Construction method of acousto-optic catalytic reactor for removing tetracycline through photoactive MOF

Abstract

The invention relates to a construction method of an acousto-optic catalytic reactor for removing tetracycline through photoactive MOF (Metal Organic Framework). A photoactive MOF material is synthesized through a solvothermal method; adding the synthesized MOF material and a tetracycline aqueous solution into a quartz reactor, and stirring for 30 minutes in a darkroom; starting circulating condensate water, a magnetic stirrer, ultrasonic waves and a light source, and carrying out acousto-optic catalysis to remove tetracycline reaction; sampling at certain time intervals, filtering, testing, and calculating the removal efficiency of tetracycline. According to the acousto-optic catalytic reactor constructed by the invention, the MOF material has excellent light absorption and photo-generated charge splitting performance, and ultrasonic catalysis is cooperated, so that the contact between MOF and tetracycline molecules is enhanced, and efficient removal of tetracycline is realized. The acousto-optic catalytic reactor disclosed by the invention is low in cost, simple in structure, high in efficiency and high in speed, and has good stability and repeatability. According to the scheme, the problem of low tetracycline removal efficiency is solved, an efficient and environment-friendly solution is provided for environmental protection and ecological restoration, and the method has wide application prospects.

Description

Technical Field

[0001] The invention belongs to the intersecting field of inorganic chemistry, material chemistry and environmental chemistry, and specifically relates to a method for constructing a sono-photocatalytic reactor for removing tetracycline using a photoactive MOF. Background Art

[0002] Tetracycline is a natural antibacterial substance produced by Streptomyces. Since the 1940s, it has been widely used in medical, agricultural and animal husbandry fields due to its wide antibacterial properties and low price. In the 1960s to 1980s, tetracycline was the main drug for treating various bacterial infectious diseases and almost became synonymous with "panacea". However, with the extensive use of tetracycline, its environmental pollution problem has gradually become prominent. Tetracycline is highly stable and not easily degraded in the environment, resulting in its large accumulation in soil, water and organisms. In addition, high concentrations of tetracycline intake can also have adverse effects on children's tooth development, causing tooth discoloration and incomplete development. At present, the pollution problem of tetracycline has received great attention worldwide. Traditional physical and chemical methods (membrane separation technology, oxidation method, reduction method and complexation method) cannot completely remove tetracycline from wastewater, resulting in the inability to achieve zero wastewater discharge. Using solar energy to remove tetracycline through heterogeneous photocatalytic technology is an environmentally friendly, efficient and simple method.

[0003] Metal organic framework (MOF) is a new type of material. It has been widely used in the field of catalysis due to its stable structure, wide visible light absorption, and efficient separation of photogenerated charges. The structure and physicochemical properties of MOF materials can be controlled according to the target reaction, so they show excellent performance in photocatalytic treatment of wastewater. In addition, ultrasonic catalysis is a green, clean and low-energy technology. Ultrasonic vibration can not only accelerate proton transfer, but also clean the catalyst surface and inhibit catalyst aggregation and deactivation. The most important thing is that the cavitation phenomenon induced by ultrasound can promote the separation efficiency of photogenerated charges of the catalyst and the generation of other active free radicals. Based on the above discussion, we synthesized a series of photoactive MOF materials, constructed a sono-photocatalytic reactor based on MOF and applied it to the tetracycline removal reaction. The experimental results show that the sono-photocatalytic reactor based on photoactive MOF shows excellent catalytic performance in the removal of tetracycline, and the efficiency of tetracycline degradation reaches more than 92%. In addition, the sono-photocatalytic reaction system can still maintain its catalytic activity after 5 cycles. Summary of the invention

[0004] The technical problem to be solved by the present invention is to develop a new catalytic strategy and provide a method for constructing an acoustic-photocatalytic reactor based on photoactive MOF for removing tetracycline. The acoustic-photocatalytic reactor utilizes the wide visible light absorption, efficient charge separation, excellent chemical stability and high catalytic activity of MOF, as well as the synergistic effect of ultrasound and visible light to efficiently remove tetracycline. The technology is simple to operate, rapid, and has good stability and repeatability. It provides an efficient and environmentally friendly solution for environmental protection and ecological restoration, and has broad application prospects.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] The present invention provides a method for constructing the above-mentioned sono-photocatalytic reactor for removing tetracycline based on photoactive MOF, which specifically comprises the following steps:

[0007] (1) Synthesize MOF materials by solvothermal method;

[0008] (2) Add the MOF catalyst prepared in (1) and tetracycline aqueous solution into a quartz reactor and stir in a dark room for 30 minutes;

[0009] (3) placing the quartz reactor in an ultrasonic bath, turning on the stirrer, ultrasound and light source, connecting to circulating condensed water, and reacting at room temperature for 60 minutes;

[0010] (4) At equal intervals, 2.5 mL of the solution was taken out from the reaction system and filtered through a water filter membrane. The filtrate was subjected to ultraviolet absorption detection with the maximum wavelength of detection being 357 nm. The removal efficiency of tetracycline was calculated.

