A method for preparing an organic-inorganic hybrid nanomaterial

Abstract

The application discloses a preparation method of an organic-inorganic hybrid nanomaterial. First, an organic ligand 1,2,4-BTC and a metal compound FeCl3*6H2O are mixed according to a set proportion; a certain amount of N,N-dimethylformamide is added into the mixture, and the mixture is ultrasonically mixed, then ethanol is added to be ultrasonically mixed again; the mixed system is placed in an oven to react under constant temperature; after the reaction is completed, the lower flocculent precipitate is taken out and placed in a plastic centrifugal tube by being naturally cooled to room temperature, centrifuged on a centrifuge at 12000 rpm for 5 min, and the supernatant is discarded; the flocculent precipitate obtained in the step 4 is cleaned with N,N-dimethylformamide and ethanol for multiple times, and finally the organic-inorganic hybrid nanomaterial is obtained. The method combines metal ions and organic ligands, so that the organic-inorganic hybrid nanomaterial has the rigidity of inorganic materials and the flexibility of organic materials, and has better adsorption capacity and chemical stability.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of hybrid materials, in particular to a preparation method of an organic-inorganic hybrid nanomaterial. BACKGROUND

[0002] Plant oils are an important part of our daily diet, but they are easily affected by mycotoxins, which pose a serious threat to human health, and adsorption is the main detoxification technology for mycotoxins due to its simple operation, high efficiency and low cost. However, how to select an efficient and safe adsorbent to remove multiple types of mycotoxins at the same time is a great challenge.

[0003] The organic-inorganic hybrid porous material is a structural material formed by self-assembly of inorganic metal centers and bridged organic ligands. The material has rigidity of inorganic materials and flexibility of organic materials. The material has extremely high specific surface area, coordinated pore size and multifunctional active sites, so that the material has great development potential in pollutant adsorption, but the existing technical solutions lack a preparation process for the organic-inorganic hybrid porous material, and there is no solution for removing multiple mycotoxins in plant oils by using the organic-inorganic hybrid nanomaterial. SUMMARY

[0004] The application aims to provide a preparation method of an organic-inorganic hybrid nanomaterial, which combines metal ions and organic ligands, so that the material has rigidity of inorganic materials and flexibility of organic materials, and the material has rich surface area, suitable channels and multifunctional sites, and can selectively recognize target molecules, so that the material has better adsorption capacity and chemical stability.

[0005] The application is achieved by the following technical scheme.

[0006] A preparation method of an organic-inorganic hybrid nanomaterial, the method comprising:

[0007] Step 1, a certain amount of organic ligand 1, 2, 4-BTC and metal compound FeCl3.6H2O are mixed according to a set ratio, wherein the organic ligand 1, 2, 4-BTC represents trimellitic acid;

[0008] Step 2, a certain amount of N, N-dimethylformamide is added to the mixture of step 1, and then ultrasonic mixing is performed, and then ethanol is added and ultrasonic mixing is performed again;

[0009] Step 3, the mixed system obtained in step 2 is placed in an oven and reacted under constant temperature conditions;

[0010] Step 4, after the reaction of step 3 is completed, the flocculent precipitate is removed from the bottom of the reactor and placed in a plastic centrifuge tube, and centrifuged at 12000 rpm for 5 min, and the supernatant is discarded;

[0011] Step 5, the flocculent precipitate obtained in step 4 is washed with N, N-dimethylformamide and ethanol multiple times, and finally the organic-inorganic hybrid nanomaterial is obtained, denoted as Fe-1,2,4-BTC.

