Indocyanine-based supramolecular polymer with photocatalytic performance and preparation method of indocyanine-based supramolecular polymer
By integrating tetraphenylethylene units with indocyanine derivatives, the prepared indocyanine supramolecular polymers solve the photoresponse and stability problems of existing photocatalytic materials, and achieve highly efficient photocatalytic degradation of bisphenol A.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-15
- Publication Date
- 2026-04-10
AI Technical Summary
Existing photocatalytic materials such as TiO2 have problems such as large band gap, narrow visible light response range and poor stability when photocatalytically degrading bisphenol A, which limits their application in water treatment.
By integrating tetraphenylethylene (TPE) units with specific functional groups through a supramolecular self-assembly strategy, indocyanine supramolecular polymers with photocatalytic properties are prepared. Utilizing their unique aggregation-induced emission behavior and excellent photoelectric properties, precise control of intermolecular synergistic effects and interfacial electronic structures can be achieved.
The prepared indocyanine supramolecular polymers have small band structures, wide visible light response range, good stability, high catalytic activity, and well-defined structures, enabling them to efficiently degrade bisphenol A.
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Figure CN121824967A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of supramolecular polymer preparation, and particularly relates to a preparation method of an indocyanine supramolecular polymer and application thereof in environmental governance, in particular, photocatalytic degradation of bisphenol A. BACKGROUND
[0002] As an important basic chemical raw material, bisphenol A (BPA) is widely used in the synthesis of polycarbonate plastics and epoxy resin and other polymer materials, and the global annual consumption has reached millions of tons. However, BPA is a typical endocrine disruptor, its molecular structure is highly similar to that of endogenous estrogen, and it can interfere with the normal hormone regulation function in the body by competitive binding to estrogen receptors. Studies have shown that even at trace levels (ng / L~μg / L), BPA can have adverse effects on the reproductive development, neural function and immune regulation of organisms. More worrying is that BPA is continuously released to the environment during production, use and waste disposal, and has been widely detected in surface water, groundwater, and even soil and sediments, becoming a “pseudo persistent pollutant”, posing a long-term and hidden threat to the ecosystem and public health.
[0003] At present, the removal technologies of BPA in water mainly include physical adsorption method, biological degradation method and advanced oxidation process. Among them, the photocatalytic technology based on semiconductor is considered as a green and sustainable pollution control strategy because it can directly utilize solar energy, has mild reaction conditions, and is expected to completely mineralize organic pollutants into CO2 and H2O and other harmless substances. However, the traditional photocatalytic materials (such as TiO2) have defects such as wide band gap (about 3.2 eV), narrow visible light response range (such as mainly responding to ultraviolet light) and poor stability (such as the photo-generated carriers are prone to rapid recombination), which seriously restricts the effective utilization of solar light and the actual catalytic efficiency, and limits its application and popularization in actual water treatment. SUMMARY
[0004] In view of the deficiencies of the above prior art, developing a new type of photocatalytic material with wide spectral response, high efficient charge separation ability and good stability has become the key to realizing the efficient degradation of BPA and other persistent organic pollutants. Tetraphenyl ethylene (TPE) and its derivatives are a new type of organic functional molecule, which not only has unique aggregation-induced emission (AIE) behavior, but also exhibits excellent optoelectronic properties and adjustable energy band structure. Through the supramolecular self-assembly strategy, the TPE unit is integrated with specific functional groups, which can realize the precise regulation of intermolecular synergistic effect and interface electronic structure, providing a new design idea and implementation approach for constructing efficient and stable visible light driven catalytic materials, and showing broad application prospects in the field of environmental photocatalysis.
[0005] The present application aims to provide a TPE and indocyanine-based supramolecular polymer with wide bandwidth, wide visible light response range and good stability, and simple synthesis route, high catalytic activity and clear structure, and application thereof in environmental governance, in particular, photocatalytic degradation of bisphenol A.
[0006] To achieve the object of the present application, the following technical solutions are provided. A preparation method of an indocyanine-based supramolecular polymer with photocatalytic performance, comprising the following steps: S1: condensation reaction of tetrakis(4-formylphenyl)ethylene and sulfonate functionalized indocyanine derivative under alkaline conditions, and monomer TPE-4SBI is obtained after a purification process; S2: the monomer TPE-4SBI obtained in the step S1 is dissolved in a good solvent, followed by vigorous stirring, and a poor solvent is continuously added, to prepare a supramolecular polymer based on TPE-4SBI, i.e., an indocyanine-based supramolecular polymer.