[0011] Furthermore, in step (1), MOF is selected from one of PCN-222, PCN-223, PCN-224, PCN-22, MOF-525, UiO-66-NH2, MIL-88B-Fe, and MIL-125-NH2.

[0012] Furthermore, in step (1), the regulator for synthesizing MOF includes one of formic acid, acetic acid, benzoic acid, and p-aminobenzoic acid.

[0013] Furthermore, in step (1), the reaction is carried out at 100°C to 150°C for 24h to 72h.

[0014] Furthermore, the mass of the MOF in step (2) is 1:4 mg.

[0015] Furthermore, the concentration of tetracycline in step (2) is 1:9 mg / L.

[0016] Furthermore, the pH range of the tetracycline aqueous solution in step (2) is 3 to 11.

[0017] Furthermore, the power of the ultrasonic wave in step (3) is 30 to 120 W and the frequency is 40 kHz.

[0018] Furthermore, the light source in step (3) is a 300W xenon lamp, and the light wavelength range is 400 to 700nm.

[0019] Furthermore, the diameter of the water filter membrane in step (4) is 0.22 μm.

[0020] Furthermore, the degradation efficiency of tetracycline in step (4) is as high as 92%.

[0021] Compared with the prior art, the method for constructing the photocatalytic reactor for removing tetracycline using the photoactive MOF of the present invention has the following advantages:

[0022] The MOF catalyst prepared by the solvothermal method of the present invention is easy to operate, has a controllable structure, good chemical stability, has wide-band visible light absorption and excellent photogenerated charge splitting characteristics, and can fully utilize sunlight;

[0023] The present invention adopts an acoustic-optical synergistic catalytic strategy. Visible light effectively excites MOF to cause electron-hole separation. Ultrasonic waves accelerate the transmission rate of tetracycline molecules in the solution, remove impurities on the catalyst surface, and inhibit catalyst aggregation and deactivation. At the same time, the cavitation effect formed by ultrasonic waves is conducive to the formation of highly active free radicals. The acoustic-optical catalytic reactor of the present invention exhibits excellent removal efficiency in the tetracycline removal reaction.

[0024] The sono-photocatalytic reactor of the present invention is easy to operate, energy-saving and environmentally friendly, has strong compatibility, mild reaction conditions and high catalytic efficiency, and fills the gap in the prior art of MOF for removing tetracycline.

[0025] On the basis of the method of the present invention, we further carried out experiments on the removal of other antibiotics and dyes. By adding other antibiotics or dye pollutants into the MOF-based sonocatalytic reactor constructed by the present invention, the antibiotics and pollutants can be removed quickly and efficiently, indicating that the sonocatalytic reactor constructed based on the photoactive MOF of the present invention has good universality. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a diagram of the sono-photocatalytic reaction device based on PCN-222 prepared by the method of Example 1.

[0027] In the figure: 1. stirring bar, 2. visible light, 3. water inlet, 4. ultrasonic vibrator, 5. reaction tank, 6. water outlet.

[0028] Figure 2 This is a scanning electron microscope image of the PCN-222 material prepared by the method of Example 1.

[0029] Figure 3 This is the powder X-Ray (PXRD) diffraction spectrum of the PCN-222 material prepared by the method of Example 1.

[0030] Figure 4 This is the infrared spectrum of the PCN-222 material prepared by the method of Example 1.

[0031] Figure 5 It is the ultraviolet-visible absorption spectrum of PCN-222 material prepared by the method of Example 1.

[0032] Figure 6 This is the fluorescence spectrum of the PCN-222 material prepared by the method of Example 1.

[0033] Figure 7 This is a spectrum diagram of the removal of antibiotics by the PCN-222-based sono-photocatalytic reactor prepared by the method of Example 1.

