A Tremella-like Zr-Fc Metal-Organic Framework Material Photocatalyst, Preparation Method and Application

Abstract

The present invention discloses a tremella-like Zr-Fc metal-organic framework material photocatalyst, a preparation method and an application thereof. In the present invention, 1,1'-ferrocenedicarboxylic acid, zirconium acetate and acetic acid are dissolved in N,N-dimethylformamide, and a tremella-like Zr-Fc metal-organic framework material with high crystallinity and good stability is prepared by a solvothermal method and used as a photocatalyst. The photocatalyst prepared by the present invention has excellent organic pollutant removal performance.

Description

Technical Field

[0001] The present invention relates to a photocatalyst in the field of organic pollutant removal, and specifically to a tremella-like Zr-Fc metal-organic framework material photocatalyst, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, water pollution problems caused by organic pollutants have attracted much attention. These organic pollutants have good stability in water, and they can enter the surrounding human body through water circulation or the food chain, etc., seriously threatening human health. Therefore, effectively removing organic pollutants from water before wastewater discharge is of great significance for environmental protection and human health. Adsorption and microbial degradation are limited in their application in industrial wastewater treatment due to reasons such as the need for secondary treatment and limited degradation ability.

[0003] Advanced oxidation technology shows great application potential in the field of sewage treatment due to advantages such as simple operation and easy recovery of the catalyst. In the system, the catalyst activates the oxidant to generate strongly oxidizing reactive oxygen species to oxidize organic pollutants, thereby achieving the purpose of degradation. However, advanced oxidation technology has disadvantages such as few active sites of the catalyst, easy agglomeration, and low activation rate of the oxidant, which seriously restricts its further application. To improve the activity of the catalytic system, introducing the catalyst into metal-organic framework materials is an effective strategy. On the one hand, the porous structure of metal-organic framework materials can enable sufficient contact between reactants; on the other hand, the catalyst can be effectively anchored in the porous network to avoid the loss and agglomeration of the catalyst. In addition, photocatalysis is considered to be one of the most effective methods to improve the activity of the catalytic system due to advantages such as simple operation and environmental friendliness. Compared with other catalysts, iron-based catalysts have attracted much attention due to advantages such as low cost and easy synthesis. Among them, ferrocene has characteristics such as high stability, environmental friendliness, reversible redox characteristics, and excellent optical properties, and is one of the ideal photocatalytic materials. Therefore, introducing ferrocene groups into metal-organic framework materials is theoretically an effective strategy to improve the activity of the catalytic system. An ideal ferrocene-group-containing metal-organic framework should have high stability, environmental friendliness, rich catalytic active sites, and excellent optical properties. Summary of the Invention

[0004] In view of the existing problems, the purpose of the present invention is to provide a metal-organic framework material photocatalyst with high-performance organic pollutant removal. The preparation method has a simple process and can meet the requirements of practical applications. The tremella-like Zr-Fc metal-organic framework material prepared by the present invention has excellent organic pollutant removal performance.

[0005] The present invention introduces ferrocene groups into metal-organic framework materials, which can effectively avoid the agglomeration effect of catalysts and improve the activation ability towards oxidants, thus overcoming the problems existing in the background art. Such materials can not only provide abundant catalytic active sites, but also effectively absorb visible light to enhance the catalytic activity of the system. Zirconium-based metal-organic frameworks are considered potential catalyst materials due to their high chemical stability.

[0006] The technical solution adopted in the present invention is as follows:

[0007] I. A Zr-Fc metal-organic framework material

[0008] The Zr-Fc metal-organic framework material is prepared by dissolving 1,1'-ferrocenedicarboxylic acid, zirconium acetate and acetic acid, and then through a solvothermal method. The metal-organic framework material has high crystallinity and good stability.

[0009] The morphology of the metal-organic framework material is in the shape of tremella.

