Preparation method and application of all-weather bimetallic porphyrin cmp material

Abstract

The application discloses a preparation method of all-weather bimetallic porphyrin CMP material, and specifically comprises the following steps: performing polycondensation reaction on M1-TCPP-COCl and 5,5'-diamino-2,2'-bipyridine in an organic solvent, performing suction filtration, washing and drying on a product to obtain M1Por-CMP; and performing coordination reaction on M1Por-CMP and metal M2 in acetonitrile, and performing suction filtration, washing and drying on a product, and the preparation method is completed. The M1Por-M2Bpy-CMP prepared by the application has rich pore structure and conjugate structure, can realize massive adsorption of pollutants through π-π interaction and physical adsorption. Meanwhile, the coordination bimetal in the CMP material can also increase the adsorption of pollutants through electrostatic interaction. The synergistic effect of the above various adsorptions can realize mass transfer strengthening before degradation.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment material preparation technology, specifically relating to a method for preparing all-weather bimetallic porphyrin CMP materials, and also relating to the application of all-weather bimetallic porphyrin CMP materials. Background Technology

[0002] Organic pollutants, including organic dyes and antibiotics, are typically characterized by complex structures, high toxicity, and difficulty in natural degradation. Once they enter the aquatic environment, they pose potential threats to ecosystems and human health. Therefore, developing efficient, stable, and adaptable materials for treating organic pollutants in water is of great significance for wastewater treatment and aquatic environment restoration.

[0003] Currently, methods for treating organic pollutants in water mainly include adsorption, biodegradation, ozone oxidation, ionizing radiation, Fenton oxidation, photocatalysis, and persulfate activation. While these methods can remove organic pollutants to some extent, they still have some shortcomings. For example, biodegradation has a long treatment cycle and is sensitive to the type of pollutant and environmental conditions; ozone oxidation has high operating costs; Fenton oxidation is usually highly dependent on pH conditions and may cause subsequent treatment problems; photocatalysis is easily limited by light conditions in practical applications, and its treatment effect decreases in darkness or insufficient light; although persulfate activation has strong oxidation capacity, its activation efficiency and catalyst stability still have room for improvement. Therefore, developing all-weather wastewater treatment materials that can be used under light, darkness, and alternating light and dark conditions has significant application value.

[0004] Conjugated microporous polymers (CMPs) possess advantages such as designable structure, high degree of conjugation, stable framework, and tunable active sites, making them promising candidates for the degradation of organic pollutants in water. Existing technologies have disclosed an iron porphyrin-based conjugated organic polymer material and its preparation method, which includes the preparation of an iron porphyrin precursor, acylation treatment, and reaction with diamine monomers to construct a porphyrin-based polymer framework. However, this material uses a single metalloporphyrin structure as the main active unit, resulting in a relatively limited range of active sites. Its adaptability to complex wastewater treatment environments, especially under conditions of darkness or alternating light and dark, remains to be improved. While bimetallic porphyrin polymers have been reported, their synthesis processes are complex, their industrialization potential is low, and they lack the ability to degrade pollutants under dark conditions. Therefore, developing porphyrin-based CMP materials with simple synthesis processes, good pollutant degradation effects, and all-weather operation is of great significance. Summary of the Invention

[0005] The primary objective of this invention is to provide a method for preparing all-weather bimetallic porphyrin CMP materials, thereby addressing the problem that existing porphyrin-based conjugated polymer materials exhibit low degradation rates of organic pollutants in wastewater under insufficient light or alternating light and dark conditions.

[0006] A second objective of this invention is to provide an all-weather bimetallic porphyrin CMP material.

[0007] A third objective of this invention is to provide the application of all-weather bimetallic porphyrin CMP materials in the degradation of organic pollutants in water.

[0008] The first technical solution adopted in this invention is a method for preparing all-weather bimetallic porphyrin CMP materials, which is specifically implemented according to the following steps: S1: M1-TCPP-COCl and 5,5'-diamino-2,2'-bipyridine were subjected to a polycondensation reaction in an organic solvent. The product was filtered, washed, and dried to obtain M1Por-CMP. S2: M1Por-CMP and metal M2 are subjected to a coordination reaction in acetonitrile. The product is filtered, washed and dried to obtain M1Por-M2Bpy-CMP, which is the bimetallic porphyrin CMP material.

