Anthraquinone-based polysulfates, methods of making and photocatalytic applications thereof
By using a conjugated polymer route based on 2,6-dihydroxyanthraquinone polysulfate and ester bonds, the problems of complex synthesis, high cost, and poor solubility of existing anthraquinone-based polymer photocatalysts have been solved, achieving efficient production of hydrogen peroxide.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHAZHOU PROFESSIONAL INST OF TECH
- Filing Date
- 2026-02-14
- Publication Date
- 2026-05-29
AI Technical Summary
Existing anthraquinone-based polymer photocatalysts are complex to synthesize, costly, have poor solubility, and have unclear microstructures, resulting in low utilization of active sites and difficulty in efficiently producing hydrogen peroxide.
Using 2,6-dihydroxyanthraquinone as the key monomer, conjugated polymers are formed by linking them through sulfate ester bonds. The preparation method includes a three-step synthetic route of bisilyl ether protection, sulfuryl fluoride activation, and potassium hydrofluoride/crown ether catalysis to form an anthraquinone-based polysulfate.
The efficient catalytic production of hydrogen peroxide from water and oxygen under visible light irradiation was achieved, with a yield of 2667 μmol·h⁻¹·g⁻¹, exhibiting excellent visible light absorption and electron transport performance.
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Figure CN122103576A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the fields of polymer synthesis and photocatalysis, specifically to anthraquinone-based polysulfate, its preparation method, and its photocatalytic application. Background Technology
[0002] Hydrogen peroxide (H2O2), as an important green oxidant and potential energy carrier, has wide applications in environmental remediation, chemical synthesis, papermaking, textiles, and energy. Currently, large-scale industrial production of H2O2 mainly relies on the "anthraquinone process." This process is mature but has drawbacks such as cumbersome steps, the use of precious metal catalysts, the generation of large amounts of organic waste, high energy consumption, and safety hazards involving high-pressure hydrogen.
[0003] Photocatalytic reduction of oxygen to H2O2 (ORR: O2 + 2H) + + 2e - → H2O2) is a promising green alternative route. This method is solar-powered, using water and oxygen as raw materials, and is theoretically clean, safe, and energy-efficient. Developing efficient, stable, and inexpensive photocatalysts is the core of this technology.
[0004] Current research on photocatalysts mainly includes inorganic semiconductors (such as TiO2, g-C3N4, etc.) and emerging organic polymer semiconductors (such as covalent organic frameworks (COFs), conjugated microporous polymers (CMPs), linear conjugated polymers, etc.). Among them, introducing anthraquinone (AQ), the active unit in the traditional anthraquinone process, into the polymer framework to construct an "artificial anthraquinone redox cycle" system is an effective strategy that has emerged in recent years. However, existing anthraquinone-based polymer photocatalysts (such as conjugated systems based on perylene imide, triazine, or benzene rings) often suffer from problems such as complex synthesis, high cost, poor solubility making them difficult to process, or unclear microstructure leading to low utilization of active sites.
[0005] Polysulfates are a class of polymers with sulfate bonds (-O-SO2-O-) in their main chain, typically synthesized by polymerization of bisphenol monomers with sulfonyl chlorides or their derivatives. Their synthesis conditions are mild, monomer sources are widely available, and the polymer structures are well-defined and easily functionalized. However, there are currently no reports on the direct introduction of photoactive anthraquinone units as structural units into the polysulfate backbone for photocatalytic H2O2 production. Summary of the Invention
[0006] The present invention aims to solve at least one of the technical problems existing in the prior art or related technologies, and provides an anthraquinone-based polysulfate, its preparation method and photocatalytic application. The polymer has good photocatalytic performance and can be used for efficient and green production of hydrogen peroxide.
[0007] In a first aspect, the present invention provides an anthraquinone-based polysulfate with the following general structural formula: ; Where n > 1.
[0008] Furthermore, the polysulfate is derived from the 2,6-dihydroxyanthraquinone structural unit with the following structural formula: .
[0009] Furthermore, the polysulfate showed a Fourier transform infrared spectrum at 1671 cm⁻¹. -1 The polysulfate exhibits a carbonyl characteristic absorption peak at 269 nm and 390 nm in the UV-Vis absorption spectrum; and it displays characteristic diffraction peaks at 15.12°, 18.20°, 22.07°, and 26.59° in the X-ray diffraction pattern.