[0010] II. A preparation method of a Zr-Fc metal-organic framework material

[0011] The preparation method includes the following steps:

[0012] 1) Dissolve 1,1'-ferrocenedicarboxylic acid and zirconium acetate in N,N-dimethylformamide, then add acetic acid, which serves as a regulating acid, and then perform ultrasonic treatment for 30 minutes to obtain a clear solution;

[0013] 2) Place the clear solution in a polytetrafluoroethylene inner liner, seal it and put it into an electrothermal blast drying oven. Heat it from room temperature to 120 °C, react for 9 hours, then naturally cool to room temperature, and obtain a precipitate after centrifugation;

[0014] 3) Wash the precipitate three times with N,N-dimethylformamide and anhydrous ethanol respectively. Specifically, first wash it three times with N,N-dimethylformamide, and then wash it three times with anhydrous ethanol; subsequently, perform vacuum drying treatment to obtain the Zr-Fc metal-organic framework material.

[0015] In the step 1), the molar ratio of acetic acid to zirconium acetate is 10 - 200:1.

[0016] III. An application of a Zr-Fc metal-organic framework material

[0017] The application of the Zr-Fc metal-organic framework material in the removal of organic pollutants.

[0018] The organic pollutants include any one or at least two combinations of bisphenol A and its analogues, organic dyes, volatile organic compounds or antibiotics.

[0019] IV. Application Method of a Zr-Fc Metal-Organic Framework Material

[0020] The application method includes the following steps:

[0021] 1) Ultrasonically disperse the Zr-Fc metal-organic framework material in a solution containing organic pollutants with a pH of 3 - 11 to obtain a uniform dispersion;

[0022] 2) Stir the uniformly dispersed liquid for 1 h under light-shielded conditions, then add an oxidant and transfer it to under a light source to initiate the reaction to achieve the degradation of organic pollutants.

[0023] The organic pollutants include any one or at least two combinations of bisphenol A and its analogs, organic dyes, volatile organic compounds, or antibiotics.

[0024] The oxidant includes any one or at least two combinations of hydrogen peroxide, peroxysulfate salts, or persulfates.

[0025] In the present invention, 1,1'-ferrocenedicarboxylic acid is used as the organic ligand, and zirconium acetate is used as the metal source. Under the regulation of acetic acid, a tremella-like Zr-Fc metal-organic framework material with high crystallinity and good stability is prepared. This material not only retains the excellent optical properties of ferrocene and can fully absorb visible light, but also has high chemical stability of the zirconium-based metal-organic framework material and can be recycled for a long time. On the other hand, the Zr-Fc metal-organic framework material has a special tremella-like morphology and a large specific surface area, which can provide abundant accessible catalytic active sites, theoretically enabling it to have high-performance organic pollutant removal performance.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. The tremella-like Zr-Fc metal-organic framework material prepared in the present invention has a high specific surface area, can provide well-dispersed catalytic active sites, effectively prevents the agglomeration effect of ferrocene groups during use, and improves the utilization rate of catalytic active sites.

[0028] 2. The present invention prepares a tremella-like Zr-Fc metal-organic framework material through a simple and effective process. This material has abundant ferrocene groups, which improves the utilization rate of visible light by the catalyst.

[0029] 3. The tremella-like Zr-Fc metal-organic framework material prepared in the present invention has high chemical stability in acidic and alkaline environments and has the value of long-term recycling. Description of the Drawings

[0030] Figure 1These are transmission electron microscope images of Zr-Fc metal-organic framework materials with different morphologies prepared by the present invention.

[0031] Figure 2 These are X-ray diffraction spectra of Zr-Fc metal-organic framework materials with different morphologies prepared by the present invention.

[0032] Figure 3 These are X-ray diffraction patterns of Zr-Fc metal-organic framework material - 100 after being soaked in different pH environments for 72 hours prepared by the present invention.

[0033] Figure 4 These are the degradation performances of bisphenol A by Zr-Fc metal-organic framework material - 100 in different pH environments prepared by the present invention.