[0012] From the above technical solutions provided by the present application, the above method combines metal ions with organic ligands, so that it has the rigidity of inorganic materials and the flexibility of organic materials, and can selectively recognize target molecules by using the large surface area, suitable channels and multifunctional sites of the material, so as to have better adsorption capacity and chemical stability. The hybrid nanomaterial prepared can be used to adsorb and remove aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2 and zearalenone in vegetable oil. BRIEF DESCRIPTION OF DRAWINGS

[0013] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0014] Figure 1 The preparation method flowchart of the organic-inorganic hybrid nanomaterial provided by the embodiments of the present application is shown in the figure;

[0015] Figure 2 The XPS graph of the hybrid nanomaterial provided by the examples of the present application is shown in the figure;

[0016] Figure 3 The nitrogen adsorption / desorption graph of the hybrid nanomaterial is shown in the figure;

[0017] Figure 4 The cumulative pore volume and pore size distribution graph of the hybrid nanomaterial is shown in the figure;

[0018] Figure 5 The TEM (left) and SEM (right) graphs of the hybrid nanomaterial are shown in the figure;

[0019] Figure 6 The adsorption efficiency column chart of the hybrid nanomaterial in standard solution for adsorbing and removing various mycotoxins is shown in the figure;

[0020] Figure 7 The adsorption efficiency column chart of the hybrid nanomaterial and common inorganic porous materials for adsorbing and removing mycotoxins in vegetable oil is shown in the figure;

[0021] Figure 8 The efficiency column chart of the hybrid nanomaterial for purifying and removing mycotoxins in the plant oil by the column adsorption;

[0022] Figure 9 The efficiency column chart of the hybrid nanomaterial in three common plant oils. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, but not all the embodiments of the present application, which does not constitute a limitation of the present application. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0024] As Figure 1 The preparation method flowchart of the organic-inorganic hybrid nanomaterial provided by the embodiments of the present application is shown in the figure, and the method comprises the following steps:

[0025] Step 1, a certain amount of organic ligand 1, 2, 4-BTC and metal compound FeCl3·6H2O are mixed according to a set ratio; wherein the organic ligand 1, 2, 4-BTC represents trimellitic acid;

[0026] In this step, the chemical molecular formula of the organic ligand 1, 2, 4-BTC is C9H6O6, and the molecular structural formula is represented as:

[0027]

[0028] Step 2, a certain amount of N, N-dimethylformamide is added to the mixture of step 1, and after ultrasonic mixing, ethanol is added and mixed again;

[0029] In the process of preparing the hybrid nanomaterial, the amount ratio of each raw material is specifically:

[0030] For every 50.0 mg of organic ligand 1, 2, 4-BTC, 52.5 mg of metal compound FeCl3·6H2O, 15 ml of N, N-dimethylformamide and 15 ml of ethanol are used. The amount ratio is obtained after repeated tests and demonstrations, and the powder synthesized under this amount ratio is more uniform and stable.

[0031] The volume ratio of the added N, N-dimethylformamide to ethanol is 1:1.

[0032] Step 3, the mixed system obtained in step 2 is placed in an oven for reaction under constant temperature conditions;

[0033] In this step, the reaction conditions are as follows: temperature is 80-90℃, time is 24-30h, and the ligand and metal can be fully coordinated under the conditions.

[0034] After the reaction in step 3 is completed, the lower flocculent precipitate is taken out and placed in a plastic centrifuge tube by natural cooling to room temperature, and centrifuged at 12000 rpm for 5 minutes, and the supernatant is discarded.

[0035] In step 5, the flocculent precipitate obtained in step 4 is washed with N,N-dimethylformamide and ethanol multiple times, and finally the organic-inorganic hybrid nanomaterial is obtained, denoted as Fe-1,2,4-BTC.

[0036] In this step, the specific cleaning method is as follows:

[0037] The flocculent precipitate is washed with N,N-dimethylformamide until the supernatant is colorless, and then washed with ethanol twice.

[0038] In addition, the method further comprises:

[0039] The hybrid nanomaterial prepared in step 5 is used to adsorb a plurality of mycotoxins, including aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2 and zearelone. Specifically, adsorption can be carried out in five single standard solutions configured by n-hexane.

