A THB@MIL-101(Cr)-NH2 adsorbent material, a preparation method thereof and application thereof

Abstract

This invention relates to a THB@MIL-101(Cr)-NH2 adsorbent material, its preparation method, and its applications. The adsorbent material is prepared by functionalizing MIL-101(Cr)-NH2 with 2,4,6-trihydroxybenzaldehyde. In this invention, a post-modification method is used to introduce 2,4,6-trihydroxybenzaldehyde (THB) into the MIL-101(Cr)-NH2 framework for functionalization, resulting in the THB@MIL-101(Cr)-NH2 adsorbent material. The prepared THB@MIL-101(Cr)-NH2 adsorbent material exhibits high adsorption capacity for aflatoxin in solutions and vegetable oil samples. Within 30 minutes, the removal efficiency of aflatoxin in aqueous solutions can reach 90%–99%, and the removal efficiency of aflatoxin in vegetable oils can reach over 85%.

Description

Technical Field

[0001] This invention relates to the field of adsorption materials technology, and in particular to a THB@MIL-101(Cr)-NH2 adsorption material, its preparation method, and its application. Background Technology

[0002] Sterigmatocystin (ST) is a mycotoxin containing a difuran-containing xanthone. Its chemical name is (3aR,12cS)-8-hydroxy-6-methoxy-3a,12c-dihydro-7H-furan[30,20:4,5]furan[2,3-c]xanthracene-7-one. It is a precursor in the biosynthesis of aflatoxin B1 and can also be a final product produced by toxic fungi. Currently, more than 50 toxic species are known to produce sterigmatocystin. Common sources of sterigmatocystin include various Aspergillus genera (such as *Aspergillus versicolor*, *Aspergillus flavus*, *Aspergillus nidus*, and *Aspergillus rubrum*), *Penicillium*, *Heliophyta*, and *Chaetoceros* fungi. Studies have shown that sterigmatocystin is mutagenic, can covalently bind to DNA to form DNA adducts, and can induce liver tumors. Therefore, effective adsorption and removal of sterigmatocystin from edible vegetable oils and other foods is crucial for ensuring food safety. Summary of the Invention

[0003] To address the aforementioned issues, this paper presents a THB@MIL-101(Cr)-NH2 adsorbent material, its preparation method, and its applications, aiming to achieve efficient removal of aflatoxin from an oil matrix.

[0004] The specific technical solution is as follows:

[0005] A THB@MIL-101(Cr)-NH2 adsorbent material is prepared by functionalizing MIL-101(Cr)-NH2 with 2,4,6-trihydroxybenzaldehyde as a modifier.

[0006] Furthermore, its preparation includes the following steps: MIL-101(Cr)-NH2 powder is poured into a round-bottom flask, anhydrous organic solvent is added, and it is ultrasonically dispersed evenly. 2,4,6-trihydroxybenzaldehyde is added and dispersed evenly. Glacial acetic acid is added dropwise, and after ultrasonic dispersion, it is refluxed under inert gas protection for a period of time. After filtration, the obtained solid is washed and vacuum dried to obtain a THB@MIL-101(Cr)-NH2 adsorbent material.

[0007] Furthermore, the molar ratio of MIL-101(Cr)-NH2 powder to 2,4,6-trihydroxybenzaldehyde is 1:(1-1.5).

[0008] Furthermore, the amount of glacial acetic acid added is 10-40 μL per 100 mg MIL-101(Cr)-NH2.

[0009] Furthermore, the reflux temperature is 35-100 ℃, and the reaction time is 2-5 days.

[0010] A second aspect of the present invention is to provide a THB@MIL-101(Cr)-NH2 adsorbent material prepared according to the above preparation method.

[0011] The third aspect of the present invention is to provide the application of THB@MIL-101(Cr)-NH2 adsorbent material, specifically, using THB@MIL-101(Cr)-NH2 adsorbent material as an adsorbent to adsorb and remove aflatoxin.

[0012] Furthermore, add 2-10 mg / g THB@MIL-101(Cr)-NH2 adsorbent material to the matrix at a content of 10-100 μg / (kg matrix), shake, and then filter to remove the THB@MIL-101(Cr)-NH2 adsorbent material, thereby adsorbing and removing Aflatoxin.

[0013] The beneficial effects of the above scheme are:

[0014] In this invention, 2,4,6-trihydroxybenzaldehyde (THB) is introduced into the MIL-101(Cr)-NH2 framework for functionalization using a post-modification method to prepare THB@MIL-101(Cr)-NH2 adsorbent material. The prepared THB@MIL-101(Cr)-NH2 adsorbent material has a high adsorption capacity for aflatoxin in solution and vegetable oil samples. The removal efficiency of ST in aqueous solution can reach 90%~99% within 30 minutes, and the removal efficiency of ST in vegetable oil can reach more than 85%. Attached Figure Description

[0015] Figure 1 The XRD diffraction pattern of THB@MIL-101(Cr)-NH2 provided in the embodiments of the present invention;

[0016] Figure 2 This is a SEM image of THB@MIL-101(Cr)-NH2 provided in an embodiment of the present invention;

[0017] Figure 3 This is an XPS image of THB@MIL-101(Cr)-NH2 provided in an embodiment of the present invention;

[0018] Figure 4The FT-IR image of THB@MIL-101(Cr)-NH2 provided in the embodiments of the present invention;

[0019] Figure 5 This is an adsorption isotherm diagram of THB@MIL-101(Cr)-NH2 provided in an embodiment of the present invention. Detailed Implementation

[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other.

