Preparation Method and Application of BiOCl / TiO2 Spherical Heterojunction Derived from Bi-Ti-Mn-MOF

Abstract

The present invention discloses a preparation method and application of BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF, belonging to the field of materials. This method belongs to the hydrothermal solvent method. The organic ligand used in the present invention is terephthalic acid, and the metal ligands are bismuth nitrate pentahydrate, tetrabutyl titanate, manganese chloride tetrahydrate, and the solvent is methanol and dimethylformamide. The method of the present invention includes four steps: ingredient preparation, oscillation and stirring, heating, and drying. The prepared BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF can be used for the adsorption and degradation of dyes, and its adsorption property is not affected by environmental temperature, acidity and alkalinity.

Description

Technical Field

[0001] The present invention relates to a preparation method and application of a BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF, belonging to the field of materials. Background Art

[0002] Synthetic dyes are widely used in industries such as leather making, coatings, and cosmetics, and are also one of the common pollutants in industrial wastewater. Even if the concentration of dye residues in the wastewater is very low, it will cause serious harm to the environment and organisms. Therefore, it is very necessary to degrade the dyes in industrial wastewater into non-toxic and harmless products before discharge. MOF has been widely used in the field of dye degradation due to its void structure, large specific surface area and a series of other advantages.

[0003] In recent years, heterojunctions derived from single-metal MOF (Bi-MOF) have been widely used in dye degradation, and these heterojunctions show very good effects on dye degradation. Heterojunctions derived from bimetallic MOF have also emerged. The patent document CN113546688B discloses a Bi-MOF-M / Bi-2MoO-6 visible light catalyst for efficiently degrading organic wastewater, which can efficiently degrade various organic dye wastewaters and high-concentration antibiotic wastewaters under visible light irradiation. The patent document CN114849782B discloses a stepped Bi-MOF-M / CdS / Bi-2S-3 heterojunction visible light catalyst and its preparation method, which has a high mineralization rate for organic pollutants and is an efficient and easily recyclable practical photocatalyst.

[0004] It can be seen that the heterojunctions derived from Bi-MOF have good degradation effects on organic dye wastewaters. However, there are still some deficiencies in the adsorption effects of some current Bi-MOF-derived heterojunctions on dyes. Some heterojunctions can only adsorb dyes in acidic or alkaline environments. Another part can only achieve the expected effect at a specific temperature. Nowadays, there are few reports on heterojunctions that can adsorb rhodamine in a short time with extremely high efficiency and a simple preparation process.

[0005] The present invention discloses the preparation of a BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF, which can efficiently adsorb organic pollutants. Summary of the Invention

[0006] One of the purposes of the present invention is to provide a BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF, which is composed of a MOF metal framework structure composed of three metals, Bi, Ti, and Mn, and BiOCl and TiO2 grow on the metal framework formed by Bi-Ti-Mn-MOF.

[0007] Another object of the present invention is to provide a method for preparing a BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF, which specifically includes the following steps:

[0008] (1) Dissolve bismuth nitrate pentahydrate and terephthalic acid in a mixed solvent composed of methanol and dimethylformamide, and stir to obtain a mixed solution A.

[0009] (2) Sequentially add tetrabutyl titanate and manganese chloride tetrahydrate to the mixed solution A, and stir evenly to obtain a mixed solution B.

[0010] (3) Ultrasonically vibrate the mixed solution B.

[0011] (4) After the vibration is completed, pour the mixed solution B into a reaction kettle for heating reaction.

[0012] (5) Centrifuge the solution after heating, wash it with methanol, and dry it to obtain a BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF.

[0013] Preferably, in step (1), the volume ratio of methanol to dimethylformamide is 1:1 to 1:2.

[0014] Preferably, in step (1), the addition amount of bismuth nitrate pentahydrate in the mixed solvent is 250-280 g / L, and the addition amount of terephthalic acid is 125-140 g / L.