[0034] Figure 5 These are the recycling performances of bisphenol A degradation by Zr-Fc metal-organic framework material - 100 prepared by the present invention. Detailed implementation manners

[0035] The technical solutions of the present invention will be further described below with reference to the accompanying drawings and through specific implementation manners.

[0036] However, the following examples are merely simple examples of the present invention and do not represent or limit the scope of the protection of the present invention. The scope of protection of the present invention is subject to the claims. Those skilled in the art should understand that the described examples are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0037] Examples of the present invention are as follows:

[0038] Example 1

[0039] Weigh 548.1 mg of 1,1'-ferrocenedicarboxylic acid and 3.2170 g of zirconium acetate and dissolve them in 60 mL of N,N-dimethylformamide to obtain a clear solution A. Then, add 1.14 mL of acetic acid to solution A and stir well to obtain a clear solution B. Place it in a polytetrafluoroethylene inner liner, seal it, and put it into an electrothermal blast drying oven. Heat it from room temperature to 120 °C and react for 9 hours. After natural cooling to room temperature, collect the obtained product by centrifugation, wash it three times with N,N-dimethylformamide and absolute ethanol respectively, and then perform vacuum drying treatment to obtain Zr-Fc metal-organic framework material - 10.

[0040] Example 2

[0041] Weigh 548.1 mg of 1,1'-ferrocenedicarboxylic acid and 3.2170 g of zirconium acetate and dissolve them in 60 mL of N,N-dimethylformamide to obtain a clear solution A. Then, add 2.86 mL of acetic acid to solution A, stir well to obtain a clear solution B, place it in a polytetrafluoroethylene inner liner, seal it, and put it into an electrothermal blast drying oven. Heat it from room temperature to 120 °C and react for 9 hours. After naturally cooling to room temperature, collect the obtained product by centrifugation, wash it three times with N,N-dimethylformamide and absolute ethanol respectively, and then perform vacuum drying treatment to obtain the Zr-Fc metal-organic framework material-25.

[0042] Example 3

[0043] Weigh 548.1 mg of 1,1'-ferrocenedicarboxylic acid and 3.2170 g of zirconium acetate and dissolve them in 60 mL of N,N-dimethylformamide to obtain a clear solution A. Then, add 5.72 mL of acetic acid to solution A, stir well to obtain a clear solution B, place it in a polytetrafluoroethylene inner liner, seal it, and put it into an electrothermal blast drying oven. Heat it from room temperature to 120 °C and react for 9 hours. After naturally cooling to room temperature, collect the obtained product by centrifugation, wash it three times with N,N-dimethylformamide and absolute ethanol respectively, and then perform vacuum drying treatment to obtain the Zr-Fc metal-organic framework material-50.

[0044] Example 4

[0045] Weigh 548.1 mg of 1,1'-ferrocenedicarboxylic acid and 3.2170 g of zirconium acetate and dissolve them in 60 mL of N,N-dimethylformamide to obtain a clear solution A. Then, add 11.44 mL of acetic acid to solution A, stir well to obtain a clear solution B, place it in a polytetrafluoroethylene inner liner, seal it, and put it into an electrothermal blast drying oven. Heat it from room temperature to 120 °C and react for 9 hours. After naturally cooling to room temperature, collect the obtained product by centrifugation, wash it three times with N,N-dimethylformamide and absolute ethanol respectively, and then perform vacuum drying treatment to obtain the Zr-Fc metal-organic framework material-100.

[0046] Example 5

[0047] 548.1 mg of 1,1'-ferrocene dicarboxylic acid and 3.2170 g of zirconium acetate were weighed and dissolved in 60 mL of N,N-dimethylformamide to obtain a clear solution A. Then, 22.88 mL of acetic acid was added to solution A and stirred thoroughly to obtain a clear solution B, which was placed in a polytetrafluoroethylene liner, sealed and placed in an electric blast drying oven, heated from room temperature to 120 ° C, and reacted for 9 hours. After naturally cooling to room temperature, the obtained product was collected by centrifugation, and then washed three times with N,N-dimethylformamide and anhydrous ethanol, respectively, and then vacuum dried to obtain Zr-Fc metal organic framework material-200.