[0009] The invention is further characterized in that, In S1, the molar ratio of M1-TCPP-COCl to 5,5'-diamino-2,2'-bipyridine is 1:1.8~2.2; the organic solvent is a mixture of CH2Cl2 and Et3N in a volume ratio of 10~15:1.

[0010] In S1, the reaction temperature is 25~30℃, the stirring speed is 120~180 rpm, and the reaction time is 24~30h; the filtration pressure is -0.06~-0.09MPa; the mixture is washed 3~5 times with anhydrous ethanol; the drying temperature is 100~110℃, and the drying time is 8~12h.

[0011] In S1, the preparation process of M1 porphyrin acyl chloride M1-TCPP-COCl is as follows: 5,10,15,20-tetra(4-carboxyphenyl)porphyrin, M1, and a solvent were reacted under reflux conditions at a temperature of 130–140 °C for 3–5 h. The solvent was a mixture of CHCl3 and DMF in a volume ratio of 4–6:1. After the reaction, the product was distilled, filtered, and washed to obtain a metal ion-TCPP solid. The metal ion-TCPP solid, an acyl chloride reagent, and CH2ClCH2Cl were then reacted under reflux conditions at a temperature of 83–85 °C for 2–4 h. After the reaction, the product was post-treated to obtain a metal ion-TCPP-COCl solid. The metal ion-TCPP solid and p-phenylenediamine were then ground and reacted for 20–40 min. After the reaction, the product was washed and dried to obtain M1-TCPP-COCl.

[0012] M1 is FeCl3·6H2O, Fe2(SO4)3·9H2O, FeCl2·6H2O, FeSO4 The reagent is any one of the following: 7H2O, CoSO4·7H2O, CoCl2·6H2O, Co(NO3)2·6H2O, Co(CH3COO)2·4H2O, CuSO4·5H2O, CuCl2·2H2O, Cu(NO3)2, MnSO4·H2O, MnCl2·4H2O, Mn(NO3)2·4H2O, NiSO4·6H2O, NiCl2·6H2O, Cr(NO3)3·9H2O, Cr2(SO4)3·6H2O, Zr(SO4)2·4H2O; the acyl chloride reagent is any one of SOCl2, PCl5, PCl3.

[0013] In S2, the molar ratio of M1Por-CMP to the metal salt M2 is 1:2~2.4; M2 is FeCl3·6H2O, Fe2(SO4)3·9H2O, FeCl2·6H2O, or FeSO4. 7H2O, CoSO4·7H2O, CoCl2·6H2O, Co(NO3)2·6H2O, Co(CH3COO)2·4H2O, CuSO4·5H2O, CuCl2·2H2O, Cu(NO3)2, MnSO4·H2 Any one of O, MnCl2·4H2O, Mn(NO3)2·4H2O, NiSO4·6H2O, NiCl2·6H2O, Cr(NO3)3·9H2O, Cr2(SO4)3·6H2O, Zr(SO4)2·4H2O.

[0014] In S2, the reaction temperature is 80~85 ℃, the reaction time is 12~18 h, the stirring speed is 100~150 rpm, the filtration pressure is -0.06~-0.09 MPa, and the product is washed 3~5 times each with acetonitrile, anhydrous ethanol and ultrapure water, respectively. The drying temperature is 100~110 ℃ and the drying time is 4~8 h.

[0015] The second technical solution adopted in this invention is an all-weather bimetallic porphyrin CMP material prepared by a method for preparing all-weather bimetallic porphyrin CMP materials.

[0016] The beneficial effects of this invention are: (1) The all-weather bimetallic porphyrin CMP material of the present invention is obtained by amidation reaction of metal 1 porphyrin acyl chloride and 5,5'-diamino-2,2'-bipyridine. Compared with the traditional COF or CMP preparation of porphyrin polymers, this method is milder, has higher yield, and simpler post-processing. Compared with conventional diamine linkage structures, 5,5'-diamino-2,2'-bipyridine can not only participate in the condensation reaction of acyl chloride groups to form a stable amide linkage structure, but also provide bipyridine sites that can coordinate with transition metal ions, providing a structural basis for the subsequent introduction of M2 active centers. Therefore, the present invention, through monomer structure design, enables the CMP backbone to simultaneously possess covalent linkage structure and post-coordination functional sites, improving the flexibility of material structure design.