[0015] Preferably, in step (2), the dosage of tetrabutyl titanate in solution A is 70-85 mL / L, and the dosage of manganese chloride tetrahydrate is 26-29 g / L.

[0016] Preferably, in step (3), the ultrasonic vibration time is not less than 10 min.

[0017] Preferably, in step (4), the reaction temperature of the solution heated in the reaction kettle is 150-220 °C and the reaction time is 30-48 h.

[0018] Preferably, in step (5), the drying condition is drying in an oven at 60 °C for 12 h.

[0019] Application of BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF in adsorbing organic pollutants.

[0020] Advantages of the present invention

[0021] (1) The BiOCl / TiO₂ spherical heterojunction derived from Bi-Ti-Mn-MOF prepared by the present invention is composed of BiOCl, TiO₂, Bi-MOF, Ti-MOF, and Mn-MOF; in the framework of Bi-Ti-Mn-MOF, flaky BiOCl and layered TiO₂ cover the spherical framework of Bi-Ti-Mn-MOF; the BiOCl / TiO₂ spherical heterojunction derived from Bi-Ti-Mn-MOF can efficiently degrade the organic pollutant rhodamine, and the adsorption rate reaches more than 96%.

[0022] (2) During the preparation process, Mn element is introduced through manganese chloride tetrahydrate. On the one hand, chlorine atoms are introduced to combine with bismuth to form bismuth oxychloride; on the other hand, Mn is introduced, and Mn combines with terephthalic acid to form Mn-MOF, strengthening the degradation effect on rhodamine.

[0023] (3) The heating temperature will affect the performance of the product. If the heating temperature is too low, the transition metal cannot combine with the organic ligand, and the reaction cannot proceed; if the temperature is too high, not only the MOF metal framework structure will be damaged, but also BiOCl and TiO₂ grown on the MOF metal framework will be damaged.

[0024] (4) The degradation of the organic pollutant rhodamine by the BiOCl / TiO₂ spherical heterojunction derived from Bi-Ti-Mn-MOF prepared by the present invention is not affected by the environmental temperature. For the BiOCl / TiO₂ spherical heterojunction derived from Bi-Ti-Mn-MOF prepared by the present invention, the required temperature is 150 - 220 °C, and the reaction time is 30 - 48 h. After centrifugation, it is placed in a reaction at 60 °C for 12 h, and it is found that its morphology presents a spherical shape, indicating that the temperature within a certain range will not affect the shape and structure of the spherical heterojunction.

[0025] (5) The degradation of the organic pollutant rhodamine by the BiOCl / TiO₂ spherical heterojunction derived from Bi-Ti-Mn-MOF prepared by the present invention is not affected by the environmental pH value. When the surface of the heterojunction is positively charged, the OH⁻, Cl⁻, and RhB negative ions with opposite charges in the solution are tightly adsorbed on the particle surface by Coulomb attraction to form an adsorption layer, forming an electric double layer. When the surface of the heterojunction is negatively charged, the H⁺ and RhB positive ions in the solution are tightly adsorbed on the particle surface by Coulomb attraction to form an adsorption layer, forming an electric double layer. The greater the ζ potential generated by the electric double layer, the greater the repulsive force and the less favorable the adsorption of RhB. Description of the Drawings

[0026] Figure 1 X-ray diffraction pattern of the BiOCl / TiO₂ spherical heterojunction derived from Bi-Ti-Mn-MOF prepared in Example 1.

[0027] Figure 2SEM image and elemental analysis diagram of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF prepared in Example 1.

[0028] Figure 3 Infrared spectrum diagram of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF prepared in Example 1.

[0029] Figure 4 UV-Vis absorption spectrum diagram of the adsorption of organic pollutant rhodamine by the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF prepared in Example 1 at different times. Detailed implementation manners

[0030] The present invention will be further described in detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the content described.

