Tetra(4-alkoxy-3-sulfonatophenyl) n-fused porphyrin dicalcium salt, its preparation method and application
Patent Information
- Application Number
- CN202610899986.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-22
- Publication Date
- 2026-08-18
AI Technical Summary
但其也存在一些局限性，例如TiO2的光响应范围较窄，主要集中在紫外光区，而太阳光中紫外光仅占约5%，对太阳能的利用率较低；此外，TiO2光生载流子复合率高，导致量子效率较低，限制了其光催化性能的进一步提升
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Abstract
Description
Technical Field
[0001] This invention relates to the field of photocatalysis technology, specifically to tetrakis(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt, its preparation method, and its application. Background Technology
[0002] Faced with the dual challenges of environmental pollution and energy shortages, developing efficient and green pollutant treatment technologies has become an important research direction in the field of environmental science. 1,5-Naphthiodiol, a typical phenolic pollutant widely found in wastewater from dye and pharmaceutical intermediate production, is highly toxic and biodegradable; its effective removal is crucial for ecological environmental protection and human health. Traditional methods such as physical adsorption, chemical oxidation, and biological treatment often suffer from low treatment efficiency, severe secondary pollution, or high energy consumption when treating 1,5-naphthiodiol. Therefore, there is an urgent need to explore more efficient and environmentally friendly treatment technologies.
[0003] Photocatalytic oxidation technology, as a green chemical transformation method, has received widespread attention in the fields of organic synthesis and environmental purification in recent years. This technology is based on the fact that photoactive materials absorb light energy to generate active species with strong oxidizing properties, thereby achieving selective transformation of organic compounds. Compared with traditional chemical oxidation methods, photocatalytic oxidation technology has significant advantages such as mild reaction conditions, low energy consumption, and environmental friendliness [3]. With the global emphasis on green chemistry and carbon neutrality, the development of efficient and stable photocatalytic systems has become a research hotspot in the field of chemistry. 1,5-naphthodiol, as an important organic intermediate, has wide applications in dyes, pharmaceuticals, polymer materials, and other fields. Its oxidation products have unique chemical structures and properties. Traditional 1,5-naphthodiol oxidation methods mainly rely on chemical oxidants, such as potassium dichromate, potassium permanganate, and manganese dioxide.
[0004] Porphyrins and their derivatives are a class of compounds with an 18π-electron conjugated macrocyclic structure. Due to their excellent photophysical and photochemical properties, they exhibit great potential in photocatalysis. Because of their unique structure and properties, they have been widely used as chemical color developers, catalysts, and solar cells. Porphyrins can also be used as DNA scavenging catalysts, photosensitizers in photodynamic therapy, and catalysts for wastewater treatment. As a photocatalyst, porphyrins are used to catalyze the oxidation of 1,5-naphthol. When porphyrin compounds absorb visible light energy, they can excite molecular oxygen, thereby generating singlet oxygen. N-displaced porphyrins also have an 18π-electron conjugated structure and can effectively generate singlet oxygen. 1,3-diphenylisobenzofuran (DBPF) was used as a singlet oxygen scavenger, and the results were detected using ultraviolet-visible spectroscopy.
[0005] Currently, studies have attempted to achieve the green oxidation of 1,5-naphthol using homogeneous catalysts, heterogeneous catalysts, or enzyme catalysis systems. However, problems such as difficult catalyst recovery, low activity, or excessively high cost still exist. For example, titanium dioxide (TiO2) has advantages such as high catalytic activity, stable chemical properties, and relatively low price, and is widely used in the field of photocatalysis. However, it also has some limitations. For instance, TiO2 has a narrow light response range, mainly concentrated in the ultraviolet region, while ultraviolet light accounts for only about 5% of sunlight, resulting in low utilization of solar energy. In addition, TiO2 has a high recombination rate of photogenerated carriers, leading to low quantum efficiency, which limits further improvement of its photocatalytic performance. Summary of the Invention
[0006] The purpose of this invention is to provide a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt and its preparation method. The calcification method simplifies the separation of the synthesized product and greatly improves the yield of the synthesized product. Furthermore, the tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt has good photocatalytic performance and can be used for the photocatalytic degradation of 1,5-naphthodiol.
[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution: The first aspect of the present invention provides a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt (4-NCTMOPPSCa), the general structural formula of which is shown in formula (I):
[0008] (I) Wherein, R is a C1~C4 alkyl group, including methyl, ethyl, propyl and butyl.
