Porphyrin iron-based biomimetic enzyme catalytic membrane for water treatment as well as preparation and application of porphyrin iron-based biomimetic enzyme catalytic membrane

Abstract

The invention relates to a porphyrin iron-based biomimetic enzyme catalytic membrane for water treatment as well as preparation and application thereof, and belongs to the technical field of catalytic membranes. The porphyrin iron-based biomimetic enzyme catalytic membrane comprises a microfiltration membrane basement membrane and a porphyrin iron-based biomimetic enzyme catalyst loaded on the surface of the basement membrane in a chemical crosslinking mode, and the porphyrin iron-based biomimetic enzyme catalyst contains a catalytic activity center structure of 'Fe-N' coordination. The porphyrin iron-based biomimetic enzyme prepared by the invention is similar to a catalytic active center structure of natural peroxidase, has high affinity with hydrogen peroxide, and can greatly improve the utilization rate of hydrogen peroxide and the steady-state concentration of reactive oxygen free radicals; the constructed bionic enzyme-membrane reactor integrates dual functions of membrane separation and enzyme catalysis, realizes efficient combination of mass transfer and reaction, and greatly improves the removal performance of new pollutants in water.

Description

Technical Field

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

[0002] The reuse of urban sewage is an important measure for sustainable water management. However, new pollutants contained in the secondary effluent of sewage treatment plants pose potential ecological risks to its reuse. Membrane water treatment technology has become one of the mainstream processes for sewage treatment and reuse. However, traditional membrane water treatment technology still faces challenges such as incomplete retention of micro-pollutants, secondary treatment of concentrated liquid, and high energy consumption in practical applications. Therefore, the development of a high-standard, green and low-consumption membrane separation technology is of practical significance for the sustainable development of membrane water treatment technology.

[0003] Enzyme catalysis has the characteristics of high efficiency, specificity and mild reaction conditions, and has certain advantages in the treatment of refractory pollutants. Using membrane materials as carriers for immobilizing enzymes, integrating the dual functions of separation and catalysis, can effectively remove trace pollutants in water. However, natural enzymes have poor stability and tolerance in actual complex environmental media, and their complex three-dimensional structure increases the contact resistance between substrates and active sites, restricting the development and application of enzyme catalysis technology. Biomimetic enzymes are a class of nanomaterials with catalytic activities similar to those of natural enzymes. By simulating the binding pockets and catalytic active centers of natural enzymes, designing simple and stable biomimetic enzymes, and effectively coupling them with membrane separation technology, it can provide new ideas for the design and preparation of high-performance catalytic membranes. Therefore, rationally designing a biomimetic enzyme catalytic membrane based on the structural and functional units of natural enzymes for the deep 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 solve the above technical problems, the present 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. The catalytic membrane uses a microfiltration membrane as the base membrane, and carboxyl porphyrin iron or amino porphyrin iron with a catalytic active center structure similar to that of peroxidase as the functional catalytic unit. The biomimetic enzyme catalyst is loaded on the membrane surface by a method of pre-filtration and post-crosslinking to construct a biomimetic enzyme catalytic membrane. A filtration module is used to assemble the biomimetic enzyme catalytic membrane into a biomimetic enzyme-membrane reactor, which is operated in a continuous or batch mode. By adding a small amount of hydrogen peroxide, reactive oxygen species can be generated under a wide range of pH conditions, realizing the efficient catalytic conversion of new pollutants, and providing an efficient and environmentally friendly new technology for the recycling of urban reclaimed water.

[0005] The first object of the present invention is to provide a porphyrin-iron-based biomimetic enzyme catalytic membrane, which includes a microfiltration membrane substrate membrane, and a porphyrin-iron-based biomimetic enzyme catalyst loaded on the surface of the substrate membrane by 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 catalyst contains carboxyl groups and / or amino groups, and the carboxyl groups and / or amino groups are connected through the benzene ring side chains in the porphine structure.

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

[0007] The second object of the present invention is to provide a preparation method of the porphyrin-iron-based biomimetic enzyme catalytic membrane, including the following steps: Dissolve the porphyrin derivative in an organic solvent, heat under reflux, and then add an iron salt and continue the reaction; After the reaction ends, wash and dry to obtain the biomimetic enzyme catalyst; Take the biomimetic enzyme catalyst and disperse it in a solvent, and load the biomimetic enzyme catalyst onto the surface of the microfiltration membrane substrate membrane by vacuum filtration; Filter the perfluorosulfonic acid solution onto the surface of the microfiltration membrane substrate membrane loaded with the biomimetic enzyme catalyst, heat and dry to obtain the porphyrin-iron-based biomimetic enzyme catalytic membrane.