[0007] Preferably, the specific method of condensation reaction under alkaline conditions is as follows: Sodium acetate is added in the system of tetrakis(4-formylphenyl)ethylene and sulfonate functionalized indocyanine derivative, and the reaction is continuously carried out at a temperature of 30-120℃ in acetic anhydride solution for a time of 2-72 hours.
[0008] Preferably, the temperature is 80℃.
[0009] Preferably, the time is 24 hours.
[0010] Preferably, the specific steps of the purification process are as follows: S11: after the condensation reaction, the mixture after the reaction is concentrated by a rotary evaporator to remove the solvent, to obtain a crude product; S12: the obtained crude product is eluted with a mixture of dichloromethane and methanol as an eluent, and a gradient elution strategy is used to separate the target product, to obtain the monomer TPE-4SBI.
[0011] Preferably, the good solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
[0012] Preferably, the poor solvent is one or more of methanol, ethanol, propanol, isopropanol, acetone and water.
[0013] The present application also discloses an indocyanine-based supramolecular polymer with photocatalytic performance, which is prepared by any one of the above methods.
[0014] The application further discloses an application of the indocyanine supramolecular polymer with photocatalytic performance.
[0015] Preferably, the specific method of the photocatalytic degradation is as follows: A certain amount of the indocyanine supramolecular polymer is added into a solution containing bisphenol A, stirring is first carried out in dark conditions for 30-80 minutes, then irradiation is carried out in a visible light environment for a certain time, and thus the degradation of the bisphenol A can be realized.
[0016] The indocyanine supramolecular polymer has the advantages of small energy band, wide visible light response range and good stability, and has the advantages of simple synthesis route, high catalytic activity and clear structure.
[0017] The monomer formed by the combination of the TPE unit and the indocyanine has the following advantages in addition to the excellent properties of the two: (1) the design of the dipolar ion structure makes the monomer connected together through electrostatic interaction, and on the other hand, the target catalyst has good hydrophilicity, which is beneficial to the exposure of the active site; (2) the four-tooth structure design is adopted, the molecules and intermoleculars are connected through non-covalent bond, forming a cross-linked network supramolecular polymer, so that the target catalyst has strong adsorption function to the reaction substrate, and the catalytic performance is enhanced. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 The synthesis route of the TPE-4SBI of the application is shown in the figure; Figure 2 The nuclear magnetic resonance hydrogen spectrum (1H NMR) of the TPE-4SBI prepared by the application is shown in the figure; Figure 3 The nuclear magnetic resonance carbon spectrum (13C NMR) of the TPE-4SBI prepared by the application is shown in the figure; Figure 4 The scanning electron microscope image of the supramolecular polymer based on the TPE-4SBI prepared by the application is shown in the figure; Figure 5 The photocatalytic degradation performance curve of the supramolecular polymer based on the TPE-4SBI prepared by the application on bisphenol A under visible light irradiation is shown in the figure. DETAILED DESCRIPTION The application will be described in more detail below with reference to some specific embodiments, which are only used to illustrate the application and not to limit the scope of the application, and the preparation scheme in the embodiments is only a preferred scheme, but the application is not limited to the embodiments.
[0019] A preparation method of an indocyanine-based supramolecular polymer with photocatalytic performance, comprising the following steps: S1: condensation reaction of tetrakis(4-formylphenyl)ethylene and sulfonate functionalized indocyanine derivative under alkaline conditions, and monomer TPE-4SBI is obtained after a purification process; S2: the monomer TPE-4SBI obtained in the above step S1 is dissolved in a good solvent, followed by vigorous stirring, and continuously adding a poor solvent, to prepare a supramolecular polymer based on TPE-4SBI, i.e. an indocyanine-based supramolecular polymer with photocatalytic performance.
[0020] Preferably, the specific method of condensation reaction under alkaline conditions is as follows: In the system of tetrakis(4-formylphenyl)ethylene and sulfonate functionalized indocyanine derivative, sodium acetate is added, and the reaction is continuously carried out at a temperature of 30-120℃ in an acetic anhydride solution for a time of 2-72 hours.
[0021] As a preferred embodiment of the present embodiment, the temperature is 80℃.
[0022] As a preferred embodiment of the present embodiment, the time is 24 hours.