[0022] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but this is not intended to limit the scope of the invention.

[0023] This invention provides a THB@MIL-101(Cr)-NH2 adsorbent material, which is prepared by functionalizing MIL-101(Cr)-NH2 with 2,4,6-trihydroxybenzaldehyde as a modifier.

[0024] Specifically, the preparation method is as follows: MIL-101(Cr)-NH2 powder is poured into a round-bottom flask, anhydrous organic solvent is added, and the mixture is ultrasonically dispersed until uniform. 2,4,6-trihydroxybenzaldehyde is added and ultrasonically dispersed until uniform. Glacial acetic acid is added dropwise, and the mixture is ultrasonically dispersed until uniform. After being refluxed at 35-100 °C for 2-5 days under inert gas protection, the mixture is filtered. The resulting solid is washed and vacuum dried to obtain a THB@MIL-101(Cr)-NH2 adsorbent material. The molar ratio of MIL-101(Cr)-NH2 powder to 2,4,6-trihydroxybenzaldehyde is 1:(1-1.5). The amount of glacial acetic acid added is 10-40 μL per 100 mg of MIL-101(Cr)-NH2. The reflux temperature is 35-100 °C, and the reaction time is 2-5 days.

[0025] Example 1

[0026] A THB@MIL-101(Cr)-NH2 adsorbent material, the preparation method of which is as follows:

[0027] 120 mg of MIL-101(Cr)-NH2 powder was poured into a 100 mL round-bottom flask, and 15 mL of anhydrous methanol was added. The suspension was sonicated for 10 minutes, and then 75 mg of 2,4,6-trihydroxybenzaldehyde was added. The resulting mixture was sonicated for 5 minutes, and 30 μL of glacial acetic acid was added dropwise. The mixture was sonicated for 1 minute, and the suspension was refluxed at 40°C for 3 days under nitrogen protection. The obtained solid product was washed three times with methanol and then soaked in methanol for 2 days to remove residual organic matter. The brick-red solid obtained was collected by centrifugation and vacuum dried at 40°C for 18 hours to obtain THB@MIL-101(Cr)-NH2 adsorbent material.

[0028] In this embodiment, MIL-101(Cr)-NH2 was synthesized by a hydrothermal method. Specifically, the preparation method is as follows: 5.329 g (20 mmol) CrCl3·6H2O and 3.623 g (20 mmol) o-aminoterephthalic acid were dispersed in 50 mL of distilled water, 1 mL of concentrated HNO3 was added, the mixture was stirred for 30 minutes and then transferred to a polytetrafluoroethylene-lined autoclave and placed in an oven at 140 °C for 14 hours; the autoclave was removed and allowed to cool naturally to room temperature, the green precipitate was collected, and washed several times with dimethylformamide and ethanol to remove residual organic matter. Finally, it was placed in an oven at 80 °C and dried overnight to obtain a green powder.

[0029] like Figure 1 As shown, the THB@MIL-101(Cr)-NH2 adsorbent material provided in this embodiment exhibits obvious diffraction peaks at 2θ values ​​of 5.3°, 6.0°, 8.7°, 9.96°, 10.6°, and 16.78°. The diffraction peaks are in good agreement with the reported diffraction peaks of MIL-101(Cr)-NH2 in the literature, indicating that the desired MIL-101(Cr)-NH2 was obtained. Subsequently, the introduction of 2,4,6-trihydroxybenzaldehyde did not cause significant changes in the diffraction peaks, indicating that the THB@MIL-101(Cr)-NH2 prepared after synthesis and modification still retains good crystallinity.

[0030] like Figure 2 As shown, the THB@MIL-101(Cr)-NH2 adsorbent material provided in this embodiment is in the form of aggregated spherical nanoparticles, which indicates that the morphology of 2,4,6-trihydroxybenzaldehyde introduced into the pores of the MOF structure after synthesis was not changed.

[0031] like Figure 3As shown, the THB@MIL-101(Cr)-NH2 adsorbent material provided in this embodiment has obvious absorption peaks at 285.1, 400.1, 532.1, 577.1 and 587.1 eV, which correspond to C 1s, N 1s, O 1s and Cr 2p, respectively. This indicates that THB@MIL-101(Cr)-NH2 is composed of C, N, O and Cr elements.