[0009] A second aspect of this invention provides a method for preparing a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt, comprising the following steps: a. 4-alkoxy nitrogen-displaced porphyrin and concentrated sulfuric acid are reacted in dichloromethane in a water bath to obtain a reaction mixture; b. Add excess lime water to the reaction mixture, allow it to stand and separate into layers after the reaction; then separate the middle layer, dry it, and obtain the tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt.
[0010] As a further improvement to the embodiments of this application, in step a, the general structural formula of the 4-alkoxy nitrogen-displaced porphyrin is as shown in formula (II):
[0011] (II).
[0012] As a further improvement to the embodiments of this application, in step a, the temperature of the water bath is 30~50℃, and the reaction time is 0.5~1 h.
[0013] As a further improvement to the embodiments of this application, in step b, the volume ratio of the reaction mixture to lime water is 1:(8~12).
[0014] As a further improvement to the embodiments of this application, the preparation method of the 4-alkoxy nitrogen-displaced porphyrin is as follows: Pyrrole and alkoxy-substituted benzaldehyde were dissolved in dichloromethane, mixed thoroughly, and then methanesulfonic acid was added. The mixture was stirred for 30-60 min. Triethylamine was then added, and after reacting for 1-2 min, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was added. The reaction was continued for 1-2 h, and the solvent was evaporated to obtain the crude product of 4-alkoxy nitrogen-displaced porphyrin.
[0015] As a further improvement to the embodiments of this application, it also includes the steps of sequentially performing dry column chromatography and wet column chromatography on the obtained crude 4-alkoxy nitrogen-displaced porphyrin product. The dry column chromatography method is as follows: dry Al2O3 is added to the chromatography column, the crude 4-alkoxy nitrogen-misaligned porphyrin product is dissolved in dichloromethane and added along the column wall into the chromatography column, eluted and filtered with dichloromethane, the green solution is collected and evaporated to dryness to obtain the dry product. The wet column chromatography process is as follows: Al2O3, which has been soaked in petroleum ether, is packed into a chromatography column. Then, the dry product is dissolved in dichloromethane and added along the column wall. The product is then eluted sequentially with a mixed solution of dichloromethane and petroleum ether. The eluted green solution is collected, evaporated to dryness, and 4-alkoxy nitrogen-displaced porphyrin is obtained.
[0016] As a further improvement to the embodiments of this application, the volume ratio of dichloromethane to petroleum ether in the mixed solution is 1:1, 2:1, and 3:1.
[0017] The third aspect of the present invention provides the application of the aforementioned tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt in the photocatalytic degradation of 1,5-naphthodiol.
[0018] As a further improvement to the embodiments of this application, the method of application is as follows: tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt is added to a solution containing 1,5-naphthol, an oxidant is added, the mixture is stirred evenly, and then irradiated with visible light with a wavelength of 400~830 nm; wherein, the oxidant is H2O2 solution.
[0019] Furthermore, the solution containing 1,5-naphthol is a two-phase system of water and dichloromethane.
[0020] As a further improvement to the embodiments of this application, the amount of the oxidant is 4.90 × 10⁻⁶. -5 mol, the amount of catalyst used is 5.60 × 10 -6 The reaction temperature was 25℃, and the reaction time was 1 h.
[0021] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention uses DCM as a solvent and pyrrole, p-alkoxybenzaldehyde, and methanesulfonic acid as raw materials to synthesize 4-NCTMOPP. The product is then sulfonated with concentrated sulfuric acid and calcified with excess lime water to obtain the final product, tetrakis(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt (4-NCTMOPPSCa). This invention simplifies the separation method of the synthesized product through calcification and significantly improves the yield of the synthesized product, reaching a yield of up to 87.08%.
