A phenanthrenequinone-based conjugated organic polymer photocatalyst, its preparation method, and its application.
By using phenanthrenequinone-based conjugated organic polymer photocatalysts and utilizing Schiff base condensation reactions to form imine bonds, the problems of high energy consumption, high cost, and environmental pollution in existing hydrogen peroxide production technologies have been solved, achieving efficient and low-cost hydrogen peroxide generation.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JIANGNAN UNIV
- Filing Date
- 2025-03-27
- Publication Date
- 2026-06-30
AI Technical Summary
Existing industrial methods for producing hydrogen peroxide suffer from high energy consumption, high cost, significant safety risks, and severe environmental pollution. In particular, the anthraquinone auto-oxidation method requires complex facilities and precious metal catalysts.
Using a phenanthrenequinone-based conjugated organic polymer photocatalyst, imine bonds are formed through Schiff base condensation reaction. By utilizing the electron push-pull effect of electron-donating and electron-accepting building blocks, hydrogen peroxide is efficiently generated from pure water and air under photocatalysis.
The efficient generation of hydrogen peroxide without sacrificial agents was achieved. The catalyst has a high specific surface area and excellent photocatalytic activity, with yields ranging from 700 to 1600 μmol·g⁻¹·h⁻¹. The synthesis method is simple and easy to implement, and is suitable for industrial applications.
Smart Images
Figure CN120289740B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a phenanthrenequinone-based conjugated organic polymer photocatalyst, its preparation method, and its application, belonging to the field of photocatalyst material preparation technology. Background Technology
[0002] Hydrogen peroxide, as an important inorganic chemical raw material and fine chemical product, plays a crucial role in numerous fields such as chemical synthesis, pulp and textile bleaching, metal mineral processing, environmental protection, electronics, military industry, and aerospace. With the rapid development of the global economy, hydrogen peroxide production is making great strides towards large-scale, high-tech, and automated control. Especially since the 1990s, with the continuous expansion of its applications in the paper, environmental protection, and electronics industries, market demand for hydrogen peroxide has remained consistently high.
[0003] Currently, the main methods for industrial production of hydrogen peroxide include anthraquinone autoxidation, electrolysis, oxygen cathode reduction, isopropanol synthesis, and direct hydrogen-oxygen synthesis. Among these, the anthraquinone autoxidation method is the mainstream production method, encompassing multiple steps such as hydrogenation, oxidation, extraction, and purification. However, this manufacturing process has significant drawbacks. It not only requires the construction of complex infrastructure and consumes a large amount of energy but also causes severe environmental pollution. Furthermore, the use of precious metal catalysts and high-pressure hydrogen in the hydrogenation stage significantly increases the production cost of hydrogen peroxide and introduces numerous safety risks.
[0004] Therefore, it is of great significance to develop a catalyst for the efficient, low-cost, and environmentally friendly preparation of hydrogen peroxide. Summary of the Invention
[0005] To address the shortcomings of existing technologies, the present invention aims to provide a phenanthrenequinone-based conjugated organic polymer photocatalyst, its preparation method, and its applications. This phenanthrenequinone-based conjugated organic polymer is formed by the Schiff base condensation reaction of an aldehyde monomer containing a phenanthrenequinone group and an amine monomer to form imine bonds. By constructing electron-donating and electron-accepting building blocks, a push-pull electron effect is induced within the material, thereby improving photocatalytic efficiency. This photocatalyst can efficiently generate hydrogen peroxide from pure water and air without the need for sacrificial agents.
[0006] To achieve the above objectives, the following technical solution is provided:
[0007] This invention provides a phenanthrenequinone-based conjugated organic polymer photocatalyst for the photocatalytic generation of hydrogen peroxide, wherein the structural formula of the structural unit of the phenanthrenequinone-based conjugated organic polymer is as follows:
[0008]
[0009] Any one of them.
[0010] This invention also provides a method for preparing the above-described phenanthrenequinone-based conjugated organic polymer photocatalyst, the method comprising the following steps:
[0011] (1) 2,7-dibromophenanthrenequinone was added to a mixed solution of 1,4-dioxane and water, and p-formylphenylboronic acid, tetra(triphenylphosphine)palladium and anhydrous potassium carbonate were added. The mixture was stirred and reacted. Ethanol and water were added to quench the reaction. The mixture was then centrifuged and filtered. The precipitate was dried to obtain a red solid powder product A.