[0031] Example 1

[0032] The specific preparation steps of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF are as follows:

[0033] (1) Weigh bismuth nitrate pentahydrate and terephthalic acid and dissolve them in a mixed solvent composed of methanol and dimethylformamide, and stir evenly with a magnetic stirrer to obtain a mixed solution A, where the volume ratio of methanol to dimethylformamide is 1:1, the addition amount of bismuth nitrate pentahydrate in the mixed solvent is 269.4 g / L, and the addition amount of terephthalic acid is 134.3 g / L.

[0034] (2) Weigh tetrabutyl titanate and manganese chloride tetrahydrate in sequence and add them to the mixed solution A, and continuously stir for 10 min to obtain a mixed solution B, where the dosage of tetrabutyl titanate in solution A is 80 mL / L, and the dosage of manganese chloride tetrahydrate is 27.4 g / L.

[0035] (3) Ultrasonically oscillate the mixed solution B for 10 min.

[0036] (4) After the ultrasonic treatment, pour the mixed solution B into a reaction kettle, heat the reaction temperature to 150 °C, and react for 33 h.

[0037] (5) Centrifuge the solution after heating, wash it three times with methanol, and place it in a drying oven to dry at 60 °C for 12 h to obtain the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF.

[0038] The X-ray diffraction pattern of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF prepared in this example is shown in Figure 1, indicating that the heterojunction is composed of BiOCl, TiO2, Bi-MOF, Ti-MOF, and Mn-MOF.

[0039] Figure 2 Figure 4 is the scanning electron microscope image and elemental analysis image of the prepared Bi-Ti-Mn-MOF-derived BiOCl / TiO2 spherical heterojunction. It can be seen from the figure that in the framework of Bi-Ti-Mn-MOF, Bi, Ti, and Mn are evenly distributed in the framework. In the framework of Bi-Ti-Mn-MOF, flaky BiOCl and layered TiO2 cover the spherical framework of Bi-Ti-Mn-MOF.

[0040] Figure 3 Figure 5 is the infrared spectrum of the prepared Bi-Ti-Mn-MOF-derived BiOCl / TiO2 spherical heterojunction. It can be seen from the figure that the peak at 535 cm -1 corresponds to Ti-O, and the peak at 745 cm -1 is the bending vibration of C-H. The peak at 1017 cm -1 is the bending vibration of the hydroxyl group bound to metal ions (Ti, Bi, and Mn). The peaks at 1357 cm -1 and 1628 cm -1 are attributed to the C-O symmetry of the hydroxyl group of the H2BDC linker and the stretching vibration of its C=O. The peak at 3413 cm -1 corresponds to -NH2.

[0041] Figure 4 Figure 6 is the UV-visible absorption spectrum of the adsorption of organic pollutant rhodamine by the prepared Bi-Ti-Mn-MOF-derived BiOCl / TiO2 spherical heterojunction at different times. It can be seen from the figure that the Bi-Ti-Mn-MOF-derived BiOCl / TiO2 spherical heterojunction can efficiently degrade rhodamine, and the adsorption rate reaches 97%.

[0042] Example 2

[0043] The specific preparation steps of the Bi-Ti-Mn-MOF-derived BiOCl / TiO2 spherical heterojunction are as follows:

[0044] (1) Weigh bismuth nitrate pentahydrate and terephthalic acid and dissolve them in a mixed solvent composed of methanol and dimethylformamide. Stir evenly with a magnetic stirrer to obtain a mixed solution A, where the volume ratio of methanol to dimethylformamide is 1:2. The addition amount of bismuth nitrate pentahydrate in the mixed solvent is 250 g / L, and the addition amount of terephthalic acid is 125 g / L.

[0045] (2) Weigh tetrabutyl titanate and manganese chloride tetrahydrate in sequence and add them to the mixed solution A, and continuously stir for 10 min to obtain the mixed solution B, where the dosage of tetrabutyl titanate in the solution A is 70 mL / L, and the dosage of manganese chloride tetrahydrate is 26 g / L.

