Hexobenzene eutectic supramolecular material as well as preparation method and application thereof in photocatalytic degradation
By preparing hexabenzobenzene eutectic supramolecular materials and utilizing their interaction with acceptor molecules, the problems of synthesis complexity and stability of organic photocatalytic materials were solved, achieving efficient and environmentally friendly photocatalytic degradation effects, especially in the application of activated persulfate.
Patent Information
- Application Number
- CN202511022815.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-24
- Publication Date
- 2025-11-25
AI Technical Summary
Existing organic photocatalytic materials suffer from synthesis complexity and stability issues in the activation of peroxide monosulfate, limiting their application in photocatalytic degradation. Furthermore, traditional carbon-based catalysts have high preparation requirements and poor reproducibility, leading to environmental pollution risks.
Hexabenzobenzene eutectic supramolecular material is used to form an ordered structure through non-covalent self-assembly, and photocatalytic degradation is carried out in combination with peroxide monosulfate. The interaction between hexabenzobenzene and acceptor molecules is utilized to improve catalytic efficiency and stability.
A simple and efficient preparation of hexabenzobenzene eutectic supramolecular materials has been achieved. This method is environmentally friendly, uses inexpensive raw materials, has good reproducibility, and significantly improves photocatalytic activity. It can efficiently activate persulfate monosulfate and promote the degradation of environmental pollutants.
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Figure CN121005907A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of supramolecular materials technology, and in particular to a hexabenzobenzene eutectic supramolecular material, its preparation method, and its application in photocatalytic degradation. Background Technology
[0002] With the continued growth of global energy demand, the non-renewable nature of traditional fossil fuels and the resulting environmental pollution problems are becoming increasingly serious. This has made the search for sustainable and clean energy alternatives a global focus. Solar energy, as an inexhaustible and renewable energy source, is considered an important alternative to traditional energy sources due to its pollution-free and highly efficient characteristics. Photocatalysis technology, as a key pathway for converting solar energy into chemical energy, has become an important means of realizing solar energy utilization.
[0003] In the field of environmental remediation, persulfate monosulfate (PMS) has shown great potential as a novel oxidant. PMS exhibits strong oxidizing properties during photocatalysis, effectively degrading organic pollutants in water. Compared to traditional oxidants, the persulfate ions generated by activated PMS possess significant advantages, including high redox potential, a wide pH range, and a long half-life, thus offering broad application prospects, particularly in water treatment and environmental pollution control.
[0004] In recent years, photocatalysts based on organic semiconductor materials have emerged as an emerging research direction, attracting widespread attention due to their excellent photoelectric properties. However, the complexity of organic material synthesis and its stability remain bottlenecks for their widespread application. Supramolecular materials, through non-covalent self-assembly, exhibit excellent molecular regulation capabilities and can significantly improve photocatalytic efficiency.
[0005] Designing and developing highly efficient organic supramolecular photocatalytic materials requires not only precise control over molecular structure and electronic properties, but also comprehensive consideration of their light absorption capacity, electron transfer rate, and catalytic activity, especially in conjunction with the application of persulfate monosulfate in photocatalytic degradation. Currently, various methods have been proposed for activating persulfate, including external energy sources, transition metals, and carbon-based catalysts. However, the use of transition metal ions may lead to secondary water pollution. In contrast, carbon-based catalysts have attracted widespread attention due to their environmental friendliness, but their high preparation requirements and poor reproducibility limit their practical application. Organic supramolecular materials, prepared through modular molecular design and self-assembly, form ordered structures through non-covalent interactions, exhibiting higher reusability and becoming an ideal choice for activating persulfate. With the continuous advancement of research on novel photocatalytic materials, their catalytic efficiency and stability are expected to be significantly improved, providing new technological pathways for solar energy conversion and environmental pollution control. Therefore, developing novel organic supramolecular photocatalytic materials, especially those capable of efficiently activating persulfate monosulfate (PMS), has become an important step in promoting green energy conversion and environmental protection. Summary of the Invention
[0006] The purpose of this invention is to address the technical deficiencies in the prior art by providing a hexabenzobenzene eutectic supramolecular material and its preparation method.
[0007] Another object of the present invention is to provide the application of the hexabenzobenzene eutectic supramolecular material in photodegradation.
[0008] The technical solution adopted to achieve the purpose of this invention is:
[0009] A hexabenzobenzene eutectic supramolecular material, wherein the eutectic donor molecule is hexabenzobenzene, has the following structural formula:
[0010]
[0011] The cocrystallized acceptor molecule is a substituted benzene derivative, and its structural formula is:
[0012] Where R is H, cyano, Cl or Br, the number of H is less than or equal to 2, and the number of cyano is greater than or equal to 2.