[0040] The hybrid nanomaterial prepared in step 5 can also be used to simultaneously adsorb five mycotoxins in vegetable oil, including aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2 and zearelone. Specifically, adsorption can be carried out in peanut oil-n-hexane (v / v=1 / 3).

[0041] The preparation process and performance of the above hybrid nanomaterial are described below with specific examples:

[0042] 1) First, the hybrid nanomaterial Fe-1,2,4-BTC is prepared, 50.0mg 1,2,4-BTC and 52.5mg FeCl3·6H2O are dissolved in 15ml N,N-dimethylformamide, ultrasonic dissolution, then add the same volume of ethanol, ultrasonic mixing again;

[0043] The obtained mixture is placed in an 80-90℃ oven for reaction;

[0044] After the reaction is completed, the lower flocculent precipitate is taken out and placed in a plastic centrifuge tube by natural cooling to room temperature, and centrifuged at 12000 rpm for 5 minutes, and the supernatant is discarded.

[0045] The hybrid nanomaterial Fe-1,2,4-BTC was obtained by repeatedly washing with N, N-dimethylformamide and ethanol.

[0046] 2) Characterization of the hybrid nanomaterial Fe-1,2,4-BTC

[0047] XPS analysis: By XPS characterization, the surface composition and chemical state of the Fe-1,2,4-BTC powder were determined, as shown in Figure 2 The XPS diagram of the hybrid nanomaterial of the example of the present application is shown in the figure, and the XPS full spectrum diagram shows that the element composition of Fe-1,2,4-BTC has four characteristic peaks at 284.3, 399.9, 531.2 and 711.41 eV. The appearance of the characteristic peak Fe2p is caused by the addition of metal salt FeCl3·6H2O during synthesis, which also indicates that the synthesis of Fe-1,2,4-BTC powder is successful.

[0048] Nitrogen adsorption / desorption: As shown in Figure 3 The nitrogen adsorption / desorption diagram of the hybrid nanomaterial is shown in the figure, and the adsorption / desorption isotherm is type II isotherm, and the N saturated adsorption amount is 434 cm 3 / g, as shown in Figure 4 The cumulative pore volume and pore size distribution diagram of the hybrid nanomaterial is shown in the figure, combined with Figure 4 The cumulative pore size distribution diagram of the material, it can be inferred that the pore structure of the material is mainly macroporous structure.

[0049] Electron microscopy and EDX-Mapping element mapping: As shown in Figure 5 The TEM (left) and SEM (right) diagrams of the hybrid nanomaterial are shown in the figure, and it can be seen that the material is ellipsoidal structure with a particle size of about 60 nm. And by viewing the EDX-Mapping element mapping diagram of the hybrid nanomaterial from the same area, namely the EDX-Mapping element mapping image of Fe, C, O and N. In the same area, Fe element is uniformly distributed with C and O elements, which proves that the metal Fe 3+ is successfully hybridized with the organic matter 1,2,4-BTC.

[0050] 3) Study on the adsorption performance of the prepared hybrid nanomaterial Fe-1,2,4-BTC

[0051] 3.0 mg of the hybrid nanomaterial Fe-1,2,4-BTC was added into 5 mL of five single standard solutions (1.0 mg / L) respectively; the mixed system was adsorbed for 20 minutes in a constant temperature shaking incubator at 24°C and 210 rpm; after centrifugation, 1 mL of n-hexane layer was fully evaporated in a 2 mL centrifuge tube, and the same volume of methanol was used for redissolution; finally, the concentration of residual mycotoxin was measured by UPLC-MS / MS.

[0052] AsFigure 6 The figure shows the adsorption efficiency of the hybrid nanomaterial in removing various fungal toxins in standard solution. Figure 6 It can be seen that the hybrid nanomaterial Fe-1,2,4-BTC has a good adsorption effect, and the removal capacity of the five toxins is above 90%.