[0017] (2) The method of the present invention further constructs M2 coordinating bipyridine sites on the basis of the original M1 porphyrin structural unit, so that the obtained material contains both M1 porphyrin sites and M2 bipyridine coordinating sites. Compared with single metalloporphyrin CMP materials, the material obtained by the present invention has a bimetallic active structure, which is beneficial to enrich the types of active sites in the material and improve the adaptability of the material in the degradation process of organic pollutants. Under light conditions, M1 and M2 can act as electron and hole trapping centers, respectively, improving the separation efficiency of photogenerated carriers and increasing photocatalytic performance; under dark conditions, both M1 and M2 can activate PDS through electron transfer of metal ions, thereby enhancing the degradation performance under dark conditions.

[0018] (3) The M1Por–M2Bpy–CMP bimetallic porphyrin CMP material prepared in this invention has abundant pore structure and conjugated structure, which can achieve a large amount of adsorption of pollutants through π-π interaction and physical adsorption. At the same time, the coordination bimetal in the CMP material can also increase its adsorption of pollutants through electrostatic interaction. The synergistic effect of the above adsorptions can achieve enhanced mass transfer before degradation.

[0019] (4) The M1Por–M2Bpy–CMP bimetallic porphyrin CMP material prepared by the present invention can be used for the degradation treatment of organic pollutants in water under light conditions, dark conditions or alternating light and dark conditions, and is especially suitable for all-weather wastewater treatment scenarios, thus expanding the application scope of porphyrin-based covalent organic polymer materials in the field of water pollution control. Attached Figure Description

[0020] Figure 1 This is a SEM (scanning electron microscope) image of the FePor–CoBpy–CMP material prepared in accordance with the present invention. Figure 2a This is a general SEM image of the FePor–CoBpy–CMP material prepared in accordance with the present invention; Figure 2b The figure shows the C element distribution in the FePor–CoBpy–CMP material prepared according to the present invention. Figure 2c The diagram shows the N element distribution in the FePor–CoBpy–CMP material prepared according to the present invention. Figure 2d The diagram shows the distribution of O element in the FePor–CoBpy–CMP material prepared according to the present invention. Figure 2e The image shows the Fe element distribution in the FePor–CoBpy–CMP material prepared according to the present invention. Figure 2f The diagram shows the distribution of Co in the FePor–CoBpy–CMP material prepared according to the present invention. Figure 3 The infrared spectrum of the FePor–CoBpy–CMP material prepared in accordance with the present invention; Figure 4 The PXRD (powder X-ray diffraction) pattern of the FePor–CoBpy–CMP material prepared in accordance with the present invention; Figure 5a The XPS spectrum of the FePor–CoBpy–CMP material prepared in accordance with the present invention is shown below. Figure 5b The fine XPS spectrum of C in the FePor–CoBpy–CMP material prepared in the present invention is shown. Figure 5c The fine XPS spectrum of N in the FePor–CoBpy–CMP material prepared in the present invention is shown. Figure 5d The fine XPS spectrum of O in the FePor–CoBpy–CMP material prepared in the present invention is shown. Figure 5eThe fine XPS spectrum of Fe in the FePor–CoBpy–CMP material prepared in accordance with the present invention is shown. Figure 5f The fine XPS spectrum of Co in the FePor–CoBpy–CMP material prepared in the present invention is shown. Figure 6a The UV-Vis diffuse reflectance spectrum of the FePor–CoBpy–CMP material prepared in accordance with the present invention is shown below. Figure 6b This is a diagram showing the band gap of the FePor–CoBpy–CMP material prepared according to the present invention. Figure 7 This is a synthetic route diagram for FePor-CMP; Figure 8 This is the synthetic route diagram for FePor–CoBpy–CMP. Detailed Implementation