[0046] (3) Ultrasonically oscillate the mixed solution B for 11 min.

[0047] (4) After the ultrasonic treatment, pour the mixed solution B into the reaction kettle, heat the reaction temperature to 180 °C, and react for 30 h.

[0048] (5) Centrifuge the solution after heating, wash it three times with methanol, and place it in a drying oven to dry at 60 °C for 12 h to obtain the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF.

[0049] The BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF prepared in this example is composed of BiOCl, TiO2, Bi-MOF, Ti-MOF, and Mn-MOF. In the framework of Bi-Ti-Mn-MOF, flaky BiOCl and layered TiO2 cover the spherical framework of Bi-Ti-Mn-MOF. The BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF can efficiently degrade rhodamine, and the adsorption rate reaches 96%.

[0050] Example 3

[0051] The specific preparation steps of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF are as follows:

[0052] (1) Weigh bismuth nitrate pentahydrate and terephthalic acid and dissolve them in the mixed solvent composed of methanol and dimethylformamide, and stir evenly with a magnetic stirrer to obtain the mixed solution A, where the volume ratio of methanol to dimethylformamide is 1:1, the addition amount of bismuth nitrate pentahydrate in the mixed solvent is 280 g / L, and the addition amount of terephthalic acid is 140 g / L.

[0053] (2) Weigh tetrabutyl titanate and manganese chloride tetrahydrate in sequence and add them to the mixed solution A, and continuously stir for 10 min to obtain the mixed solution B, where the dosage of tetrabutyl titanate in the solution A is 85 mL / L, and the dosage of manganese chloride tetrahydrate is 29 g / L.

[0054] (3) Ultrasonically oscillate the mixed solution B for 12 min.

[0055] (4) After the ultrasonic treatment, pour the mixed solution B into the reaction kettle, heat the reaction temperature to 200 °C, and react for 36 h.

[0056] (5) The solution after heating is centrifuged and washed three times with methanol, then placed in a drying oven and dried at 60 °C for 12 h to obtain a BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF.

[0057] The BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF prepared in this example is composed of BiOCl, TiO2, Bi-MOF, Ti-MOF, and Mn-MOF. In the framework of Bi-Ti-Mn-MOF, flaky BiOCl and layered TiO2 cover the spherical framework of Bi-Ti-Mn-MOF. The BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF can efficiently degrade rhodamine, and the adsorption rate reaches 96.7%.

[0058] Example 4

[0059] The specific preparation steps of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF are as follows:

[0060] (1) Weigh bismuth nitrate pentahydrate and terephthalic acid and dissolve them in a mixed solvent composed of methanol and dimethylformamide. Stir evenly with a magnetic stirrer to obtain a mixed solution A, where the volume ratio of methanol to dimethylformamide is 1:1, the addition amount of bismuth nitrate pentahydrate in the mixed solvent is 250 g / L, and the addition amount of terephthalic acid is 125 g / L.

[0061] (2) Weigh tetrabutyl titanate and manganese chloride tetrahydrate in sequence and add them to the mixed solution A, and continuously stir for 10 min to obtain a mixed solution B, where the dosage of tetrabutyl titanate in solution A is 70 mL / L, and the dosage of manganese chloride tetrahydrate is 29 g / L.

[0062] (3) Ultrasonically oscillate the mixed solution B for 13 min.

[0063] (4) After the ultrasonic treatment, pour the mixed solution B into a reaction kettle, heat the reaction temperature to 220 °C, and react for 48 h.

[0064] (5) The solution after heating is centrifuged and washed three times with methanol, then placed in a drying oven and dried at 60 °C for 12 h to obtain a BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF.

