A porphyrin iron-based biomimetic enzyme catalytic membrane for water treatment, its preparation and application

Abstract

This invention relates to a porphyrin iron-based biomimetic enzyme catalytic membrane for water treatment, its preparation, and its application, belonging to the field of catalytic membrane technology. The porphyrin iron-based biomimetic enzyme catalytic membrane of this invention comprises a microfiltration membrane substrate and a porphyrin iron-based biomimetic enzyme catalyst supported on the surface of the substrate membrane via chemical cross-linking. The porphyrin iron-based biomimetic enzyme catalyst contains a catalytic active center structure with "Fe-N" coordination. The porphyrin iron-based biomimetic enzyme prepared by this invention has a similar catalytic active center structure to that of natural peroxidase, exhibits high affinity for hydrogen peroxide, and can significantly improve hydrogen peroxide utilization and the steady-state concentration of reactive oxygen species. The constructed biomimetic enzyme-membrane reactor integrates the dual functions of membrane separation and enzyme catalysis, achieving a highly efficient combination of mass transfer and reaction, and greatly improving the removal performance of new pollutants in water.

Description

Technical Field

[0001] This invention relates to the field of catalytic membrane technology for water treatment, and in particular to a porphyrin iron-based biomimetic enzyme catalytic membrane for water treatment, its preparation and application. Background Technology

[0002] Urban wastewater reuse is an important measure for sustainable water management. However, the presence of new pollutants in secondary effluent from wastewater treatment plants poses potential ecological risks to its reuse. Membrane water treatment technology has become one of the mainstream processes for wastewater treatment and reuse. However, traditional membrane water treatment technologies still face challenges in practical applications, such as incomplete removal of micropollutants, secondary treatment of concentrate, and high energy consumption. Therefore, developing high-standard, green, and low-energy-consumption membrane separation technologies is of practical significance for achieving the sustainable development of membrane water treatment technologies.

[0003] Enzyme catalysis, characterized by high efficiency, specificity, and mild reaction conditions, offers advantages in treating recalcitrant pollutants. Using membrane materials as carriers for immobilized enzymes integrates both separation and catalysis, enabling the effective removal of trace pollutants from water. However, natural enzymes exhibit poor stability and tolerance in complex environmental media, and their complex three-dimensional structure increases the contact resistance between the substrate and the active site, limiting the development and application of enzyme catalysis technology. Biomimetic enzymes are a class of nanomaterials with catalytic activity similar to natural enzymes. By mimicking the binding pockets and catalytic active centers of natural enzymes, simple and stable biomimetic enzymes can be designed and effectively coupled with membrane separation technology, providing new ideas for the design and fabrication of high-performance catalytic membranes. Therefore, the rational design of a biomimetic enzyme catalytic membrane based on the structure and functional units of natural enzymes for the advanced treatment of new pollutants in secondary effluent is of great significance for promoting the recycling of urban reclaimed water. Summary of the Invention

[0004] To address the above technical problems, this invention provides a porphyrin iron-based biomimetic enzyme catalytic membrane, its preparation method, and its application as a catalytic membrane in enzyme-like catalytic reactions. This catalytic membrane uses a microfiltration membrane as the base membrane and carboxyporphyrin iron or aminoporphyrin iron with a peroxidase-like catalytic active center structure as the functional catalytic unit. The biomimetic enzyme catalyst is loaded onto the membrane surface through a pre-filtration-post-crosslinking method to construct the biomimetic enzyme catalytic membrane. The biomimetic enzyme catalytic membrane is assembled into a biomimetic enzyme-membrane reactor using a filtration assembly. Operating in continuous or batch mode, the addition of a small amount of hydrogen peroxide generates reactive oxygen species under a wide pH range, achieving highly efficient catalytic conversion of new pollutants. This provides a highly efficient and environmentally friendly new technology for the recycling of urban reclaimed water.

[0005] The first objective of this invention is to provide a porphyrin iron-based biomimetic enzyme catalytic membrane, comprising a microfiltration membrane substrate membrane and a porphyrin iron-based biomimetic enzyme catalyst supported on the surface of the substrate membrane via chemical cross-linking. The porphyrin iron-based biomimetic enzyme catalyst contains a catalytic active center structure with "Fe-N" coordination and contains carboxyl and / or amino groups, wherein the carboxyl and / or amino groups are connected via benzene ring side chains in a porphyrin structure.