[0021] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0022] The preparation method of the all-weather bimetallic porphyrin CMP material of the present invention is specifically implemented according to the following steps: S1: M1 porphyrin chloromethyl chloride M1-TCPP-COCl and 5,5'-diamino-2,2'-bipyridine were subjected to a polycondensation reaction in an organic solvent. The product was filtered, washed and dried to obtain M1Por-CMP material. The molar ratio of M1-TCPP-COCl to 5,5'-diamino-2,2'-bipyridine is 1:1.8~2.2; The organic solvent is a mixture of CH2Cl2 and Et3N in a volume ratio of 10~15:1; The reaction temperature is 25~30 ℃, the stirring speed is 120~180 rpm, and the reaction time is 24~30 h; the filtration pressure is -0.06~-0.09 MPa; the mixture is washed 3~5 times with anhydrous ethanol; the drying temperature is 100~110 ℃ and the time is 8~12 h. The preparation process of M1 porphyrinyl chloride M1-TCPP-COCl is as follows: 5,10,15,20-tetra(4-carboxyphenyl)porphyrin, metal salt 1 (M1), and solvent were reacted under reflux conditions at a temperature of 130-140°C for 3-5 h. The solvent was a mixture of CHCl3 and DMF in a volume ratio of 4-6:1. After the reaction, the product was distilled, filtered, and washed to obtain metal ion-TCPP solid. The metal ion-TCPP solid, acyl chloride reagent, and CH2Cl were reacted under reflux conditions at a temperature of 83-85°C for 2-4 h. After the reaction, the product was post-treated to obtain metal ion-TCPP-COCl solid. The metal ion-TCPP solid and p-phenylenediamine were ground and reacted for 20-40 min. After the reaction, the product was washed and dried to obtain M1 porphyrin acyl chloride M1-TCPP-COCl. Metal salt 1 is FeCl3·6H2O, Fe2(SO4)3·9H2O, FeCl2·6H2O, FeSO4 7H2O, CoSO4·7H2O, CoCl2·6H2O, Co(NO3)2·6H2O, Co(CH3COO)2·4H2O, CuSO4·5H2O, CuCl2·2H2O, Cu(NO3)2, MnSO4·H2 Any one of O, MnCl2·4H2O, Mn(NO3)2·4H2O, NiSO4·6H2O, NiCl2·6H2O, Cr(NO3)3·9H2O, Cr2(SO4)3·6H2O, Zr(SO4)2·4H2O; The acyl chloride reagent is any one of SOCl2, PCl5, and PCl3; S2: M1Por-CMP and metal M2 are subjected to a coordination reaction in acetonitrile. The product is filtered, washed and dried to obtain M1Por-M2Bpy-CMP, which is a bimetallic porphyrin CMP material. The molar ratio of M1Por-CMP solid to metal salt M2 is 1:2~2.4; Metal salt 2 is FeCl3·6H2O, Fe2(SO4)3·9H2O, FeCl2·6H2O, FeSO4 7H2O, CoSO4·7H2O, CoCl2·6H2O, Co(NO3)2·6H2O, Co(CH3COO)2·4H2O, CuSO4·5H2O, CuCl2·2H2O, Cu(NO3)2, MnSO4·H2 Any one of O, MnCl2·4H2O, Mn(NO3)2·4H2O, NiSO4·6H2O, NiCl2·6H2O, Cr(NO3)3·9H2O, Cr2(SO4)3·6H2O, Zr(SO4)2·4H2O; The reaction temperature is 80~85 ℃, the reaction time is 12~18 h, and the stirring speed is 100~150 rpm; The filtration pressure was -0.06 to -0.09 MPa; the sample was washed 3 to 5 times each with acetonitrile, anhydrous ethanol, and ultrapure water; the drying temperature was 100 to 110 ℃ and the time was 4 to 8 h.

[0023] In S1, if M1 is FeCl3·6H2O, then the ferric porphyrin chloride Fe... 3+ FePor-CMP material was obtained by polycondensation of TCPP-COCl solid and 5,5'-diamino-2,2'-bipyridine in an organic solvent. The reaction route is shown below. Figure 7 Fe 3+ The acyl chloride group in the TCPP-COCl solid undergoes a condensation reaction with the amino group in 5,5'-diamino-2,2'-bipyridine to generate amide-linked FePor-CMP materials. Since the 5,5'-diamino-2,2'-bipyridine molecule contains a bipyridine structure, this structure can still provide metal coordination sites after polymerization. Therefore, the resulting FePor-CMP material can serve as a precursor material for further introduction of M2 ions.

[0024] In S2, if M1 is FeCl3·6H2O and M2 is Co(CH3COO)2·4H2O, then the synthetic route for bimetallic porphyrin CMP is as follows: Figure 8 As shown, the nitrogen atoms of the bipyridine structural units in FePor-CMP materials undergo coordination reactions with cobalt ions to form FePor–CoBpy–CMP bimetallic porphyrin CMP materials.