[0012] (2) The product A obtained in step (1) is mixed with ammonia monomer molecules and placed in a reactor. A mixed solution of acetic acid, n-butanol and o-dichlorobenzene is added. The mixture is frozen in liquid nitrogen, vacuumed, and then thawed. This freezing-vacuuming-thawing operation is repeated 3 to 5 times. After the reactor is cooled to room temperature, the reaction is heated. After the reaction is completed, the temperature is lowered to room temperature. The product in the reactor is filtered and washed to obtain the phenanthrenequinone conjugated organic polymer photocatalyst.
[0013] In one embodiment, the volume ratio of 1,4-dioxane to water in the mixed solution of step (1) is 6 to 8:1.
[0014] In one embodiment, the molar ratio of 2,7-dibromophenanthroquinone, p-formylphenylboronic acid, tetrakis(triphenylphosphine)palladium and anhydrous potassium carbonate in step (1) is 0.2-0.5:2:0.05:2.
[0015] In one embodiment, the temperature of the stirring reaction in step (1) is 80-90°C and the time is 24-36 hours.
[0016] In one embodiment, the centrifugation parameters in step (1) are: 1000-3000 rpm, time 5-10 min.
[0017] In one embodiment, the drying temperature in step (1) is 80-90°C.
[0018] In one embodiment, the amine monomer molecule in step (2) is 1,3,5-tris(4-aminophenyl)benzene or 1,3,6,8-tetra-(p-aminophenyl)pyrene.
[0019] In one embodiment, the molar ratio of product A to ammonia monomer molecules in step (2) is 3 to 4:2.
[0020] In one embodiment, the concentration of the acetic acid solution in step (2) is 3 to 6 mol / L.
[0021] In one embodiment, the volume ratio of acetic acid solution, n-butanol and o-dichlorobenzene in the mixed solution in step (2) is 0.2 to 0.5:1:1.
[0022] In one embodiment, the solid-liquid ratio in the reactor in step (2) is 0.02-0.06:2-5 g / mL.
[0023] In one embodiment, the heating reaction in step (2) is carried out at a temperature of 80–90°C for 24–36 hours.
[0024] This invention also provides the application of the above-described phenanthrenequinone-based conjugated organic polymer photocatalyst in the catalytic production of hydrogen peroxide.
[0025] The present invention also provides a method for photocatalytic production of hydrogen peroxide, the method comprising:
[0026] Water and phenanthrenequinone-based conjugated organic polymer photocatalyst are added to a Pyrex glass bottle, the opening is sealed with a rubber stopper, and the bottle is sonicated. Oxygen is then introduced into the water through a needle to maintain pressure balance inside the bottle. An oxygen balloon is used to ensure an oxygen atmosphere inside the glass bottle. Finally, the glass bottle is irradiated with a xenon lamp fitted with a 420nm filter to carry out the reaction.
[0027] In one embodiment, the ultrasonic treatment time is 20 to 30 minutes.
[0028] In one embodiment, the phenanthrenequinone-based conjugated organic polymer photocatalyst is added at a rate of 0.1–0.2 mg per milliliter of water.
[0029] The present invention also provides a method for improving the efficiency of photocatalytic hydrogen peroxide production, the method comprising:
[0030] Water and phenanthrenequinone-based conjugated organic polymer photocatalyst are added to a Pyrex glass bottle, the opening is sealed with a rubber stopper, and the bottle is sonicated. Oxygen is then introduced into the water through a needle to maintain pressure balance inside the bottle. An oxygen balloon is used to ensure an oxygen atmosphere inside the glass bottle. Finally, the glass bottle is irradiated with a xenon lamp fitted with a 420nm filter to carry out the reaction.