[0006] In some embodiments of the present invention, the material of the microfiltration membrane substrate includes one or more of polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, nylon 66, and ceramic membrane.

[0007] The pore size of the microfiltration membrane substrate is 0.01 ~ 0.45 μm;

[0008] The loading of the porphyrin iron-based biomimetic enzyme catalyst is 0.05 ~ 1.5 mg / cm³. 2 .

[0009] A second objective of this invention is to provide a method for preparing the porphyrin iron-based biomimetic enzyme catalytic membrane, comprising the following steps:

[0010] The porphyrin derivative was dissolved in an organic solvent, heated to reflux, and then an iron salt was added to continue the reaction.

[0011] After the reaction is complete, the biomimetic enzyme catalyst is obtained by washing and drying.

[0012] The biomimetic enzyme catalyst was taken and dispersed in a solvent, and then loaded onto the surface of the microfiltration membrane substrate by vacuum filtration.

[0013] The perfluorosulfonic acid solution was filtered onto the surface of a microfiltration membrane substrate loaded with a biomimetic enzyme catalyst, and then heated and dried to obtain the porphyrin iron-based biomimetic enzyme catalytic membrane.

[0014] In some embodiments of the present invention, the porphyrin derivative includes meso-tetra(4-carboxyphenyl)porphyrin and / or meso-tetra(4-aminophenyl)porphyrin;

[0015] The organic solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), and triethylene glycol.

[0016] In some embodiments of the present invention, the iron salt is one or more of divalent or trivalent hydrochloride, sulfate, and nitrate.

[0017] In some embodiments of the present invention, the reflux temperature is 120-150 °C and the reaction time is 8-14 h.

[0018] In some embodiments of the present invention, the molar ratio of porphyrin derivative to iron salt is (0.5~2):10;

[0019] The concentration of the perfluorosulfonic acid solution is 2-8 wt%, and the volume used is 25-100 μL.

[0020] A third objective of the present invention is to provide a biomimetic enzyme-membrane reactor device, comprising the porphyrin iron-based biomimetic enzyme catalytic membrane.

[0021] In some embodiments of the present invention, the membrane flux in the biomimetic enzyme-membrane reactor is 50 ~ 400 L / (m²). 2 ·h).

[0022] In some embodiments of the present invention, the biomimetic enzyme-membrane reactor device is further provided with a feeding system, a main reaction system, and an effluent system.

[0023] A fourth objective of this invention is to provide the application of the porphyrin iron-based biomimetic enzyme catalytic membrane and the biomimetic enzyme-membrane reactor device in the deep treatment of wastewater / wastewater containing new pollutants.

[0024] In some embodiments of the present invention, the novel contaminant includes one or more of acetaminophen, bisphenol A, and 2,4-dichlorophenol.

[0025] In some embodiments of the present invention, the concentration of the new pollutant is 0.5 to 20 mg / L.

[0026] The technical solution of the present invention has the following advantages compared with the prior art:

[0027] 1. This invention uses neu-tetra(4-carboxyphenyl)porphyrin or neu-tetra(4-aminophenyl)porphyrin as iron salt ligands. After the ligands modified with carboxyl or amino groups coordinate with ferrous or ferric ions, they can regulate the charge density of the catalytic center, thereby regulating the adsorption energy and activation pathway of hydrogen peroxide on the biomimetic enzyme catalyst, and thus achieving the directional regulation of the biomimetic enzyme catalytic performance.

[0028] 2. This invention is based on the principle of peroxidase-like catalysis of hydrogen peroxide to generate reactive oxygen free radicals. By mimicking the catalytic active center structure of natural peroxidase with "Fe-N" coordination, the prepared porphyrin iron-based biomimetic enzyme has a high affinity for hydrogen peroxide, which can significantly improve the utilization rate of hydrogen peroxide and generate reactive oxygen free radicals to achieve efficient degradation of new pollutants.

[0029] 3. The biomimetic enzyme catalytic membrane prepared by the present invention through pre-filtration and post-crosslinking is highly operable, can effectively prevent catalyst shedding from the membrane surface, can be reused, and effectively extends the service life of the biomimetic enzyme catalytic membrane.

[0030] 4. The biomimetic enzyme-membrane reactor provided by this invention integrates the dual functions of membrane separation and enzyme catalysis, achieving a highly efficient combination of mass transfer and reaction, and greatly improving the removal performance of new pollutants in water.