[0008] In some embodiments of the present invention, the porphyrin derivative includes meso-tetra(4-carboxyphenyl)porphine and / or meso-tetra(4-aminophenyl)porphine; The organic solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), and triethylene glycol.

[0009] In some embodiments of the present invention, the iron salt is one or more of divalent or trivalent hydrochlorides, sulfates, and nitrates.

[0010] In some embodiments of the present invention, the temperature of heating under reflux is 120 - 150 °C, and the reaction time is 8 - 14 h.

[0011] In some embodiments of the present invention, the molar ratio of the porphyrin derivative to the iron salt is (0.5 - 2):10; The concentration of the perfluorosulfonic acid solution is 2 - 8 wt%, and the volume used is 25 - 100 μL.

[0012] The third object of the present invention is to provide a biomimetic enzyme-membrane reactor device, including the porphyrin iron-based biomimetic enzyme catalytic membrane.

[0013] In some embodiments of the present invention, the membrane flux in the biomimetic enzyme-membrane reactor is 50 - 400 L / (m 2 ·h).

[0014] 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 a water outlet system.

[0015] The fourth object of the present invention is to provide the application of the porphyrin iron-based biomimetic enzyme catalytic membrane and the biomimetic enzyme-membrane reactor device in the advanced treatment of sewage / wastewater containing new pollutants.

[0016] In some embodiments of the present invention, the new pollutants include one or more of paracetamol, bisphenol A, and 2,4-dichlorophenol.

[0017] In some embodiments of the present invention, the concentration of the new pollutants is 0.5 - 20 mg / L.

[0018] The above technical solutions of the present invention have the following advantages compared with the prior art: 1. The present invention uses meso-tetrakis(4-carboxyphenyl)porphine or meso-tetrakis(4-aminophenyl)porphine as the iron salt ligand. After the ligand modified by carboxyl or amino group coordinates with ferrous or ferric ions, it can regulate the charge density of the catalytic center, and then regulate the adsorption energy and activation path of hydrogen peroxide on the biomimetic enzyme catalyst, so as to realize the directional regulation of the catalytic performance of the biomimetic enzyme.

[0019] 2. Based on the principle that the peroxidase-like enzyme catalyzes hydrogen peroxide to generate reactive oxygen species, by simulating the catalytic active center structure of natural peroxidase "Fe-N" coordination, the prepared porphyrin iron-based biomimetic enzyme has a high affinity for hydrogen peroxide, can greatly improve the utilization rate of hydrogen peroxide, and generates reactive oxygen species to achieve the efficient degradation of new pollutants.

[0020] 3. The biomimetic enzyme catalytic membrane prepared by the present invention through the way of pre-filtration and post-crosslinking has strong operability, can effectively avoid the shedding of the catalyst on the membrane surface, can be reused, and effectively extends the service life of the biomimetic enzyme catalytic membrane.

[0021] 4. The biomimetic enzyme-membrane reactor provided by the present invention integrates the dual functions of membrane separation and enzyme catalysis, realizes the efficient combination of mass transfer and reaction, and greatly improves the removal performance of new pollutants in water bodies.

