An nh2-UiO-66@btt-bpda core-shell material, a preparation method and application thereof

Abstract

An NH2-UiO-66@BTT-BPDA core-shell material takes NH2-UiO-66 as a core and BTT-BPDA as a shell; a preparation method comprises the following steps: uniformly mixing zirconium tetroxide / 2-amino terephthalic acid, DMF and acetic acid, heating, washing the solid product with a mixed solution of methanol and DMF after heating, drying to obtain NH2-UiO-66; uniformly mixing NH2-UiO-66, benzotriphene triformaldehyde and dioxane, heating, washing the solid product with tetrahydrofuran after heating to obtain aldehyde-based NH2-UiO-66; dissolving the aldehyde-based NH2-UiO-66, benzotriphene triformaldehyde and (2,2'-dipyridyl)-5,5'-diamine in a glass bottle containing dioxane and glacial acetic acid; heating the glass bottle to obtain a brown product; centrifuging the brown product, washing the solid product with anhydrous tetrahydrofuran to obtain the NH2-UiO-66@BTT-BPDA core-shell material. The NH2-UiO-66@BTT-BPDA core-shell material is used for adsorbing harmful substances in industrial wastewater. The core-shell material prepared by the method is connected through a dynamic carbon-nitrogen covalent bond, has good structural stability, is rich in high-density benzene rings and pyridine rings, and has the advantages of high adsorption capacity, fast adsorption rate, good selectivity, easy regeneration and the like for iodine and organic dyes.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of adsorbent materials, and particularly relates to a NH2-UiO-66@BTT-BPDA core-shell material and a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of industrialization, water pollution is still a serious problem that endangers public health and the environment. The chemical industry (such as pesticides, dyes, pharmaceuticals, coke and surfactants) has a large number of products, complex reactions, and uses a large amount of harmful raw materials such as halogen compounds and nitro compounds, resulting in complex pollutant components, high organic pollutant content, high salt content, high colority, high toxicity and difficulty in degradation in wastewater. The treatment method mainly based on biodegradation cannot meet the current situation of modern industrial development. Adsorption is considered an effective wastewater treatment technology due to its low cost, simple operation, environmental friendliness, simple regeneration and large-scale application. However, existing adsorbents often have defects such as low thermal stability, poor regeneration, poor adsorption performance and complex preparation process.

[0003] COFs have the advantages of low mass density, high thermal stability, permanent porosity and large specific surface area, and are one of the materials for industrial wastewater treatment. MOFs, as another kind of organic porous material, are good candidates for constructing heterostructures with COFs to improve the performance of monomers. MOF / COF composite materials not only inherit their own characteristics such as rich porous structure, ultra-high porosity and large specific surface area, but also often exhibit unexpected new properties through the synergistic effect of each component, thereby showing great application potential in different fields such as membrane separation, sensing and catalysis. However, the research on this kind of composite material in the field of solid phase extraction still needs further exploration. Therefore, it is of great significance to prepare a MOF@COF composite adsorbent for the treatment of industrial wastewater. SUMMARY

[0004] Therefore, the application designs a NH2-UiO-66@BTT-BPDA core-shell material, which is used for the treatment of industrial wastewater, has low preparation cost, good structural stability, high adsorption capacity for iodine and organic dyes, fast adsorption rate, good selectivity, easy regeneration and other advantages.

[0005] A NH2-UiO-66@BTT-BPDA core-shell material, wherein NH2-UiO-66 (MOF) is used as the core, BTT-BPDA (COF) is used as the shell, and carbon-nitrogen covalent bonds are used as the connection between the core and the shell; wherein the core-shell material is an octahedral porous crystalline core-shell hybrid material.

[0006] A preparation method of a NH2-UiO-66@BTT-BPDA core-shell material, and the method specifically comprises the following steps:

[0007] Step 1: Preparation of NH2-UiO-66: Zirconium tetrachloride and 2-aminoterephthalic acid were mixed uniformly in N,N-dimethylformamide, and acetic acid solution was added dropwise to obtain a first premix solution; the first premix solution was heated in an oven at 120°C for 24 hours, and the heated first premix solution was subjected to solid-liquid separation, and the solid product was washed with a mixture of methanol and N,N-dimethylformamide for 3 times, and dried in an oven at 70°C for 12 hours, and the dried solid product was obtained to obtain the NH2-UiO-66;

