A broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst and its preparation method and application

Abstract

The present invention discloses a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst, its preparation method, and application. This invention, for the first time, employs bismuth oxybromide as a carrier and iron porphyrin as an imprinting layer to prepare a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient electron-deficient carrier separation. Compared with existing reports, the present invention significantly broadens the material's light absorption range, reduces the recombination rate of photogenerated carriers, and utilizes the Fenton effect to synergistically promote the degradation of target substances, exhibiting high specific selectivity and reusability. Experimental verification demonstrated that under light irradiation, the material achieved a degradation rate of greater than 90% for norfloxacin hydrochloride in a simulated sewage environment, maintaining high stability and selectivity after ten reuses. The present invention has broad applications in the enrichment, separation, and removal of norfloxacin hydrochloride in water, as well as in photocatalysis.

Description

Technical Field

[0001] The present invention belongs to the technical field of molecular imprinting photocatalyst preparation, and specifically relates to a wide-spectrum responsive iron porphyrin molecular imprinting photocatalyst with efficient separation of electron-deficient driven carriers, and a preparation method and application thereof. Background Art

[0002] Norfloxacin hydrochloride, a widely used fluoroquinolone antibiotic, enters the aquatic environment through domestic sewage, hospital and pharmaceutical wastewater, aquaculture, and livestock and poultry wastewater. Its high ecotoxicity at low concentrations poses a serious threat to the aquatic environment and human health. Molecular imprinting technology (MIP) is a method for constructing molecularly imprinted polymers (MIPs) with specific recognition sites. MIPs can selectively adsorb trace pollutants in aquatic environments, which is extremely beneficial for removing antibiotic residues in these environments. However, traditional MIPs primarily transfer pollutants and cannot completely degrade or remove them.

[0003] In recent years, the use of photocatalytic technology for the advanced treatment of residual antibiotics in wastewater environments has been widely studied. Bismuth oxybromide (BiOBr)-based molecularly imprinted photocatalysts, as a highly selective photocatalytic material for pollutant degradation, are capable of deep removal of specific pollutants in wastewater. However, currently reported BiOBr-based molecularly imprinted photocatalysts still suffer from shortcomings such as insufficient utilization of sunlight and the easy recombination of photogenerated carriers. Further optimization is needed to improve their photocatalytic activity. Summary of the Invention

[0004] In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a wide-spectrum responsive iron porphyrin molecularly imprinted photocatalyst and its preparation method and application, so as to solve the technical problems that the existing photocatalysts have insufficient utilization of sunlight and the photogenerated carriers are easy to recombine, resulting in low photocatalytic activity.

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

[0006] The present invention discloses a method for preparing a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient separation of electron-deficient driven carriers, comprising the following steps:

[0007] 1) adding norfloxacin hydrochloride to a solvent containing bismuth oxybromide, ultrasonically mixing, and then performing a pre-adsorption treatment to obtain a mixed system;

[0008] 2) adding aminoporphyrin and trialdehyde phloroglucinol to the above-mentioned mixed system, and then adding acetic acid and heating and stirring to obtain a uniform dispersion;

[0009] 3) heating and stirring the dispersion to react, centrifuging, washing, and drying to obtain a solid product;

[0010] 4) The solid product is dispersed with dimethylformamide, and then a dimethylformamide solution of ferrous chloride tetrahydrate is added, ultrasonically dispersed evenly, heated and stirred, and then washed and dried to prepare a wide-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient separation of electron-deficient driven carriers.

[0011] Preferably, in step 1), the solvent used is a mixed solvent of dimethylformamide and 1,4-dioxane, and the volume ratio of dimethylformamide to 1,4-dioxane in the mixed solvent is 4:1.

[0012] More preferably, the usage ratio of bismuth oxybromide to the mixed solvent is (10-100) mg: (10-100) mL; and the usage ratio of norfloxacin hydrochloride to the mixed solvent is (2-20) mg: (10-100) mL.