[0023] As a preferred embodiment of the present embodiment, the specific steps of the purification process are as follows: S11: after the condensation reaction is completed, the mixture after the reaction is concentrated by a rotary evaporator to remove the solvent, and a crude product is obtained; S12: the obtained crude product is eluted with a mixed solution of dichloromethane and methanol as an eluent, and a gradient elution strategy is used to separate the target product, and monomer TPE-4SBI is obtained.
[0024] As a preferred embodiment of the present embodiment, the good solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl pyrrolidone.
[0025] As a preferred embodiment of the present embodiment, the poor solvent is one or more of methanol, ethanol, propanol, isopropanol, acetone, and water.
[0026] The embodiments of the present application also disclose an indocyanine-based supramolecular polymer with photocatalytic performance, which is prepared by any one of the above methods.
[0027] The embodiment of the application also discloses application of the indocyanine supramolecular polymer with photocatalytic performance.
[0028] As a preferred embodiment of the present embodiment, the specific method of photocatalytic degradation is as follows: A certain amount of indocyanine supramolecular polymer is added to a solution containing bisphenol A, and stirring is first carried out in dark conditions for 30-80 minutes, and then irradiation is carried out in a visible light environment for a certain time, so that the degradation of the bisphenol A can be realized.
[0029] The technical idea of the application is that the TPE unit and specific functional groups are integrated through a supramolecular self-assembly strategy, the intermolecular synergistic effect and the precise regulation of the interface electronic structure can be realized, a new design idea and implementation approach are provided for constructing a high-efficiency and stable visible light driven catalytic material, and the application prospect in the field of environmental photocatalysis is broad.
[0030] In the technical scheme of the application, tetraphenyl ethylene (TPE) and its derivatives are used as a new type of organic functional molecule, which not only has unique aggregation-induced emission (AIE) behavior, but also has excellent photoelectric properties and adjustable energy band structure. The indocyanine supramolecular polymer prepared by the method has a small energy band, a wide visible light response range and good stability, and has the advantages of simple synthesis route, high catalytic activity and clear structure.
[0031] In the technical scheme of the application, the monomer generated by combining the TPE unit and the indocyanine has the following advantages in addition to the excellent properties of the two: (1) The design of the dipolar ion structure makes the monomer connected together through electrostatic interaction, and on the other hand, the target catalyst has good hydrophilicity, which is beneficial to the exposure of the active site; (2) The tetradentate structure is used for design, the molecules and the intermolecular non-covalent bond interaction form a cross-linked network supramolecular polymer, so that the target catalyst has strong adsorption function for the reaction substrate, and the catalytic performance is enhanced.
[0032] Embodiment 1 S1: 1.968 g TPE-4CHO, 4 g sulfonate-functionalized indocyanine derivative, and 1.12 g sodium acetate were added to 30 mL acetic anhydride and reacted at 80 °C for 24 hours. After the reaction, the solvent was removed from the mixture by rotary evaporation to obtain the crude product. The crude product was then separated and purified by column chromatography using a mixed solution of dichloromethane and methanol as the eluent, and the volume ratio was gradually adjusted by gradient elution (from 10:1 to 1:1) to finally obtain the target supramolecular photocatalyst TPE-4SBI (yield: 46.5%).
[0033] S2: The prepared TPE-4SBI monomer is dissolved in dimethyl sulfoxide, and a mixed solvent of ethanol and water is added under vigorous stirring to prepare a supramolecular polymer based on TPE-4SBI, namely an indocyanine supramolecular polymer with photocatalytic properties.