[0010] A second aspect of the present invention provides a method for preparing the above-mentioned polysulfate, comprising the following steps: Preparation of compound 1: 2,6-dihydroxyanthraquinone and imidazole were dissolved in dichloromethane, tert-butyldimethylchlorosilane was added, and the mixture was reacted at 20℃~30℃ for 20h~30h. After post-treatment, compound 1 was obtained. Preparation of compound 2: 2,6-dihydroxyanthraquinone and triethylamine were dissolved in dichloromethane, sulfuryl fluoride gas was introduced, and the reaction was carried out for 20-30 h. After post-treatment, compound 2 was obtained. Preparation of polysulfate: Compound 1 and compound 2 were polymerized in N-methylpyrrolidone at 125°C to 135°C under the catalysis of potassium hydrofluoric acid and 18-crown-6. After the reaction was completed, the polysulfate was obtained by precipitation in methanol.
[0011] Furthermore, the preparation of compound 1 includes: The molar ratio of 2,6-dihydroxyanthraquinone, imidazole and tert-butyldimethylchlorosilane is 1:(2~3):(2~3); The post-treatment is as follows: dichloromethane is removed by vacuum distillation, the product is dissolved in ethyl acetate, the organic phase is washed successively with deionized water, saturated NaHCO3 solution and NaCl solution, and then purified by column chromatography; wherein the eluent used in column chromatography is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:(5~10).
[0012] Furthermore, the preparation of compound 2 includes: The molar ratio of 2,6-dihydroxyanthraquinone to triethylamine is 1:(2~3), and the amount of sulfuryl fluoride gas introduced is such that the pressure of the reaction system reaches 1.1~1.3 times the atmospheric pressure; The post-treatment is as follows: dichloromethane is removed by vacuum distillation, the product is dissolved in ethyl acetate, the organic phase is washed successively with HCl solution, saturated NaHCO3 solution and NaCl solution, and then purified by column chromatography; wherein the eluent used in column chromatography is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to 1:5.
[0013] Furthermore, in the preparation of polysulfate, the molar ratio of compound 1 to compound 2 is 1:(1~1.2).
[0014] Furthermore, in the preparation of polysulfate, the volume of methanol used for precipitation is 3 to 5 times the volume of the polymerization reaction liquid.
[0015] A third aspect of the invention provides the use of the above-described anthraquinone-based polysulfate in the photocatalytic production of hydrogen peroxide from oxygen and / or air.
[0016] Furthermore, the polysulfate was dispersed as a photocatalyst in an aqueous solution containing 10% isopropanol by volume, and the photocatalytic reaction was carried out under the conditions of 300 W xenon lamp irradiation and air as the oxygen source, achieving a hydrogen peroxide yield of 2667 μmol·h⁻¹. -1 ·g -1 .
[0017] Compared with the prior art, the present invention has at least the following beneficial effects: The polysulfate provided by this invention uses a 2,6-dihydroxyanthraquinone derivative as the key monomer, forming a conjugated polymer through sulfate bonds, exhibiting excellent visible light absorption and electron transport properties. The preparation method uses 2,6-dihydroxyanthraquinone as the starting material to synthesize a bisilyl-protected anthraquinone intermediate and a thioyl fluoride-activated anthraquinone intermediate, respectively. Finally, the two intermediates are polycondensed in a potassium hydrofluoric acid / crown ether catalytic system. Under visible light irradiation, this material can efficiently catalyze the production of hydrogen peroxide from water and oxygen, achieving a yield of 2667 μmol·h⁻¹. -1 ·g -1 . Attached Figure Description
[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in the embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings.