[0022] 2. The tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt provided by this invention exhibits excellent photocatalytic performance and can be used as a catalyst for the photocatalytic oxidation of 1,5-naphthol. Furthermore, when the amount of hydrogen peroxide as the oxidant is 4.90 × 10⁻⁶... -5 The amount of catalyst tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt was 5.60 × 10⁻⁶ mol. -6 When reacted at a constant temperature of 25℃ for 1 hour, the conversion rate of 1,5-naphthyldiphenol reached as high as 93.58%. Therefore, this tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt can be used for photocatalytic degradation of phenolic pollutants 1,5-naphthyldiphenol in wastewater from dye and pharmaceutical intermediate production. Compared with conventional TiO2 catalysts, tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt extends the photoresponse range from the ultraviolet region to the visible light region of 400~830 nm, greatly improving the utilization rate of solar energy. Attached Figure Description
[0023] Figure 1 The synthesis route diagram for 4-NCTMOPP; Figure 2 The synthesis route for 4-NCTMPPS; Figure 3 The synthetic route for 4-NCTMOPPSCa; Figure 4 The UV-Vis absorption spectra of 4-NCTMOPP in DMF and DCM; Figure 5The UV absorption spectrum of 4-NCTMOPPSCa in DMF and HAc-NaAc buffer solution is shown. Figure 6 Molecular structure diagram of N-displaced porphyrin tautomer; Figure 7 The mass spectrum of 4-NCTMOPPSCa; Figure 8 The graph shows the change in absorbance of DBPF at 417 nm over time. Figure 9 The conversion rate of 1,5-naphthol at different amounts of oxidant is shown in the graph. Figure 10 The conversion rate of 1,5-naphthol at different catalyst dosages is shown in the graph. Figure 11 The graph shows the conversion rate of 1,5-naphthol at different temperatures. Detailed Implementation
[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings and the embodiments of the present invention.
[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.
[0026] Comparative Example 1: Synthesis of tetrakis(4-methoxy-3-sulfonic acid phenyl)N-misaligned porphyrin (4-NCTMPPS) 1. Synthesis of tetra(4-methoxyphenyl)N-displaced porphyrin Measure 100 mL of dichloromethane (DCM) solution using a graduated cylinder and pour it into a clean 250 mL round-bottom flask. Then, add 70 μL of pyrrole and 101 μL of p-methylbenzaldehyde, mix thoroughly, and then add 45 μL of methanesulfonic acid while stirring. Continue the reaction for 30 min, then add 390 μL of triethylamine and react for 1 min. After that, add 227 mg of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and continue the reaction for 1 h. The reaction is then terminated by turning off the magnetic stirrer and evaporating the solvent. The synthetic route is as follows: Figure 1 As shown.
[0027] Dry column chromatography: Add dry Al2O3 to the chromatography column to about 1 / 3 full. Dissolve the evaporated product in small amounts several times with DCM, then slowly add it along the column wall. Elute and filter with DCM to remove some impurities, such as DDQ. Collect the green liquid and evaporate it to dryness. Store in a sealed container away from light.
[0028] Wet column chromatography: Al₂O₃, pre-prepared and soaked in petroleum ether, is packed into another clean chromatography column to approximately one-third full. A small amount of DCM is then dissolved in the dry product and slowly added along the column wall. Elution is then performed using solutions of DCM and petroleum ether prepared in ratios of 1:1, 2:1, and 3:1. The eluted green liquid is collected and evaporated to dryness to obtain the final product 4-NCTMOPP, with a separation yield of 21%.
[0029] 2. Synthesis of tetrakis(4-methoxy-3-sulfonic acid phenyl)N-displaced porphyrin Weigh 0.031g (0.04×10⁻⁶) -3 1 mol) tetrakis(4-methoxyphenyl)N-displaced porphyrin was added to a reaction vessel, followed by the addition of 5 mL DCM and 0.16 mL (1.2 × 10⁻⁶ mol) of chlorine. -3 98% concentrated sulfuric acid (mol) was reacted in a constant temperature water bath at 40℃ for 0.5 h. After the reaction was complete, the reaction solution was added to 10 mL of methanol, followed by 40 mL of acetone. The mixture was stirred to precipitate, which was then centrifuged to obtain a green solid. This process was repeated three times. The obtained solid was dried to obtain tetrakis(4-methoxy-3-sulfonic acid phenyl)N-displaced porphyrin solid. The synthetic route is as follows: Figure 2 As shown.
[0030] In this comparative example, the yield of 4-NCTMPPS was 17.33 mg, with a separation yield of 38.94%.
[0031] Example 1: Synthesis of tetrakis(4-methoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt (4-NCTMOPPSCa) Weigh 0.050 g (0.068 × 10⁻⁶) of 4-NCTMOPP using an electronic balance. -3 0.111 mL of 2.04 × 10⁻⁶ mol) was placed in a reaction vessel. Then, 5 mL of DCM was added to the system, followed by 0.111 mL of (2.04 × 10⁻⁶ mol) of [amount missing]. -3 The sulfonated product was reacted with 98% H₂SO₄ at 40°C in a constant temperature water bath for 0.5 h. An excess of lime water (approximately 1:10) was added to the product in a one-pot, two-step process. After the reaction was complete, the mixture was allowed to stand for a period of time, resulting in layer separation. The intermediate layer was separated using a separatory funnel, dried, sealed, and stored in a refrigerator. The synthetic route is as follows: Figure 3 As shown.