[0048] Figure 1 The transmission electron microscope images of the Zr-Fc metal organic framework materials of Examples 1, 2, 3, 4 and 5 of the present invention are shown. It can be seen that as the amount of acetic acid added gradually increases, the Zr-Fc metal organic framework material-X gradually changes from an amorphous state to an ordered tremella-like structure composed of multiple nanosheets, and then presents an irregular granular state, which indicates that only an appropriate amount of acetic acid can form a tremella-like Zr-Fc metal organic framework material.

[0049] Figure 2 The X-ray diffraction spectra of the products of Examples 1, 2, 3, 4 and 5 of the present invention are shown. It can be seen that as the amount of acetic acid added gradually increases, the Zr-Fc metal organic framework material -X gradually forms an ordered structure with high crystallinity from an amorphous state, and then presents an amorphous structure again, which indicates that only an appropriate amount of acetic acid can form a Zr-Fc metal organic framework material with high crystallinity.

[0050] The metal organic framework material can be stably retained for a long time in an acidic and alkaline environment without changing its crystal structure. The following stability test is performed.

[0051] Stability test 1

[0052] 1) Ultrasonic dispersion of the prepared Zr-Fc metal organic framework material-100 in an aqueous solution with a pH of 3.0 to obtain a uniform dispersion;

[0053] 2) After the dispersion is allowed to stand for 72 hours, the immersed sample is collected by centrifugation, and the sample is tested by an X-ray diffractometer to obtain the phase information of the sample, i.e., the X-ray diffraction spectrum;

[0054] 3) Compare the phase information of the tested sample with that of the freshly prepared sample to obtain the stability of the sample.

[0055] Stability Test 2

[0056] 1) Ultrasonic dispersion of the prepared Zr-Fc metal organic framework material-100 in an aqueous solution with a pH of 6.0 to obtain a uniform dispersion;

[0057] 2) After allowing the dispersion to stand for 72 h, collect the soaked sample by centrifugation. After testing the sample with an X-ray diffractometer, obtain the phase information of the sample, that is, the X-ray diffraction spectrogram;

[0058] 3) Compare the phase information of the tested sample with the phase information of the freshly prepared sample to obtain the stability of the sample.

[0059] Stability test 3

[0060] 1) Ultrasonically disperse the prepared Zr-Fc metal-organic framework material-100 in an aqueous solution with a pH of 9.0 to obtain a uniform dispersion;

[0061] 2) After allowing the dispersion to stand for 72 h, collect the soaked sample by centrifugation. After testing the sample with an X-ray diffractometer, obtain the phase information of the sample, that is, the X-ray diffraction spectrogram;

[0062] 3) Compare the phase information of the tested sample with the phase information of the freshly prepared sample to obtain the stability of the sample.

[0063] Stability test 4

[0064] 1) Ultrasonically disperse the prepared Zr-Fc metal-organic framework material-100 in an aqueous solution with a pH of 11.0 to obtain a uniform dispersion;

[0065] 2) After allowing the dispersion to stand for 72 h, collect the soaked sample by centrifugation. After testing the sample with an X-ray diffractometer, obtain the phase information of the sample, that is, the X-ray diffraction spectrogram;

[0066] 3) Compare the phase information of the tested sample with the phase information of the freshly prepared sample to obtain the stability of the sample.

[0067] Figure 3 The X-ray diffraction spectrograms of stability tests 1-4 of the present invention. It can be seen that the Zr-Fc metal-organic framework material-100 has almost the same X-ray diffraction spectrogram in different environments, which indicates that the Zr-Fc metal-organic framework material-100 has good stability.