[0031] Beneficial effects:
[0032] (1) In this invention, the synthesized ligand product A and 1,3,6,8-tetra-(p-aminophenyl)-pyrene or 1,3,5-tris(4-aminophenyl)benzene were reacted in an aqueous system of n-butanol / o-dichlorobenzene / acetic acid to obtain two conjugated organic polymers containing phenanthrenequinone imine bonds via a solvothermal method. These polymers have a large specific surface area (typically 30-40 m²). 2 ·g -1 It can efficiently produce hydrogen peroxide (at a rate between 700-1600 μmol·g⁻¹) by oxygen reduction reaction under light in an oxygen atmosphere. -1 ·h-1 ).
[0033] (2) The phenanthrenequinone-imine-linked conjugated organic polymer provided by this invention, with its extended two-dimensional π-conjugated framework combining the electron-donating tetraphenylpyrene and the electron-withdrawing phenanthrenequinone, not only enhances visible light capture capability but also accelerates the separation and migration of photogenerated charges. Simultaneously, the phenanthrenequinone moiety, as the redox center, can accept photogenerated electrons from the conduction band and transfer them to the adsorbed O2 molecules to generate hydrogen peroxide, thereby improving photocatalytic activity. The well-defined structure of the conjugated organic polymer with the specific phenanthrenequinone redox center provides molecular-level insights into the mechanism of effective photocatalytic H2O2 production.
[0034] (3) The synthesis method of the present invention is simple and easy to implement, and the reagents and raw materials used are easy to obtain. It has high industrial application value and is easy to promote and apply. Attached Figure Description
[0035] Figure 1 The 1H NMR spectrum of the phenanthrenequinone-containing PQ monomer obtained in Example 1;
[0036] Figure 2 A comparison of the Fourier transform infrared spectra of the photocatalyst PQ-PTB-COP prepared in Example 1 and the monomers used in its synthesis;
[0037] Figure 3 A comparison of the Fourier transform infrared spectra of the photocatalyst PQ-TPB-COP material prepared in Example 2 and the monomers used in its synthesis;
[0038] Figure 4 N2 adsorption-desorption isotherm of the photocatalyst PQ-PTB-COP prepared in Example 1;
[0039] Figure 5 N2 adsorption-desorption isotherm of the photocatalyst PQ-TPB-COP prepared in Example 2;
[0040] Figure 6 The solid-state carbon NMR spectrum of the photocatalyst PQ-PTB-COP prepared in Example 1;
[0041] Figure 7 The solid-state carbon NMR spectrum of the photocatalyst PQ-TPB-COP prepared in Example 2;
[0042] Figure 8 The graph shows the relationship between the photocatalytic hydrogen peroxide production yield and time for PQ-PTB-COP and PQ-TPB-COP prepared in Examples 1 and 2, and QP-PTB-COP and QP-TPB-COP prepared in Comparative Examples 1 and 2, under an oxygen atmosphere. Detailed Implementation
[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. The specific embodiments described below further illustrate the present invention.
[0044] Example 1
[0045] The preparation of the photocatalyst PQ-PTB-COP includes the following steps:
[0046] (1) 0.183 g (0.5 mmol) of 2,7-dibromophenanthroline was added to a mixed solution of 6 mL of 1,4-dioxane and 1 mL of water, along with 0.3 g (2 mmol) of p-formylphenylboronic acid, 0.05 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium and 0.276 g (2 mmol) of anhydrous potassium carbonate. The mixture was stirred at 90 °C for 24 h, then 10 mL of ethanol and 10 mL of water were added to quench the reaction. The mixture was then centrifuged at 1000 rpm for 10 min, and the precipitate was dried at 90 °C to obtain a red solid powder product, PQ monomer. The reaction formula is as follows:
[0047]
[0048] (2) 0.033 g (0.08 mmol) of PQ monomer and 0.023 g (0.04 mmol) of 1,3,6,8-tetra-(p-aminophenyl)-pyrene were mixed and placed in a 10 ml glass tube. A mixed solution consisting of 0.2 ml of 6 mol / L acetic acid solution, 1 ml of n-butanol and 1 ml of o-dichlorobenzene was added. The mixture was frozen in liquid nitrogen, then vacuumed to remove air, and then thawed. This freezing-vacuuming-thawing operation was repeated 3 times. The glass tube was then sealed and placed in an oven at 90 °C for 48 h after cooling to room temperature. After cooling to room temperature, the product in the tube was filtered, washed and dried to obtain 0.048 g of PQ-PTB-COP. The reaction formula is as follows:
[0049]
[0050] Example 2
