减性能评价
配制含5.6,11.2,16.8和22.4ppb AFB 1的花生油200mL，以流速50mL/min让花生油在实例1研制的复合滤膜上流动，随后，将复合滤膜置于自然太阳照射下10h，用蒸馏水和甲醇清洗表面3次，回收复合滤膜，重复以上操作。利用液相色谱测试花 生油中AFB 1的含量，计算消减率。
图4为10％WO 3/g-C 3N 4复合薄膜消减不同初始浓度AFB 1花生油效果图，通过一次消减，复合薄膜消减毒素均能达到80％以上，说明其能高效消减花生油中黄曲霉毒素。
图5为10％WO 3/g-C 3N 4复合薄膜的重复使用性能评价，从图可知，复合滤膜对初始浓度为16.8ppb的花生油进行重复消减，其减少率均在92％左右，说明复合薄膜性能稳定，可重复使用。
不同质量比WO 3和g-C 3N研制的复合滤膜一次消减花生油中AFB 1效果如下表1，从结果可知，10％WO 3/g-C 3N 4效果最好(AFB 1初始浓度为16.8ppb)。综上所述，复合滤膜不仅可高效脱除黄曲霉毒素，也可利用太阳光催化降解毒素，该技术具有绿色、节能、经济等优点，有望成为花生油等食用植物油中黄曲霉毒素防控技术之一。
表1不同质量比复合材料光催化消减初始浓度16.8ppb AFB 1花生油性能
Figure PCTCN2021131472-appb-000001
实例3：复合薄膜对花生油中总酚的影响
利用福林酚法测试花生油中总酚含量，以评价过滤消减过程对花生油中总酚含量的影响，结果如图6。经过4轮的重复过滤，花生油中总酚含量未见明显的变化，说明该薄膜不仅能有效去除花生油中AFB 1，还能保证花生油中含苯环芳香基团的功能活性成分酚类不损失，该方法具有绿色、低能耗、高效和安全等特点。这是因为虽然这些酚类物质含有苯环结构，也可能与氮化碳中环芳香族共轭结构形成π-π堆积，但相比复合薄膜与AFB 1的吸附协同作用，其结合并不紧密，花生油在复合薄膜持续流动或经搅拌震荡，这些酚类物质都能很好保存在样品中。
实例4：复合薄膜光催化电子传递机制
采用电子自旋共振ESR方法测定复合薄膜产生的氧自由基，特别是羟基自由基，来证实复合薄膜的光催化电子传递机制为Z-型体系。以DMPO(5,5-dimethyl-1-pyrroline N-oxide)作为标记物，采用德国布鲁克公司A200S-9.5/12型电子顺磁共振波谱仪进行测定，条件为微波频率9.8GHz，功率2.2mW，场强为3500G，测试过程中以氙灯为光源光照,波长：420～700nm。
ESR测试羟基自由基结果如图7a所示，DMPO-OH图谱由峰高1:2:2:1的四重***峰组成，验证了羟基自由基的存在，证明WO 3/g-C 3N 4受光激发后能产生羟基自由基。如图7所示，WO 3和g-C 3N 4的价带分别为3.2V和1.4V，如果两者形成异质结，光生空穴从WO 3传到g-C 3N 4，其不能直接产生羟基自由基，因为g-C 3N 4价带比OH -/·OH(+2.4V vs NHE)更正，难以氧化H 2O或者OH -生成羟基。因此，WO 3和g-C 3N 4可推断为Z型体系，首先受光激发后，WO 3导带上电子与g-C 3N 4价带上空穴发生复合，而WO 3的空穴保留在其价带，拥有强的氧化能力，比OH-/·OH(+2.4V vs NHE)更负，有足够的能力氧化水中OH -，产生羟基自由基。由此可见，复合材料电子传递为Z型体系，能利用强的氧化和还原能力，具有优异光催化活性，高效消减黄曲霉毒素。