[0008] Step 2: Aldehyde group modification of NH2-UiO-66: the NH2-UiO-66 and benzotriphene triformaldehyde were mixed uniformly in dioxane to obtain a second premix solution, and the second premix solution was heated in an oven at 110°C for 72 hours, and the solid-liquid product was separated by centrifugation after natural cooling to room temperature, and the solid product was washed with tetrahydrofuran and dried in an oven at 70°C for 12 hours to obtain the aldehyde group modified NH2-UiO-66;

[0009] Step 3: Preparation of NH2-UiO-66@BTT-BPDA core-shell material: the aldehyde group modified NH2-UiO-66, benzotriphene triformaldehyde and (2,2'-bipyridine)-5,5'-diamine were dissolved in a glass bottle containing dioxane and glacial acetic acid; the glass bottle was heated at 110°C for three days to obtain a brown product; the brown product was centrifuged, and the solid product was washed with anhydrous tetrahydrofuran and vacuum dried at 70°C for 12 hours to obtain a brown solid powder, which was the NH2-UiO-66@BTT-BPDA core-shell material.

[0010] In the reaction, the MOF first reacts with benzotriphene triformaldehyde to cover the -CHO group on the surface of the MOF core octahedron, and then the -CHO group reacts with the -NH2 group to cover the BTT-BPDA-COF shell layer on the core through the Schiff base reaction.

[0011] Preferably, the molar ratio of the zirconium tetrachloride and 2-aminoterephthalic acid in step 1 is (0.5-1.5):(0.5-1.5); and the volume ratio of the N,N-dimethylformamide and acetic acid is (8-12):(0.5-1.6).

[0012] Preferably, the mass ratio of the NH2-UiO-66 and benzotriphene triformaldehyde in step 2 is (1.5-2.5):(0.5-1.5).

[0013] Preferably, the molar ratio of (2,2'-bipyridine)-5,5'-diamine to benzotriphene triformaldehyde in step 3 is (2-4):(1-3), the mass ratio of the aldehyde-based NH2-UiO-66 and benzotriphene triformaldehyde is (2-6):(0.5-1.5), and the volume ratio of glacial acetic acid and dioxane is (0.5-1.5):(10-20).

[0014] The application of the NH2-UiO-66@BTT-BPDA core-shell material is to disperse the NH2-UiO-66@BTT-BPDA core-shell material in industrial wastewater, oscillate and adsorb until adsorption equilibrium is reached, and then regenerate the core-shell material after adsorption equilibrium is reached.

[0015] The NH2-UiO-66@BTT-BPDA core-shell material is used for adsorbing harmful substances in industrial wastewater.

[0016] Preferably, the industrial wastewater is one of dye wastewater or iodine-containing wastewater.

[0017] Preferably, the application specifically refers to dispersing the NH2-UiO-66@BTT-BPDA core-shell material in industrial wastewater, oscillating and adsorbing until adsorption equilibrium is reached, and then regenerating the core-shell material after adsorption equilibrium is reached. Generally, the regeneration method specifically refers to soaking the NH2-UiO-66@BTT-BPDA core-shell adsorbent adsorbing dyes in alcohol, desorbing by ultrasonic oscillation for 20-40 minutes, and then washing with deionized water and centrifugal separation to complete the regeneration of the NH2-UiO-66@BTT-BPDA core-shell adsorbent.

[0018] Preferably, the dye wastewater is one of methylene blue, crystal violet, malachite green, rhodamine B, and methyl orange wastewater.

[0019] COFs have low mass density, high thermal stability, permanent porosity, and large specific surface area, etc. advantages, and are one of the most application potential materials in environmental pollution treatment. Compared with traditional adsorbents, the ordered pore structure of COFs provides abundant adsorption sites, accelerates the rapid diffusion of pollutants, and the pore size and shape of COFs are easy to adjust, which provides the possibility for the separation of different pollutants, and COFs have high chemical and thermal stability, and the low density of COFs means that they have high adsorption capacity. MOFs, as another kind of organic porous material, can be a good candidate for building heterojunctions with COFs to improve the performance of monomers. MOF / COF composite materials not only inherit their own characteristics such as rich porous structure, ultra-high porosity and large specific surface area, but also often exhibit unexpected new properties through the synergistic effect of each component. The application designs a new type of NH2-UiO-66@BTT-BPDA core-shell composite material and a rapid preparation method thereof, the composite material prepared by the method has a structure stable and good, and the building blocks are rich in high-density benzene rings and pyridine rings, and the composite material has high adsorption capacity, fast adsorption rate, good selectivity, easy regeneration and the like for iodine and organic dyes. The dye adsorbent prepared by the preparation method of the application has the advantages of simple dye wastewater treatment method, no need to adjust the reaction temperature, and the treatment can be carried out at room temperature. The pH value of the wastewater does not need to be strictly adjusted, and the removal effect is good in a wide pH range from acid to alkali; and the adsorption efficiency of the composite material for iodine is higher than that of pure MOFs, and the adsorption capacity per unit time is larger. BRIEF DESCRIPTION OF DRAWINGS