[0051] The preparation of the photocatalyst PQ-TPB-COP includes the following steps:
[0052] (1) 0.183 g (0.5 mmol) of 2,7-dibromophenanthroline was added to a mixed solution of 6 mL of 1,4-dioxane and 1 mL of water, along with 0.3 g (2 mmol) of p-formylphenylboronic acid, 0.05 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium and 0.276 g (2 mmol) of anhydrous potassium carbonate. After stirring at 90 °C for 24 h, 10 mL of ethanol and 10 mL of water were added for quenching. The mixture was then centrifuged at 1000 rpm for 10 min, and the precipitate was dried at 90 °C to obtain a red solid powder product, PQ monomer. The reaction formula is as follows:
[0053]
[0054] (2) 0.025 g (0.06 mmol) of PQ monomer and 0.014 g (0.04 mmol) of 1,3,5-tris(4-aminophenyl)benzene were mixed and placed in a 10 mL glass tube. A mixed solution consisting of 0.2 mL of 6 mol / L acetic acid solution, 1 mL of n-butanol and 1 mL of o-dichlorobenzene was added. The mixture was frozen in liquid nitrogen, then vacuumed to remove air, and then thawed. This freezing-vacuuming-thawing operation was repeated 3 times. The glass tube was then sealed and placed in an oven at 90 °C for 48 h after cooling to room temperature. After cooling to room temperature, the product in the tube was filtered, washed and dried to obtain 0.03 g of PQ-TPB-COP. The reaction formula is as follows:
[0055]
[0056] Comparative Example 1
[0057] (1) 4,4-Dibromobiphenyl (156 mg, 0.5 mmol, 1.0 eq.), 4-formylphenylboronic acid (300 mg, 2.0 mmol, 4 eq.), K2CO3 (276 mg, 2.0 mmol, 4 eq.) and Pd(PPh3)4 (50 mg, 0.05 mmol, 10 mol%) were added to a mixture of 6 mL 1,4-dioxane and 1.5 mL H2O. The mixture was heated under reflux at 90 °C for 24 h in a 25 mL Shrek tube. After cooling to room temperature, the precipitate was collected by filtration and washed with water and ethanol until the washings were clear. The product was then dried in a vacuum drying oven to obtain a gray powder QP monomer. The reaction formula is as follows:
[0058]
[0059] (2) QP monomer (29.0 mg, 0.08 mmol) and 1,3,6,8-tetra-(p-aminophenyl)-pyrene (22.6 mg, 0.04 mmol) were added to a 25 mL Shrek tube, followed by a mixed solution of 1.5 mL of o-dichlorobenzene and 1.5 mL of n-butanol. The mixture was ultrasonically dispersed for 15 min, then 0.2 mL of 6 mol / L acetic acid solution was added, and the mixture was ultrasonically dispersed for another 15 min. The Shrek tube was then frozen under liquid nitrogen and evacuated. After thawing, this step was repeated three times. After the glass tube returned to room temperature, it was placed in an oven and reacted at 90 °C for 48 h. After cooling to room temperature, the product in the tube was filtered, washed, and dried to obtain 0.04 g of QP-PTB-COP. The reaction formula is as follows:
[0060]
[0061] Comparative Example 2
[0062] (1) 4,4-Dibromobiphenyl (156 mg, 0.5 mmol, 1.0 eq.), 4-formylphenylboronic acid (300 mg, 2.0 mmol, 4 eq.), K₂CO₃ (276 mg, 2.0 mmol, 4 eq.), and Pd(PPh₃)₄ (50 mg, 0.05 mmol, 10 mol%) were added to a mixture of 6 mL of 1,4-dioxane and 1.5 mL of H₂O, and heated under reflux at 90 °C for 24 h in a 25 mL Shrek tube. After cooling to room temperature, the precipitate was collected by filtration and washed with water and ethanol until the washings were clear. The product was dried in a vacuum drying oven to obtain a gray powder QP monomer. The reaction formula is as follows:
[0063]
[0064] (2) QP monomer (21.7 mg, 0.06 mmol) and 1,3,5-tris(4-aminophenyl)benzene (14.0 mg, 0.04 mmol) were added to a 25 mL Shrek tube, followed by a mixed solution of 1.5 mL o-dichlorobenzene and 1.5 mL n-butanol. The mixture was ultrasonically dispersed for 15 min, then 0.2 mL 6 mol / L acetic acid solution was added, and the mixture was ultrasonically dispersed for another 15 min. The Shrek tube was then frozen under liquid nitrogen and evacuated. After thawing, this step was repeated three times. Once the glass tube had returned to room temperature, it was placed in an oven and reacted at 90 °C for 48 h. After cooling to room temperature, the product in the tube was filtered, washed, and dried to obtain 0.03 g QP-TPB-COP. The reaction formula is as follows:
[0065]
[0066] Performance Analysis
[0067] Figure 1The image shows the 1H NMR spectrum of the PQ monomer prepared in Example 1. The characteristic peaks of the monomer in the image confirm that the reaction proceeded smoothly and the corresponding structure was synthesized.