[0031] 5. The biomimetic enzyme-membrane reactor provided by this invention is applied to the advanced treatment of sewage / wastewater. Compared with the traditional homogeneous Fenton technology, this invention has a wider pH adaptation range, stronger anti-interference ability, lower oxidant dosage, and no iron sludge precipitation, significantly improving technical feasibility. Attached Figure Description

[0032] To make the content of this invention easier to understand, the invention will be further described in detail below with reference to specific embodiments and accompanying drawings, wherein...

[0033] Figure 1 This is a comparison chart showing the effect of the free biomimetic enzyme catalyst prepared in Example 1 of the present invention on the activation of hydrogen peroxide to degrade acetaminophen with other catalysts in the comparative example;

[0034] Figure 2 This is a diagram showing the experimental effect of the free biomimetic enzyme catalyst prepared in Example 1 of this invention against KSCN poisoning.

[0035] Figure 3 The graph shows the degradation effect of the free biomimetic enzyme catalyst prepared in Example 1 of this invention on acetaminophen under different pH conditions.

[0036] Figure 4 The graph shows the degradation effect of the free biomimetic enzyme catalyst prepared in Example 1 of this invention on different pollutants.

[0037] Figure 5 This is a photograph of the carboxylated porphyrin iron-based biomimetic enzyme catalytic membrane used in water treatment according to Example 2 of the present invention.

[0038] Figure 6 This is a scanning electron microscope image of the carboxylated porphyrin iron-based biomimetic enzyme catalytic membrane for water treatment prepared in Example 2 of the present invention;

[0039] Figure 7 This is a schematic diagram of the structure of the biomimetic enzyme-membrane reactor provided in Embodiment 2 of the present invention for removing new pollutants from water;

[0040] Figure 8 This is a diagram showing the effect of the biomimetic enzyme-membrane reactor provided in Embodiment 2 of the present invention on the removal of acetaminophen;

[0041] Figure 9 This is a diagram showing the degradation effect of the biomimetic enzyme-membrane reactor provided in Example 3 of the present invention on acetaminophen under the condition of coexistence of cations / anions and natural organic matter;

[0042] Figure 10 The diagram shows the effect of the biomimetic enzyme-membrane reactor provided in Example 4 of the present invention on removing organic pollutants such as acetaminophen, bisphenol A, and 2,4-dichlorophenol from surface water or secondary effluent.

[0043] Figure 11 This is a diagram showing the stable operation performance of the biomimetic enzyme-membrane reactor provided in Example 5 of the present invention for simultaneously removing acetaminophen, bisphenol A, and 2,4-dichlorophenol from secondary effluent.

[0044] Figure 12 A schematic diagram of the mechanism for removing new pollutants from water using a biomimetic enzyme-membrane reactor.

[0045] Explanation of the markings on the attached diagrams: 1-Water inlet hole, 2-Water inlet chamber, 3-PTFE gasket, 4-Porous stainless steel sheet, 5-Water outlet chamber, 6-Water outlet hole, 7-Bionic enzyme catalytic membrane. Detailed Implementation

[0046] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0047] Example 1

[0048] This embodiment provides a porphyrin iron-based biomimetic enzyme catalyst for water treatment, its preparation, and its application, as detailed below:

[0049] Preparation method of porphyrin iron-based biomimetic enzyme catalyst:

[0050] I. Preparation of Carboxylated Porphyrin Iron-Based Bionic Enzyme Catalyst: 0.1 mM of methyl-4-tetra(4-carboxyphenyl)porphyrin was dissolved in 20 mL of anhydrous N,N-dimethylformamide by sonication. The dissolved solution was transferred to a three-necked flask equipped with a reflux condenser and heated to 130 °C. After 30 min, reflux was observed. 1 mM ferrous chloride tetrahydrate was added, and the reaction was continued for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and the reaction vessel walls were washed with ultrapure water. The solution was collected, and the precipitate was obtained by centrifugation. The precipitate was repeatedly washed with ultrapure water and then thoroughly freeze-dried for later use to obtain the carboxylated porphyrin iron-based biomimetic enzyme catalyst.

[0051] Preparation of the aminoporphyrin iron-based biomimetic enzyme catalyst: 0.1 mM of 4-aminophenyl porphyrin was dissolved in 20 mL of anhydrous N,N-dimethylformamide by sonication. The dissolved solution was transferred to a three-necked flask equipped with a reflux condenser and heated to 130 °C. After 30 min, reflux was observed. 1 mM ferrous chloride tetrahydrate was added, and the reaction was continued for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and the reaction vessel walls were washed with ultrapure water. The solution was collected, and the precipitate was obtained by centrifugation. The precipitate was repeatedly washed with ultrapure water and then thoroughly freeze-dried for later use to obtain the aminoporphyrin iron-based biomimetic enzyme catalyst.