[0019] Figure 1 This is a flowchart of a method for preparing anthraquinone-based polysulfate according to Embodiment 1 of the present invention; Figure 2Nuclear magnetic resonance (NMR) of compound 1 in the preparation method of anthraquinone-based polysulfate provided in Example 1 of this invention. 1 H NMR spectrum; Figure 3 Nuclear magnetic resonance (NMR) of compound 1 in the preparation method of anthraquinone-based polysulfate provided in Example 1 of this invention. 13 C NMR spectrum; Figure 4 Nuclear magnetic resonance (NMR) of compound 2 in the preparation method of anthraquinone-based polysulfate provided in Example 1 of this invention. 1 H NMR spectrum; Figure 5 Nuclear magnetic resonance (NMR) of the polysulfate in the preparation method of anthraquinone-based polysulfate provided in Example 1 of this invention. 1 H NMR spectrum; Figure 6 The FT-IR image of the polysulfate in the preparation method of anthraquinone-based polysulfate provided in Example 1 of the present invention; Figure 7 The UV-Vis absorption spectrum of the polysulfate in the preparation method of anthraquinone-based polysulfate provided in Example 1 of the present invention; Figure 8 The PXRD pattern of polysulfate powder in the preparation method of anthraquinone-based polysulfate provided in Embodiment 1 of the present invention; Figure 9 The CV (cyclic voltammetry) curve of the polysulfate solution in the preparation method of anthraquinone-based polysulfate provided in Example 1 of the present invention; Figure 10 The graph shows the performance of photocatalytic H2O2 production of polysulfate in the preparation method of anthraquinone-based polysulfate provided in Example 1 of this invention. Detailed Implementation
[0020] To better understand the above technical solutions, the technical solutions of the embodiments of this application will be described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the embodiments of this application and the specific features in the embodiments are detailed descriptions of the technical solutions of the embodiments of this application, rather than limitations on the technical solutions of this application. In the absence of conflict, the embodiments of this application and the technical features in the embodiments can be combined with each other.
[0021] A first aspect of the present invention provides an anthraquinone-based polysulfate with the following general structural formula: ; Where n > 1; Polysulfate derived from 2,6-dihydroxyanthraquinone structural units has the following structural formula: ; Polysulfate at 1671 cm⁻¹ in Fourier transform infrared spectroscopy -1 It has a carbonyl characteristic absorption peak; Polysulfate exhibits characteristic absorption peaks at 269 nm and 390 nm in the UV-Vis absorption spectrum; Polysulfate exhibits characteristic diffraction peaks at 15.12°, 18.20°, 22.07°, and 26.59° in X-ray diffraction patterns.
[0022] A second aspect of the present invention provides a method for preparing the above-mentioned polysulfate, comprising the following steps: Step 1, Preparation of Compound 1: 2,6-dihydroxyanthraquinone and imidazole were dissolved in dichloromethane, tert-butyldimethylchlorosilane was added, and the mixture was reacted at 20℃~30℃ for 20h~30h. After post-treatment, Compound 1 was obtained. The structural formula of compound 1 is as follows: ; The reaction formula is as follows: ; The molar ratio of 2,6-dihydroxyanthraquinone, imidazole and tert-butyldimethylchlorosilane is 1:(2~3):(2~3); preferably, the molar ratio of 2,6-dihydroxyanthraquinone, imidazole and tert-butyldimethylchlorosilane is 1:2.5:2.5. The post-processing includes: removing dichloromethane by vacuum distillation, dissolving the product in ethyl acetate, washing the organic phase sequentially with deionized water, saturated NaHCO3 solution and NaCl solution, and then purifying by column chromatography. The eluent used in the column chromatography is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to 1:5. Preferably, the volume ratio of ethyl acetate to petroleum ether in the eluent used in the column chromatography is 1:5.
[0023] Specifically, to promote the reaction, the phenolic hydroxyl group of 2,6-dihydroxyanthraquinone was converted into a stable tert-butyldimethylsilyl (TBS) ether during the actual reaction process. Using 2,6-dihydroxyanthraquinone as the starting material, imidazole and anhydrous dichloromethane were added, and the mixture was pre-stirred for 30 minutes under nitrogen protection to activate the phenolic hydroxyl group. Subsequently, tert-butyldimethylchlorosilane (TBSCl) was slowly added dropwise to complete the nucleophilic substitution reaction. After the reaction, extraction and purification yielded compound 1. Imidazole, acting as a catalyst, exhibited both nucleophilic catalysis and acid-binding effects. It abstracted a proton from the phenolic hydroxyl group of 2,6-dihydroxyanthraquinone to generate a phenoxy anion (enhancing nucleophilicity), which attacked the silicon atom of tert-butyldimethylchlorosilane to form a TBS ether bond. Simultaneously, it neutralized the byproduct HCl, preventing the deactivation of the phenoxy anion and hydrolysis of TBSCl, thus improving conversion and selectivity and ensuring subsequent functionalization modification.