[0013] In the above technical solution, the ratio of donor molecules to acceptor molecules is 1:1 based on the amount of matter.
[0014] Another aspect of the present invention includes a method for preparing the hexabenzobenzene eutectic supramolecular material, comprising the following steps:
[0015] The donor molecule, acceptor molecule and grinding solvent are mixed; the mixture is then ground at room temperature for 5 to 30 minutes to obtain the hexabenzobenzene eutectic supramolecular material.
[0016] In the above technical solution, the grinding solvent is one or a mixture of tetrahydrofuran, dichloromethane, acetonitrile, acetone, ethanol and toluene in any proportion.
[0017] In the above technical solution, the ratio of the total amount of donor molecules and acceptor molecules to the volume of the grinding solvent is (2-6):1, where the amount of substance is measured in mmol and the volume is measured in mL.
[0018] Another aspect of the present invention includes the application of the hexabenzobenzene eutectic supramolecular material in photocatalytic degradation.
[0019] In the above technical solution, under light irradiation, the hexabenzobenzene eutectic supramolecular material is uniformly dispersed in environmental pollutants for photocatalytic degradation;
[0020] Alternatively, under illumination, the hexabenzobenzene eutectic supramolecular material and peroxide monosulfate are uniformly dispersed in environmental pollutants and undergo photocatalytic degradation.
[0021] In the above technical solution, the light source used for illumination is a xenon lamp, a mercury lamp, or an LED lamp.
[0022] In the above technical solution, the wavelength of the light source used for illumination is 420-1200nm.
[0023] In the above technical solution, the concentration of the hexabenzobenzene eutectic supramolecular material in environmental pollutants is 0.1-10 mg / mL, and the concentration of oxidized monosulfate in environmental pollutants is 50-200 mg / L.
[0024] Compared with the prior art, the beneficial effects of the present invention are:
[0025] 1. The preparation method of hexabenzobenzene eutectic supramolecular material provided by the present invention has the advantages of being simple, efficient, environmentally friendly, using inexpensive raw materials, and having low synthesis cost; it also has high versatility and good reproducibility.
[0026] 2. The hexabenzobenzene eutectic supramolecular material provided by this invention exhibits a significantly enhanced photocatalytic ability due to the interaction between the donor and acceptor.
[0027] 3. The hexabenzobenzene eutectic supramolecular material provided by this invention accelerates the degradation of pollutants by activating persulfate peroxide, and has great application value in environmental remediation. Attached Figure Description
[0028] Figure 1 An optical microscope image of the eutectic supramolecular material obtained in Example 1;
[0029] Figure 2The powder XRD diffraction pattern of the eutectic supramolecular material obtained in Example 1;
[0030] Figure 3 The UV-Vis absorption spectrum of the eutectic supramolecular material obtained in Example 1;
[0031] Figure 4 An optical microscope image of the eutectic supramolecular material obtained in Example 2;
[0032] Figure 5 The powder XRD diffraction pattern of the eutectic supramolecular material obtained in Example 2;
[0033] Figure 6 The UV-Vis absorption spectrum of the eutectic supramolecular material obtained in Example 2;
[0034] Figure 7 An optical microscope image of the eutectic supramolecular material obtained in Example 3;
[0035] Figure 8 The powder XRD diffraction pattern of the eutectic supramolecular material obtained in Example 3;
[0036] Figure 9 The UV-Vis absorption spectrum of the eutectic supramolecular material obtained in Example 3;
[0037] Figure 10 The crystal structure of the eutectic supramolecular material obtained in Example 3;
[0038] Figure 11 The degradation curves of the environmental pollutants obtained in Example 4 are shown.
[0039] Figure 12 The curves showing the degradation of environmental pollutants by activated peroxide monosulfate under darkness obtained in Example 4;
[0040] Figure 13 The curves showing the degradation of environmental pollutants by activated peroxide monosulfate under light irradiation obtained in Example 4;
[0041] Figure 14 The degradation curves of the environmental pollutants obtained in Example 5 are shown.
[0042] Figure 15 The curves showing the degradation of environmental pollutants by activated peroxide monosulfate under darkness obtained in Example 5;
[0043] Figure 16 The curves showing the degradation of environmental pollutants by activated peroxide monosulfate under light irradiation obtained in Example 5;
[0044] Figure 17 The degradation curves of the environmental pollutants obtained in Example 6 are shown.