[0022] 5. The bionic enzyme-membrane reactor provided by the present invention is applied to the advanced treatment of sewage / wastewater. Compared with the traditional homogeneous Fenton technology, the present invention has a wider pH adaptation range, strong anti-interference ability, low oxidant dosage, no iron sludge precipitation, and significantly improved technical feasibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to make the content of the present invention easier to be clearly understood, the following further details the present invention according to the specific embodiments of the present invention in combination with the drawings, wherein, Figure 1 It is a comparison diagram of the effects of the free bionic enzyme catalyst prepared in Example 1 of the present invention and other catalysts in the comparative example on the degradation of paracetamol by activating hydrogen peroxide; Figure 2 It is an experimental effect diagram of the free bionic enzyme catalyst prepared in Example 1 of the present invention against KSCN poisoning; Figure 3 It is an effect diagram of the free bionic enzyme catalyst prepared in Example 1 of the present invention for degrading paracetamol under different pH conditions; Figure 4 It is an effect diagram of the free bionic enzyme catalyst prepared in Example 1 of the present invention for degrading different pollutants; Figure 5 It is a physical diagram of the carboxylated porphyrin iron-based bionic enzyme catalytic membrane for water treatment prepared in Example 2 of the present invention; Figure 6 It is a scanning electron microscope diagram of the carboxylated porphyrin iron-based bionic enzyme catalytic membrane for water treatment prepared in Example 2 of the present invention; Figure 7 It is a schematic structural diagram of the device of the bionic enzyme-membrane reactor provided in Example 2 of the present invention for removing new pollutants in water; Figure 8 It is an effect diagram of the bionic enzyme-membrane reactor provided in Example 2 of the present invention for removing paracetamol; Figure 9 It is an effect diagram of the bionic enzyme-membrane reactor provided in Example 3 of the present invention for degrading paracetamol under the coexistence of cations / anions and natural organic matter; Figure 10 It is an effect diagram of the bionic enzyme-membrane reactor provided in Example 4 of the present invention for removing organic pollutants such as paracetamol, bisphenol A, and 2,4-dichlorophenol contained in surface water or secondary effluent; Figure 11 It is a stable operation performance diagram of the bionic enzyme-membrane reactor provided in Example 5 of the present invention for simultaneously removing paracetamol, bisphenol A, and 2,4-dichlorophenol contained in secondary effluent; Figure 12 It is a schematic diagram of the mechanism of the bionic enzyme-membrane reactor for removing new pollutants in water.

[0024] Description of the reference numerals in the drawings: 1 - water inlet hole, 2 - water inlet chamber, 3 - polytetrafluoroethylene gasket, 4 - porous stainless steel sheet, 5 - water outlet chamber, 6 - water outlet hole, 7 - biomimetic enzyme catalytic membrane. Specific embodiments

[0025] The present invention will be further described below in conjunction with the drawings and specific embodiments, so that those skilled in the art can better understand the present invention and be able to implement it, but the specific embodiments cited are not intended to limit the present invention.

[0026] Example 1 This example provides a porphyrin iron-based biomimetic enzyme catalyst for water treatment, its preparation and application, which are specifically as follows: Preparation method of the porphyrin iron-based biomimetic enzyme catalyst: I. Preparation of the carboxylated porphyrin iron-based biomimetic enzyme catalyst: 0.1 mM of meso-tetra(4-carboxyphenyl)porphine was fully dissolved in 20 mL of anhydrous N,N-dimethylformamide by ultrasonic means. The dissolved solution was transferred to a three-necked flask equipped with a condenser reflux tube, heated to 130 °C, and after 30 min, the solution was observed to reflux. 1 mM of ferrous chloride tetrahydrate was added and the reaction continued for 12 h. After the reaction ended, it was cooled to room temperature, ultra-pure water was added to wash the wall of the reaction vessel, the solution was collected and the precipitate was obtained by centrifugation. The precipitate was repeatedly washed with ultra-pure water and then dried thoroughly by freeze-drying for standby, obtaining the carboxylated porphyrin iron-based biomimetic enzyme catalyst.

[0027] Preparation of the aminated porphyrin iron-based biomimetic enzyme catalyst: 0.1 mM of meso-tetra(4-aminophenyl)porphine was fully dissolved in 20 mL of anhydrous N,N-dimethylformamide by ultrasonic means. The dissolved solution was transferred to a three-necked flask equipped with a condenser reflux tube, heated to 130 °C, and after 30 min, the solution was observed to reflux. 1 mM of ferrous chloride tetrahydrate was added and the reaction continued for 12 h. After the reaction ended, it was cooled to room temperature, ultra-pure water was added to wash the wall of the reaction vessel, the solution was collected and the precipitate was obtained by centrifugation. The precipitate was repeatedly washed with ultra-pure water and then dried thoroughly by freeze-drying for standby, obtaining the aminated porphyrin iron-based biomimetic enzyme catalyst.

[0028] II. Application: 1. In a solution with a paracetamol concentration of 20 mg / L and pH = 5.2, carboxylated iron porphyrin or amino-functionalized iron porphyrin was added. Subsequently, hydrogen peroxide was added such that the concentrations of the carboxylated iron porphyrin or amino-functionalized iron porphyrin biomimetic enzyme catalyst and hydrogen peroxide were 0.05 g / L and 5 mM, respectively. After thorough stirring and reaction for 60 min, the removal effect of carboxylated iron porphyrin and amino-functionalized iron porphyrin on paracetamol was close to 100%. Among them, after 5 min of reaction, the removal rate of carboxylated iron porphyrin on paracetamol could reach 80% (as Figure 1 shown).