[0024] Step 2, Preparation of Compound 2: 2,6-Dihydroxyanthraquinone and triethylamine were dissolved in dichloromethane. The entire system was evacuated and then sulfuryl fluoride gas was introduced. The reaction was carried out for 20-30 hours. After post-treatment, Compound 2 was obtained. The structural formula of compound 2 is as follows: ; The reaction formula is as follows: ; The molar ratio of 2,6-dihydroxyanthraquinone to triethylamine is 1:(2~3), preferably, the molar ratio of 2,6-dihydroxyanthraquinone to triethylamine is 1:2.5; The amount of sulfuryl fluoride gas introduced is such that the pressure of the reaction system reaches 1.1 to 1.3 times the atmospheric pressure; The post-processing includes: removing dichloromethane by vacuum distillation, dissolving the product in ethyl acetate, washing the organic phase sequentially with HCl solution, saturated NaHCO3 solution and NaCl solution, and then purifying by column chromatography. The eluent used in the column chromatography is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to 1:5. Preferably, the volume ratio of ethyl acetate to petroleum ether in the eluent used in the column chromatography is 1:5.
[0025] Specifically, in the reaction process, 2,6-dihydroxyanthraquinone and triethylamine were dissolved in dichloromethane. After the entire system was evacuated, sulfuryl fluoride (SO2F2) gas was introduced. After stirring for 20-30 hours, compound 2 was obtained by extraction and purification. The reaction process is that 2,6-dihydroxyanthraquinone undergoes a nucleophilic substitution reaction with sulfuryl fluoride under triethylamine bound acid, and the phenolic hydroxyl group is converted into a sulfuryl fluoride group (-SO2F), generating a sulfuryl fluoride anthraquinone derivative.
[0026] Step 3, Preparation of polysulfate: Compound 1 and compound 2 were polymerized in N-methylpyrrolidone at 125℃~135℃ under the catalysis of potassium hydrofluoric acid and 18-crown-6. After the reaction was completed, the polysulfate was obtained by precipitation in methanol. The molar ratio of compound 1 to compound 2 is 1:(1~1.2). During the precipitation process, the amount of methanol used is 3 to 5 times the volume of the polymerization reaction liquid.
[0027] Specifically, this reaction catalytic system uses potassium hydrofluoride (KHF2) as the fluorine source and 18-crown-6 as the phase transfer catalyst to synergistically promote the polycondensation reaction: KHF2 dissociates to release K + and F - 18-crown-6 complexes with K via a cavity + [K(18-crown-6)] is formed. + F -Significantly reduce F - The solvation energy is increased and its nucleophilicity is enhanced; F - As a generalized base, it abstracts the proton from the phenolic hydroxyl group of the BB monomer to generate a highly reactive phenolic anion (ArO). - ArO - Nucleophilic attack on the sulfur atom of the thioacryl fluoride group (-SO2F) of the AA monomer, via S n 2-substitution removes HF to form a sulfate ester bond (-O-SO2-O-), achieving monomer chain growth.
[0028] A third aspect of the present invention provides the application of the above-described anthraquinone-based polysulfate in the photocatalytic production of hydrogen peroxide from oxygen and / or air.
[0029] Because the anthraquinone groups in the anthraquinone-based polysulfate prepared in the embodiments of the present invention have strong visible light absorption capabilities, the material possesses excellent visible light capturing performance. The conjugated structure of the polymer backbone further broadens the light absorption range and enhances the delocalization of photogenerated carriers.
[0030] In some embodiments, polysulfate was dispersed as a photocatalyst in an aqueous solution containing 10% isopropanol by volume, and the photocatalytic reaction was carried out under irradiation by a 300W xenon lamp and with air as the oxygen source, achieving a hydrogen peroxide yield of 2667 μmol·h⁻¹. -1 ·g -1 Among the reported polysulfate-based photocatalytic systems, the H2O2 yield showed excellent performance. The hydrogen peroxide concentration was determined using iodometric titration at 350 nm: the reaction solution was mixed with KI solution and potassium hydrogen phthalate solution, and then left to stand in the dark for 3 hours. The amount of I3 generated was then measured. - The absorbance was used to calculate the H2O2 concentration. The reaction was carried out under mild conditions (at room temperature and normal pressure).