[0034] Figure 8 This is a degradation diagram of antibiotic removal by the PCN-222-based sono-photocatalytic reactor prepared by the method of Example 1.

[0035] Fig. 9 This is a spectrum diagram of the removal of ciprofloxacin by the PCN-222-based sono-photocatalytic reactor prepared by the method of Example 1.

[0036] Fig.10 This is a spectrum diagram of the removal of Rhodamine 6G by the PCN-222-based sono-photocatalytic reactor prepared by the method of Example 1.

[0037] Fig.11 This is a cycle performance diagram of the removal of antibiotics by the PCN-222-based sono-photocatalytic reactor prepared by the method of Example 1. DETAILED DESCRIPTION

[0038] The present invention will be further explained below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0039] Example 1: The method for constructing the sono-photocatalytic reactor for removing tetracycline using photoactive PCN-222 in this example is carried out according to the following steps:

[0040] (1) Synthesis of PCN-222 material: 65 mg of metal salt ZrCl4 was weighed into 7.5 mL of N,N-dimethylformamide (DMF), and 150 mg of porphyrin ligand TCPP was weighed into 7.5 mL of DMF. The two solutions were ultrasonicated for 30 minutes and then transferred to a reactor. 7 mL of formic acid was added as a regulator. The reaction was carried out at 120°C for 72 hours. The mixture was centrifuged and washed with DMF and ethanol at a centrifugal speed of 9000 rpm for 2 minutes. The obtained solid was placed in a vacuum drying oven at 50°C and dried for 3 hours to obtain a purple PCN-222 powder.

[0041] (2) Add 10 mg of the PCN-222 catalyst prepared in (1) to a 100 mL quartz reactor, add 67 mL of a 20 mg / L tetracycline aqueous solution, adjust the solution pH to 7, and place the quartz reactor in a dark room and stir for 30 minutes;

[0042] (3) Place the quartz reactor in an ultrasonic bath, adjust the ultrasonic frequency and power to 40 kHz and 90 W respectively, turn on the stirrer, ultrasound and xenon lamp, adjust the wavelength range of the light source to 400-700 nm, connect the circulating condensed water, and react for 60 minutes.

[0043] (4) Take out 2.5 mL of solution from the reaction system every 5 minutes, filter it with a water filter membrane with a diameter of 0.22 μm, and perform ultraviolet absorption detection on the filtrate. The maximum wavelength of the detection is 357 nm. Figure 7 As shown in Figure 2, the absorbance of tetracycline decreased rapidly within 0-30 minutes, and the removal efficiency of tetracycline was calculated to be as high as 92% at 60 minutes. Figure 8 shown.

[0044] Basic characterization

[0045] like Figure 2 As shown, the PCN-222 described in Example 1 is block-shaped in shape and has a size of approximately 1 to 5 μm.

[0046] like Figure 3 As shown in the PXRD spectra, (a) is the XRD spectrum of PCN-222 simulated by standard data exported from Materials Studio software; (b) is the PXRD spectrum of PCN-222 synthesized in Example 1. The peak positions of (a) and (b) are completely consistent, indicating that PCN-222 was successfully prepared and has no impurities.

[0047] like Figure 4 The infrared spectrum of is the infrared spectrum of PCN-222 in Example 1. The presence of the carboxyl group, CN single bond and C=N double bond of the ligand is determined by the characteristic peaks of the spectrum, which further illustrates the structure of PCN-222.

[0048] Figure 5 This is the solid UV-visible absorption spectrum of PCN-222 described in Example 1. The absorption edge of the spectrum peak indicates that the material has a broad-band visible light absorption in the range of 400 to 700 nm.

[0049] Figure 6 Figures 1 and 2 are fluorescence spectra of the PCN-222 described in Example 1, (a) is the fluorescence spectrum of the ligand TCPP; (b) is the fluorescence spectrum of the PCN-222 described in Example 1. It can be seen from the figures that the emission peak intensity of PCN-222 is significantly lower than that of the ligand TCPP, indicating that the PCN-222 catalyst has a high photogenerated charge separation efficiency.

[0050] Example 2: The method for constructing the sono-photocatalytic reactor for removing tetracycline using photoactive PCN-223 in this example is carried out according to the following steps:

[0051] (1) Synthesis of PCN-223 material: 52 mg of metal salt ZrOCl2, 98 mg of TCPP and 4 mL of glacial acetic acid were weighed into a glass bottle and stirred at room temperature for 30 minutes. The mixture was then transferred to a reactor and reacted at 100°C for 18 hours. The mixture was washed by centrifugation three times with 5 mL of DMF and once with 5 mL of anhydrous EtOH at a centrifugal speed of 9000 rpm for 3 minutes. The precipitate was dried in a vacuum oven at 50°C for 3 hours to obtain a purple PCN-223 powder.