[0032] In this embodiment, the yield of 4-NCTMOPPSCa was 67.050 mg, with a separation yield of 87.08%, which significantly improved the separation yield compared to 4-NCTMPPS.
[0033] The UV absorption spectra of 4-NCTMOPP dissolved in DMF and DCM are as follows: Figure 4 As shown, the UV absorption spectrum of 4-NCTMOPPSCa dissolved in DMF and HAc-NaAc buffer solution is as follows: Figure 5 As shown.
[0034] The unique delocalized large π-conjugated system of porphyrin molecules gives them typical absorption characteristics in the UV-Vis spectrum, namely a significant absorption peak in the Soret band and a relatively weak absorption intensity in the Q band. (Observation) Figure 4 The data revealed that 4-NCTMOPP exhibited a strong absorption response in the Soret band under various solvent conditions, a spectral characteristic that is highly consistent with the UV-Vis absorption behavior of N-displaced porphyrins.
[0035] Depend on Figure 5 The data shows that 4-NCTMOPPSCa exhibits a strong absorption peak in the Soret band in both DMF solvent and buffer solution systems, and also shows a relatively weak characteristic absorption signal in the Q band. Combined with... Figure 6 Molecular structure modeling analysis revealed that this spectroscopic phenomenon is attributed to the NH group on the pyrrole ring outside the 4-NCTMOPPSCa molecule, which can form hydrogen bonds with DMF molecules or solvent molecules in buffer solutions. This intermolecular interaction causes the compound to exist stably in the solution system in the isomer B conformation, thereby affecting its spectral absorption characteristics.
[0036] The molecular formula of tetra(4-methoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt (4-NCYMOPPSCa) is C 48 H 34 Ca2N4O 16 S4 has a relative molecular mass of 1130.0104. Figure 7 The mass spectrum of 4-NCTMOPPSCa shows that the actual relative molecular mass of the substance being measured is 1131.3136. Since the mass spectrometry uses positive ion mode, the substance is measured as M+1. Therefore, the relative molecular mass of tetra(4-methoxy-3-sulfonic acid)N-displaced porphyrin dicalcium salt is correct, confirming that it is the compound.
[0037] Experimental Example 1: Generation and Detection of Singlet Oxygen 1,3-Diphenylisobenzofuran (DBPF) was used as a singlet oxygen scavenger to monitor singlet oxygen in N-misaligned porphyrin compounds. Singlet oxygen is an excited-state oxygen molecule generated by the excitation of triplet oxygen (ground-state oxygen molecule) and exhibits high activity. Porphyrin compounds not only show good photoelectrocatalytic activity but also high triplet quantum yield and singlet oxygen quantum yield. Using 4-NCTMOPPSCa as a reference, DBPF and... 1 The O2 reaction was observed, and the value of the UV-Vis characteristic absorption peak at λ=417 nm was recorded. 4-NCTMOPPSCa was mixed with DBPF and dissolved in... N,N The mixture was dissolved in dimethylformamide (DMF) and then irradiated with a white lamp with a wavelength of 400–830 nm. The absorbance of the system at 417 nm was measured in real time every 10 seconds. The results are as follows: Figure 8 As shown.
[0038] See Figure 8 When 4-NCTMOPPSCa was not added to the system, the absorbance of the characteristic absorption peak of the UV-Vis absorption spectrum of DBPF decreased slightly and remained basically unchanged thereafter; after adding 4-NCTMOPPSCa, the absorbance of the absorption peak of the UV absorption spectrum of DBPF decreased significantly, indicating that the photosensitizer can continuously generate singlet oxygen under light irradiation.
[0039] Experimental Example 2: 4-NCTMOPPSCa for photocatalysis of 1,5-naphthyldiol (1) Preparation of buffer solution Weigh 5.1 g of anhydrous sodium acetate, dissolve it in a small amount of water, add 20 mL of acetic acid, and pour the solution into a 250 mL volumetric flask to make up to volume, preparing a buffer solution with a pH of 3.6. Take 33.3 mL of the buffer solution and dissolve 0.0011 g of 1,5-naphthol in a beaker to prepare a 2×10⁻⁶ solution. -4 A mol / L solution of 1,5-naphthol.