[0013] Preferably, in step 1), the bismuth oxybromide is BiOBr, which is prepared by mixing bismuth nitrate pentahydrate, potassium bromide, copper nitrate trihydrate, polyvinyl pyrrolidone and ethylene glycol, stirring them uniformly, reacting them at a temperature of 140° C. for 10 hours, washing and drying the reaction product.

[0014] Preferably, in step 1), the pre-adsorption treatment time is 0.5 to 1.5 hours.

[0015] Preferably, in step 2), the final concentration of the added aminoporphyrin in the mixed solvent is 0.4 to 4 mg mL -1 The final concentration of trialdehyde phloroglucinol in the mixed solvent is 0.2-2 mg·mL -1 ; The volume of acetic acid added is 2% to 3% of the volume of the mixed solvent.

[0016] Preferably, in step 4), the concentration of the added ferrous chloride tetrahydrate dimethylformamide solution is 10 mmol·L -1 The dosage ratio of solid product to dimethylformamide and ferrous chloride tetrahydrate dimethylformamide solution is 20mg:10mL:(5~30)mL

[0017] Preferably, in steps 1) and 4), the ultrasonic power is 100-150 W, the ultrasonic temperature is 16-28° C., and the ultrasonic time is 10-60 min.

[0018] Preferably, in steps 2) and 3), the heating and stirring treatment adopts magnetic heating and stirring, the stirring speed is 200-600 rpm, the stirring time is 2-6h, and the heating temperature is 45-70°C.

[0019] Preferably, in step 4), the heating and stirring treatment adopts magnetic heating and stirring, the stirring speed is 200-600 rpm, the stirring time is 8-16h, and the heating temperature is 100-160°C.

[0020] The invention also discloses a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with electron-deficient driven carrier efficient separation, which is prepared by the above-mentioned preparation method.

[0021] The present invention also discloses the application of the above-mentioned electron-deficient driven carrier efficient separation wide-spectrum responsive iron porphyrin molecularly imprinted photocatalyst. The degradation rate of the electron-deficient driven carrier efficient separation wide-spectrum responsive iron porphyrin molecularly imprinted photocatalyst for norfloxacin hydrochloride in a simulated water environment system is greater than 90%.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The present invention discloses a method for preparing a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst for efficient electron-deficient carrier separation. The method comprises using bismuth oxybromide as a carrier, aminoporphyrin and trialdehyde phloroglucinol as functional monomers and crosslinkers, polymerizing the catalyst via a Schiff base reaction, and then heating and stirring the catalyst. The iron ions in ferrous chloride tetrahydrate are then modified at the aminoporphyrin center via the coordination of the iron ions with nitrogen atoms, resulting in a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst (BiOBr@Fe-TAPP-TP) for efficient electron-deficient carrier separation. Iron porphyrins have the characteristics of a large π-conjugated system and strong visible light absorption. On the one hand, they can provide abundant target-specific adsorption sites, achieving selectivity for the target; on the other hand, they can broaden the light absorption range of BiOBr and improve the utilization rate of sunlight. Furthermore, the iron center of the porphyrin can effectively catalyze the Fenton reaction, and its electron-deficient nature can induce electron injection into BiOBr, thereby reducing the recombination of photogenerated carriers in BiOBr and synergizing the Fenton reaction.

[0024] The molecularly imprinted photocatalyst prepared by the present invention uses bismuth oxybromide as a carrier, which has a large specific surface area that is conducive to a high amount of template molecular imprinting, and has good photocatalytic performance, which is conducive to the response to simulated sunlight and the removal of the target. The molecularly imprinted photocatalyst uses iron porphyrin as an imprinting layer and has target-specific adsorption sites. It can effectively adsorb the target in a sewage environment and eliminate interference. At the same time, the iron porphyrin imprinting layer can broaden the light absorption range of the material, significantly reduce the recombination of photogenerated carriers, and improve the photocatalytic efficiency. After adding hydrogen peroxide, a Fenton effect can be generated under the condition of visible light irradiation, which synergistically promotes the degradation of the target and improves the photodegradation efficiency.

