A method for photocatalytic production of hydrogen peroxide using bisinandanthrazoline compounds

Abstract

This invention discloses a method for photocatalytic production of hydrogen peroxide using bis-indenzoanthrazoline compounds. The bis-indenzoanthrazoline compound is used as the catalyst, which has a simple preparation method, good absorption in the visible light range, and good crystallinity and structural controllability. Under visible light irradiation, the bis-indenzoanthrazoline compound of this invention exhibits excellent photocatalytic hydrogen peroxide production capability without sacrificial agents or air. Compared with the anthraquinone method or electrocatalytic methods for hydrogen peroxide production in industrial production, this invention is safe, environmentally friendly, efficient, and low-cost. It only requires visible light, air, and water to synthesize hydrogen peroxide, avoiding the large energy consumption and severe pollution required by the anthraquinone method or electrocatalytic methods, thus providing a clean, economical, and safe method for hydrogen peroxide production.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen peroxide preparation technology, specifically relating to a method for photocatalytic production of hydrogen peroxide using bisindenanthrazoline compounds. Background Technology

[0002] Hydrogen peroxide (H2O2) is a high-value industrial chemical, commonly used as an oxidant, bleaching agent, and disinfectant, and widely applied in medical disinfection, pulp bleaching, wastewater treatment, chemical synthesis, military electronics, and other fields. In particular, H2O2 plays a crucial role in human health. Traditional methods for producing H2O2 include the anthraquinone oxidation method and the hydrogen-oxygen synthesis method. Over 95% of the H2O2 on the market is produced via the anthraquinone method. However, with the increasing market demand for hydrogen peroxide, the rapid development of synthesis processes, and the continuous expansion of production scale, this method has revealed drawbacks such as high production costs, complex and cumbersome operation processes, flammable raw materials, and severe pollution. The mixture of H2 and O2 in the hydrogen-oxygen synthesis method poses a potential explosion risk, requiring extremely strict requirements for production, transportation, and storage. Furthermore, its reaction selectivity is low, necessitating expensive catalysts. These drawbacks significantly hinder its widespread application in industrial production.

[0003] Solar energy boasts advantages such as enormous energy reserves, renewability, cleanliness, safety, and inexhaustibility. Photocatalytic production of hydrogen peroxide is an economical, safe, and sustainable method. This method uses water and oxygen from the air as raw materials, sunlight as the energy source, and semiconductors as photocatalysts. The reaction conditions are mild, and the operation is simple. Converting H2O and O2 into H2O2 using sunlight is a green and low-cost production method, making it a highly promising production method due to its environmental friendliness. However, current photocatalytic H2O2 production requires the addition of organic sacrificial agents as oxidizing hole acceptors, which not only reduces the theoretical quantum yield and increases economic and energy consumption but also makes it difficult to separate the product H2O2 from the organic sacrificial agent and its oxidation products. Summary of the Invention

[0004] The purpose of this invention is to provide a method for photocatalytic production of hydrogen peroxide using bisindoanthrazoline compounds under sacrificial agent-free conditions.

[0005] To achieve the above objectives, the technical solution provided by the present invention is as follows: dispersing a bisindoanthrazoline compound in deionized water, then continuously introducing air into the resulting dispersion while continuously stirring at room temperature, and reacting under visible light irradiation to prepare hydrogen peroxide.

[0006] The above-mentioned bisinandanthrazoline compounds are any one of the following formulas:

[0007]

[0008] In the formula, X1 and X2 each independently represent any one of carbonyl, sulfone, cyano, oxygen, and sulfur; R1, R2, R3, and R4 each independently represent any one of hydrogen, carboxyl, hydroxyl, cyano, and amino.

[0009] Furthermore, the amount of bisindoanthrazoline compounds added to the above-mentioned deionized water is 0.10–3.00 mg / mL.

[0010] Furthermore, the air flow rate is 50.00–150.00 mL / min. -1 .

[0011] Furthermore, the intensity of the aforementioned visible light is 50.00–500.0 mW / cm². -2 .

[0012] Furthermore, the reaction time under visible light irradiation is 1 to 8 hours.

[0013] Furthermore, the aforementioned visible light comes from a xenon lamp with an external 420nm cutoff filter.

[0014] The preparation method of the bisindrone anthrazoline compounds of the present invention is as follows: 2,5-dibenzoyl-1,4-p-phenylenediamine or 4,6-dibenzoyl-1,3-m-phenylenediamine is dispersed in toluene and stirred in an anaerobic environment until completely dissolved. Then, indanone compound I, indanone compound II, and diphenyl phosphate are added and stirred. The resulting solution is heated to 100-120°C and reacted for 5-24 hours. After the reaction is completed, it is cooled to room temperature, and a mixed solution of methanol and triethylamine is added. The solid is collected by filtration and recrystallized with ethanol. After drying, the bisindrone anthrazoline compounds are obtained. The reaction equation is shown below:

[0015]

[0016] The molar ratio of the above-mentioned 2,5-dibenzoyl-1,4-p-phenylenediamine or 4,6-dibenzoyl-1,3-m-phenylenediamine to indanone compound I, indanone compound II, and diphenyl phosphate is 1:1~3:1~3:8~15.