[0052] II. Applications:

[0053] 1. Carboxylated porphyrin iron or aminoporphyrin iron was added to a solution of acetaminophen at a concentration of 20 mg / L and pH = 5.2. Hydrogen peroxide was then added to bring the concentrations of the carboxylated porphyrin iron or aminoporphyrin iron biomimetic catalyst and hydrogen peroxide to 0.05 g / L and 5 mM, respectively. After thorough stirring for 60 min, the removal efficiency of acetaminophen by carboxylated porphyrin iron and aminoporphyrin iron approached 100%. Specifically, carboxylated porphyrin iron achieved an acetaminophen removal rate of up to 80% after 5 min of reaction (e.g., ...). Figure 1 (As shown).

[0054] 2. Anti-poisoning performance test

[0055] Carboxylated porphyrin iron or aminoporphyrin iron was added to a solution of acetaminophen at a concentration of 20 mg / L and pH = 5.2, followed by the addition of 2 mM KSCN and then hydrogen peroxide, so that the concentrations of the carboxylated porphyrin iron or aminoporphyrin iron biomimetic catalyst and hydrogen peroxide were 0.05 g / L and 5 mM, respectively. After stirring the reaction thoroughly for 60 min, the removal efficiency of acetaminophen by carboxylated porphyrin iron and aminoporphyrin iron remained essentially unchanged (e.g., Figure 2 As shown in the figure, this demonstrates that the biomimetic enzyme catalyst has good anti-poisoning properties.

[0056] 3. pH adaptability test

[0057] Carboxylated porphyrin iron or aminoporphyrin iron was added to acetaminophen solutions at different pH values ​​(20 mg / L), followed by hydrogen peroxide. The concentrations of the carboxylated porphyrin iron or aminoporphyrin iron biomimetic catalyst and the hydrogen peroxide were 0.05 g / L and 5 mM, respectively. After thorough stirring for 60 min, the carboxylated porphyrin iron and aminoporphyrin iron were able to remove acetaminophen over a wide pH range, with removal rates exceeding 80% (e.g., ...). Figure 3 As shown in the figure, this demonstrates that the biomimetic enzyme catalyst has a wide pH adaptability.

[0058] 4. Specific catalytic experiments of pollutants

[0059] Five pollutants—acetaminophen (APAP), bisphenol A (BPA), 2,4-dichlorophenol (2,4-DCP), p-cresol (PC), and p-nitrophenol (PNP)—were selected at a concentration of 20 mg / L. Carboxylated porphyrin iron or aminolated porphyrin iron was added to a solution with pH = 5.2, followed by hydrogen peroxide, to achieve concentrations of 0.05 g / L for the carboxylated porphyrin iron or aminolated porphyrin iron biomimetic catalyst, and 5 mM for the hydrogen peroxide. After thorough stirring for 60 min, the removal efficiency of carboxylated porphyrin iron and aminolated porphyrin iron for the five pollutants was as follows: Figure 4 As shown, carboxylated porphyrin iron and aminolated porphyrin iron showed the best removal effect on APAP, demonstrating the specific catalytic effect of biomimetic enzyme catalysts on APAP.

[0060] Example 2

[0061] This embodiment provides a method for preparing a porphyrin iron-based biomimetic enzyme catalytic membrane for water treatment, as detailed below:

[0062] I. Preparation of Porphyrin Iron-Based Bionic Enzyme Catalyst: 0.1 mM of methyl-4-tetra(4-carboxyphenyl)porphyrin was dissolved in 20 mL of anhydrous N,N-dimethylformamide by sonication. The dissolved solution was transferred to a three-necked flask equipped with a reflux condenser and heated to 130 °C. After 30 min, reflux was observed. 1 mM ferric chloride tetrahydrate was added, and the reaction was continued for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and the reaction vessel walls were washed with ultrapure water. The solution was collected, and the precipitate was obtained by centrifugation. The precipitate was repeatedly washed with ultrapure water and then freeze-dried to obtain the porphyrin iron-based biomimetic enzyme catalyst.