[0052] (2) Add 15 mg of the PCN-223 catalyst prepared in (1) to a 100 mL quartz reactor, add 67 mL of a 20 mg / L tetracycline aqueous solution, adjust the solution pH to 5, and place the quartz reactor in a dark room and stir for 30 minutes;

[0053] (3) Place the quartz reactor in an ultrasonic bath, adjust the ultrasonic frequency and power to 40 kHz and 120 W respectively, turn on the stirrer, ultrasound and xenon lamp, adjust the wavelength range of the light source to 400-700 nm, connect the circulating condensed water, and react for 60 minutes.

[0054] (4) Every 10 minutes, 2.5 mL of the solution was taken out from the reaction system and filtered through a water filter membrane with a diameter of 0.22 μm. The filtrate was subjected to ultraviolet absorption detection. The maximum wavelength of the detection was 357 nm. It was calculated that the removal efficiency of tetracycline was as high as 90%.

[0055] Example 3: The method for constructing the sono-photocatalytic reactor for removing tetracycline using photoactive PCN-224 in this example is carried out according to the following steps:

[0056] (1) Synthesis of PCN-224 material: 60 mg of metal salt ZrCl4, 25 mg of TCPP ligand and 600 mg of benzoic acid were weighed into a glass bottle, and 4 mL of DMF was added thereto. The glass bottle was placed in an ultrasonic bath and sonicated until all solids were completely dissolved. The resulting solution was transferred to an autoclave, heated at 120°C for 24 hours, and centrifuged and washed three times with 5 mL of DMF and once with 5 mL of anhydrous EtOH at a centrifugal speed of 9000 rpm for 3 minutes. The resulting precipitate was dried in a vacuum oven at 50°C for 3 hours to obtain a purple PCN-224 powder;

[0057] (2) Add 10 mg of the PCN-224 catalyst prepared in (1) to a 100 mL quartz reactor, add 67 mL of a 20 mg / L tetracycline aqueous solution, adjust the solution pH to 7, and place the quartz reactor in a dark room and stir for 30 minutes;

[0058] (3) Place the quartz reactor in an ultrasonic bath, adjust the ultrasonic frequency and power to 40 kHz and 120 W respectively, turn on the stirrer, ultrasound and xenon lamp, adjust the wavelength of the light source to 400-700 nm, connect the circulating condensed water, and react for 60 minutes.

[0059] (4) 2.5 mL of the solution was taken out from the reaction system every 10 minutes, filtered through a water filter membrane with a diameter of 0.22 μm, and the filtrate was subjected to ultraviolet absorption detection. The maximum wavelength of the detection was 357 nm, and the removal efficiency of tetracycline was calculated to be as high as 95%.

[0060] Example 4: The method for constructing the sono-photocatalytic reactor for removing tetracycline using photoactive PCN-22 in this example is carried out according to the following steps:

[0061] (1) Synthesis of PCN-22 material: 104 μL of isopropyl tert-butyl ester and 192 mg of 4-aminobenzoic acid were added to 6 mL of isopropanol solution and stirred at room temperature for 30 minutes. The resulting orange-yellow solution was reacted at 100°C for 72 hours and washed with isopropanol three times to obtain bright yellow titanium oxide cluster Ti6O6(OiPr)6(abz)6 (abz = 4-aminobenzoate) crystals;

[0062] Weigh 40 mg of titanium oxide cluster, 100 mg of TCPP ligand and 1000 mg of benzoic acid into a glass reagent bottle, and add 20 mL of N, N-dimethylacetamide (DEF) thereto, transfer the mixture into an autoclave, heat at 150 ° C for 48 hours, wash three times with 5 mL of DMF and once with 5 mL of anhydrous EtOH, and place the obtained solid in a vacuum drying oven at 50 ° C for 3 hours to obtain black-red PCN-22 crystals;

[0063] (2) Add 15 mg of the PCN-22 catalyst prepared in (1) to a 100 mL quartz reactor, add 67 mL of a 20 mg / L tetracycline aqueous solution, adjust the solution pH to 5, and place the quartz reactor in a dark room and stir for 30 minutes;

[0064] (3) Place the quartz reactor in an ultrasonic bath, adjust the ultrasonic frequency and power to 40 kHz and 60 W respectively, turn on the stirrer, ultrasound and xenon lamp, adjust the wavelength range of the light source to 400-700 nm, connect the circulating condensed water, and react for 60 minutes.