[0025] Furthermore, the photodegradation removal efficiency of the target object can be controlled by adjusting the ratio of aminoporphyrin to bismuth oxybromide, the feeding amount of ferrous chloride tetrahydrate, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a scanning electron micrograph of BiOBr@Fe-TAPP-TP;

[0027] Figure 2 XRD analysis data of BiOBr@Fe-TAPP-TP. DETAILED DESCRIPTION

[0028] In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts should fall within the scope of protection of the present invention.

[0029] It should be noted that the terms "first", "second", etc. in the description and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that the numbers used in this way can be interchanged where appropriate, so that the embodiments of the present invention described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0030] The present invention is described in further detail below with reference to the accompanying drawings:

[0031] Example 1

[0032] A method for preparing a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient separation of electron-deficient driven carriers comprises the following steps:

[0033] 1) Add norfloxacin hydrochloride (2 mg) to a bismuth oxybromide (10 mg) solution in a dimethylformamide / 1,4-dioxane mixture (10 mL, 4 / 1) and mix thoroughly by ultrasonication at 100 W, 16° C., and 10 min. Allow to pre-adsorb for 0.5 h.

[0034] 2) adding aminoporphyrin (4 mg) and trialdehyde phloroglucinol (2 mg) to the mixture prepared in step 1), and then adding acetic acid (0.2 mL) and heating and stirring to obtain a uniform dispersion;

[0035] 3) magnetically stirring the dispersion obtained in step 2) at 45° C. at 200 rpm for 2 h. After the reaction, centrifugation, washing, and drying were performed to obtain a solid product.

[0036] 4) The solid product (20 mg) obtained in step 3) was dispersed in dimethylformamide (10 mL), and then a dimethylformamide solution of ferrous chloride tetrahydrate (10 mmol·L -1 , 5 mL) was ultrasonically dispersed uniformly with an ultrasonic power of 100 W, an ultrasonic temperature of 16°C, and an ultrasonic time of 10 min, followed by heating and stirring to obtain a uniform dispersion.

[0037] 5) The dispersion obtained in step 4) was subjected to magnetic stirring (200 rpm) at 100° C. and reacted for 8 h to obtain a solid product loaded with iron ions.

[0038] 6) The solid product after loading iron ions was washed and dried to prepare a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst (BiOBr@Fe-TAPP-TP) with efficient separation of electron-deficient driven carriers.

[0039] Example 2

[0040] A method for preparing a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient separation of electron-deficient driven carriers comprises the following steps:

[0041] 1) Add norfloxacin hydrochloride (4 mg) to a mixed solution of bismuth oxybromide (20 mg) in dimethylformamide / 1,4-dioxane (20 mL, 4 / 1) and mix by ultrasonication at 120 W, 25° C., and 20 min. Pre-adsorb for 0.5 h.

[0042] 2) adding aminoporphyrin (15 mg) and trialdehyde phloroglucinol (10 mg) to the mixture prepared in step 1), and then adding acetic acid (0.4 mL) and heating and stirring to obtain a uniform dispersion;

[0043] 3) magnetically stirring the dispersion obtained in step 2) at 50° C. (300 rpm) for 3 h. After the reaction, centrifugation, washing, and drying were performed to obtain a solid product.

[0044] 4) The solid product (20 mg) obtained in step 3) was dispersed in dimethylformamide (10 mL), and then a dimethylformamide solution of ferrous chloride tetrahydrate (10 mmol·L -1 , 10 mL) was ultrasonically dispersed uniformly with an ultrasonic power of 120 W, an ultrasonic temperature of 25° C., and an ultrasonic time of 20 min, followed by heating and stirring to obtain a uniform dispersion.

[0045] 5) The dispersion obtained in step 4) was subjected to magnetic stirring (300 rpm) at 120° C. and reacted for 10 h to obtain a solid product loaded with iron ions.

[0046] 6) The solid product after loading iron ions was washed and dried to prepare a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst (BiOBr@Fe-TAPP-TP) with efficient separation of electron-deficient driven carriers.

[0047] Example 3

[0048] A method for preparing a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient separation of electron-deficient driven carriers comprises the following steps:

[0049] 1) Add norfloxacin hydrochloride (6 mg) to a mixed solution of bismuth oxybromide (30 mg) in dimethylformamide / 1,4-dioxane (30 mL, 4 / 1) and mix by ultrasonication at 120 W, 25°C, and 20 min, followed by pre-adsorption for 1 h.