[0032] like Figure 4 As shown, the THB@MIL-101(Cr)-NH2 adsorbent provided in this embodiment exhibits performance at 3500–3200 cm⁻¹. -1 The presence of a broad band at 1580 cm⁻¹ indicates that THB@MIL-101(Cr)-NH₂ contains abundant hydroxyl groups; –1 A distinct absorption peak is observed at 1498 cm⁻¹, indicating the formation of C=N bonds; –1 and 1428 cm –1 The absorption peak at 1387 cm⁻¹ corresponds to the -OCO- stretching vibration; at 1387 cm⁻¹ –1 The distinct absorption peak at 1332 cm⁻¹ corresponds to the O–C=O symmetric vibration, confirming the presence of terephthalic acid within the MOF framework; –1 and 1262 cm –1 The absorption peak at 800–600 cm⁻¹ corresponds to the CN stretching vibration of aromatic amines. -1 The absorption peaks appearing within this range are attributed to the in-plane and out-of-plane bending vibrations of the carboxyl group. 541 cm⁻¹ -1 The absorption peaks at the point correspond to Cr-O bonds; these results indicate the formation of the THB@MIL-101(Cr)-NH2 structure.

[0033] like Figure 5 As shown, the adsorption curve of the THB@MIL-101(Cr)-NH2 adsorbent material provided in this embodiment under nitrogen adsorption at 77 K can be classified as a Type I isotherm (IUPAC classification), indicating that the THB@MIL-101(Cr)-NH2 framework mainly consists of micropores. However, a hysteresis loop appears at relatively high pressures, indicating that a small number of mesopores exist in the THB@MIL-101(Cr)-NH2 structure. The calculated BET specific surface area and total pore volume of THB@MIL-101(Cr)-NH2 are 1887 m². 2 / g and 0.24cm 3 / g.

[0034] To evaluate the removal efficiency of THB@MIL-101(Cr)-NH2 adsorbent on ST, a 100 ng / mL ST solution was prepared using 1% acetonitrile aqueous solution as the solvent. 5 mg of adsorbent was added to the solution, and the mixture was vigorously shaken for 30 minutes. The treated solution was then collected by centrifugation. The residual ST in the sample was determined using HPLC-MS / MS. The ST removal efficiency was calculated using the following formula:

[0035] P%=(C0 C) / C0×100%

[0036] Wherein, C0 and C represent the original concentration and residual concentration of ST in the sample, respectively.

[0037] The results showed that 90%-99% of ST in the aqueous solution could be removed within 30 minutes, indicating that the prepared adsorbent material can effectively remove ST from the solution.

[0038] To verify the practicality of the THB@MIL-101(Cr)-NH2 adsorbent in actual samples, blank peanut oil with added ST was used to test the adsorbent's adsorption effect on ST in the oil matrix. The specific experimental method was as follows: 1 g of spiked vegetable oil (50 μg / kg) was mixed with 5 mg of adsorbent and shaken vigorously for 30 minutes. The oil treated with the adsorbent was then collected by centrifugation. The residual amount of ST in the sample was determined by HPLC-MS / MS, and the removal efficiency was calculated according to the above formula.

[0039] The results showed that more than 85% of ST in vegetable oil samples could be removed within 30 minutes, indicating that the prepared THB@MIL-101(Cr)-NH2 material can effectively remove ST from edible oil.

[0040] The above description is merely a preferred embodiment of the present invention and does not limit the implementation and protection scope of the present invention. Those skilled in the art should realize that any equivalent substitutions and obvious changes made based on the description and illustrations of the present invention should be included within the protection scope of the present invention.

Claims

1. The application of THB@MIL-101(Cr)-NH2 adsorbent material, characterized in that, THB@MIL-101(Cr)-NH2 adsorbent was used as an adsorbent to remove Aspergillus violaceus. The preparation method of the THB@MIL-101(Cr)-NH2 adsorbent material is as follows: MIL-101(Cr)-NH2 is functionalized with 2,4,6-trihydroxybenzaldehyde as a modifier to obtain a THB@MIL-101(Cr)-NH2 adsorbent material, including the following steps: MIL-101(Cr)-NH2 powder is poured into a round-bottom flask at a molar ratio of 1:(1-1.5) with an anhydrous organic solvent added and ultrasonically dispersed evenly. 2,4,6-trihydroxybenzaldehyde is then added and dispersed evenly. Glacial acetic acid is added dropwise, and the mixture is ultrasonically dispersed evenly. The mixture is then refluxed under inert gas protection for a period of time, filtered, and the resulting solid is washed and vacuum dried to obtain a THB@MIL-101(Cr)-NH2 adsorbent material.

2. The application of the THB@MIL-101(Cr)-NH2 adsorbent material according to claim 1, characterized in that, The amount of glacial acetic acid added is 10-40 μL per 100 mg MIL-101(Cr)-NH2.

3. The application of the THB@MIL-101(Cr)-NH2 adsorbent material according to claim 1, characterized in that, The reflux temperature is 35-100 ℃, and the reaction time is 2-5 days.

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