[0031] Specifically, this invention uses water as a hydrogen source and oxygen as an oxygen source, driven by clean solar energy. The product, H2O2, is itself a green oxidant, making the entire process environmentally friendly. It provides a promising material solution for large-scale, distributed, and low-carbon-footprint green synthesis of H2O2.
[0032] In summary, the anthraquinone-based polysulfate provided in this invention is a fully conjugated organic polymer linked by strong polar sulfate bonds (-O-SO2-O-). Its core skeleton consists of 2,6-dihydroxyanthraquinone (DHAQ) or its functionalized derivatives (e.g., introducing alkyl, alkoxy, amino, halogen, or other substituents at other positions on the anthraquinone ring to regulate solubility, band structure, or active sites) as key repeating units.
[0033] Anthraquinone groups themselves have strong visible light absorption capabilities in the wavelength range of approximately 400 nm to 550 nm, giving the material excellent visible light capture performance; while the conjugated structure of the polymer backbone further broadens the light absorption range and enhances the delocalization of photogenerated carriers.
[0034] In terms of preparation method, this invention, for the first time, integrates anthraquinone structural units into the conjugated polymer backbone via sulfate ester bonds, developing a three-step synthetic route based on disilyl ether protection, thioyl fluoride activation, and potassium hydrofluoride / crown ether catalysis. This route is clearly designed and the conditions are relatively controllable, providing a new approach for the controllable preparation of this type of polymer.
[0035] The prepared polysulfate has strong light-harvesting ability, efficient charge transport characteristics and multiple catalytic active sites, and exhibits excellent H2O2 yield in the visible light catalytic synthesis of H2O2.
[0036] Example 1: A method for preparing and applying anthraquinone-based polysulfate. (I) Preparation method See Figure 1 It includes the following steps: Step 1: Preparation of Compound 1, the specific steps are as follows: 2.40 g (0.01 mol) of 2,6-dihydroxyanthraquinone, 1.70 g (0.025 mol) of imidazole, and 50 mL of dichloromethane were added to a 250 mL beaker. After stirring for 30 minutes, 3.77 g (0.025 mol) of tert-butyldimethylchlorosilane was slowly added to the system. After stirring at 25 °C for 24 hours, the product was removed by vacuum distillation. The product was dissolved in 40 mL of ethyl acetate and washed successively with deionized water, saturated NaHCO3 aqueous solution, and NaCl aqueous solution. The product was concentrated by vacuum distillation and then subjected to column chromatography to obtain a light yellow solid powder with a yield of 86%.
[0037] Step 2: Preparation of compound 2, the specific steps are as follows: 2.40 g (0.01 mol) of 2,6-dihydroxyanthraquinone, 2.53 g (0.025 mol) of triethylamine, and 50 mL of dichloromethane were added to a 1000 mL single-necked flask. The entire system was evacuated, and sulfuryl fluoride (SO₂F₂) gas was introduced. After stirring for 24 hours, the dichloromethane was removed by vacuum distillation, and the product was dissolved in 50 mL of ethyl acetate. The product was washed successively with HCl, NaHCO₃, and NaCl solutions, concentrated by vacuum distillation, and then subjected to column chromatography to obtain a pale yellow solid powder. Yield: 85%.
[0038] Step 3: Preparation of polysulfate, the specific steps are as follows: Compound 1 was used as the AA monomer and compound 2 as the BB monomer. The specific polymerization conditions were as follows: in N-methylpyrrolidone (NMP) solvent at 130℃, 2 mol% potassium hydrofluoric acid (KHF2) and 1 mol% 18-crown-6 were used as the catalyst system. After the polymerization was completed, the reaction solution was dropped into methanol to precipitate a yellow solid powder. The yield was 90%.