[0063] II. Preparation of Porphyrin Iron-Based Bionic Enzyme Catalytic Membrane: 0.015 g of the biomimetic enzyme catalyst obtained in step one was weighed and uniformly dispersed in 10 mL of deionized water by ultrasonication. The biomimetic enzyme catalyst was then loaded onto the surface of a 0.22 μm polyethersulfone microfiltration membrane by vacuum filtration to obtain a primary biomimetic enzyme catalytic membrane. 50 μL of a 5% perfluorosulfonic acid membrane solution was quantitatively measured and added to 10 mL of deionized water. After ultrasonic dispersion, the solution was filtered onto the surface of the aforementioned primary biomimetic enzyme catalytic membrane and dried in a 40 ℃ oven for 4 h to obtain the biomimetic enzyme catalytic membrane with a loading of 1 mg / cm³. 2 (like Figure 5 and 6 As shown in the figure, the biomimetic enzyme is uniformly loaded on the surface of the polyethersulfone microfiltration membrane, the catalytic layer thickness is about 86 micrometers, and the biomimetic enzyme catalytic membrane has good flexibility and is not easy to detach from the surface of the polyethersulfone microfiltration membrane.

[0064] III. Application: The prepared biomimetic enzyme catalytic membrane was used to construct a biomimetic enzyme-membrane reactor. The biomimetic enzyme catalytic membrane was sandwiched between two 0.5 mm thick porous stainless steel sheets and placed between two polytetrafluoroethylene (PTFE) gaskets (e.g., ...). Figure 7 As shown, this is a conventional membrane reactor in the field. The 0.5 mm thick porous stainless steel sheet serves to support the catalytic membrane and prevent it from deforming due to excessive pressure during pressure filtration experiments, thereby extending the membrane's service life. After tightening the bolts, the inlet of the biomimetic enzyme-membrane reactor is connected to the digital display pressure sensor and the wastewater tank via a peristaltic pump, and the outlet is connected to the high-precision digital display gear flow meter and the water storage tank.

[0065] Using acetaminophen at a concentration of 20 mg / L as the research object, the membrane flux was 96 L / (m²) at a hydrogen peroxide concentration of 5 mM. 2 Under operating conditions of ·h), the biomimetic enzyme-membrane reactor maintained a removal rate of over 90% for acetaminophen within 60 min (e.g., h). Figure 8 (As shown).

[0066] Comparative Example 1

[0067] This comparative example provides a porphyrin iron biomimetic enzyme catalyst without carboxyl and amino group modification for the removal of acetaminophen, which is exactly the same as step two in Example 2. Experimental results are shown below. Figure 1 The porphyrin iron used was commercially available, corresponding to... Figure 1 The porphyrin iron group in the middle.

[0068] Comparative Example 2

[0069] This comparative example provides a carboxyl-modified porphyrin (i.e. Figure 1 The carboxylated porphyrin, officially named neu-tetra(4-carboxyphenyl)porphyrin, contains no iron. Therefore, the resulting biomimetic enzyme catalyst does not possess an "Fe-N" structure. The experimental procedure is exactly the same as step two in Example 1. The experimental results are shown below. Figure 1 .

[0070] This comparative example provides an amino-modified porphyrin (i.e., Figure 1 The aminated porphyrin, also known as neu-tetra(4-aminophenyl)porphyrin, does not contain iron. Therefore, the resulting biomimetic enzyme catalyst does not possess an "Fe-N" structure. The experimental procedure is exactly the same as step two in Example 1. The experimental results are shown below. Figure 1 .

[0071] Comparative Example 3

[0072] This comparative example provides a method for directly constructing a membrane reactor using a polyethersulfone microfiltration membrane for the removal of acetaminophen, as detailed below:

[0073] This comparative example only provides a polyethersulfone microfiltration membrane without any loaded substances, which is directly used to construct a membrane reactor. It is exactly the same as step three in Example 2. The experimental results are shown in 8.

[0074] Example 3

[0075] The biomimetic enzyme-membrane reactor constructed using the method described in Example 2 was applied to an anti-interference experiment, as shown below:

[0076] Common aquatic cations (sodium, potassium, calcium, and magnesium) were added to the deionized water to achieve concentrations of 20, 20, 10, and 10 mM, respectively. Anions (chloride, sulfate, hydrogen phosphate, carbonate, and nitrate) were added to achieve a concentration of 10 mM. Additionally, common aquatic organic compounds (humic acid (HA) and fulvic acid (FA)) were added to the deionized water to achieve concentrations of 20 mg / L. The membrane was prepared at a hydrogen peroxide concentration of 5 mM and a membrane flux of 96 L / (m²). 2 Under operating conditions of ·h), the removal efficiency of the biomimetic enzyme-membrane reactor for acetaminophen remains essentially unchanged (e.g., Figure 9 As shown in the figure, the constructed biomimetic enzyme-membrane reactor has excellent anti-interference performance.