[0040] (2) Photocatalytic method: Measure 30 mL of DCM and 30 mL of 0.2×10 -3 A mol / L solution of 1,5-naphthol was placed in a reaction vessel, and certain amounts of 4-NCTMOPPSCa and H2O2 were added respectively. The solution was stirred evenly with a magnetic stirrer and irradiated with a white lamp with a wavelength of 400–830 nm. The supernatant was sampled periodically, and the degradation process of 1,5-naphthol catalyzed by porphyrin was monitored using the UV-Vis method, with a buffer solution as a reference. The aqueous phase and water-dichloromethane biphase catalytic systems were explored, and relatively ideal reaction conditions were determined. In the UV-Vis region, the characteristic absorption peaks of 1,5-naphthol were at 297 nm, 315 nm, and 330 nm, and the concentration of 1,5-naphthol was 0–2 × 10⁻⁶. -4 Within the range, it follows the Lambert-Beer law. The conversion rate at the strongest characteristic absorption peak of 330 nm is calculated using the following formula:
[0041] A0 is the absorbance measurement of the system before light treatment, A t A0 represents the absorbance measurement of the system after illumination for t min. ’ The absorbance values are the measurements of the system without the addition of 1,5-naphthol.
[0042] 1. Effect of H2O2 dosage on photocatalysis By changing the amount of H2O2 used, successively to 0 mol and 4.90 × 10⁻⁶ mol, the yield was determined. -6 mol, 1.96 × 10 -5 mol, 2.94 × 10 -5 mol and 4.90×10 -5 Using mol as a constant, and keeping other conditions unchanged, the conversion rate at different times was calculated based on the absorbance values measured by a UV-Vis absorption spectrometer, thus determining the optimal amount of oxidant. The results are as follows: Figure 9 As shown.
[0043] Depend on Figure 9 Experimental data show that the conversion rate of 1,5-naphthyldiol increases with the increase of hydrogen peroxide dosage. Without any added oxidant, after 1 hour of reaction, the conversion rate of 1,5-naphthyldiol is only low; however, when the amount of hydrogen peroxide added reaches 4.90 × 10⁻⁶, the conversion rate increases significantly. -5 When the reaction temperature was 1 mol and the reaction time was also 1 hour, the conversion rate of 1,5-naphthyldiol was 91.15%. Compared with the reaction system without the introduction of hydrogen peroxide, the conversion efficiency of 1,5-naphthyldiol was significantly improved.
[0044] Therefore, it can be seen that in the photocatalytic reaction of 1,5-naphthyldiol, 4.90 × 10⁻⁶ is the optimal choice. -5 Using mol of hydrogen peroxide and controlling the reaction time to 1 hour are relatively ideal reaction conditions.
[0045] 2. Effect of catalyst dosage on photocatalysis By changing the amount of catalyst, successively to 1.12 × 10 -6 mol, 2.24 × 10 -6 mol, 3.36 × 10 -6 mol, 4.48 × 10 -6 mol and 5.60×10 -6 By measuring absorbance values using a UV-Vis absorption spectrometer and keeping other conditions constant, the conversion rate at different times can be calculated to determine the optimal catalyst dosage. The results are as follows: Figure 10 As shown.
[0046] Depend on Figure 10 Experimental data show that the conversion rate of 1,5-naphthyldiol increases with the increase of the amount of catalyst 4-NCTMOPPSCa. The study found that when the amount of catalyst 4-NCTMOPPSCa was 5.60 × 10⁻⁶, the conversion rate was optimal. -6 At a concentration of 1 mol, and with the reaction lasting for 1 hour, the conversion rate of 1,5-naphthyldiol reached its highest value of 93.58%. Based on this, the optimal amount of 4-NCTMOPPSCa in this catalytic system was determined to be 5.60 × 10⁻⁶ mol. -6 The optimal conditions for the photocatalytic oxidation of 1,5-naphthol are mol and a reaction time of 1 hour.
[0047] 3. Effect of reaction temperature on photocatalysis With other reaction conditions fixed, the reaction temperatures were set at 20℃, 25℃, 30℃, 35℃, and 40℃, respectively. The absorbance of the reaction system at each temperature was measured using a UV-Vis absorption spectrometer. The conversion rate at different times was calculated to determine the optimal reaction temperature. The results are as follows: Figure 11 As shown.