[0034] like Figure 2 As shown, it is the ¹H NMR spectrum of TPE-4SBI prepared in this invention. 1H NMR(600 MHz, DMSO-d6) δ 8.52 (d, J = 15.3 Hz, 4H), 8.36 (dd, J = 19.5, 7.5 Hz,12H), 8.24 (d, J = 8.5 Hz, 4H), 8.17 (d, J = 7.5 Hz, 8H), 7.88 (d, J = 6.8Hz, 12H), 7.76 (d, J = 7.2 Hz, 4H), 7.74 – 7.64 (m, 12H), 7.19 (d, J = 6.7Hz, 8H), 4.86 (s, 8H), 2.56 (t, J = 6.4 Hz, 8H), 2.04 (s, 8H), 1.98 (s, 24H),1.86 (d, J = 6.2 Hz, 8H). like Figure 3The carbon nuclear magnetic resonance spectrum (13C NMR) of the TPE-4SBI prepared by the present application is shown. 13C NMR (151 MHz, DMSO-d6) δ 182.72, 152.60, 143.86, 140.81, 139.11, 138.81, 137.23, 134.23, 133.67, 132.17, 131.92, 131.53, 130.47, 128.85, 127.70, 127.36, 127.08, 126.99, 123.56, 113.94, 112.57, 54.26, 50.61, 47.25, 27.79, 26.01, 22.66. Example 2 S1: 1.968 g of TPE-4CHO, 4 g of sulfonate functionalized indocyanine derivative and 1.2 g of potassium acetate were added to 30 mL of acetic anhydride, and the reaction was continued at 80°C for 24 hours. After the reaction was completed, the solvent was removed from the mixed system by rotary evaporation to obtain a crude product. Then, column chromatography was used to separate and purify the crude product, using a mixture of dichloromethane and methanol as the eluent, and gradually adjusting the volume ratio by gradient elution (from 10:1 to 1:1), and finally obtaining the target supramolecular photocatalyst TPE-4SBI (yield: 58%).
[0035] S2: The monomer of the prepared TPE-4SBI was dissolved in N,N-dimethylformamide, and then added to water under vigorous stirring to prepare a supramolecular polymer based on TPE-4SBI, i.e., an indocyanine supramolecular polymer with photocatalytic properties.
[0036] Example 3 S1: 1.968 g of TPE-4CHO, 4 g of sulfonate functionalized indocyanine derivative and 1.2 g of potassium acetate were added to 30 mL of acetic anhydride, and the reaction was continued at 80°C for 24 hours. After the reaction was completed, the solvent was removed from the mixed system by rotary evaporation to obtain a crude product. Then, column chromatography was used to separate and purify the crude product, using a mixture of dichloromethane and methanol as the eluent, and gradually adjusting the volume ratio by gradient elution (from 10:1 to 1:1), and finally obtaining the target supramolecular photocatalyst TPE-4SBI (yield: 58%).
[0037] S2: The monomer of the prepared TPE-4SBI was dissolved in N,N-dimethylformamide, and then added to water under vigorous stirring to prepare a supramolecular polymer based on TPE-4SBI, i.e., an indocyanine supramolecular polymer with photocatalytic properties.
[0038] Example 4 S1: 1.968 g TPE-4CHO, 4 g sulfonate functionalized indocyanine derivative and 1.2 g potassium acetate were added into 30 mL acetic anhydride, and the reaction was continued at 120°C for 2 hours. After the reaction was completed, the mixed system was removed by rotary evaporation to obtain a crude product. Then the crude product was separated and purified by column chromatography, using a mixed solution of dichloromethane and methanol as the eluent, and adjusting the volume ratio gradually (from 10:1 to 1:1) by gradient elution, and finally obtaining the target supramolecular photocatalyst TPE-4SBI (yield: 51.5%).
[0039] S2: The monomer of the prepared TPE-4SBI was dissolved in N,N-dimethylformamide, and then added into water under the condition of vigorous stirring, to prepare a supramolecular polymer based on TPE-4SBI, i.e. an indocyanine supramolecular polymer with photocatalytic properties.
[0040] Example 5 S1: 1.968 g TPE-4CHO, 4 g sulfonate functionalized indocyanine derivative and 1.2 g potassium acetate were added into 30 mL acetic anhydride, and the reaction was continued at 120°C for 2 hours. After the reaction was completed, the mixed system was removed by rotary evaporation to obtain a crude product. Then the crude product was separated and purified by column chromatography, using a mixed solution of dichloromethane and methanol as the eluent, and adjusting the volume ratio gradually (from 10:1 to 1:1) by gradient elution, and finally obtaining the target supramolecular photocatalyst TPE-4SBI (yield: 51.5%).
[0041] S2: The monomer of the prepared TPE-4SBI was dissolved in N,N-dimethylformamide, and then added into water under the condition of vigorous stirring, to prepare a supramolecular polymer based on TPE-4SBI, i.e. an indocyanine supramolecular polymer with photocatalytic properties.