[0068] Figure 2 and Figure 3 The Fourier transform infrared spectra of the phenanthrenequinone-modified imine-linked conjugated organic polymers prepared in Examples 1 and 2, and the monomers used in the synthesis, are compared. The presence of characteristic peaks corresponding to the carbon-nitrogen double bonds in the products in the figures proves the formation of imine bonds.
[0069] Figure 4 and Figure 5 N2 adsorption-desorption isotherms of the phenanthrenequinone-modified imine-linked conjugated organic polymers PQ-PTB-COP and PQ-TPB-COP prepared in Examples 1 and 2.
[0070] Figure 6 and Figure 7 Solid-state carbon NMR spectra of the phenanthrenequinone-modified imine-linked conjugated organic polymers PQ-PTB-COP and PQ-TPB-COP prepared in Examples 1 and 2; the positions of the carbon peaks in the spectra confirm the correctness of the material structure.
[0071] Example 3
[0072] 10 mg of the photocatalysts PQ-PTB-COP, PQ-TPB-COP, QP-PTB-COP, and QP-TPB-COP prepared in Examples 1 and 2, and Comparative Examples 1 and 2, were added to Pyrex glass bottles, followed by 50 ml of deionized water. The openings were sealed with rubber stoppers and sonicated for 30 min. Oxygen was then introduced into the water through a needle while maintaining pressure balance inside the bottle for 30 min. An oxygen balloon was used to maintain an oxygen atmosphere inside the glass bottle. Next, the glass bottle was irradiated with a xenon lamp fitted with a 420 nm filter. Every hour, 0.5 ml of the sample was taken through a needle and filtered. The filtered liquid was mixed with 1.5 ml of potassium titanium oxalate solution, gently shaken under light-protected conditions, and left to stand for 30 min. The peak of the solution was measured using liquid ultraviolet light and compared with that of potassium titanium oxalate standard solution. The amount of hydrogen peroxide was calculated by the correlation between peak value and concentration and the reaction ratio in the chemical reaction equation.
[0073] The results are as follows Figure 8 As shown in the results, after 1 hour of reaction, the yield of hydrogen peroxide using the photocatalyst PQ-PTB-COP prepared in Example 1 was 1550 μmol·g. -1 ·h -1 The photocatalyst PQ-TPB-COP prepared in Example 2 yielded a hydrogen peroxide yield of 748 μmol·g. -1 ·h-1 The photocatalyst QP-PTB-COP prepared using Comparative Example 1 yielded a hydrogen peroxide yield of 224 μmol·g⁻¹. -1 ·h -1 The photocatalyst QP-TPB-COP prepared using Comparative Example 2 yielded a hydrogen peroxide yield of 86 μmol·g. -1 ·h -1 ;
[0074] When the reaction proceeded for 4 hours, the total yield of hydrogen peroxide using the photocatalyst PQ-PTB-COP prepared in Example 1 was 4100 μmol·g. -1 The total yield of hydrogen peroxide was 2800 μmol·g using the photocatalyst PQ-TPB-COP prepared in Example 2. -1 The photocatalyst QP-PTB-COP prepared using Comparative Example 1 achieved a total hydrogen peroxide yield of 718 μmol·g. -1 The photocatalyst QP-TPB-COP prepared using Comparative Example 2 achieved a total hydrogen peroxide yield of 316 μmol·g. -1 ;
[0075] The results show that the photocatalysts PQ-PTB-COP and PQ-TPB-COP have higher catalytic activity and can effectively improve the yield of hydrogen peroxide under the same reaction conditions.