[0020] FIG. 1 is a schematic diagram of the synthesis of the composite material in Example 1. Figure 1

[0021] FIG. 2 is an FT-IR spectrum of NH2-UiO-66@BTT-BPDA in Example 1. Figure 2

[0022] FIG. 3 is a SEM image of the MOF in Example 1. Figure 3

[0023] FIG. 4 is a SEM image of NH2-UiO-66@BTT-BPDA in Example 1. Figure 4

[0024] FIG. 5 is a TEM image of NH2-UiO-66@BTT-BPDA in Example 1. Figure 5

[0025] FIG. 6 is an N element mapping image of NH2-UiO-66@BTT-BPDA in Example 1. Figure 6

[0026] FIG. 7 is a schematic diagram of the synthesis of the composite material in Example 2.​​​​​​Figure 7 This is the S element mapping diagram of NH2-UiO-66@BTT-BPDA in Example 1.

[0027] Appendix Figure 8 This is the Zr element mapping diagram of NH2-UiO-66@BTT-BPDA in Example 1.

[0028] Appendix Figure 9 The graph shows the dye removal rate using NH2-UiO-66@BTT-BPDA as the adsorbent.

[0029] Appendix Figure 10 This is a graph showing the adsorption capacity of iodine using NH2-UiO-66@BTT-BPDA as the adsorbent. Detailed implementation method:

[0030] To make the technical solution of the present invention easier to understand, specific embodiments are now used to clearly and completely describe the technical solution of the present invention.

[0031] Example 1:

[0032] This embodiment describes a method for preparing an NH2-UiO-66@BTT-BPDA core-shell material, comprising the following steps:

[0033] (1) Preparation of NH2-UiO-66 material:

[0034] 0.045 mmol of zirconium tetrachloride and 0.045 mmol of 2-aminoterephthalic acid were dissolved in 1.2 mL of acetic acid and 10 mL of N,N-dimethylformamide, respectively, and placed in a 20 mL glass bottle. After sonication for 30 minutes, the bottle was sealed and heated in an oven at 120 °C for 24 hours. After centrifugation, the product was washed three times with a mixture of methanol and N,N-dimethylformamide (volume ratio 1:4), and then dried under vacuum at 70 °C for 12 hours to obtain NH₂-UiO-66 crystals with an octahedral structure.

[0035] (2) Aldehyde-modified NH2-UiO-66 materials:

[0036] 20 mg of NH2-UiO-66 was added to a glass bottle containing 8 mL of 1,4-dioxane and sonicated for 10 min to obtain a suspension. Then, 10 mg of benzotrithiophene tricarboxaldehyde was added to the suspension and sonicated for 30 min to obtain a second suspension. 0.5 mL of glacial acetic acid was added to the second suspension, and the mixture was heated in an oven at 110 °C for 72 h. After naturally cooling to room temperature, the solid and liquid products were separated by centrifugation. The solid product was washed with tetrahydrofuran and dried in an oven at 70 °C for 12 h to obtain the NH2-UiO-66@BTT composite material, labeled U@BTT.

[0037] (3) Preparation of NH2-UiO-66@BTT-BPDA core-shell material:

[0038] Synthesized 0.026g U@BTT was added to a glass vial containing 8mL 1,4-dioxane to obtain a suspension, and the suspension was ultrasonically dispersed for 5 minutes. 0.02mmol benzotri th iole aldehyde and 0.03mmol (2,2'-bipyridine)-5,5'-diamine were dispersed into the suspension, and a second suspension was obtained by ultrasonic treatment for 30min. 0.5mL glacial acetic acid was added to the second suspension, and the mixture was heated in an oven at 110°C for 72h. The solid-liquid product was separated by centrifugation, the solid product was washed with tetrahydrofuran and dried in a vacuum oven at 70°C for 12h to obtain the NH2-UiO-66@BTT-BPDA core-shell material.