[0042] Application Example 1 In a 100 mL quartz reactor, 45 mL of a 10 ppm concentration bisphenol A aqueous solution was added. 27 mg of the supramolecular polymer based on TPE-4SBI prepared in Example 1 was added to the solution. First, the suspension was magnetically stirred in the dark for 60 minutes to achieve adsorption-desorption equilibrium of the supramolecular polymer to BPA. Then, a 300 W xenon lamp was used as a visible light source (equipped with a 420 nm cutoff filter, λ>420 nm) to irradiate the reactor. During the irradiation, 1 mL was taken every 10 minutes and filtered through a 0.22 μm filter membrane to remove catalyst particles.
[0043] Test results: The concentration of bisphenol A in the filtrate was determined using high performance liquid chromatography (HPLC). The degradation rate (D%) of BPA was calculated by the formula D% = (C0- C t ) / C0x 100%, wherein C0is the initial concentration of BPA after adsorption equilibrium, C t is the concentration of BPA at illumination time t. After 120 minutes of visible light irradiation, the degradation rate of bisphenol A can reach 99.5%. As a comparison, under the conditions without catalyst or without light, the concentration of bisphenol A hardly decreased. The results show that the TPE-4SBI supramolecular polymer prepared in the application exhibits excellent photocatalytic degradation activity for bisphenol A under visible light driving.
[0044] Based on the above scheme, the application provides a TPE and indocyanine-based supramolecular polymer which has a wide energy band, a wide visible light response range and good stability, and at the same time has a simple synthesis route, high catalytic activity and a clear structure. Meanwhile, the indocyanine-based supramolecular polymer prepared in the application also has good application effects in environmental governance, especially in photocatalytic degradation of bisphenol A.
[0045] Although embodiments of the application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the application, and the scope of the application is defined by the appended claims and their equivalents.
Claims
1. A method for preparing an indocyanine supramolecular polymer with photocatalytic properties, characterized in that, Includes the following steps: S1: Tetra(4-formylphenyl)ethylene and sulfonate-functionalized indocyanine derivatives were condensed under alkaline conditions, and the monomer TPE-4SBI was obtained after purification. S2: Dissolve the monomer TPE-4SBI obtained in step S1 in a good solvent, then stir vigorously and continuously add a poor solvent to prepare a supramolecular polymer based on TPE-4SBI.
2. The method for preparing the indocyanine supramolecular polymer with photocatalytic properties according to claim 1, characterized in that, The specific method for carrying out the condensation reaction under alkaline conditions is as follows: Sodium acetate was added to a system of tetra(4-formylphenyl)ethylene and sulfonate-functionalized indocyanine derivatives, and the reaction was carried out in acetic anhydride solution at a temperature of 30-120°C for 2-72 hours.
3. The method for preparing the indocyanine supramolecular polymer with photocatalytic properties according to claim 2, characterized in that, The temperature is 80°C.
4. The method for preparing the indocyanine supramolecular polymer with photocatalytic properties according to claim 2, characterized in that, The time frame is 24 hours.
5. The method for preparing the indocyanine supramolecular polymer with photocatalytic properties according to claim 1, characterized in that, The specific steps of the purification process are as follows: S11: After the condensation reaction is completed, the mixture after the reaction is concentrated by a rotary evaporator to remove the solvent and obtain the crude product; S12: The crude product was used as an eluent by a mixed solution of dichloromethane and methanol, and a gradient elution strategy was employed to separate the target product, thereby obtaining the monomer TPE-4SBI.
6. The method for preparing the indocyanine supramolecular polymer with photocatalytic properties according to claim 1, characterized in that, The good solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
7. The method for preparing the indocyanine supramolecular polymer with photocatalytic properties according to claim 1, characterized in that, The unsuitable solvent is one or more of methanol, ethanol, propanol, isopropanol, acetone, and water.
8. An indocyanine supramolecular polymer with photocatalytic properties, characterized in that, The indocyanine supramolecular polymer was prepared by the method described in any one of claims 1 to 7.
9. An application of an indocyanine supramolecular polymer with photocatalytic properties, characterized in that, The indocyanine supramolecular polymer described in claim 8 can be applied to the photocatalytic degradation of bisphenol A.
10. The application of the indocyanine supramolecular polymer with photocatalytic properties according to claim 9, characterized in that, The specific method for photocatalytic degradation is as follows: The degradation of bisphenol A can be achieved by adding a certain amount of indocyanine supramolecular polymer to a solution containing bisphenol A, stirring in the dark for 30-80 minutes, and then irradiating it with visible light for a certain period of time.