[0029] 2. Anti-poisoning performance experiment In a solution with a paracetamol concentration of 20 mg / L and pH = 5.2, carboxylated iron porphyrin or amino-functionalized iron porphyrin was added. Subsequently, 2 mM KSCN was added, and then hydrogen peroxide was added such that the concentrations of the carboxylated iron porphyrin or amino-functionalized iron porphyrin biomimetic enzyme catalyst and hydrogen peroxide were 0.05 g / L and 5 mM, respectively. After thorough stirring and reaction for 60 min, the removal effect of carboxylated iron porphyrin and amino-functionalized iron porphyrin on paracetamol remained basically unchanged (as Figure 2 shown), demonstrating that the biomimetic enzyme catalyst has good anti-poisoning performance.

[0030] 3. pH adaptability experiment In solutions with different pH values and a paracetamol concentration of 20 mg / L, carboxylated iron porphyrin or amino-functionalized iron porphyrin was added. Subsequently, hydrogen peroxide was added such that the concentrations of the carboxylated iron porphyrin or amino-functionalized iron porphyrin biomimetic enzyme catalyst and hydrogen peroxide were 0.05 g / L and 5 mM, respectively. After thorough stirring and reaction for 60 min, carboxylated iron porphyrin and amino-functionalized iron porphyrin could remove paracetamol in a wide pH range, and the removal rate exceeded 80% (as Figure 3 shown), demonstrating that the biomimetic enzyme catalyst has a wide pH adaptability.

[0031] 4. Specific catalytic experiment on pollutants Five pollutants, namely paracetamol (APAP), bisphenol A (BPA), 2,4-dichlorophenol (2,4-DCP), p-cresol (PC), and p-nitrophenol (PNP), with a concentration of 20 mg / L each, were selected. Carboxylated iron porphyrin or amino-functionalized iron porphyrin was added to a solution with pH = 5.2. Subsequently, hydrogen peroxide was added such that the concentrations of the carboxylated iron porphyrin or amino-functionalized iron porphyrin biomimetic enzyme catalyst and hydrogen peroxide were 0.05 g / L and 5 mM, respectively. After thorough stirring and reaction for 60 min, the removal effects of carboxylated iron porphyrin and amino-functionalized iron porphyrin on the five pollutants were as Figure 4 shown. Among them, the removal effect of carboxylated iron porphyrin and amino-functionalized iron porphyrin on APAP was the best, demonstrating the specific catalytic effect of the biomimetic enzyme catalyst on APAP.

[0032] Example 2 This example provides a preparation method for a porphyrin iron-based biomimetic enzyme catalytic membrane for water treatment, which is specifically as follows: I. Preparation of porphyrin iron-based biomimetic enzyme catalyst: 0.1 mM of meso-tetra(4-carboxyphenyl)porphine was fully dissolved in 20 mL of anhydrous N,N-dimethylformamide by ultrasonic treatment. The dissolved solution was transferred to a three-necked flask equipped with a reflux condenser and heated to 130 °C. After 30 minutes, the solution was observed to reflux, and 1 mM of ferric chloride tetrahydrate was added and the reaction continued for 12 h. After the reaction was completed, it was cooled to room temperature, and ultrapure water was added to wash the wall of the reaction vessel. The solution was collected and the precipitate was obtained by centrifugation. The precipitate was repeatedly washed with ultrapure water and thoroughly freeze-dried to obtain the porphyrin iron-based biomimetic enzyme catalyst.

[0033] II. Preparation of porphyrin iron-based biomimetic enzyme catalytic membrane: Weigh 0.015 g of the biomimetic enzyme catalyst obtained in step I and disperse it uniformly in 10 mL of deionized water by ultrasonic treatment. The biomimetic enzyme catalyst was loaded onto the surface of a 0.22 μm polyethersulfone microfiltration membrane by vacuum filtration to obtain a primary biomimetic enzyme catalytic membrane. Quantitatively measure 50 μL of 5% perfluorosulfonic acid membrane solution into 10 mL of deionized water. After ultrasonic dispersion, the solution was filtered onto the surface of the above primary biomimetic enzyme catalytic membrane and placed in an oven at 40 °C for 4 h to obtain the biomimetic enzyme catalytic membrane, with a loading amount of 1 mg / cm 2 (as Figure 5 and 6 shown), it can be seen that the biomimetic enzyme is uniformly loaded on the surface of the polyethersulfone microfiltration membrane, the thickness of the catalytic layer is about 86 microns, and the biomimetic enzyme catalytic membrane has good flexibility and is not easily detached from the surface of the polyethersulfone microfiltration membrane.