[0039] Example 2:

[0040] The preparation method of the NH2-UiO-66@BTT-BPDA core-shell material in this example includes the following steps:

[0041] (1) Preparation of NH2-UiO-66 material:

[0042] 0.023mmol zirconium tetrachloride and 0.068mmol 2-amino terephthalic acid were respectively dissolved in 1.6mL acetic acid and 8mL N,N-dimethylformamide, and were placed in a 20mL glass bottle. After ultrasonic treatment for 30 minutes, the vial was sealed and heated in an oven at 120°C for 24 hours. The product was centrifuged, washed with a mixture containing methanol and N,N-dimethylformamide (volume ratio 1:4) for 3 times, and then dried in a vacuum oven at 70°C for 12 hours to obtain NH2-UiO-66 crystals with an octahedral structure.

[0043] (2) Aldehyde group modified NH2-UiO-66 material:

[0044] 15mg NH2-UiO-66 was added to a glass bottle containing 8mL 1,4-dioxane, and a suspension was obtained by ultrasonic treatment for 10min. 15mg benzotri th iole aldehyde was added to the suspension, and a second suspension was obtained by ultrasonic treatment for 30min. 0.5mL glacial acetic acid was added to the second suspension, and the mixture was heated in an oven at 110°C for 72h. After natural cooling to room temperature, the solid-liquid product was separated by centrifugation, the solid product was washed with tetrahydrofuran and dried in an oven at 70°C for 12 hours to obtain the NH2-UiO-66@BTT composite material, which was labeled as U@BTT.

[0045] (3) Preparation of NH2-UiO-66@BTT-BPDA core-shell material:

[0046] Synthesized 0.04 g U@BTT was added to a glass vial containing 10 mL of 1,4-dioxane to obtain a suspension, and the suspension was ultrasonically dispersed for 5 minutes. 0.03 mmol of benzotri th iole aldehyde and 0.02 mmol of (2,2'-bipyridine)-5,5'-diamine were dispersed into the suspension, and a second suspension was obtained by ultrasonic treatment for 30 min. 0.25 mL of glacial acetic acid was added to the second suspension, and heating was performed in an oven at 110°C for 72 h. The solid-liquid product was centrifuged and separated, the solid product was washed with tetrahydrofuran and dried in a 70°C oven for 12 h to obtain the NH2-UiO-66@BTT-BPDA core-shell material.

[0047] Example 3:

[0048] The preparation method of the NH2-UiO-66@BTT-BPDA core-shell material in this example includes the following steps:

[0049] (1) Preparation of NH2-UiO-66 material:

[0050] 0.068 mmol of zirconium tetrachloride and 0.023 mmol of 2-amino terephthalic acid were respectively dissolved in 0.5 mL of acetic acid and 12 mL of N,N-dimethylformamide, and were placed in a 20 mL glass bottle. After ultrasonic treatment for 30 min, the vial was sealed and heated in an oven at 120°C for 24 h. The product was centrifuged and washed with a mixture containing methanol and N,N-dimethylformamide (volume ratio of 1:4) for 3 times, and then dried in a 70°C oven for 12 h to obtain NH2-UiO-66 crystals with an octahedral structure.

[0051] (2) Aldehyde group modified NH2-UiO-66 material:

[0052] 25 mg of NH2-UiO-66 was added to a glass bottle containing 8 mL of 1,4-dioxane, and ultrasonic treatment was performed for 10 min to obtain a suspension. Then 5 mg of benzotri th iole aldehyde was added to the suspension, and a second suspension was obtained by ultrasonic treatment for 30 min. 0.5 mL of glacial acetic acid was added to the second suspension, and heating was performed in an oven at 110°C for 72 h. After natural cooling to room temperature, the solid-liquid product was centrifuged and separated, the solid product was washed with tetrahydrofuran and dried in a 70°C oven for 12 h to obtain the NH2-UiO-66@BTT composite material, which was labeled as U@BTT.