[0025] Example 1 A method for preparing all-weather bimetallic porphyrin CMP materials includes the following steps: Step 1: Add ferric porphyrin chloride Fe 3+ -TCPP-COCl solid and 5,5'-diamino-2,2'-bipyridine were subjected to a polycondensation reaction in an organic solvent, and the product was post-treated to obtain FePor-CMP material; wherein, Fe... 3+The molar ratio of TCPP-COCl solid to 5,5'-diamino-2,2'-bipyridine was 1:1.8; the solvent was a mixture of CH2Cl2 and Et3N in a volume ratio of 10:1; the reaction conditions were: temperature 25℃, stirring speed 120 rpm, and reaction time 24 h. Post-treatment conditions included: filtration pressure of... The sample was dried at 0.06 MPa, washed three times with anhydrous ethanol, dried at 100 ℃ for 8 h.

[0026] Step 2: FePor-CMP and cobalt salt were subjected to a coordination reaction in an organic solvent. The product was then post-treated to obtain FePor-CoBpy-CMP bimetallic porphyrin CMP material. The molar ratio of FePor-COP solid to divalent cobalt salt was 1:2; the organic solvent was acetonitrile (60 ml); the divalent cobalt salt was Co(CH3COO)2·4H2O; the reaction conditions were: temperature 80 ℃, time 12 h, stirring speed 100 rpm; the post-treatment conditions were: filtration pressure -0.06 MPa; washing was performed three times each with acetonitrile, anhydrous ethanol, and ultrapure water; drying temperature was 100 ℃, drying time was 4 h.

[0027] Example 2 A method for preparing all-weather bimetallic porphyrin CMP materials includes the following steps: Step 1: Add ferric porphyrin chloride Fe 3+ -TCPP-COCl solid and 5,5'-diamino-2,2'-bipyridine were subjected to a polycondensation reaction in an organic solvent, and the product was post-treated to obtain FePor-CMP material; wherein, Fe... 3+ The molar ratio of TCPP-COCl solid to 5,5'-diamino-2,2'-bipyridine was 1:2.0; the solvent was a mixture of CH2Cl2 and Et3N in a volume ratio of 13:1; the reaction conditions were: temperature 27℃, stirring speed 150 rpm, and reaction time 26 h. Post-treatment conditions included: filtration pressure of... The material was subjected to a pressure of 0.07 MPa, washed four times with anhydrous ethanol, dried at 110 ℃ for 10 h.

[0028] Step 2: FePor-CMP and cobalt salt were subjected to a coordination reaction in an organic solvent. The product was then post-treated to obtain FePor-CoBpy-CMP bimetallic porphyrin CMP material. The molar ratio of FePor-COP solid to divalent cobalt salt was 1:2.2; the organic solvent was 70 ml of acetonitrile; the divalent cobalt salt was Co(CH3COO)2·4H2O; the reaction conditions were: temperature 70 ℃, time 16 h, stirring speed 130 rpm; the post-treatment conditions were: filtration pressure -0.07 MPa; washing was performed with acetonitrile, anhydrous ethanol, and ultrapure water four times each; drying temperature was 105 ℃, drying time was 6 h.

[0029] Example 3 A method for preparing all-weather bimetallic porphyrin CMP materials includes the following steps: Step 1: Add ferric porphyrin chloride Fe 3+ -TCPP-COCl solid and 5,5'-diamino-2,2'-bipyridine were subjected to a polycondensation reaction in an organic solvent, and the product was post-treated to obtain FePor-CMP material; wherein, Fe... 3+ The molar ratio of TCPP-COCl solid to 5,5'-diamino-2,2'-bipyridine was 1:2.2; the solvent was a mixture of CH2Cl2 and Et3N in a volume ratio of 15:1; the reaction conditions were: temperature 30 °C, stirring speed 180 rpm, and reaction time 30 h. Post-treatment conditions included: filtration pressure of... The sample was dried at 0.09 MPa, washed five times with anhydrous ethanol, dried at 120 ℃ for 12 h.