[0077] Example 4

[0078] This embodiment uses the biomimetic enzyme-membrane reactor constructed by the method described in Example 2 for the removal of various organic pollutants, as detailed below:

[0079] Using actual surface water or secondary effluent as the background water body, acetaminophen (APAP), bisphenol A (BPA), and 2,4-dichlorophenol (2,4-DCP) were added to the background water body to achieve a concentration of 0.5 mg / L for each of the three organic pollutants. The hydrogen peroxide concentration was 5 mM, and the membrane flux was 96 L / (m²). 2 Under operating conditions of ·h), the biomimetic enzyme-membrane reactor maintained a removal rate of over 85% for acetaminophen, bisphenol A, and 2,4-dichlorophenol (e.g., h). Figure 10 (As shown).

[0080] Example 5

[0081] This embodiment uses the biomimetic enzyme-membrane reactor constructed using the method described in Example 2.

[0082] Using actual secondary effluent as the background water, acetaminophen, bisphenol A, and 2,4-dichlorophenol were added to the background water to achieve a concentration of 0.5 mg / L for the three organic pollutants. The hydrogen peroxide concentration was 5 mM, and the membrane flux was 96 L / (m²). 2Under operating conditions of ·h), the biomimetic enzyme-membrane reactor was run for an extended period. Results showed that the removal rates of acetaminophen and bisphenol A remained above 95% during the 60-h operation, while the removal efficiency of 2,4-dichlorophenol remained above 80% (e.g., ...). Figure 11 (As shown in the figure). Therefore, the biomimetic enzyme-membrane reactor obtained in this invention possesses certain specificity for acetaminophen and bisphenol A.

[0083] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. Application of a porphyrin iron-based biomimetic enzyme catalytic membrane in the advanced treatment of sewage / wastewater containing new pollutants, characterized in that, The catalytic membrane comprises a microfiltration membrane substrate and a porphyrin iron-based biomimetic enzyme catalyst loaded on the surface of the substrate by chemical cross-linking, wherein the porphyrin iron-based biomimetic enzyme catalyst contains a catalytically active center structure of "Fe-N" coordination, and the porphyrin iron-based biomimetic enzyme catalyst contains carboxyl or amino groups; and the new pollutant comprises acetaminophen. The catalytic membrane is prepared by the following method: The porphyrin derivative is dissolved in an organic solvent, heated to reflux, and then an iron salt is added and the reaction is continued; the porphyrin derivative comprises meso-tetra(4-carboxyphenyl) porphine and / or meso-tetra(4-aminophenyl) porphine; After the reaction is completed, the biomimetic enzyme catalyst is obtained after washing and drying; The biomimetic enzyme catalyst is taken and dispersed in a solvent, and the biomimetic enzyme catalyst is loaded on the surface of the microfiltration membrane substrate by vacuum filtration; A perfluorosulfonic acid solution is filtered onto the surface of the microfiltration membrane substrate loaded with the biomimetic enzyme catalyst, and heated and dried to obtain the porphyrin iron-based biomimetic enzyme catalyst membrane.

2. Use according to claim 1, characterized in that, The material of the microfiltration membrane substrate includes one or more of polyether sulfone, polyvinylidene fluoride, polytetrafluoroethylene, nylon 66, and ceramic membrane. The pore size of the microfiltration membrane substrate is 0.01-0.45 μm. The loading amount of the porphyrin iron-based biomimetic enzyme catalyst is 0.05 ~ 1.5 mg / cm 2 .

3. Use according to claim 1, characterized in that, The organic solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and triethylene glycol.

4. Use according to claim 1, characterized in that, The iron salt is one or more of divalent or trivalent hydrochloride, sulfate, and nitrate.

5. The use according to claim 1, characterized in that, The temperature of the heating reflux is 120-150 ℃, and the reaction time is 8-14 h.

6. Use according to claim 1, characterized in that, The ratio of the amount of porphyrin derivative to the amount of iron salt is (0.5-2):10; and the concentration of the perfluorosulfonic acid solution is 2-8 wt%.

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