[0045] Figure 18 The curves showing the degradation of environmental pollutants by activated peroxide monosulfate under darkness obtained in Example 6;
[0046] Figure 19 The curves showing the degradation of environmental pollutants by activated peroxide monosulfate under light irradiation obtained in Example 6 are shown. Detailed Implementation
[0047] The present invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0048] Example 1
[0049] A method for preparing a hexabenzobenzene eutectic supramolecular material involves mixing 0.3 mmol of the donor molecule hexabenzobenzene, 0.3 mmol of the acceptor molecule tetrachlorophthalic acid, and 200 μL of tetrahydrofuran in an agate mortar; manually grinding the mixture for 3 minutes at room temperature; and observing the formation of a new substance with a color different from the two monomers, thus obtaining the hexabenzobenzene eutectic supramolecular material, namely hexabenzobenzene-tetrachlorophthalic acid eutectic.
[0050] The structural formula of the acceptor molecule tetrachlorophthalic acid is:
[0051]
[0052] Figure 1 The image shown is an optical microscope photograph of the obtained hexabenzobenzene eutectic supramolecular material. Measurements were taken using a DM2700M upright metallographic microscope. The image shows that the eutectic supramolecular material formed by the co-assembly of hexabenzobenzene and tetrachloro-o-phthalic acid exhibits a yellow-green color.
[0053] Figure 2 The XRD patterns of the obtained hexabenzobenzene, tetrachlorophthalic acid, and their eutectic supramolecular materials are shown. The diffraction peaks differ from those of the monomers, confirming that the powders obtained in batches after liquid-assisted milling are eutectic.
[0054] Figure 3 The UV-Vis absorption spectrum of the obtained hexabenzobenzene eutectic supramolecular material is shown. Measurements were taken using a Shimadzu UV-3600Plus UV-Vis spectrophotometer. The graph shows a shift in the absorption peak of the eutectic supramolecular material due to the interaction between the aromatic hydrocarbon and the hexabenzobenzene acceptor.
[0055] Example 2
[0056] A method for preparing a hexabenzobenzene eutectic supramolecular material involves mixing 0.3 mmol of the donor molecule hexabenzobenzene, 0.3 mmol of the acceptor molecule tetrachlorom-phenylenediamine, and 200 μL of dichloromethane in an agate mortar; grinding for 2 minutes at room temperature; and observing the formation of a new substance with a color different from the two monomers, thus obtaining the hexabenzobenzene eutectic supramolecular material, namely hexabenzobenzene-tetrachlorom-phenylenediamine eutectic.
[0057] The structural formula of the acceptor molecule tetrachloro-m-phenylenediamine is:
[0058]
[0059] Figure 4 The image shown is an optical microscope photograph of the obtained hexabenzobenzene eutectic supramolecular material. Measurements were taken using a DM2700M upright metallographic microscope. The image shows that the eutectic supramolecular material formed by the co-assembly of hexabenzobenzene and tetrachloro-m-phenylenediamine exhibits an orange-yellow color.
[0060] Figure 5 The XRD patterns of the obtained hexabenzobenzene, tetrachloro-m-phenylenediamine, and their eutectic supramolecular materials are shown. The diffraction peak positions, different from those of the monomers, prove that the powders obtained in batches after liquid-assisted grinding are eutectic.
[0061] Figure 6 The UV-Vis absorption spectrum of the obtained hexabenzobenzene eutectic supramolecular material is shown. Measurements were taken using a Shimadzu UV-3600Plus UV-Vis spectrophotometer. The graph shows a shift in the absorption peak of the eutectic supramolecular material due to the interaction between the aromatic hydrocarbon and the hexabenzobenzene acceptor.
[0062] Example 3
[0063] A method for preparing a hexabenzobenzene eutectic supramolecular material involves mixing 0.3 mmol of the donor molecule hexabenzobenzene, 0.3 mmol of the acceptor molecule tetrachloro-p-phenylenediamine, and 200 μL of dichloromethane in an agate mortar; grinding for 2 minutes at room temperature; and observing the formation of a new substance with a color different from the two monomers, thus obtaining the hexabenzobenzene eutectic supramolecular material, namely hexabenzobenzene-tetrachloro-p-phenylenediamine eutectic.