[0048] Please see Figure 11 The conversion rate of 1,5-naphthyldiol showed an increasing trend with increasing temperature. When the reaction time was set to 1 hour, the conversion rates of 1,5-naphthyldiol at 25℃ and 40℃ were quite similar, with a conversion rate of 90.12% at 25℃ and 89.87% at 40℃. Considering both the convenience of actual experimental operation and the economic cost of the experiment, it was ultimately determined that a photocatalytic reaction at 25℃ for 1 hour was the most ideal experimental condition for processing 1,5-naphthyldiol.
[0049] Therefore, when the amount of hydrogen peroxide as the oxidant is 4.90 × 10⁻⁶, -5 mol, catalyst dosage is 5.60 × 10 -6The highest conversion rate of 1,5-naphthol can be obtained by reacting at a constant temperature of 25℃ for 1 hour.
[0050] In summary, the tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt provided by this invention can degrade 1,5-naphthol under visible light irradiation with a high conversion rate. It can be used for photocatalytic degradation of phenolic pollutants 1,5-naphthol in wastewater from dye and pharmaceutical intermediate production. Compared with conventional TiO2 catalysts, tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt extends the light response range from the ultraviolet region to the visible light region of 400~830 nm, greatly improving the utilization rate of solar energy.
[0051] The above-described embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention. The scope of protection of the present invention is defined by the claims.
Claims
1. A tetrakis(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt, characterized in that, The general structural formula of the tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt is shown in formula (I): Wherein, R is a C1~C4 alkyl group.
2. The method for preparing a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt according to claim 1, characterized in that, Includes the following steps: a. 4-alkoxy nitrogen-displaced porphyrin and concentrated sulfuric acid are reacted in dichloromethane in a water bath to obtain a reaction mixture; b. Add excess lime water to the reaction mixture, allow it to stand and separate into layers after the reaction; then separate the middle layer, dry it, and obtain the tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt.
3. The method for preparing a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt according to claim 2, characterized in that, In step a, the general structural formula of the 4-alkoxy nitrogen-delayed porphyrin is shown in formula (II): 。 4. The method for preparing a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt according to claim 3, characterized in that, In step a, the temperature of the water bath is 30~50℃, and the reaction time is 0.5~1 h.
5. The method for preparing a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt according to claim 3, characterized in that, In step b, the volume ratio of the reaction mixture to lime water is 1:(8~12).
6. The method for preparing a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt according to claim 3, characterized in that, The preparation method of the 4-alkoxy nitrogen-displaced porphyrin is as follows: Pyrrole and alkoxy-substituted benzaldehyde were dissolved in dichloromethane, mixed thoroughly, and then methanesulfonic acid was added. The mixture was stirred for 30-60 min. Triethylamine was then added, and after reacting for 1-2 min, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was added. The reaction was continued for 1-2 h, and the solvent was evaporated to obtain the crude product of 4-alkoxy nitrogen-displaced porphyrin.
7. The method for preparing a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt according to claim 6, characterized in that, It also includes the steps of sequentially performing dry column chromatography and wet column chromatography on the obtained crude 4-alkoxy nitrogen-displaced porphyrin product; The dry column chromatography method is as follows: dry Al2O3 is added to the chromatography column, the crude 4-alkoxy nitrogen-misaligned porphyrin product is dissolved in dichloromethane and added along the column wall into the chromatography column, eluted and filtered with dichloromethane, the green solution is collected and evaporated to dryness to obtain the dry product. The wet column chromatography process is as follows: Al2O3, which has been soaked in petroleum ether, is packed into a chromatography column. Then, the dry product is dissolved in dichloromethane and added along the column wall. The product is then eluted sequentially with a mixed solution of dichloromethane and petroleum ether. The eluted green solution is collected, evaporated to dryness, and 4-alkoxy nitrogen-displaced porphyrin is obtained.
8. The method for preparing a tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt according to claim 7, characterized in that, In the mixed solution, the volume ratio of dichloromethane to petroleum ether is 1:1, 2:1, and 3:
1.
9. The application of the tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt according to claim 1 in the photocatalytic degradation of 1,5-naphthol.
10. The application according to claim 9, characterized in that, The method of application is as follows: add tetra(4-alkoxy-3-sulfonic acid phenyl)N-displaced porphyrin dicalcium salt to a solution containing 1,5-naphthol, add an oxidant, stir evenly, and then irradiate with visible light with a wavelength of 400~830 nm. The oxidant is an H2O2 solution.