[0065] The BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF prepared in this example is composed of BiOCl, TiO2, Bi-MOF, Ti-MOF, and Mn-MOF. In the framework of Bi-Ti-Mn-MOF, flaky BiOCl and layered TiO2 cover the spherical framework of Bi-Ti-Mn-MOF. The BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF can efficiently degrade rhodamine, and the adsorption rate reaches 96.4%.

[0066] Comparative Example 1

[0067] As a control, the only difference between this example and Example 1 is that manganese dichloride tetrahydrate is not added, and other steps and the dosages of each reagent are the same as those in Example 1. The specific operation steps are as follows:

[0068] (1) Weigh bismuth nitrate pentahydrate and terephthalic acid and dissolve them in a mixed solvent composed of methanol and dimethylformamide, and stir evenly with a magnetic stirrer to obtain a mixed solution A, where the volume ratio of methanol to dimethylformamide is 1:1, the dosage of bismuth nitrate pentahydrate in the mixed solvent is 269.4 g / L, and the dosage of terephthalic acid is 134.3 g / L.

[0069] (2) Weigh tetrabutyl titanate and manganese dichloride tetrahydrate in sequence and add them to the mixed solution A, and continuously stir for 10 min to obtain a mixed solution B, where the dosage of tetrabutyl titanate in solution A is 80 mL / L, and the dosage of manganese dichloride tetrahydrate is 27.4 g / L.

[0070] (3) Ultrasonically oscillate the mixed solution B for 10 min.

[0071] (4) After the ultrasonic treatment, pour the mixed solution B into a reaction kettle, heat the reaction temperature to 150 °C, and react for 33 h.

[0072] (5) Centrifuge the solution after heating, wash it three times with methanol, and place it in a drying oven to dry at 60 °C for 12 h to obtain the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-MOF.

[0073] The difference between Comparative Example 1 and Example 1 is that manganese dichloride tetrahydrate is not added. The addition of manganese dichloride tetrahydrate successfully introduces manganese atoms and chlorine atoms. The manganese atoms will combine with terephthalic acid to form Mn-MOF, and the chlorine atoms will combine with the added bismuth nitrate pentahydrate to form BiOCl. Both Mn-MOF and BiOCl can degrade dyes.

[0074] Comparative Example 2

[0075] As a control, the only difference between this example and Example 1 lies in the different heating reaction conditions, and other operations and drug dosages are the same as those in Example 1. Specifically:

[0076] (1) Weigh bismuth nitrate pentahydrate and terephthalic acid and dissolve them in a mixed solvent composed of methanol and dimethylformamide. Stir evenly with a magnetic stirrer to obtain a mixed solution A, where the volume ratio of methanol to dimethylformamide is 1:1. The addition amount of bismuth nitrate pentahydrate in the mixed solvent is 269.4 g / L, and the addition amount of terephthalic acid is 134.3 g / L.

[0077] (2) Weigh tetrabutyl titanate and manganese chloride tetrahydrate in sequence and add them to the mixed solution A. Continuously stir for 10 min to obtain a mixed solution B, where the dosage of tetrabutyl titanate in solution A is 80 mL / L, and the dosage of manganese chloride tetrahydrate is 27.4 g / L.

[0078] (3) Ultrasonically oscillate the mixed solution B for 10 min.

[0079] (4) After the ultrasonic treatment, pour the mixed solution B into a reaction kettle, heat the reaction temperature to 100 °C, and react for 24 h.

[0080] (5) Centrifuge the solution after heating and wash it three times with methanol. Place it in a drying oven and dry it at 60 °C for 12 h to obtain a BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF.

[0081] The adsorption performance of the BiOCl / TiO2 spherical heterojunction prepared in this comparative example is not as good as that in Example 1. The reason is that the reaction temperature is relatively lower than that in Example 1, and the MOF framework is not completely formed. Secondly, the reaction time is too short and the reaction is not complete.