[0064] The structural formula of the acceptor molecule tetrachloro-p-phenylenediamine is:
[0065]
[0066] Figure 7 The image shown is an optical microscope photograph of the obtained hexabenzobenzene eutectic supramolecular material. Measurements were taken using a DM2700M upright metallographic microscope. The image shows that the eutectic supramolecular material formed by the co-assembly of hexabenzobenzene and tetrachloro-p-phenylenediamine exhibits an orange color.
[0067] Figure 8 The images show the powder XRD patterns of the obtained hexabenzobenzene, tetrachloro-p-phenylenediamine, and their eutectic supramolecular materials. The diffraction peak positions, different from those of the monomers, prove that the powders obtained in batches after liquid-assisted milling are eutectic.
[0068] Figure 9 The UV-Vis absorption spectrum of the obtained hexabenzobenzene eutectic supramolecular material is shown. Measurements were taken using a Shimadzu UV-3600Plus UV-Vis spectrophotometer. The graph shows a shift in the absorption peak of the eutectic supramolecular material due to the interaction between the aromatic hydrocarbon and the hexabenzobenzene acceptor.
[0069] Figure 10 The crystal structure of the obtained hexabenzobenzene eutectic supramolecular material is shown. The crystal structure analysis was performed using a Bruker SMART APEX-II instrument for data acquisition and single-crystal structure analysis using Olex2 software. The cell parameters of the crystal are: a = 7.3434(1), b = 9.3386(1), c = 17.1948(3), α = 90°, β = 101.786(2)°, γ = 90°.
[0070] Example 4
[0071] This example describes the application of the hexabenzobenzene-tetrachlorophthalic acid eutectic prepared in Example 1 in catalytically degrading tetracycline hydrochloride.
[0072] First, 50 mg of hexabenzobenzene-tetrachloro-o-phthalic acid eutectic supramolecular material was ultrasonically dispersed in 40 mL of deionized water. Then, 10 mL of tetracycline hydrochloride with a concentration of 100 mg / L was added to obtain 50 mL of mixed solution; the concentration of tetracycline hydrochloride in the mixed solution was 20 mg / L.
[0073] Wrap the beaker in aluminum foil to protect it from light, then stir for 30 minutes to ensure adsorption-desorption equilibrium is reached. After adsorption equilibrium is reached, take about 2 mL of sample, filter it through a filter head to remove a small amount of supramolecular photocatalytic solid (hexabenzobenzene-tetrachloro-o-phthalic acid eutectic supramolecular material), and measure the pollutant concentration C0 after adsorption equilibrium in the dark using a UV-Vis spectrophotometer.
[0074] A 300W xenon lamp was used as the excitation source to conduct a simulated visible light catalysis experiment. The xenon lamp used for the hexabenzobenzene-tetrachloro-o-phthalic acid eutectic supramolecular material had a wavelength range of 420-1200 nm.
[0075] Samples of approximately 2 mL were taken at the 15th, 30th, 45th, and 60th minutes of illumination, centrifuged, and the supernatant was preserved for concentration determination using a UV-Vis spectrophotometer. The degree of degradation was expressed as C0. t / CO It means that C O C represents the pollutant concentration after adsorption equilibrium in the dark. t This refers to the concentration of samples taken at specific time intervals.
[0076] Figure 11 The degradation curves of the obtained environmental pollutants are shown. Figure 11 It can be concluded that after 60 minutes of light irradiation, the hexabenzobenzene-tetrachlorophthalic acid eutectic supramolecular material can degrade 73.8% of tetracycline hydrochloride. Under the same experimental conditions, the hexabenzobenzene monomer can only degrade 33.9% of tetracycline hydrochloride, and tetrachlorophthalic acid can only degrade 21.9% of tetracycline hydrochloride.
[0077] Experiments were conducted in the dark to activate persulfate peroxide using a eutectic process. Three systems were prepared: ① 50 mg of hexabenzobenzene-tetrachlorophthalic acid eutectic supramolecular material was ultrasonically dispersed in 41 mL of deionized water as a photocatalyst. Then, 10 mL of 100 mg / L tetracycline hydrochloride was added, and the mixture was stirred in the dark for 30 minutes to obtain a 51 mL mixed solution. ② 50 mg of hexabenzobenzene-tetrachlorophthalic acid eutectic supramolecular material was ultrasonically dispersed in 40 mL of deionized water as a photocatalyst. Then, 10 mL of 100 mg / L tetracycline hydrochloride was added, and the mixture was stirred in the dark for 30 minutes. 1 mL of 5 g / L persulfate peroxide was then added, and the mixture was stirred in the dark for 10 minutes to obtain a 51 mL mixed solution. ③ 10 mL of 100 mg / L tetracycline hydrochloride and 1 mL of 5 g / L persulfate peroxide were added to 40 mL of deionized water, and the mixture was stirred in the dark for 10 minutes to obtain a 51 mL mixed solution.