[0030] Step 2: FePor-CMP and cobalt salt were subjected to a coordination reaction in an organic solvent. The product was then post-treated to obtain FePor-CoBpy-CMP bimetallic porphyrin CMP material. The molar ratio of FePor-COP solid to divalent cobalt salt was 1:2.4; the organic solvent was acetonitrile (80 ml); the divalent cobalt salt was Co(CH3COO)2·4H2O; the reaction conditions were: temperature 90 ℃, time 18 h, stirring speed 150 rpm; the post-treatment conditions were: filtration pressure -0.09 MPa; washing was performed by washing five times each with acetonitrile, anhydrous ethanol, and ultrapure water sequentially; drying temperature was 110 ℃, drying time was 8 h.

[0031] Example 4 A method for preparing all-weather bimetallic porphyrin CMP materials includes the following steps: Step 1: Add ferric porphyrin chloride Fe 3+-TCPP-COCl solid and 5,5'-diamino-2,2'-bipyridine were subjected to a polycondensation reaction in an organic solvent, and the product was post-treated to obtain FePor-CMP material; wherein, Fe... 3+ The molar ratio of TCPP-COCl solid to 5,5'-diamino-2,2'-bipyridine was 1:1.8; the solvent was a mixture of CH2Cl2 and Et3N in a volume ratio of 10:1; the reaction conditions were: temperature 25℃, stirring speed 120 rpm, and reaction time 24 h. Post-treatment conditions included: filtration pressure of... The sample was dried at 0.06 MPa, washed three times with anhydrous ethanol, dried at 100 ℃ for 8 h.

[0032] Step 2: FePor-CMP and cobalt salt were subjected to a coordination reaction in an organic solvent. The product was then post-treated to obtain FePor-CoBpy-CMP bimetallic porphyrin CMP material. The molar ratio of FePor-COP solid to divalent cobalt salt was 1:2; the organic solvent was acetonitrile (60 ml); the divalent cobalt salt was CoSO4·7H2O; the reaction conditions were: temperature 80 ℃, time 12 h, stirring speed 100 rpm; the post-treatment conditions were: filtration pressure -0.06 MPa; washing was performed three times each with acetonitrile, anhydrous ethanol, and ultrapure water; drying temperature was 100 ℃, drying time was 4 h.

[0033] Example 5 A method for preparing all-weather bimetallic porphyrin CMP materials includes the following steps: Step 1: Add ferric porphyrin chloride Fe 3+ -TCPP-COCl solid and 5,5'-diamino-2,2'-bipyridine were subjected to a polycondensation reaction in an organic solvent, and the product was post-treated to obtain FePor-CMP material; wherein, Fe... 3+ The molar ratio of TCPP-COCl solid to 5,5'-diamino-2,2'-bipyridine was 1:1.8; the solvent was a mixture of CH2Cl2 and Et3N in a volume ratio of 10:1; the reaction conditions were: temperature 25℃, stirring speed 120 rpm, and reaction time 24 h. Post-treatment conditions included: filtration pressure of... The sample was dried at 0.06 MPa, washed three times with anhydrous ethanol, dried at 100 ℃ for 8 h.

[0034] Step 2: FePor-CMP and cobalt salt were subjected to a coordination reaction in an organic solvent. The product was then post-treated to obtain FePor-CoBpy-CMP bimetallic porphyrin CMP material. The molar ratio of FePor-COP solid to divalent cobalt salt was 1:2; the organic solvent was acetonitrile (60 ml); the divalent cobalt salt was CoCl2·6H2O; the reaction conditions were: temperature 80 ℃, time 12 h, stirring speed 100 rpm; the post-treatment conditions were: filtration pressure -0.06 MPa; washing was performed three times each with acetonitrile, anhydrous ethanol, and ultrapure water; drying temperature was 100 ℃, drying time was 4 h.

[0035] Example 6 The degradation performance of FePor–CoBpy–CMP material prepared in this invention was tested for organic pollutants in water. The test method was in accordance with GB / T 23762-2009 "Test Method for Purification of Aqueous Solution Systems of Photocatalytic Materials". The test results are shown in Table 1. Tetracycline represents antibiotic pollutants, and Rhodamine B represents dye pollutants. Table 1 shows that the FePor–CoBpy–CMP material prepared in this invention has a good degradation effect on tetracycline in water; specifically, after 50 min of reaction under light conditions, the pollutant degradation rate reaches 99.09%; after 90 min of reaction under dark conditions, the pollutant degradation rate reaches 94.09%. For the organic dye Rhodamine B in water, it is completely degraded after 30 min of reaction under light conditions and after 50 min of reaction under dark conditions. The above results indicate that the FePor–CoBpy–CMP material prepared in this invention has good pollutant degradation ability under both light and dark conditions, and is suitable for the degradation treatment of organic pollutants in water under all-weather conditions.