[0082] Comparative Example 3

[0083] As a control, the only difference between this example and Example 1 lies in the different heating reaction conditions, and other operations and drug dosages are the same as those in Example 1. Specifically:

[0084] (1) Weigh bismuth nitrate pentahydrate and terephthalic acid and dissolve them in a mixed solvent composed of methanol and dimethylformamide. Stir evenly with a magnetic stirrer to obtain a mixed solution A, where the volume ratio of methanol to dimethylformamide is 1:1. The addition amount of bismuth nitrate pentahydrate in the mixed solvent is 269.4 g / L, and the addition amount of terephthalic acid is 134.3 g / L.

[0085] (2) Weigh tetrabutyl titanate and manganese chloride tetrahydrate in sequence and add them to the mixed solution A. Continuously stir for 10 min to obtain a mixed solution B, where the dosage of tetrabutyl titanate in solution A is 80 mL / L, and the dosage of manganese chloride tetrahydrate is 27.4 g / L.

[0086] (3) Ultrasonically oscillate the mixed solution B for 10 min.

[0087] (4) After the ultrasonic treatment, pour the mixed solution B into the reaction kettle, heat the reaction temperature to 300 °C, and react for 60 h.

[0088] (5) Centrifuge the solution after heating, wash it three times with methanol, place it in a drying oven and dry it at 60 °C for 12 h to obtain the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF.

[0089] The adsorption performance of the BiOCl / TiO2 spherical heterojunction prepared in this comparative example is not as good as that in Example 1. The reason is that the reaction temperature is relatively higher than that in Example 1 and the reaction time is relatively longer than that in Example 1, resulting in the destruction of the formed MOF structure. In addition, TiO2 and BiOCl grown on the MOF framework are both damaged to a certain extent. Therefore, the degradation effect on rhodamine is affected to a certain extent.

Claims

1. A preparation method of Bi-Ti-Mn-MOF-derived BiOCl / TiO2 spherical heterojunction, characterized in that: The specific preparation method is as follows: (1) Dissolve bismuth nitrate pentahydrate and terephthalic acid in a mixed solvent composed of methanol and dimethylformamide, and stir to obtain a mixed solution A; (2) Sequentially add tetrabutyl titanate and manganese chloride tetrahydrate to the mixed solution A, and stir evenly to obtain a mixed solution B; (3) Ultrasonically vibrate the mixed solution B; (4) After the vibration is completed, pour the mixed solution B into a reaction kettle for heating reaction; (5) The solution after heating is centrifuged, washed with methanol, and dried to obtain a BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF; In step (4), the reaction temperature of the mixed solution B in the reaction kettle for heating reaction is 150 - 220 °C and the reaction time is 30 - 48 h; The BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF prepared by the said method is: The BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF is a MOF metal framework structure composed of three metals Bi, Ti, and Mn. BiOCl and TiO2 grow on the metal framework formed by Bi-Ti-Mn-MOF.

2. The preparation method of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF according to claim 1, characterized in that: In step (1), the volume ratio of methanol to dimethylformamide is 1:1 - 1:

2.

3. The preparation method of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF according to claim 1, characterized in that: In step (1), the addition amount of bismuth nitrate pentahydrate in the mixed solution A is 250 - 280 g / L, and the addition amount of terephthalic acid is 125 - 140 g / L.

4. The preparation method of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF according to claim 1, characterized in that: In step (2), the dosage of tetrabutyl titanate in the mixed solution B is 70 - 85 mL / L, and the dosage of manganese chloride tetrahydrate is 26 - 29 g / L.

5. The preparation method of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF according to claim 1, characterized in that: In step (3), the ultrasonic vibration time is not less than 10 min.

6. The preparation method of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF according to claim 1, characterized in that: In step (5), the drying condition is drying in an oven at 60 °C for 12 h.

7. Application of the BiOCl / TiO2 spherical heterojunction derived from Bi-Ti-Mn-MOF prepared by the method according to any one of claims 1 - 6 in adsorbing organic pollutants.

Images