[0034] III. Application: The prepared biomimetic enzyme catalytic membrane was used to construct a biomimetic enzyme-membrane reactor. Among them, the biomimetic enzyme catalytic membrane was clamped by two porous stainless steel sheets with a thickness of 0.5 mm and placed between two polytetrafluoroethylene gaskets (as Figure 7 shown, which is a conventional membrane reactor in the art. The 0.5 mm thick porous stainless steel sheet serves to support the catalytic membrane and prevent the membrane from being deformed under high pressure during the pressure filtration experiment, thereby achieving the effect of extending the service life of the membrane). After tightening the bolts, the inlet of the biomimetic enzyme-membrane reactor was connected to a wastewater tank through a peristaltic pump and a digital display pressure sensor, and the outlet was connected to a high-precision digital display gear flowmeter and a water storage tank.

[0035] Using 20 mg / L of paracetamol as the research object, at a hydrogen peroxide concentration of 5 mM and a membrane flux of 96 L / (m 2· Under the operating conditions of (h), the removal rate of acetaminophen by the biomimetic enzyme-membrane reactor remained above 90% within 60 min (as Figure 8 shown).

[0036] Comparative Example 1 This comparative example provided a porphyrin iron biomimetic enzyme catalyst without carboxyl and amino modifications for the removal of acetaminophen, which was exactly the same as the second step in Example 2. The experimental results are shown in Figure 1 ; The porphyrin iron used was commercially available, corresponding to the Figure 1 porphyrin iron group.

[0037] Comparative Example 2 This comparative example provided a carboxyl-modified porphyrin (i.e., the carboxylated porphyrin in Figure 1 , with the full name of meso-tetrakis(4-carboxyphenyl)porphine), which contained no iron element. Therefore, the obtained biomimetic enzyme catalyst did not have the "Fe-N" structure. The experimental steps were exactly the same as the second step in Example 1. The experimental results are shown in Figure 1 .

[0038] This comparative example provided an amino-modified porphyrin (i.e., the aminoated porphyrin in Figure 1 , with the full name of meso-tetrakis(4-aminophenyl)porphine), which contained no iron element. Therefore, the obtained biomimetic enzyme catalyst did not have the "Fe-N" structure. The experimental steps were exactly the same as the second step in Example 1. The experimental results are shown in Figure 1 .

[0039] Comparative Example 3 This comparative example provided a polyethersulfone microfiltration membrane directly constructed membrane reactor for the removal of acetaminophen, which was specifically as follows: This comparative example only provided a polyethersulfone microfiltration membrane without loading any substances, which was directly used to construct a membrane reactor, exactly the same as the third step in Example 2. The experimental results are shown in 8.

[0040] Example 3 The biomimetic enzyme-membrane reactor constructed by the method described in Example 2 was applied to an anti-interference experiment, which was specifically as follows: Common cations in water: sodium, potassium, calcium, and magnesium ions were added to deionized water, and the concentrations of each cation were 20, 20, 10, and 10 mM, respectively. Anions: chloride, sulfate, hydrogen phosphate, carbonate, and nitrate ions were added, and the concentrations of each anion were 10 mM. In addition, common natural organic matters in water: humic acid (HA) and fulvic acid (FA) were added to deionized water, and their concentrations were 20 mg / L, respectively. At a hydrogen peroxide concentration of 5 mM and a membrane flux of 96 L / (m 2· Under the operating conditions of h), the removal efficiency of the biomimetic enzyme-membrane reactor for paracetamol basically remains unchanged (as Figure 9 shown), which proves that the constructed biomimetic enzyme-membrane reactor has excellent anti-interference performance.