[0053] (3) Preparation of NH2-UiO-66@BTT-BPDA core-shell material:

[0054] The synthesized 0.01 g U@BTT was added to a glass vial containing 5 mL of 1,4-dioxane to obtain a suspension, and the suspension was ultrasonically dispersed for 5 minutes. 0.01 mmol of benzotriphene triformaldehyde and 0.04 mmol of (2,2'-dipyridyl)-5,5'-diamine were dispersed into the suspension, and a second suspension was obtained by ultrasonic treatment for 30 min. 0.5 mL of glacial acetic acid was added to the second suspension, and heating was carried out in an oven at 110°C for 72 h. The solid-liquid product was separated by centrifugation, the solid product was washed with tetrahydrofuran and dried under vacuum at 70°C for 12 h, thereby obtaining the NH2-UiO-66@BTT-BPDA core-shell material.

[0055] Figure 2 The FT-IR spectrum of the NH2-UiO-66@BTT-BPDA composite material prepared in Example 1 was obtained, and it can be seen from the figure that the characteristic peaks of the NH2-UiO-66@BTT-BPDA hybrid material are similar to those of NH2-UiO-66. Among them, the characteristic peaks at 1600 cm -1 The characteristic peaks are derived from the C=N stretching vibration of BTT-BPDA.

[0056] Figure 3 The SEM image of NH2-UiO-66 prepared in Example 1 is shown, and the structure of the MOF is octahedral, with a smooth surface.

[0057] Figure 4 The SEM image of the NH2-UiO-66@BTT-BPDA composite material prepared in Example 1 is shown, Figure 5 The TEM image of NH2-UiO-66@BTT-BPDA is shown, and it can be seen from the figure that there is a clear shell structure on the surface of NH2-UiO-66, so the NH2-UiO-66@BTT-BPDA core-shell structure is successfully synthesized.

[0058] Figures 6-8 The mapping image of the NH2-UiO-66@BTT-BPDA composite material prepared in Example 1 is shown, and the Zr element of the MOF is uniformly distributed, and the N and S elements of BTT-BPDA cover the entire structure, further confirming that the NH2-UiO-66@BTT-BPDA core-shell structure with a BTT-BPDA shell and a NH2-UiO-66 core structure is successfully synthesized.

[0059] Application Example 1:

[0060] NH2-UiO-66@BTT-BPDA core-shell adsorbent prepared in Example 1 (5 mg) was dispersed in 5 mL of dye (malachite green, green rhodamine b, methylene blue, methyl orange, crystal violet) wastewater to be treated, and the dye concentration was 50 μM. A conical flask containing the NH2-UiO-66@BTT-BPDA core-shell adsorbent and the dye mixture was placed on a shaker at a speed of 190 r / min for 30 min, then removed and filtered with a water filter head, and then the filtered solution was detected in a UV spectrophotometer. The initial concentration and the concentration after adsorption of the dye were obtained according to the standard curve between the absorbance and the concentration of each dye. The removal rate of NH2-UiO-66@BTT-BPDA for different dyes was calculated, and the results were as follows Figure 9 .

[0061] The obtained NH2-UiO-66@BTT-BPDA core-shell adsorbent showed excellent adsorption effect on methyl orange, malachite green and rhodamine B dyes, with a removal rate of 99%, a removal rate of 90% for crystal violet, and a removal rate of 65% for methylene blue.

[0062] Application Example 2

[0063] NH2-UiO-66@BTT-BPDA core-shell adsorbent (10 mg) and iodine (200 mg) prepared in Example 1 were respectively placed in different glass bottles (in this application example, the adsorption performance of NH2-UiO-66@BTT-BPDA core-shell adsorbent prepared in Example 1 for iodine was explored by directly using the method of adsorbing elemental iodine), and then the two glass bottles were placed in the same wide-mouth bottle. After sealing the bottle mouth, it was placed in an oven at a temperature of 75°C, and the pressure was normal pressure. After 0-100 h, the mass after adsorption was weighed for calculating the adsorption amount, and the results were as follows Figure 10 .

[0064] The obtained NH2-UiO-66@BTT-BPDA core-shell adsorbent had an adsorption amount of 167% for iodine, which was much higher than the adsorption amount (67%) of the original MOF.

[0065] Table 1 Comparison of adsorption performance of adsorbent prepared in Example 1 with other adsorbents

[0066]

[0067] As can be seen from Table 1, NH2-UiO-66@BTT-BPDA has a higher adsorption amount for various dyes than other adsorbents, indicating that the composite material synthesized in this study has excellent adsorption performance. In addition, the adsorption performance of the composite material for iodine is also better than existing adsorbents. Therefore, NH2-UiO-66@BTT-BPDA has application value for adsorbing dyes in actual high-concentration wastewater.