[0068] Example 6

[0069] Weigh 5 mg of Zr-Fc metal-organic framework material-100 powder and disperse it in 50 mL of 20 mg / L BPA solution with a pH of 3.0. Stir for 1 h under dark conditions to ensure that the system reaches adsorption-desorption equilibrium. Subsequently, add 10 mg of potassium peroxymonosulfate compound salt under light conditions to initiate the BPA degradation reaction. Set the reaction temperature at 25 °C and the rotation speed at 500 r / min. Use a 300 W xenon lamp as the light source and filter the ultraviolet light with a UVIRCUT400 filter to make its wavelength range 400 - 780 nm. Set specific time intervals to take 2 mL of liquid samples from the reaction solution, and immediately quench the remaining active substances with 2 mL of methanol. Then, immediately test the absorbance of the clarified solution obtained after filtering and separating the catalyst with a 0.22 μm hydrophilic polytetrafluoroethylene filter membrane at 276 nm using a UV spectrophotometer, and calculate the concentration of residual BPA according to the standard curve, and further process and calculate the degradation efficiency of the catalyst for BPA.

[0070] The experimental results show that the degradation efficiency of bisphenol A in this experimental example is 93.9%.

[0071] Example 7

[0072] Weigh 5 mg of Zr-Fc metal-organic framework material-100 powder and disperse it in 50 mL of 20 mg / L BPA solution with a pH of 6.0. Stir for 1 h under dark conditions to ensure that the system reaches adsorption-desorption equilibrium. Subsequently, add 10 mg of potassium peroxymonosulfate compound salt under light conditions to initiate the BPA degradation reaction. Set the reaction temperature at 25 °C and the rotation speed at 500 r / min. Use a 300 W xenon lamp as the light source and filter the ultraviolet light with a UVIRCUT400 filter to make its wavelength range 400 - 780 nm. Set specific time intervals to take 2 mL of liquid samples from the reaction solution, and immediately quench the remaining active substances with 2 mL of methanol. Then, immediately test the absorbance of the clarified solution obtained after filtering and separating the catalyst with a 0.22 μm hydrophilic polytetrafluoroethylene filter membrane at 276 nm using a UV spectrophotometer, and calculate the concentration of residual BPA according to the standard curve, and further process and calculate the degradation efficiency of the catalyst for BPA.

[0073] The experimental results show that the degradation efficiency of bisphenol A in this experimental example is 100.0%.

[0074] Example 8

[0075] Weigh 5 mg of Zr-Fc metal-organic framework material-100 powder and disperse it in 50 mL of a 20 mg / L BPA solution with a pH of 9.0. Stir for 1 h under dark conditions to ensure that the system reaches adsorption-desorption equilibrium. Subsequently, add 10 mg of potassium peroxymonosulfate compound salt under light conditions to initiate the BPA degradation reaction. Set the reaction temperature at 25 °C and the rotation speed at 500 r / min. Use a 300 W xenon lamp as the light source and filter out ultraviolet light with a UVIRCUT400 filter to make its wavelength range 400 - 780 nm. Set specific time intervals to take 2 mL of liquid samples from the reaction solution and immediately quench the remaining active substances with 2 mL of methanol. Then, immediately use a 0.22 μm hydrophilic polytetrafluoroethylene filter membrane to filter and separate the catalyst, and test the absorbance of the resulting clarified solution at 276 nm with a UV spectrophotometer. Calculate the concentration of residual BPA according to the standard curve, and further process the calculation to obtain the degradation efficiency of the catalyst for BPA.

[0076] The experimental results show that the degradation efficiency of bisphenol A in this experimental example is 75.6%.

[0077] Example 9

[0078] Weigh 5 mg of Zr-Fc metal-organic framework material-100 powder and disperse it in 50 mL of a 20 mg / L BPA solution with a pH of 11.0. Stir for 1 h under dark conditions to ensure that the system reaches adsorption-desorption equilibrium. Subsequently, add 10 mg of potassium peroxymonosulfate compound salt under light conditions to initiate the BPA degradation reaction. Set the reaction temperature at 25 °C and the rotation speed at 500 r / min. Use a 300 W xenon lamp as the light source and filter out ultraviolet light with a UVIRCUT400 filter to make its wavelength range 400 - 780 nm. Set specific time intervals to take 2 mL of liquid samples from the reaction solution and immediately quench the remaining active substances with 2 mL of methanol. Then, immediately use a 0.22 μm hydrophilic polytetrafluoroethylene filter membrane to filter and separate the catalyst, and test the absorbance of the resulting clarified solution at 276 nm with a UV spectrophotometer. Calculate the concentration of residual BPA according to the standard curve, and further process the calculation to obtain the degradation efficiency of the catalyst for BPA.