[0078] The three systems were placed in the dark, and approximately 2 mL samples were taken at 10, 20, 30, and 40 minutes, centrifuged, and the supernatant was saved. The concentration was determined using a UV-Vis spectrophotometer. The degree of degradation was expressed as C. t / C O It means that C O C represents the concentration of pollutants after stirring treatment. t This refers to the concentration of samples taken at specific time intervals.
[0079] Figure 12 The resulting curves show the degradation of environmental pollutants by activated peroxide monosulfate under dark conditions. After 40 minutes of reaction in the dark, the hexabenzobenzene-tetrachlorophthalic acid eutectic supramolecular material showed almost no degradation effect on tetracycline hydrochloride. Peroxide monosulfate could degrade 9.4% of tetracycline hydrochloride. However, the combined action of the hexabenzobenzene-tetrachlorophthalic acid eutectic supramolecular material and peroxide monosulfate could degrade 38.3% of tetracycline hydrochloride, demonstrating the activation effect of the hexabenzobenzene-tetrachlorophthalic acid eutectic supramolecular material on peroxide monosulfate.
[0080] Experiments were conducted to activate persulfate peroxide under illumination using a eutectic process. Two systems were prepared: ① 50 mg of hexabenzobenzene-tetrachlorophthalic acid eutectic supramolecular material was ultrasonically dispersed in 40 mL of deionized water. Then, 10 mL of 100 mg / L tetracycline hydrochloride was added, and the mixture was stirred in the dark for 30 minutes. Next, 1 mL of 5 g / L persulfate peroxide was added, and the mixture was stirred in the dark for 10 minutes, yielding a 51 mL mixed solution. ② 10 mL of 100 mg / L tetracycline hydrochloride and 1 mL of 5 g / L persulfate peroxide were added to 40 mL of deionized water, and the mixture was stirred in the dark for 10 minutes, yielding a 51 mL mixed solution.
[0081] Both systems were placed under xenon lamp irradiation, and approximately 2 mL samples were taken at 0, 2.5, 5, 7.5, and 10 minutes. The samples were centrifuged, and the supernatant was preserved. Concentration was determined using a UV-Vis spectrophotometer. The degree of degradation was expressed as C0. t / C O It means that C O C represents the concentration of pollutants after stirring treatment. t This refers to the concentration of samples taken at specific time intervals.
[0082] Figure 13 The resulting light-activated peroxide monosulfate degradation curves show the degradation of environmental pollutants. After 10 minutes of reaction under light irradiation, peroxide monosulfate was able to degrade 8.6% of tetracycline hydrochloride. The combined action of the hexabenzobenzene-tetrachlorophthalic acid eutectic supramolecular material and peroxide monosulfate resulted in a degradation of 43.2% of tetracycline hydrochloride, demonstrating the activation effect of the hexabenzobenzene-tetrachlorophthalic acid eutectic supramolecular material on peroxide monosulfate.
[0083] Example 5
[0084] This example describes the application of the hexabenzobenzene-tetrachlorom-phenylenediamine eutectic prepared in Example 2 in catalytically degrading tetracycline hydrochloride.
[0085] First, 50 mg of hexabenzobenzene-tetrachloro-m-phenylenediamine eutectic supramolecular was ultrasonically dispersed in 40 mL of deionized water as a photocatalytic material. Then, 10 mL of tetracycline hydrochloride with a concentration of 100 mg / L was added to obtain 50 mL of mixed solution; the concentration of tetracycline hydrochloride in the mixed solution was 20 mg / L.
[0086] Wrap the beaker in aluminum foil to protect it from light, then stir for 30 minutes to ensure adsorption-desorption equilibrium is reached. After adsorption equilibrium is reached, take about 2 mL of sample, filter it through a filter head to remove a small amount of supramolecular photocatalytic solid (hexabenzobenzene-tetrachlorom-phenylenediamine eutectic supramolecular), and determine the initial concentration C0 on a UV-Vis spectrophotometer.
[0087] A 300W xenon lamp was used as the excitation source to conduct a simulated visible light catalysis experiment. The xenon lamp used for the hexabenzobenzene-tetrachlorom-phenylenediamine eutectic supramolecular material had a wavelength range of 420-1200 nm.