[0053] 4) Application of the prepared hybrid nanomaterial Fe-1,2,4-BTC in the adsorption of mixed fungal toxins in vegetable oils

[0054] 1. First, the comparison between Fe-1,2,4-BTC hybrid nanomaterials and inorganic porous adsorption materials

[0055] The vegetable oil used in the adsorption experiments was peanut oil purchased from a local supermarket and diluted with n-hexane (v / v = 1 / 3) to simulate industrial production. The Fe-1,2,4-BTC hybrid nanomaterial obtained in this application and the inorganic porous adsorption material (5.0 mg) were added to peanut oil supplemented with five mycotoxins (each at a concentration of 50.0 μg / L). The resulting mixture was adsorbed at 24°C and 210 rpm for 60 minutes. After extraction, the mycotoxins in the supernatant were detected using UPLC-MS / MS.

[0056] like Figure 7 A bar chart shows the adsorption efficiency of the hybrid nanomaterial and common inorganic porous materials for the removal of mycotoxins from vegetable oils. Compared with existing porous materials, some inorganic porous materials and MOFs are highly effective for AFTs but have weaker adsorption capacity for zearalenone. Under the same conditions, only the Fe-1,2,4-BTC hybrid nanomaterial can efficiently remove five mycotoxins from vegetable oils.

[0057] The Fe-1,2,4-BTC hybrid nanomaterials described in this application have adsorption efficiencies of 99.1%, 98.9%, 99.6%, 99.5%, and 73.1% for aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2, and zearalenone, respectively. The superior adsorption performance of the Fe-1,2,4-BTC hybrid nanomaterial is due to its high specific surface area and diverse interactions, enabling it to interact with a variety of toxin molecules.

[0058] 2. Application of Fe-1,2,4-BTC in purification columns

[0059] Firstly, put the outlet sieve plate (made of polyethylene material) at the bottom of the empty column tube (diameter 10mm) of polypropylene, then put 100mg of Fe-1,2,4-BTC prepared in the application, gently tap to make it evenly distributed, finally vertically press the inlet sieve plate, and press tightly and fill, so that the packing height of the column after filling is kept at 5+0.05mm.

[0060] The vegetable oil used in the adsorption experiment is represented by peanut oil purchased from a local supermarket, and is diluted with n-hexane (v / v=1 / 3) to simulate industrial production. Figure 8 As shown in the column chart of the purification efficiency of the hybrid nanomaterial purification column for removing mycotoxins in peanut oil, when a certain volume of spiked peanut oil mixture (the concentration of each toxin is 50.0μg / L) passes through the purification column at a flow rate of 1mL / min, 1,2,4-BTC can achieve rapid capture of the five mycotoxins in peanut oil, and the removal efficiency is more than 99%. In addition, when 90ml of peanut oil-n-hexane (v / v=1 / 3) mixture flows through the purification column filled with 100mg of Fe-1,2,4-BTC material at a flow rate of 1mL / min, the removal rate of mycotoxins remains at a high level, so the purification material can treat peanut oil in batches, and is expected to be applied to the rapid removal of toxins in the vegetable oil industry.

[0061] 3. Application of Fe-1,2,4-BTC hybrid nanomaterial in various vegetable oils

[0062] The vegetable oil used in the adsorption experiment is purchased from a local supermarket, and is diluted with n-hexane (v / v=1 / 3) to simulate industrial production. The Fe-1,2,4-BTC hybrid nanomaterial (5.0mg) prepared in the application is added to three kinds of vegetable oil-n-hexane mixtures (the concentration of each toxin is 50.0μg / L) containing five kinds of mycotoxins, respectively, and the obtained mixture is adsorbed for 60 minutes at 24℃ and a rotation speed of 210rpm. After extraction, the mycotoxins in the supernatant are detected by UPLC-MS / MS. As shown in the column chart of the adsorption efficiency of the hybrid nanomaterial in three kinds of common vegetable oils, the hybrid nanomaterial can efficiently remove the five kinds of mycotoxins in peanut oil, corn oil and soybean oil. Figure 9 As shown in the column chart of the adsorption efficiency of the hybrid nanomaterial in three kinds of common vegetable oils, the hybrid nanomaterial can efficiently remove the five kinds of mycotoxins in peanut oil, corn oil and soybean oil. Therefore, the purification performance of the Fe-1,2,4-BTE prepared in the application is generally applicable to various vegetable oils, and the composite material has good application prospect.