[0050] 2) adding aminoporphyrin (30 mg) and trialdehyde phloroglucinol (24 mg) to the mixture prepared in step 1), and then adding acetic acid (0.8 mL) and heating and stirring to obtain a uniform dispersion;

[0051] 3) magnetically stirring the dispersion obtained in step 2) at 55° C. (500 rpm) for 4 h. After the reaction, centrifugation, washing, and drying were performed to obtain a solid product.

[0052] 4) The solid product (20 mg) obtained in step 3) was dispersed in dimethylformamide (10 mL), and then a dimethylformamide solution of ferrous chloride tetrahydrate (10 mmol·L -1 , 15 mL) was ultrasonically dispersed uniformly with an ultrasonic power of 120 W, an ultrasonic temperature of 25° C., and an ultrasonic time of 20 min, followed by heating and stirring to obtain a uniform dispersion.

[0053] 5) The dispersion obtained in step 4) was subjected to magnetic stirring (500 rpm) at 140° C. and reacted for 12 h to obtain a solid product loaded with iron ions.

[0054] 6) The solid product after loading iron ions was washed and dried to prepare a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst (BiOBr@Fe-TAPP-TP) with efficient separation of electron-deficient driven carriers.

[0055] Example 4

[0056] A method for preparing a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient separation of electron-deficient driven carriers comprises the following steps:

[0057] 1) Add norfloxacin hydrochloride (10 mg) to a mixed solution of bismuth oxybromide (50 mg) in dimethylformamide / 1,4-dioxane (50 mL, 4 / 1) and mix by ultrasonication at 120 W, 25°C, and 20 min, followed by pre-adsorption for 1 h.

[0058] 2) adding aminoporphyrin (60 mg) and trialdehyde phloroglucinol (50 mg) to the mixture prepared in step 1), and then adding acetic acid (1.2 mL) and heating and stirring to obtain a uniform dispersion;

[0059] 3) magnetically stirring the dispersion obtained in step 2) at 60° C. for 4 h. After the reaction, centrifugation, washing, and drying were performed to obtain a solid product.

[0060] 4) The solid product (20 mg) obtained in step 3) was dispersed in dimethylformamide (10 mL), and then a dimethylformamide solution of ferrous chloride tetrahydrate (10 mmol·L -1 , 20 mL) was ultrasonically dispersed uniformly with an ultrasonic power of 120 W, an ultrasonic temperature of 25° C., and an ultrasonic time of 25 min, followed by heating and stirring to obtain a uniform dispersion.

[0061] 5) The dispersion obtained in step 4) was subjected to magnetic stirring (600 rpm) at 150° C. and reacted for 14 h to obtain a solid product loaded with iron ions.

[0062] 6) The solid product after loading iron ions was washed and dried to prepare a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst (BiOBr@Fe-TAPP-TP) with efficient separation of electron-deficient driven carriers.

[0063] Example 5

[0064] A method for preparing a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient separation of electron-deficient driven carriers comprises the following steps:

[0065] 1) Add norfloxacin hydrochloride (14 mg) to a mixed solution of bismuth oxybromide (70 mg) in dimethylformamide / 1,4-dioxane (70 mL, 4 / 1) and mix by ultrasonication at 150 W, 25°C, and 40 min, followed by pre-adsorption for 1.5 h.

[0066] 2) adding aminoporphyrin (140 mg) and trialdehyde phloroglucinol (70 mg) to the mixture prepared in step 1), and then adding acetic acid (2 mL) and heating and stirring to obtain a uniform dispersion;

[0067] 3) magnetically stirring the dispersion obtained in step 2) at 60° C. at 600 rpm for 5 h. After the reaction, centrifugation, washing, and drying were performed to obtain a solid product.