[0079] The experimental results show that the degradation efficiency of bisphenol A in this experimental example is 85.2%.

[0080] Figure 4 For the adsorption performance of bisphenol A in Examples 6, 7, 8 and 9 of the present invention. It can be seen that Zr-Fc metal-organic framework material-100 has good degradation performance for BPA in different pH environments, especially in a slightly neutral environment, and can completely remove BPA in water.

[0081] Example 10

[0082] Weigh 20 mg of Zr-Fc metal-organic framework material-100 powder and disperse it in 100 mL of 20 mg / L BPA solution with a pH of 6.0. Stir for 1 h under dark conditions to ensure that the system reaches adsorption-desorption equilibrium. Subsequently, add 10 mg of potassium peroxymonosulfate compound salt under light conditions to initiate the BPA degradation reaction. Set the reaction temperature at 25 °C and the rotation speed at 500 r / min. Use a 300 W xenon lamp as the light source and filter out ultraviolet light with a UVIRCUT400 filter to make its wavelength range 400 - 780 nm. Set specific time intervals to take 2 mL of liquid samples from the reaction solution, and immediately quench the remaining active substances with 2 mL of methanol. Then, immediately test the absorbance of the clarified solution obtained after filtering and separating the catalyst with a 0.22 μm hydrophilic polytetrafluoroethylene membrane at 276 nm using a UV spectrophotometer, and calculate the concentration of residual BPA according to the standard curve. Further processing is carried out to calculate the degradation efficiency of the catalyst for BPA.

[0083] The experimental results show that the degradation efficiency of bisphenol A in this experimental example is 100.0%.

[0084] Example 11

[0085] After centrifuging and drying the Zr-Fc metal-organic framework material-100 used in Example 10, activate it by keeping it at 150 °C for 2 h, and adjust the volume of the degradation reaction system to keep the catalyst concentration at 100 mg / L unchanged. Stir for 1 h under dark conditions to ensure that the system reaches adsorption-desorption equilibrium. Subsequently, add an appropriate amount of potassium peroxymonosulfate compound salt under light conditions to initiate the BPA degradation reaction. Set the reaction temperature at 25 °C and the rotation speed at 500 r / min. Use a 300 W xenon lamp as the light source and filter out ultraviolet light with a UVIRCUT400 filter to make its wavelength range 400 - 780 nm. Set specific time intervals to take 2 mL of liquid samples from the reaction solution, and immediately quench the remaining active substances with 2 mL of methanol. Then, immediately test the absorbance of the clarified solution obtained after filtering and separating the catalyst with a 0.22 μm hydrophilic polytetrafluoroethylene membrane at 276 nm using a UV spectrophotometer, and calculate the concentration of residual BPA according to the standard curve. Further processing is carried out to calculate the degradation efficiency of the catalyst for BPA.

[0086] The experimental results show that the degradation efficiency of bisphenol A in the experimental example is 90.7%.