[0076] The embodiments provided above are not intended to limit the scope of the invention, nor are the described steps intended to limit the order of execution. Any obvious modifications made to the invention by those skilled in the art based on existing common knowledge also fall within the scope of protection defined by the claims.
Claims
1. A phenanthrenequinone-based conjugated organic polymer photocatalyst for photocatalytic generation of hydrogen peroxide, characterized in that, The structural formula of the structural unit of the phenanthrenequinone-based conjugated organic polymer is as follows: Any one of them.
2. The method for preparing the phenanthrenequinone-based conjugated organic polymer photocatalyst according to claim 1, characterized in that, The preparation method includes the following steps: (1) 2,7-dibromophenanthrenequinone was added to a mixed solution of 1,4-dioxane and water, and p-formylphenylboronic acid, tetra(triphenylphosphine)palladium and anhydrous potassium carbonate were added. The mixture was stirred and reacted. Ethanol and water were added to quench the reaction. The mixture was then centrifuged and filtered. The precipitate was dried to obtain a red solid powder product A. (2) The product A obtained in step (1) is mixed with ammonia monomer molecules and placed in a reactor. A mixed solution of acetic acid, n-butanol and o-dichlorobenzene is added. The mixture is frozen in liquid nitrogen, vacuumed, and then thawed. This freezing-vacuuming-thawing operation is repeated 3 to 5 times. After the reactor is cooled to room temperature, the reaction is heated. After the reaction is completed, the temperature is lowered to room temperature. The product in the reactor is filtered and washed to obtain the phenanthrenequinone conjugated organic polymer photocatalyst.
3. The preparation method according to claim 2, characterized in that, In step (1), the volume ratio of 1,4-dioxane to water in the mixed solution is 6 to 8:
1.
4. The preparation method according to claim 2, characterized in that, The molar ratio of 2,7-dibromophenanthroline, p-formylphenylboronic acid, tetrakis(triphenylphosphine)palladium and anhydrous potassium carbonate in step (1) is 0.2-0.5:2:0.05:
2.
5. The preparation method according to claim 2, characterized in that, The ammonia monomer molecule mentioned in step (2) is 1,3,5-tris(4-aminophenyl)benzene or 1,3,6,8-tetra-(p-aminophenyl)pyrene.
6. The preparation method according to claim 2, characterized in that, The molar ratio of product A to ammonia monomers in step (2) is 3-4:
2.
7. The preparation method according to claim 2, characterized in that, In step (2), the volume ratio of acetic acid solution, n-butanol and o-dichlorobenzene in the mixed solution is 0.2-0.5:1:
1.
8. The application of the phenanthrenequinone-based conjugated organic polymer photocatalyst of claim 1 in the catalytic production of hydrogen peroxide.
9. A method for photocatalytic production of hydrogen peroxide, characterized in that, The method includes: Water and the phenanthrenequinone-based conjugated organic polymer photocatalyst of claim 1 were added to a Pyrex glass bottle. The opening was sealed with a rubber stopper and ultrasonically treated. Then, oxygen was introduced into the water through a needle to maintain the pressure balance inside the bottle. An oxygen balloon was used to ensure the oxygen atmosphere inside the glass bottle. Finally, the glass bottle was irradiated with a xenon lamp fitted with a 420nm filter to carry out the reaction.
10. A method for improving the efficiency of photocatalytic hydrogen peroxide production, characterized in that, The method includes: Water and the phenanthrenequinone-based conjugated organic polymer photocatalyst of claim 1 were added to a Pyrex glass bottle. The opening was sealed with a rubber stopper and ultrasonically treated. Then, oxygen was introduced into the water through a needle to maintain the pressure balance inside the bottle. An oxygen balloon was used to ensure the oxygen atmosphere inside the glass bottle. Finally, the glass bottle was irradiated with a xenon lamp fitted with a 420nm filter to carry out the reaction.