[0063] It is worth noting that the contents not described in detail in the embodiments of the application belong to the prior art known to those skilled in the art.

[0064] In summary, the method of the embodiment of the application combines metal ions with organic ligands, so that it has the rigidity of inorganic materials and the flexibility of organic materials, and can selectively recognize target molecules by using the abundant surface area, suitable channels and multifunctional sites of the material, so that it has better adsorption capacity and chemical stability.

[0065] The above merely provides the preferred embodiments of the present application, but the protection scope of the present application is not limited to this. Any changes or replacements easily conceived by those skilled in the art within the technical scope disclosed by the present application should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims. The information disclosed in the background section of the present application is merely intended to deepen the understanding of the general background of the present application, and should not be regarded as acknowledging or implying in any form that the information constitutes the prior art known by those skilled in the art.

Claims

1. A method for preparing an organic-inorganic hybrid nanomaterial, characterized in that: The method comprises: Step 1: Mixing a certain amount of an organic ligand 1,2,4-BTC and a metal compound FeCl3·6H2O in a set ratio; wherein the organic ligand 1,2,4-BTC represents trimellitic acid; The chemical formula of the organic ligand 1,2,4-BTC is C9H6O6, and its molecular structure is expressed as follows: Step 2: Add a certain amount of N,N-dimethylformamide to the mixture of step 1, mix by ultrasonication, and then add ethanol and mix by ultrasonication again; In step 2, the volume ratio of N,N-dimethylformamide to ethanol is 1:1; Step 3: placing the mixed system obtained in step 2 in an oven and reacting under constant temperature conditions; In step 3, the reaction conditions are specifically as follows: temperature at 80-90° C. and reaction time at 24-30 h. Under these conditions, the ligand and the metal can be fully coordinated. Step 4: After the reaction in step 3 is completed, the mixture is cooled naturally to room temperature, and the flocculent precipitate is removed and placed in a plastic centrifuge tube. The mixture is centrifuged at 12,000 rpm for 5 minutes, and the supernatant is discarded. Step 5: washing the flocculent precipitate obtained in step 4 with N,N-dimethylformamide and ethanol multiple times to finally obtain an organic-inorganic hybrid nanomaterial, represented by Fe-1,2,4-BTC; The specific cleaning method in step 5 is: The flocculent precipitate was washed with N,N-dimethylformamide until the supernatant was colorless, and then washed twice with ethanol; Among them, in the process of preparing hybrid nanomaterials, the usage ratio of each raw material is specifically as follows: Every 50.0 mg of the organic ligand 1,2,4-BTC corresponds to 52.5 mg of the metal compound FeCl3·6H2O, 15 ml of NN-dimethylformamide and 15 ml of ethanol.

2. An application of an organic-inorganic hybrid nanomaterial prepared by the method for preparing an organic-inorganic hybrid nanomaterial according to claim 1, characterized in that: The hybrid nanomaterial prepared in step 5 is used to adsorb multiple mycotoxins, including aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2 and zearalenone; specifically, the adsorption can be performed in five single standard solutions prepared with n-hexane.

3. An application of the organic-inorganic hybrid nanomaterial prepared by the method for preparing the organic-inorganic hybrid nanomaterial according to claim 1, characterized in that: The hybrid nanomaterial prepared in step 5 is used to simultaneously adsorb five mycotoxins in vegetable oil, wherein the five mycotoxins include aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2 and zearalenone.

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