Claims (10)

  1. 消减黄曲霉毒素的方法，其特征在于：将含黄曲霉毒素的样品充分接触用于消减黄曲霉毒素的复合薄膜，复合薄膜先选择性吸附脱除样品中黄曲霉毒素，然后将复合薄膜置于太阳光或氙灯光源下照射，逐步降解黄曲霉毒素，所述用于消减黄曲霉毒素的复合薄膜包括基底和基底上的g-C 3N 4/WO 3复合材料，g-C 3N 4为片层结构，WO 3纳米颗粒均匀分散在片层g-C 3N 4表面，结合紧密，形成复合半导体光催化材料。
  2. 根据权利要求1所述的消减黄曲霉毒素的方法，其特征在于：复合材料WO 3/g-C 3N 4中WO 3的质量比例为5～20wt％，WO 3纳米颗粒尺寸均一，大小为10nm左右，g-C 3N 4片层大小为100～200nm。
  3. 根据权利要求1所述的消减黄曲霉毒素的方法，其特征在于：所述的基底为氧化铟锡ITO玻璃或掺杂氟的SnO 2导电玻璃FTO。
  4. 根据权利要求1所述的消减黄曲霉毒素的方法，其特征在于：所述的含黄曲霉毒素的样品接触复合薄膜方法为：将复合薄膜固定于生产流水线，生产过程中样品缓缓流过复合薄膜，与复合薄膜接触；或将复合薄膜固定在旋桨式搅拌机的叶片，放入存放样品的容器，搅拌接触。
  5. 根据权利要求1所述的消减黄曲霉毒素的方法，其特征在于：所述的样品为食用植物油，包括易受黄曲霉毒素污染的花生油、玉米油。
  6. 一种用于消减黄曲霉毒素的复合薄膜，其特征在于：包括基底和基底上的g-C 3N 4/WO 3复合材料，g-C 3N 4为片层结构，WO 3纳米颗粒均匀分散在片层g-C 3N 4表面，结合紧密，形成复合半导体光催化材料。
  7. 权利要求6所述的用于消减黄曲霉毒素的复合薄膜材料的制备方法：
    1)首先通过高温热解制备氮化碳，再通过高温剥离处理得到氮化碳纳米片；
    2)将氮化碳纳米片分散于水中搅拌后超声分散，然后加入一定量钨酸钠，搅拌溶解，加酸，将钨酸钠转化钨酸黄色沉淀，离心取沉淀物，清洗，然后加入酸，调整pH值为1.2～1.5，置于反应釜，在180～200℃水热反应，制备WO 3/g-C 3N 4复合材料；
    3)复合材料加水分散，加入有机溶剂，充分研磨至均一、粘稠的悬浮体，然后将悬浮体滴在基底上自然流延成膜，在惰性气体保护下，煅烧固定烧结，使复合材料与基底结合更紧密，制成消减黄曲霉毒素复合薄膜。
  8. 根据权利要求7所述的制备方法，其特征在于：步骤1)所述的高温热解法 制备氮化碳为：将尿素和二氰二胺按质量比为1：2～3溶于50～60℃蒸馏水中，置于烘箱重结晶，结晶研磨均匀后，放入坩埚，加盖，然后置于管式炉或马弗炉，升温至550～560℃，保持3～4h；
  9. 根据权利要求7所述的制备方法，其特征在于：所述的高温剥离温度为580～600℃，保持2～3h；
    步骤2)所述的水热时间为24～30h。
  10. 根据权利要求7所述的制备方法，其特征在于：步骤3)为:称取1.0～2.0g复合光催化材料，溶于20～30mL蒸馏水中，超声分散，加入3～5mL二甲基甲酰胺或甲醇，充分研磨至均一、粘稠的悬浮体，然后将悬浮体滴在基底上自然流延成膜，在惰性气体保护下，300～350℃煅烧固定烧结，使复合滤膜结合更紧密，制成消减黄曲霉毒素复合薄膜。
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