[0068] 4) The solid product (20 mg) obtained in step 3) was dispersed in dimethylformamide (10 mL), and then a dimethylformamide solution of ferrous chloride tetrahydrate (10 mmol·L -1 , 25 mL) was ultrasonically dispersed uniformly with an ultrasonic power of 150 W, an ultrasonic temperature of 25° C., and an ultrasonic time of 40 min, followed by heating and stirring to obtain a uniform dispersion.

[0069] 5) The dispersion obtained in step 4) was subjected to magnetic stirring (600 rpm) at 160° C. and reacted for 15 h to obtain a solid product loaded with iron ions.

[0070] 6) The solid product after loading iron ions was washed and dried to prepare a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst (BiOBr@Fe-TAPP-TP) with efficient separation of electron-deficient driven carriers.

[0071] Example 6

[0072] A method for preparing a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient separation of electron-deficient driven carriers comprises the following steps:

[0073] 1) Add norfloxacin hydrochloride (20 mg) to a mixed solution of bismuth oxybromide (100 mg) in dimethylformamide / 1,4-dioxane (100 mL, 4 / 1) and mix by ultrasonication at 150 W, 28°C, and 60 min, followed by pre-adsorption for 1.5 h.

[0074] 2) adding aminoporphyrin (400 mg) and trialdehyde phloroglucinol (200 mg) to the mixed system prepared in step 1), and then adding acetic acid (3 mL) and heating and stirring to obtain a uniform dispersion;

[0075] 3) magnetically stirring the dispersion obtained in step 2) at 70° C. at 600 rpm for 6 h. After the reaction, centrifugation, washing, and drying were performed to obtain a solid product.

[0076] 4) The solid product (20 mg) obtained in step 3) was dispersed in dimethylformamide (10 mL), and then a dimethylformamide solution of ferrous chloride tetrahydrate (10 mmol·L -1 , 30 mL) was ultrasonically dispersed uniformly with an ultrasonic power of 150 W, an ultrasonic temperature of 28° C., and an ultrasonic time of 60 min, followed by heating and stirring to obtain a uniform dispersion.

[0077] 5) The dispersion obtained in step 4) was subjected to magnetic stirring (600 rpm) at 160° C. for 16 h to obtain a solid product loaded with iron ions.

[0078] 6) The solid product after loading iron ions was washed and dried to prepare a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst (BiOBr@Fe-TAPP-TP) with efficient separation of electron-deficient driven carriers.

[0079] Example 7

[0080] The BiOBr@Fe-TAPP-TP prepared in Example 2 was used as an experimental example. The obtained catalyst was characterized by scanning electron microscopy (SEM) and XRD analysis. The results are as follows:

[0081] (1) Morphological characterization

[0082] The morphology of the prepared BiOBr@Fe-TAPP-TP was observed using a Gemini SEM 500 scanning electron microscope. Figure 1 As shown. Figure 1 It can be seen that the prepared BiOBr@Fe-TAPP-TP imprinted layer is relatively uniform.

[0083] (2) X-ray diffraction analysis

[0084] The crystal structure and phase purity of the prepared BiOBr@Fe-TAPP-TP and BiOBr were determined by XRD-6100 X-ray diffraction analyzer. Figure 2 As shown in the figure, the positions and relative intensities of all diffraction peaks of BiOBr and BiOBr@Fe-TAPP-TP are consistent with those of the JCPDS card (09-0393) of bismuth oxybromide, confirming that the crystal form of the product did not change during the preparation process.

[0085] Example 8

[0086] 5.0 mg of BiOBr@Fe-TAPP-TP prepared in Example 1, Example 2, Example 3, Example 4, Example 5 and Example 6 were weighed and dispersed in 30 mL of an aqueous solution of norfloxacin hydrochloride (20 mg·L -1 ) was stirred magnetically at room temperature for 30 minutes, then a certain amount of 30% hydrogen peroxide was added. The system was then exposed to visible light for 60 minutes. After the reaction, the absorbance of the supernatant was measured using a UV-visible spectrometer, and the concentration of norfloxacin hydrochloride in the supernatant was calculated. Calculations (Table 1) show that the broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst, with efficient electron-deficient carrier separation, exhibited degradation rates exceeding 90% for norfloxacin hydrochloride, demonstrating its excellent visible light degradation performance.