[0039] (ii) Material Characterization Compound 1 1 H NMR and 13 The C NMR spectrum is as follows Figure 2 and Figure 3 As shown, the ¹H NMR of compound 2 is as follows: Figure 4 As shown. It can be seen that, Figures 2-4 The peaks are free of impurities, sharp, and their integral ratios match the theoretical hydrogen atom / carbon environment number, meeting the polymerization requirements. The ¹H NMR spectrum of the polysulfate is shown below. Figure 5 As shown, it can be seen that Figure 5 The sample showed no obvious impurity peaks, indicating that the purity met the standards, providing a reliable raw material for subsequent research. The structure of the polysulfate was further analyzed using Fourier transform infrared spectroscopy (FT-IR), such as... Figure 6 As shown, it can be seen that at 1671 cm -1 The infrared characteristic absorption peak observed at the point is attributed to the characteristic absorption peak of the carbonyl group, further indicating that the polymer material was successfully prepared.
[0040] The light absorption capacity of the synthesized polysulfate was evaluated using ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis). Figure 7 As shown, the DMF solution of polysulfate exhibits two absorption peaks at 269 nm and 390 nm, with the absorption peak at 269 nm attributed to the π-π group of the aromatic ring. The electronic transition at 390 nm is the n-π transition of the anthraquinone group. The electronic transitions indicate that the polymer has a certain light absorption capacity.
[0041] The structure of polysulfate was analyzed using powder X-ray diffraction (PXRD). Figure 8 As shown, the prepared polysulfate exhibited four strong Bragg diffraction peaks at 15.12°, 18.20°, 22.07°, and 26.59°, indicating that the prepared polysulfate has extremely high crystallinity. This may be related to the intermolecular hydrogen bonds formed between the residual terminal phenolic hydroxyl (-OH) groups and the carbonyl groups of the polymer.
[0042] (III) Electrochemical Characterization A standard three-electrode electrochemical cell was used, with glassy carbon as the working electrode, a platinum electrode as the auxiliary electrode, and an Ag / AgCl electrode as the reference electrode. These electrodes were inserted into a DMF solution containing 0.1 M tetrabutylammonium hexafluorophosphate and polysulfate. The initial oxidation potential and reduction potential of the polysulfate were measured to be -0.68 V and -0.64 V, respectively. Figure 9 As shown, this pair of reversible redox peaks are attributed to the anthraquinone group in the polymer chain, which is closely related to the photocatalytic H2O2 production performance of polysulfate.
[0043] (iv) Application in photocatalytic production of hydrogen peroxide The photocatalytic H2O2 production performance of the polysulfate prepared in Example 1 was tested, and the specific steps are as follows: First, polysulfate (10 mg), deionized water (45 mL), and isopropanol (5 mL) were added to a custom-made double-walled glass reactor. Then, the reactor was ultrasonically treated for 10 min to obtain a homogeneous suspension. Next, the suspension was magnetically stirred for 30 min in the dark to reach adsorption-desorption equilibrium. The photocatalytic experiment used a 300 W xenon lamp as the trigger light source, and circulating condensate was used to maintain the reactor temperature at room temperature during the catalytic process. During the experiment, every 10 min, 2 mL of the reaction solution was removed from the glass reactor and filtered through a water-based microporous filter to remove powder samples. Finally, H2O2 was detected using iodometric titration. The procedure is briefly described as follows: 1.5 mL of the filtered reaction solution was mixed with potassium iodide solution (KI, 0.4 mol / L, 0.5 mL) and potassium hydrogen phthalate (C8H5O4K, 0.1 mol / L, 0.5 mL) and allowed to stand in the dark for 3 h. Under acidic conditions, H2O2 reacts with I... - The reaction produces I3 - And I3 - It has a strong absorption peak at 350 nm. Finally, I3 was quantitatively determined by ultraviolet-visible spectrophotometry. - The amount of H2O2 produced by photocatalysis in the polymer sample was then used to calculate the concentration of H2O2 produced by photocatalysis in the polymer sample.
[0044] Test results are as follows Figure 10 As shown, under 60 minutes of light irradiation, the amount of H2O2 generated reached approximately 2.7 mmol·g. -1 The calculated yield was 2667 μmol·h⁻¹. -1 ·g -1 This indicates that in an isopropanol aqueous solution (10 vol%, hole sacrificial agent) under open conditions with air as the oxygen source, the amount of H2O2 produced by the polymer steadily increases with prolonged light exposure, and the H2O2 production rate is 2667 μmol·h⁻¹.-1 ·g -1 This indicates that the polysulfate has practical application potential for photocatalytic H2O2 production.