[0088] Samples of approximately 2 mL were taken at the 15th, 30th, 45th, and 60th minutes of illumination, centrifuged, and the supernatant was preserved for concentration determination using a UV-Vis spectrophotometer. The degree of degradation was expressed as C0. t / C O It means that C O C represents the pollutant concentration after adsorption equilibrium in the dark. t This refers to the concentration of samples taken at specific time intervals.
[0089] Figure 14 The degradation curves of the obtained environmental pollutants are shown. Figure 13 It can be concluded that after 60 minutes of light irradiation, the hexabenzobenzene-tetrachloro-m-phenylenediamine eutectic supramolecular material can degrade 79.5% of tetracycline hydrochloride. Under the same experimental conditions, the hexabenzobenzene monomer can only degrade 33.9% of tetracycline hydrochloride, and the tetrachloro-m-phenylenediamine can only degrade 10.6% of tetracycline hydrochloride.
[0090] Experiments were conducted in the dark to activate persulfate peroxide eutectic. Three systems were prepared: ① 50 mg of hexabenzobenzene-tetrachloro-m-phenylenediamine eutectic supramolecular material was ultrasonically dispersed in 41 mL of deionized water. Then, 10 mL of 100 mg / L tetracycline hydrochloride was added, and the mixture was stirred in the dark for 30 minutes to obtain a 51 mL mixed solution. ② 50 mg of hexabenzobenzene-tetrachloro-m-phenylenediamine eutectic supramolecular material was ultrasonically dispersed in 40 mL of deionized water. Then, 10 mL of 100 mg / L tetracycline hydrochloride was added, and the mixture was stirred in the dark for 30 minutes. 1 mL of 5 g / L persulfate peroxide was then added, and the mixture was stirred in the dark for 10 minutes to obtain a 51 mL mixed solution. ③ 10 mL of 100 mg / L tetracycline hydrochloride and 1 mL of 5 g / L persulfate peroxide were added to 40 mL of deionized water, and the mixture was stirred in the dark for 10 minutes to obtain a 51 mL mixed solution.
[0091] The three systems were placed in the dark, and approximately 2 mL samples were taken at 10, 20, 30, and 40 minutes, centrifuged, and the supernatant was saved. The concentration was determined using a UV-Vis spectrophotometer. The degree of degradation was expressed as C. t / C O It means that C O C represents the concentration of pollutants after stirring treatment. t This refers to the concentration of samples taken at specific time intervals.
[0092] Figure 15The resulting curves show the degradation of environmental pollutants by activated peroxide monosulfate under dark conditions. After 40 minutes of reaction in the dark, the hexabenzobenzene-tetrachloro-m-phenylenediamine eutectic supramolecular material showed almost no degradation effect on tetracycline hydrochloride. Peroxide monosulfate could degrade 9.4% of tetracycline hydrochloride. However, the combined action of the hexabenzobenzene-tetrachloro-m-phenylenediamine eutectic supramolecular material and peroxide monosulfate could degrade 0.366% of tetracycline hydrochloride, demonstrating the activation effect of the hexabenzobenzene-tetrachloro-m-phenylenediamine eutectic supramolecular material on peroxide monosulfate.
[0093] Experiments were conducted to activate persulfate peroxide under illumination using a eutectic process. Two systems were prepared: ① 50 mg of hexabenzobenzene-tetrachlorom-phenylenediamine eutectic supramolecular material was ultrasonically dispersed in 40 mL of deionized water. Then, 10 mL of 100 mg / L tetracycline hydrochloride was added, and the mixture was stirred in the dark for 30 minutes. Next, 1 mL of 5 g / L persulfate peroxide was added, and the mixture was stirred in the dark for 10 minutes, yielding a 51 mL mixed solution. ② 10 mL of 100 mg / L tetracycline hydrochloride and 1 mL of 5 g / L persulfate peroxide were added to 40 mL of deionized water, and the mixture was stirred in the dark for 10 minutes, yielding a 51 mL mixed solution.
[0094] Both systems were placed under xenon lamp irradiation, and approximately 2 mL samples were taken at 0, 2.5, 5, 7.5, and 10 minutes. The samples were centrifuged, and the supernatant was preserved. Concentration was determined using a UV-Vis spectrophotometer. The degree of degradation was expressed as C0. t / C O It means that C O C represents the concentration of pollutants after stirring treatment. t This refers to the concentration of samples taken at specific time intervals.