[0087] Table 1. Degradation rate of norfloxacin hydrochloride by BiOBr@Fe-TAPP-TP prepared in each example

[0088]

[0089] In summary, this invention, for the first time, employs bismuth oxybromide as a carrier and iron porphyrin as an imprinting layer to prepare a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient electron-deficient carrier separation. Compared with existing reports, this invention significantly broadens the material's light absorption range, reduces the recombination rate of photogenerated carriers, and utilizes the Fenton effect to synergistically promote the degradation of target substances, exhibiting high specific selectivity and reusability. Experimental verification demonstrated that under light irradiation, the degradation rate of norfloxacin hydrochloride in a simulated sewage environment exceeded 90%, and the catalyst maintained high stability and selectivity after ten reuses. This invention has broad applications in the enrichment, separation, and removal of norfloxacin hydrochloride in water, as well as in photocatalysis.

[0090] The above content is only for explaining the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst, characterized in that: The following steps are involved: 1) adding norfloxacin hydrochloride to a solvent containing bismuth oxybromide, ultrasonically mixing, and then performing a pre-adsorption treatment to obtain a mixed system; 2) Adding aminoporphyrin and trialdehyde phloroglucinol to the above-mentioned mixed system, then adding acetic acid and heating and stirring to obtain a uniform dispersion; the final concentration of the added aminoporphyrin in the mixed solvent is 0.4 to 4 mg mL -1 The final concentration of trialdehyde phloroglucinol in the mixed solvent is 0.2-2 mg·mL -1 ; The volume of acetic acid added is 2% to 3% of the volume of the mixed solvent; 3) heating and stirring the dispersion, then centrifuging, washing, and drying to obtain a solid product; 4) The solid product is dispersed with dimethylformamide, and then a dimethylformamide solution of ferrous chloride tetrahydrate is added, ultrasonically dispersed evenly, heated and stirred, and then washed and dried to prepare a wide-spectrum responsive iron porphyrin molecularly imprinted photocatalyst with efficient separation of electron-deficient driven carriers.

2. The method for preparing the broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst according to claim 1, characterized in that: In step 1), the solvent used is a mixed solvent of dimethylformamide and 1,4-dioxane, and the volume ratio of dimethylformamide to 1,4-dioxane in the mixed solvent is 4:

1.

3. The method for preparing the broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst according to claim 2, wherein: The usage ratio of bismuth oxybromide to the mixed solvent is (10-100) mg:(10-100) mL; the usage ratio of norfloxacin hydrochloride to bismuth oxybromide is (2-20) mg:(10-100) mg.

4. The method for preparing the broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst according to claim 1, wherein: In step 1), the pre-adsorption treatment time is 0.5 to 1.5 hours.

5. The method for preparing the broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst according to claim 1, wherein: In step 4), the concentration of the added ferrous chloride tetrahydrate dimethylformamide solution is 10 mmol·L -1 The usage ratio of the solid product to dimethylformamide and ferrous chloride tetrahydrate dimethylformamide solution is 20 mg:10 mL:(5-30) mL.

6. The method for preparing the broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst according to claim 1, characterized in that: In steps 2) and 3), the heating and stirring treatment adopts magnetic heating and stirring, the stirring speed is 200 to 600 rpm, the stirring time is 2 to 6 hours, and the heating temperature is 45 to 70°C; in step 4), the heating and stirring treatment adopts magnetic heating and stirring, the stirring speed is 200 to 600 rpm, the stirring time is 8 to 16 hours, and the heating temperature is 100 to 160°C.

7. The method for preparing the broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst according to claim 1, characterized in that: In steps 1) and 4), the ultrasonic power is 100-150 W, the ultrasonic temperature is 16-28° C., and the ultrasonic time is 10-60 min.

8. A broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the broad-spectrum responsive iron porphyrin molecularly imprinted photocatalyst according to claim 8 in removing norfloxacin hydrochloride from sewage, characterized in that: The degradation rate of norfloxacin hydrochloride in sewage is greater than 90%.

Images