[0045] It will be readily understood by those skilled in the art that the above-described advantageous methods can be freely combined and superimposed without conflict. The above are merely preferred embodiments of this application and are not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application. The above are merely preferred embodiments of this application. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of this application, and these improvements and modifications should also be considered within the protection scope of this application.
Claims
1. An anthraquinone-based polysulfate, characterized in that, The general structural formula is: ； Where n > 1.
2. The anthraquinone-based polysulfate according to claim 1, characterized in that, The polysulfate is derived from the 2,6-dihydroxyanthraquinone structural unit, and its structural formula is as follows: 。 3. The anthraquinone-based polysulfate according to claim 1, characterized in that, The polysulfate was detected at 1671 cm⁻¹ in the Fourier transform infrared spectrum. -1 The polysulfate exhibits a carbonyl characteristic absorption peak at 269 nm and 390 nm in the UV-Vis absorption spectrum; and it displays characteristic diffraction peaks at 15.12°, 18.20°, 22.07°, and 26.59° in the X-ray diffraction pattern.
4. A method for preparing polysulfate, characterized in that, The method for preparing the polysulfate according to any one of claims 1-3 includes the following steps: Preparation of compound 1: 2,6-dihydroxyanthraquinone and imidazole were dissolved in dichloromethane, tert-butyldimethylchlorosilane was added, and the mixture was reacted at 20℃~30℃ for 20h~30h. After post-treatment, compound 1 was obtained. Preparation of compound 2: 2,6-dihydroxyanthraquinone and triethylamine were dissolved in dichloromethane, sulfuryl fluoride gas was introduced, and the reaction was carried out for 20-30 h. After post-treatment, compound 2 was obtained. Preparation of polysulfate: Compound 1 and compound 2 were polymerized in N-methylpyrrolidone at 125°C to 135°C under the catalysis of potassium hydrofluoric acid and 18-crown-6. After the reaction was completed, the polysulfate was obtained by precipitation in methanol.
5. The preparation method according to claim 4, characterized in that, The preparation of compound 1 includes: The molar ratio of 2,6-dihydroxyanthraquinone, imidazole and tert-butyldimethylchlorosilane is 1:(2~3):(2~3); The post-treatment is as follows: dichloromethane is removed by vacuum distillation, the product is dissolved in ethyl acetate, the organic phase is washed successively with deionized water, saturated NaHCO3 solution and NaCl solution, and then purified by column chromatography; wherein the eluent used in column chromatography is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:(5~10).
6. The preparation method according to claim 4, characterized in that, The preparation of compound 2 includes: The molar ratio of 2,6-dihydroxyanthraquinone to triethylamine is 1:(2~3), and the amount of sulfuryl fluoride gas introduced is such that the pressure of the reaction system reaches 1.1~1.3 times the atmospheric pressure; The post-treatment is as follows: dichloromethane is removed by vacuum distillation, the product is dissolved in ethyl acetate, the organic phase is washed successively with HCl solution, saturated NaHCO3 solution and NaCl solution, and then purified by column chromatography; wherein the eluent used in column chromatography is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to 1:
5.
7. The preparation method according to claim 4, characterized in that, In the preparation of polysulfate, the molar ratio of compound 1 to compound 2 is 1:(1~1.2).
8. The preparation method according to claim 4, characterized in that, In the preparation of polysulfate, the volume of methanol used for precipitation is 3 to 5 times the volume of the polymerization reaction liquid.
9. The use of an anthraquinone-based polysulfate according to any one of claims 1-3 in the photocatalytic production of hydrogen peroxide from oxygen and / or air.
10. The application according to claim 9, characterized in that, The polysulfate was dispersed as a photocatalyst in an aqueous solution containing 10% isopropanol by volume. The photocatalytic reaction was carried out under 300 W xenon lamp irradiation and with air as the oxygen source, achieving a hydrogen peroxide yield of 2667 μmol·h⁻¹. -1 ·g -1 .