[0095] Figure 16 The resulting light-activated peroxide monosulfate degradation curves show the degradation of environmental pollutants. After 10 minutes of reaction under light irradiation, peroxide monosulfate was able to degrade 8.6% of tetracycline hydrochloride. The combined action of the hexabenzobenzene-tetrachlorom-phenylenediamine eutectic supramolecular material and peroxide monosulfate resulted in the degradation of 40.5% of tetracycline hydrochloride, demonstrating the activation effect of the hexabenzobenzene-tetrachlorom-phenylenediamine eutectic supramolecular material on peroxide monosulfate.
[0096] Example 6
[0097] This embodiment describes the application of the hexabenzobenzene-tetrachloro-terephthalic acid eutectic supramolecular material prepared in Example 3 in catalytically degrading tetracycline hydrochloride.
[0098] First, 50 mg of hexabenzobenzene-tetrachloro-terephthalic acid eutectic supramolecular material was ultrasonically dispersed in 40 mL of deionized water. Then, 10 mL of tetracycline hydrochloride with a concentration of 100 mg / L was added to obtain 50 mL of mixed solution; the concentration of tetracycline hydrochloride in the mixed solution was 20 mg / L.
[0099] Wrap the beaker in aluminum foil to protect it from light, then stir for 30 minutes to ensure adsorption-desorption equilibrium is reached. After adsorption equilibrium is reached, take about 2 mL of sample, filter it through a filter head to remove a small amount of supramolecular photocatalytic solid (hexabenzobenzene-tetrachloro-p-phenylenediamine eutectic supramolecular material), and measure the pollutant concentration C0 after adsorption equilibrium in the dark using a UV-Vis spectrophotometer.
[0100] A 300W xenon lamp was used as the excitation source to conduct a simulated visible light catalysis experiment. The xenon lamp used for the hexabenzobenzene-tetrachloro-p-phenylenediamine eutectic supramolecular material had a wavelength range of 420-1200 nm.
[0101] Samples of approximately 2 mL were taken at the 15th, 30th, 45th, and 60th minutes of illumination, centrifuged, and the supernatant was preserved for concentration determination using a UV-Vis spectrophotometer. The degree of degradation was expressed as C0. t / C O It means that C O C represents the pollutant concentration after adsorption equilibrium in the dark. t This refers to the concentration of samples taken at specific time intervals.
[0102] Figure 17 The degradation curves of the obtained environmental pollutants are shown. Figure 15 It can be concluded that after 60 minutes of light irradiation, the hexabenzobenzene-tetrachloro-terephthalic acid eutectic supramolecular material can degrade 69.9% of tetracycline hydrochloride. Under the same experimental conditions, the hexabenzobenzene monomer can only degrade 33.9% of tetracycline hydrochloride, and tetrachloro-terephthalic acid can degrade 26.1% of tetracycline hydrochloride.
[0103] Experiments were conducted in the dark to activate persulfate peroxide eutectic. Three systems were prepared: ① 50 mg of hexabenzobenzene-tetrachloro-terephthalic acid eutectic supramolecular material was ultrasonically dispersed in 41 mL of deionized water. Then, 10 mL of 100 mg / L tetracycline hydrochloride was added, and the mixture was stirred in the dark for 30 minutes to obtain a 51 mL mixed solution. ② 50 mg of hexabenzobenzene-tetrachloro-terephthalic acid eutectic supramolecular material was ultrasonically dispersed in 40 mL of deionized water. Then, 10 mL of 100 mg / L tetracycline hydrochloride was added, and the mixture was stirred in the dark for 30 minutes. 1 mL of 5 g / L persulfate peroxide was then added, and the mixture was stirred in the dark for 10 minutes to obtain a 51 mL mixed solution. ③ 10 mL of 100 mg / L tetracycline hydrochloride and 1 mL of 5 g / L persulfate peroxide were added to 40 mL of deionized water, and the mixture was stirred in the dark for 10 minutes to obtain a 51 mL mixed solution.
[0104] The three systems were placed in the dark, and approximately 2 mL samples were taken at 10, 20, 30, and 40 minutes, centrifuged, and the supernatant was saved. The concentration was determined using a UV-Vis spectrophotometer. The degree of degradation was expressed as C. t / C O It means that C O C represents the concentration of pollutants after stirring treatment. t This refers to the concentration of samples taken at specific time intervals.