[0068] It should be noted that the embodiments described herein are merely some embodiments of the present application, rather than all implementation manners of the present application, and are only exemplary, and their role is only to provide a more intuitive and clear way to understand the content of the present application, and are not a limitation on the technical solutions of the present application. Without departing from the concept of the present application, all other implementation manners that can be thought of by those of ordinary skill in the art without creative labor, and other simple replacements and various changes of the technical solutions of the present application, all belong to the protection scope of the present application.

Claims

1. An NH2-UiO-66@BTT-BPDA core-shell material, characterized in that, The core-shell material takes NH2-UiO-66 as the core, BTT-BPDA as the shell, and carbon-nitrogen covalent bond as the connection between the core and the shell; wherein the core-shell material is an octahedral porous crystalline core-shell hybrid material.

2. A method for preparing a NH2-UiO-66@BTT-BPDA core-shell material, characterized in that, The method is specifically: Step 1: preparation of NH2-UiO-66: zirconium tetrachloride and 2-amino terephthalic acid are mixed uniformly in N,N-dimethylformamide, and acetic acid solution is added dropwise to obtain a first premix solution; the first premix solution is heated in an oven at 120 DEG C for 24 hours, and after the heated first premix solution is separated into solid and liquid, the solid product is washed with a mixed solution of methanol and N,N-dimethylformamide, and the solid product is dried to obtain NH2-UiO-66; Step 2: aldehyde group of NH2-UiO-66: the NH2-UiO-66 and benzotriphene triformaldehyde are mixed uniformly in dioxane to obtain a second premix solution, the second premix solution is heated in an oven at 110 DEG C for 72 hours, and after cooling to room temperature, the solid-liquid product is centrifuged, the solid product is washed with tetrahydrofuran and dried to obtain the aldehyde group of NH2-UiO-66; Step 3: preparation of NH2-UiO-66@BTT-BPDA core-shell material: the aldehyde group of NH2-UiO-66, benzotriphene triformaldehyde and (2,2'-dipyridyl)-5,5'-diamine are dissolved in a glass bottle containing dioxane and glacial acetic acid; the glass bottle is heated at 110 DEG C for three days to obtain a brown product; the brown product is centrifuged, the solid product is washed with anhydrous tetrahydrofuran and vacuum dried to obtain a brown solid powder, which is the NH2-UiO-66@BTT-BPDA core-shell material.

3. A method of preparing a NH2-UiO-66@BTT-BPDA core-shell material according to claim 2, wherein, In step 1, the molar ratio of zirconium tetrachloride and 2-amino terephthalic acid is (0.5-1.5):(0.5-1.5); the volume ratio of N,N-dimethylformamide and acetic acid is (8-12):(0.5-1.6).

4. The method for preparing an NH2-UiO-66@BTT-BPDA core-shell material as described in claim 2, characterized in that, In step 2, the mass ratio of NH2-UiO-66 and benzotriphene triformaldehyde is (1.5-2.5):(0.5-1.5).

5. The method for preparing an NH2-UiO-66@BTT-BPDA core-shell material as described in claim 2, characterized in that, In step 3, the molar ratio of (2,2'-dipyridyl)-5,5'-diamine and benzotriphene triformaldehyde is (2-4):(1-3), and the mass ratio of the aldehyde group of NH2-UiO-66 and benzotriphene triformaldehyde is (2-6):(0.5-1.5); the volume ratio of glacial acetic acid and dioxane is (0.5-1.5):(10-20).

6. Use of a NH2-UiO-66@BTT-BPDA core-shell material, characterized in that, The NH2-UiO-66@BTT-BPDA core-shell material is used for adsorption of harmful substances in industrial wastewater.

7. Use of a NH2-UiO-66@BTT-BPDA core-shell material according to claim 6, characterized in that, The industrial wastewater is one of dye wastewater or iodine-containing wastewater.

8. Use of a NH2-UiO-66@BTT-BPDA core-shell material according to claim 6, characterized in that, The application is specifically: dispersing the NH2-UiO-66@BTT-BPDA core-shell material in industrial wastewater, oscillating adsorption, until adsorption equilibrium is reached.

9. Use of a NH2-UiO-66@BTT-BPDA core-shell material according to claim 7, characterized in that, The dye wastewater is one of methylene blue, crystal violet, malachite green, rhodamine B, and methyl orange wastewater.

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