[0036] Table 1. Pollutant degradation performance of FePor–CoBpy–CMP materials prepared in the examples.

[0037] Note: All experiments were conducted at room temperature of 25℃, pH value of 7, and xenon lamp power of 300W.

[0038] Figure 1 The image shows a SEM image of the FePor-CoBpy-CMP material prepared according to the present invention. As can be seen from the image, the obtained material has a porous aggregate structure formed by particle stacking, with a rough surface and many pores, which means that the bimetallic porphyrin CMP material prepared by the present invention has very good adsorption performance.

[0039] Figures 2a-2fThese are elemental point scan images of the FePor-CoBpy-CMP material prepared in accordance with the present invention. Figure 2a SEM overview; Figure 2b A distribution diagram of C elements; Figure 2c A distribution map of element N; Figure 2d A distribution map of element O; Figure 2e This is a distribution map of Fe element; Figure 2f The diagram shows the distribution of Co. It can be seen that C, O, N, Fe, and Co are uniformly distributed in the bimetallic porphyrin (COP) material, indicating that the material prepared by this invention contains iron and cobalt bimetallic elements, providing a basis for the successful preparation of FePor-CoBpy-CMP materials.

[0040] Figure 3 The infrared spectrum of the FePor-CoBpy-CMP material prepared according to the present invention is shown. As can be seen from the figure, the material exhibits high infrared intensity at 1618 cm⁻¹. -1 and 1544 cm -1 Absorption peaks appear nearby, corresponding to the C=C stretching vibration in the aromatic conjugated structure and the C=N stretching vibration in the nitrogen-containing structure, respectively; furthermore, at 1000 cm⁻¹... -1 The presence of Fe-N related absorption peaks nearby indicates that the iron porphyrin structural units are retained in the material. These results demonstrate that the material prepared in this invention possesses a porphyrin conjugated framework and a nitrogen-containing coordination structure, providing a basis for the formation of FePor-CoBpy-CMP materials.

[0041] Figure 4 The PXRD pattern of the FePor-CoBpy-CMP material prepared in this invention shows that the sample exhibits broad and diffuse diffraction peaks overall, without obvious sharp crystalline diffraction peaks, indicating that the FePor-CoBpy-CMP material is mainly composed of an amorphous or low-crystallinity structure. Figures 5a-5f The XPS spectrum of the FePor-CoBpy-CMP material prepared in this invention is shown below. Figure 5a It is the XPS score; Figure 5b This is the fine XPS spectrum of C; Figure 5c It is the fine XPS spectrum of N; Figure 5d This is the fine XPS spectrum of O; Figure 5e This is the fine XPS spectrum of Fe; Figure 5fThis is the XPS fine spectrum of Co; we can see that the C 1s fine spectrum is located at 284.22, 285.69, 287.38 and 290.91 eV, the N 1s fine spectrum is located at 398.42 eV, the O 1s fine spectrum is located at 530.70 eV, the Fe 2p fine spectrum is located at 710.44 and 721.29 eV, and the Co 2p fine spectrum is located at 780.23 and 795.89 eV, with a satellite peak around each peak, further proving the successful synthesis of trivalent iron porphyrin and divalent cobalt porphyrin CMP.

[0042] Figure 6a and Figure 6b The image shows the UV-Vis diffuse reflectance spectrum and band gap of the FePor-CoBpy-CMP material prepared in this invention. As can be seen, thanks to the highly conjugated porphyrin structure of the porphyrin CMP material, FePor-CoBpy-CMP exhibits a full-spectrum response (200-800 nm), almost covering the entire visible light region. The band gap of FePor-CoBpy-CMP is calculated to be 1.55 eV using the Kubelka–Munk equation.

Claims

1. A method for preparing all-weather bimetallic porphyrin CMP materials, characterized in that, The specific steps are as follows: S1: M1-TCPP-COCl and 5,5'-diamino-2,2'-bipyridine were subjected to a polycondensation reaction in an organic solvent. The product was filtered, washed, and dried to obtain M1Por-CMP. S2: M1Por-CMP and metal M2 are subjected to a coordination reaction in acetonitrile. The product is filtered, washed and dried to obtain M1Por-M2Bpy-CMP, which is the bimetallic porphyrin CMP material.