[0065] (4) 2.5 mL of the solution was taken out from the reaction system every 10 minutes, filtered through a water filter membrane with a diameter of 0.22 μm, and the filtrate was subjected to ultraviolet absorption detection. The maximum wavelength of the detection was 357 nm, and the removal efficiency of tetracycline was calculated to be as high as 93%.

[0066] Example 5: The method for constructing the photocatalytic reactor for removing tetracycline using the photoactive MIL-88B-Fe of this example is carried out according to the following steps:

[0067] (1) Synthesis of MIL-88B-Fe material: 128 mg of ferric nitrate nonahydrate and 60 mg of terephthalic acid ligand were weighed and ultrasonically dissolved in a mixed solution of 4 mL of DMF and 4 mL of acetonitrile, and the mixture was transferred to an autoclave, heated at 110°C for 24 hours, centrifuged and washed three times with 5 mL of DMF and once with 5 mL of anhydrous EtOH at a centrifugal speed of 9000 rpm for 3 minutes, and the obtained solid was placed in a vacuum drying oven at 50°C and dried for 3 hours to obtain flesh-pink MIL-88B-Fe powder;

[0068] (2) Add 20 mg of the MIL-88B-Fe catalyst prepared in (1) to a 100 mL quartz reactor, add 67 mL of a 20 mg / L tetracycline aqueous solution, adjust the solution pH to 9, and place the quartz reactor in a dark room and stir for 30 minutes;

[0069] (3) Place the quartz reactor in an ultrasonic bath, adjust the ultrasonic frequency and power to 40 kHz and 60 W respectively, turn on the stirrer, ultrasound and xenon lamp, adjust the wavelength range of the light source to 400-700 nm, connect the circulating condensed water, and react for 60 minutes.

[0070] (4) Every 10 minutes, 2.5 mL of the solution was taken out from the reaction system and filtered through a water filter membrane with a diameter of 0.22 μm. The filtrate was subjected to ultraviolet absorption detection. The maximum wavelength of the detection was 357 nm. The removal efficiency of tetracycline was calculated to be 87%.

[0071] Based on Example 1, the following examples explore the effects of pH, tetracycline concentration, PCN-222 catalyst amount, ultrasonic frequency, and light source wavelength on the efficiency of tetracycline removal.

[0072] Example 6

[0073] The experiment in Example 1 was repeated by replacing the tetracycline solution with a pH of 7 in Example 1 with a tetracycline solution with a pH of 11. The removal rate of tetracycline was 82%.

[0074] Example 7

[0075] The tetracycline solution with a pH of 9 was used instead of the tetracycline solution with a pH of 7 in Example 1. The experiment in Example 1 was repeated, and the removal rate of tetracycline was 85%.

[0076] Example 8

[0077] The experiment in Example 1 was repeated by replacing the tetracycline solution with a pH of 7 in Example 1 with a tetracycline solution with a pH of 5. The removal rate of tetracycline was 80%.

[0078] Example 9

[0079] The experiment in Example 1 was repeated by using 5 mg of PCN-222 catalyst instead of 10 mg of PCN-222 in Example 1. The removal rate of tetracycline was 56%.

[0080] Example 10

[0081] The experiment in Example 1 was repeated by using 15 mg of PCN-222 catalyst instead of 10 mg of PCN-222 in Example 1. The removal rate of tetracycline was 95%.

[0082] Embodiment 11

[0083] The tetracycline solution in Example 1 was replaced with a 10 mg / L tetracycline solution, and the experiment in Example 1 was repeated. The removal rate of tetracycline was 97%.

[0084] Example 12

[0085] The tetracycline solution in Example 1 was replaced with a 30 mg / L tetracycline solution, and the experiment in Example 1 was repeated. The removal rate of tetracycline was 75%.

[0086] Embodiment 13

[0087] The experiment in Example 1 was repeated with an ultrasonic power of 30 W instead of the ultrasonic power in Example 1, and the removal rate of tetracycline was 63%.

[0088] Embodiment 14

[0089] The experiment in Example 1 was repeated with an ultrasonic power of 120 W instead of the ultrasonic power in Example 1. The removal rate of tetracycline was 98%.