[0041] Example 4 The biomimetic enzyme-membrane reactor constructed by the method described in Example 2 was applied to the removal of various organic pollutants in this example, as specifically shown below: Using actual surface water or secondary effluent as the background water body, paracetamol (APAP), bisphenol A (BPA), and 2,4-dichlorophenol (2,4-DCP) were added to the background water body, so that the concentrations of the three organic pollutants were 0.5 mg / L respectively. Under the operating conditions of a hydrogen peroxide concentration of 5 mM and a membrane flux of 96 L / (m 2 ·h), the removal rates of the biomimetic enzyme-membrane reactor for paracetamol, bisphenol A, and 2,4-dichlorophenol all remained above 85% (as Figure 10 shown).

[0042] Example 5 The biomimetic enzyme-membrane reactor constructed by the method described in Example 2 was used in this example.

[0043] Using actual secondary effluent as the background water body, paracetamol, bisphenol A, and 2,4-dichlorophenol were added to the background water body, so that the concentrations of the three organic pollutants were 0.5 mg / L. Under the operating conditions of a hydrogen peroxide concentration of 5 mM and a membrane flux of 96 L / (m 2 ·h), the biomimetic enzyme-membrane reactor was operated for a long time. The results showed that the removal rates of paracetamol and bisphenol A remained above 95% during the 60-hour operation, and the removal efficiency of 2,4-dichlorophenol remained above 80% (as Figure 11 shown). It can be seen that the obtained biomimetic enzyme-membrane reactor of the present invention has a certain specificity for paracetamol and bisphenol A.

[0044] Obviously, the above examples are only for clearly illustrating the examples and are not limitations on the implementation methods. For those of ordinary skill in the art, other different forms of changes or variations can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. And the obvious changes or variations derived therefrom are still within the protection scope of the present invention.

Claims

1. A porphyrin-iron-based biomimetic enzyme catalytic membrane, characterized in that, It includes a microfiltration membrane substrate, and a porphyrin-iron-based biomimetic enzyme catalyst loaded on the surface of the substrate by chemical cross-linking. The porphyrin-iron-based biomimetic enzyme catalyst contains a catalytic active center structure with "Fe-N" coordination, and the porphyrin-iron-based biomimetic enzyme catalyst contains carboxyl groups or amino groups.

2. The porphyrin-iron-based biomimetic enzyme catalytic membrane according to claim 1, characterized in that, The material of the microfiltration membrane substrate includes one or more of polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, nylon 66, and ceramic membranes; 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. A preparation method of the porphyrin-iron-based biomimetic enzyme catalytic membrane as described in claim 1 or 2, characterized in that, It includes the following steps: Dissolve the porphyrin derivative in an organic solvent, heat under reflux, and then add an iron salt and continue the reaction; After the reaction ends, wash and dry to obtain the biomimetic enzyme catalyst; Take the biomimetic enzyme catalyst and disperse it in a solvent, and load the biomimetic enzyme catalyst onto the surface of the microfiltration membrane substrate by vacuum filtration; Filter the perfluorosulfonic acid solution onto the surface of the microfiltration membrane substrate loaded with the biomimetic enzyme catalyst, heat and dry to obtain the porphyrin-iron-based biomimetic enzyme catalytic membrane.

4. The preparation method according to claim 3, characterized in that, The porphyrin derivative includes meso-tetrakis(4-carboxyphenyl)porphine and / or meso-tetrakis(4-aminophenyl)porphine; The organic solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and triethylene glycol.

5. The preparation method according to claim 3, characterized in that, The iron salt is one or more of divalent or trivalent hydrochlorides, sulfates, and nitrates.

6. The preparation method according to claim 3, characterized in that, The temperature of heating under reflux is 120 - 150 °C, and the reaction time is 8 - 14 h.

7. The preparation method according to claim 3, characterized in that, The molar ratio of the porphyrin derivative to the iron salt is (0.5 - 2):10; The concentration of the perfluorosulfonic acid solution is 2 - 8 wt%.

8. A biomimetic enzyme-membrane reactor device, characterized in that, It includes the porphyrin-iron-based biomimetic enzyme catalytic membrane described in claim 1 or 2.

9. Application of the porphyrin-iron-based biomimetic enzyme catalytic membrane described in claim 1 or 2 and the biomimetic enzyme-membrane reactor device described in claim 8 in the advanced treatment of sewage / wastewater containing new pollutants.

10. The application according to claim 9, characterized in that, The new pollutants include one or more of paracetamol, bisphenol A, and 2,4-dichlorophenol.

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