2. The preparation method of the all-weather bimetallic porphyrin CMP material as described in claim 1, characterized in that, In S1, the molar ratio of M1-TCPP-COCl and 5,5'-diamino-2,2'-bipyridine is 1:1.8~2.2; the organic solvent is a mixture of CH2Cl2 and Et3N in a volume ratio of 10~15:

1.

3. The preparation method of the all-weather bimetallic porphyrin CMP material as described in claim 1, characterized in that, In step S1, the reaction temperature is 25~30℃, the stirring speed is 120~180 rpm, the reaction time is 24~30h; the filtration pressure is -0.06~-0.09MPa; the mixture is washed 3~5 times with anhydrous ethanol; the drying temperature is 100~110℃, and the drying time is 8~12h.

4. The preparation method of the all-weather bimetallic porphyrin CMP material as described in claim 1, characterized in that, In S1, the preparation process of M1 porphyrin acyl chloride M1-TCPP-COCl is as follows: 5,10,15,20-tetra(4-carboxyphenyl)porphyrin, M1, and a solvent were reacted under reflux conditions at a temperature of 130–140 °C for 3–5 h. The solvent was a mixture of CHCl3 and DMF in a volume ratio of 4–6:

1. After the reaction, the product was distilled, filtered, and washed to obtain a metal ion-TCPP solid. The metal ion-TCPP solid, an acyl chloride reagent, and CH2ClCH2Cl were then reacted under reflux conditions at a temperature of 83–85 °C for 2–4 h. After the reaction, the product was post-treated to obtain a metal ion-TCPP-COCl solid. The metal ion-TCPP solid and p-phenylenediamine were then ground and reacted for 20–40 min. After the reaction, the product was washed and dried to obtain M1-TCPP-COCl.

5. The preparation method of the all-weather bimetallic porphyrin CMP material as described in claim 4, characterized in that, M1 is FeCl3·6H2O, Fe2(SO4)3·9H2O, FeCl2·6H2O, FeSO4 The reagent is any one of the following: 7H2O, CoSO4·7H2O, CoCl2·6H2O, Co(NO3)2·6H2O, Co(CH3COO)2·4H2O, CuSO4·5H2O, CuCl2·2H2O, Cu(NO3)2, MnSO4·H2O, MnCl2·4H2O, Mn(NO3)2·4H2O, NiSO4·6H2O, NiCl2·6H2O, Cr(NO3)3·9H2O, Cr2(SO4)3·6H2O, Zr(SO4)2·4H2O; the acyl chloride reagent is any one of SOCl2, PCl5, PCl3.

6. The preparation method of the all-weather bimetallic porphyrin CMP material as described in claim 1, characterized in that, In S2, the molar ratio of M1Por-CMP to metal salt M2 is 1:2~2.4; M2 is FeCl3·6H2O, Fe2(SO4)3·9H2O, FeCl2·6H2O, or FeSO4. 7H2O, CoSO4·7H2O, CoCl2·6H2O, Co(NO3)2·6H2O, Co(CH3COO)2·4H2O, CuSO4·5H2O, CuCl2·2H2O, Cu(NO3)2, MnSO4·H2 Any one of O, MnCl2·4H2O, Mn(NO3)2·4H2O, NiSO4·6H2O, NiCl2·6H2O, Cr(NO3)3·9H2O, Cr2(SO4)3·6H2O, Zr(SO4)2·4H2O.

7. The preparation method of the all-weather bimetallic porphyrin CMP material as described in claim 1, characterized in that, In step S2, the reaction temperature is 80~85 ℃, the reaction time is 12~18 h, the stirring speed is 100~150 rpm, the filtration pressure is -0.06~-0.09 MPa, and the product is washed 3~5 times each with acetonitrile, anhydrous ethanol and ultrapure water, respectively. The drying temperature is 100~110 ℃ and the drying time is 4~8 h.

8. The all-weather bimetallic porphyrin CMP material prepared by the preparation method of any one of claims 1-7.

9. The application of the all-weather bimetallic porphyrin CMP material as described in any one of claims 1-7 in the degradation of organic pollutants in water.

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