[0105] Figure 18 The resulting curves show the degradation of environmental pollutants by activated peroxide monosulfate under dark conditions. After 40 minutes of reaction in the dark, the hexabenzobenzene-tetrachloro-p-phenylenediamine eutectic supramolecular material showed almost no degradation effect on tetracycline hydrochloride. Peroxide monosulfate could degrade 9.4% of tetracycline hydrochloride. However, the combined action of the hexabenzobenzene-tetrachloro-p-phenylenediamine eutectic supramolecular material and peroxide monosulfate could degrade 0.363% of tetracycline hydrochloride, demonstrating the activation effect of the hexabenzobenzene-tetrachloro-p-phenylenediamine eutectic supramolecular material on peroxide monosulfate.
[0106] Experiments were conducted to activate persulfate peroxide under illumination using a eutectic process. Two systems were prepared: ① 50 mg of hexabenzobenzene-tetrachloro-terephthalic acid eutectic supramolecular material was ultrasonically dispersed in 40 mL of deionized water. Then, 10 mL of 100 mg / L tetracycline hydrochloride was added, and the mixture was stirred in the dark for 30 minutes. Next, 1 mL of 5 g / L persulfate peroxide was added, and the mixture was stirred in the dark for 10 minutes, yielding a 51 mL mixed solution. ② 10 mL of 100 mg / L tetracycline hydrochloride and 1 mL of 5 g / L persulfate peroxide were added to 40 mL of deionized water, and the mixture was stirred in the dark for 10 minutes, yielding a 51 mL mixed solution.
[0107] Both systems were placed under xenon lamp irradiation, and approximately 2 mL samples were taken at 0, 2.5, 5, 7.5, and 10 minutes. The samples were centrifuged, and the supernatant was preserved. Concentration was determined using a UV-Vis spectrophotometer. The degree of degradation was expressed as C0. t / C O It means that C O C represents the concentration of pollutants after stirring treatment. t This refers to the concentration of samples taken at specific time intervals.
[0108] Figure 19 The resulting light-activated peroxide monosulfate degradation curves show the degradation of environmental pollutants. After 10 minutes of reaction under light irradiation, peroxide monosulfate was able to degrade 8.6% of tetracycline hydrochloride. The combined action of the hexabenzobenzene-tetrachloro-p-phenylenediamine eutectic supramolecular material and peroxide monosulfate resulted in a degradation of 34.2% of tetracycline hydrochloride, demonstrating the activation effect of the hexabenzobenzene-tetrachloro-p-phenylenediamine eutectic supramolecular material on peroxide monosulfate.
[0109] The above description is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A hexabenzobenzene eutectic supramolecular material, characterized in that, The eutectic donor molecule is hexabenzobenzene, and its structural formula is: The cocrystallized acceptor molecule is a substituted benzene derivative, and its structural formula is: Where R is H, cyano, Cl or Br, the number of H is less than or equal to 2, and the number of cyano is greater than or equal to 2.
2. The hexabenzobenzene eutectic supramolecular material as described in claim 1, characterized in that, The ratio of donor molecules to acceptor molecules is 1:1 in terms of molar amounts.
3. The method for preparing the hexabenzobenzene eutectic supramolecular material as described in claim 1, characterized in that, Includes the following steps: The donor molecule, acceptor molecule and grinding solvent are mixed; the mixture is then ground at room temperature for 5 to 30 minutes to obtain the hexabenzobenzene eutectic supramolecular material.
4. The preparation method according to claim 3, characterized in that, The grinding solvent is one or a mixture of tetrahydrofuran, dichloromethane, acetonitrile, acetone, ethanol and toluene in any proportion.
5. The preparation method according to claim 3, characterized in that, The ratio of the total amount of donor and acceptor molecules to the volume of the grinding solvent is (2-6):1, where the amount of substance is measured in mmol and the volume is measured in mL.
6. The application of the hexabenzobenzene eutectic supramolecular material as described in claim 1 in photocatalytic degradation.
7. The application as described in claim 6, characterized in that, Under light irradiation, the hexabenzobenzene eutectic supramolecular material is uniformly dispersed in environmental pollutants for photocatalytic degradation. Alternatively, under illumination, the hexabenzobenzene eutectic supramolecular material and peroxide monosulfate are uniformly dispersed in environmental pollutants and undergo photocatalytic degradation.
8. The application as described in claim 7, characterized in that, The light source used for illumination is a xenon lamp, mercury lamp, or LED lamp.
9. The application as described in claim 7, characterized in that, The wavelength of the light source used for illumination is 420–1200 nm.
10. The application as described in claim 7, characterized in that, The concentration of the hexabenzobenzene eutectic supramolecular material in environmental pollutants is 0.1–10 mg / mL, and the concentration of oxidized monosulfate in environmental pollutants is 50–200 mg / L.