[0087] Example 12

[0088] After the Zr-Fc metal-organic framework material-100 used in Example 11 was collected by centrifugation, dried, and then activated by holding at 150 °C for 2 h before use, the volume of the degradation reaction system was adjusted to keep the concentration of the catalyst at 100 mg / L unchanged. It was stirred for 1 h under dark conditions to ensure that the system reached adsorption-desorption equilibrium. Subsequently, an appropriate amount of potassium monopersulfate compound salt was added under light conditions to initiate the BPA degradation reaction. The reaction temperature was set at 25 °C and the rotation speed was set at 500 r / min. A 300 W xenon lamp was used as the light source, and a UVIRCUT400 filter was used to filter ultraviolet light so that its wavelength range was 400 - 780 nm. At specific time intervals, 2 mL of liquid samples were taken from the reaction solution, and the remaining active substances were immediately quenched with 2 mL of methanol. The clarified solution obtained after filtering and separating the catalyst with a 0.22 μm hydrophilic polytetrafluoroethylene filter membrane was immediately tested for its absorbance at 276 nm with a UV spectrophotometer, and the concentration of residual BPA was calculated according to the standard curve. Further processing was carried out to calculate the degradation efficiency of the catalyst for BPA.

[0089] The experimental results showed that the degradation efficiency of bisphenol A in this experimental example was 83.1%.

[0090] Example 13

[0091] After the Zr-Fc metal-organic framework material-100 used in Example 12 was collected by centrifugation, dried, and then activated by holding at 150 °C for 2 h before use, the volume of the degradation reaction system was adjusted to keep the concentration of the catalyst at 100 mg / L unchanged. It was stirred for 1 h under dark conditions to ensure that the system reached adsorption-desorption equilibrium. Subsequently, an appropriate amount of potassium monopersulfate compound salt was added under light conditions to initiate the BPA degradation reaction. The reaction temperature was set at 25 °C and the rotation speed was set at 500 r / min. A 300 W xenon lamp was used as the light source, and a UVIRCUT400 filter was used to filter ultraviolet light so that its wavelength range was 400 - 780 nm. At specific time intervals, 2 mL of liquid samples were taken from the reaction solution, and the remaining active substances were immediately quenched with 2 mL of methanol. The clarified solution obtained after filtering and separating the catalyst with a 0.22 μm hydrophilic polytetrafluoroethylene filter membrane was immediately tested for its absorbance at 276 nm with a UV spectrophotometer, and the concentration of residual BPA was calculated according to the standard curve. Further processing was carried out to calculate the degradation efficiency of the catalyst for BPA.

[0092] The experimental results showed that the degradation efficiency of bisphenol A in this experimental example was 89.2%.

[0093] Figure 5The cyclic degradation performance of bisphenol A in Examples 10, 11, 12 and 13 of the present invention. It can be seen that the Zr-Fc metal-organic framework material-100 still maintains good degradation performance for bisphenol A after being continuously used four times, indicating that the Zr-Fc metal-organic framework material-100 has long-term recycling value.

[0094] The applicant declares that the present invention uses the above examples to illustrate the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for applying a Zr-Fc metal-organic framework material, characterized in that, The application method comprises the following steps: First, ultrasonically disperse the Zr-Fc metal-organic framework material in a solution containing organic pollutants with a pH of 3-11 to obtain a uniform dispersion; Then, stir the uniform dispersion for 1 h under light-shielded conditions, then add an oxidant and transfer it to under the light source to initiate the reaction to achieve the degradation of organic pollutants; The oxidant comprises any one or a combination of at least two of peroxymonosulfate or persulfate; The Zr-Fc metal-organic framework material is prepared by the following preparation method, and the preparation method comprises the following steps: 1) Dissolve 548.1 mg of 1,1'-ferrocenedicarboxylic acid and 3.2170 g of zirconium acetate in N,N-dimethylformamide, then add 5.72 ml or 11.44 ml of acetic acid. Acetic acid is used as the adjusting acid, and then ultrasonically treat for 30 minutes to obtain a clear solution; 2) Place the clear solution in a polytetrafluoroethylene inner liner, seal it and put it into an electrothermal blast drying oven, heat it from room temperature to 120 °C, react for 9 hours, then naturally cool to room temperature, and centrifuge to obtain a precipitate; 3) Wash the precipitate three times with N,N-dimethylformamide and absolute ethanol respectively, and then perform vacuum drying treatment to obtain the Zr-Fc metal-organic framework material; The organic pollutants comprise bisphenol A and its analogues.

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