[0090] Embodiment 15

[0091] The filter in Example 1 was replaced by a 460 nm single wavelength filter, and the experiment in Example 1 was repeated. The removal rate of tetracycline was 62%.

[0092] Example 16

[0093] The filter in Example 1 was replaced by a 520 nm single wavelength filter, and the experiment in Example 1 was repeated. The removal rate of tetracycline was 55%.

[0094] Based on Example 1, the following examples explore the performance of PCN-222 catalyst in removing other antibiotics and pollutants.

[0095] Embodiment 17

[0096] The tetracycline solution in Example 1 was replaced with a 20 mg / L ciprofloxacin solution, and the experiment in Example 1 was repeated. The removal rate of tetracycline was 69%. Fig. 9 shown.

[0097] Embodiment 18

[0098] The tetracycline solution in Example 1 was replaced with a 20 mg / L Rh6G solution, and the experiment in Example 1 was repeated. The removal rate of tetracycline was 60%. Fig.10 shown.

[0099] Embodiment 19

[0100] Acoustophotocatalytic cycling experiment: The PCN-222 material after the acoustic-photocatalytic reaction in Example 1 was centrifuged, washed twice with anhydrous ethanol, and dried in a vacuum drying oven at 50°C. The recovered PCN-222 material was further used as a catalyst to repeat the experiment in Example 1. The results showed that the PCN-222 material could undergo 5 cycling experiments. Fig.11 shown.

[0101] It should be noted that the above content only illustrates the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. For ordinary technicians in this technical field, they can make corresponding changes and substitutions based on the technical scheme and inventive concept of the present invention, and the performance or use is the same, which should be regarded as the protection scope of the present invention.

Claims

1. A method for constructing a sono-photocatalytic reactor for removing tetracycline using a photoactive MOF, characterized in that: The construction method comprises the following steps: (1) Synthesize MOF materials by solvothermal method; (2) Add the MOF catalyst prepared in (1) and tetracycline aqueous solution into a quartz reactor and stir in a dark room for 30 minutes; (3) placing the quartz reactor in an ultrasonic bath, turning on the stirrer, ultrasound and light source, connecting to circulating condensed water, and reacting at room temperature for 60 minutes; (4) At equal intervals, 2.5 mL of the solution was taken out from the reaction system and filtered through a water filter membrane. The filtrate was subjected to ultraviolet absorption detection with the maximum wavelength of detection being 357 nm. The removal efficiency of tetracycline was calculated.

2. The method for constructing a photocatalytic reactor for removing tetracycline using a photoactive MOF according to claim 1, characterized in that: In step (1), MOF is selected from one of PCN-222, PCN-223, PCN-224, MOF-525, PCN-22, UiO-66-NH2, MIL-88B-Fe, and MIL-125-NH2.

3. The method for constructing a photocatalytic reactor for removing tetracycline using a photoactive MOF according to claim 1, characterized in that: In step (1), the regulator for synthesizing MOF includes one of formic acid, acetic acid, benzoic acid, and p-aminobenzoic acid.

4. The method for constructing a photocatalytic reactor for removing tetracycline using a photoactive MOF according to claim 1, characterized in that: In step (1), the reaction is carried out at 100°C to 150°C for 24h to 72h.

5. The method for constructing a photocatalytic reactor for removing tetracycline using a photoactive MOF according to claim 1, characterized in that: The mass of the MOF in step (2) is 1:4 mg.

6. The method for constructing a photocatalytic reactor for removing tetracycline using a photoactive MOF according to claim 1, characterized in that: The concentration of tetracycline in step (2) is 1:9 mg / L.

7. The method for constructing a photocatalytic reactor for removing tetracycline using a photoactive MOF according to claim 1, characterized in that: The pH range of the tetracycline aqueous solution in step (2) is 3 to 11.

8. The method for constructing a sono-photocatalytic reactor for removing tetracycline using a photoactive MOF according to claim 1, characterized in that: The power of the ultrasonic wave in step (3) is 30-120W and the frequency is 40kHz.

9. The method for constructing a photocatalytic reactor for removing tetracycline using a photoactive MOF according to claim 1, characterized in that: The light source in step (3) is a 300W xenon lamp with a light wavelength ranging from 400 to 700nm.

10. The method for constructing a photocatalytic reactor for removing tetracycline using a photoactive MOF according to claim 1, characterized in that: The diameter of the water filter membrane in step (4) is 0.22 μm.

Images