[0017] The volume ratio of methanol to triethylamine is 1:5 to 10.

[0018] The beneficial effects of this invention are as follows:

[0019] 1. The bisinandanthrazoline compounds used in this invention have good absorption, good crystallinity and structural controllability in the visible light range, and have excellent charge separation and transport efficiency, which improves the electron-hole transport rate, thereby promoting the generation of hydrogen peroxide and inhibiting its decomposition.

[0020] 2. The present invention provides a method for photocatalytic production of hydrogen peroxide using bisinandanthrazoline compounds as catalysts. This method does not use organic solvents as sacrificial agents (methanol, ethanol, isopropanol, benzyl alcohol, etc.), making it green, environmentally friendly, and pollution-free.

[0021] 3. This invention provides a sacrificial-free photocatalytic method for hydrogen peroxide production using bis(indenzoanthrazoline) compounds as catalysts. Operating at room temperature and pressure with air as the oxygen source and visible light as the energy source, this method offers advantages over industrial production methods such as the anthraquinone process or electrocatalytic hydrogen peroxide preparation. It features lower energy consumption, higher safety, simpler operation, and milder conditions. This method eliminates the difficulty in separating organic sacrificial agents and their oxidation products at the source. Therefore, the method described in this invention offers advantages such as high yield, high catalytic efficiency, and stability in hydrogen peroxide preparation, demonstrating promising application prospects. Attached Figure Description

[0022] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of photocatalyst A11.

[0023] Figure 2 This is the 1H NMR spectrum of photocatalyst B11.

[0024] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of photocatalyst A22.

[0025] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of photocatalyst B22.

[0026] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of photocatalyst A33.

[0027] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of photocatalyst B33.

[0028] Figure 7 These are the XRD patterns of photocatalysts A11, B11, A22, B22, A33, and B33.

[0029] Figure 8 It is Ce 4+ Absorbance-concentration standard curve at a wavelength of 316 nm.

[0030] Figure 9 The photocatalytic hydrogen peroxide production performance of photocatalysts A11, B11, A22, B22, A33, and B33 is discussed. Detailed Implementation

[0031] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the scope of protection of the present invention is not limited to these embodiments.

[0032] Example 1

[0033]

[0034] 4,6-Dibenzoyl-1,3-m-phenylenediamine (316.0 mg, 1.0 mmol) was dispersed in 10 mL of toluene and stirred in an anaerobic environment until completely dissolved. Then, 1,3-indanedione (440.0 mg, 3.0 mmol) and 3.0 g diphenyl phosphate (DPP) (3.0 g, 12.0 mmol) were added and stirred. The resulting solution was heated to 110 °C and reacted for 16 hours. After the reaction was completed, it was cooled to room temperature, and a mixture of 10 mL methanol and 70 mL triethylamine was added. The solid was collected by filtration and recrystallized from ethanol. After drying at 60 °C, photocatalyst A11 was obtained. The structural characterization data of the obtained photocatalyst A11 are shown below. Figure 1 and Figure 7 .

[0035] Example 2

[0036]

[0037] 2,5-Dibenzoyl-1,4-p-phenylenediamine (316.0 mg, 1.0 mmol) was dispersed in 10 mL of toluene and stirred in an anaerobic environment until completely dissolved. Then, 1,3-indanedione (440.0 mg, 3.0 mmol) and diphenyl phosphate (DPP) (3.0 g, 12.0 mmol) were added and stirred. The resulting solution was heated to 110 °C and reacted for 16 hours. After the reaction was completed, it was cooled to room temperature, and a mixture of 10 mL of methanol and 70 mL of triethylamine was added. The solid was collected by filtration and recrystallized from ethanol. After drying at 60 °C, photocatalyst B11 was obtained. The structural characterization data of the obtained photocatalyst B11 are shown below. Figure 2 and Figure 7 .

[0038] Example 3

[0039]

[0040] 4,6-Dibenzoyl-1,3-m-phenylenediamine (316.0 mg, 1.0 mmol) was dispersed in 10 mL of toluene and stirred in an anaerobic environment until completely dissolved. Then, 1,1-dioxobenzothiophene-3(2H)-one (546.0 mg, 3.0 mmol) and diphenyl phosphate (DPP) (3.0 g, 12.0 mmol) were added and stirred. The resulting solution was heated to 110 °C and reacted for 16 hours. After the reaction was completed, it was cooled to room temperature, and a mixture of 10 mL of methanol and 70 mL of triethylamine was added. The solid was collected by filtration and recrystallized from ethanol. After drying at 60 °C, photocatalyst A22 was obtained. The structural characterization data of the obtained photocatalyst A22 are shown below. Figure 3 and Figure 7 .

[0041] Example 4

[0042]

[0043] 2,5-Dibenzoyl-1,4-p-phenylenediamine (316.0 mg, 1.0 mmol) was dispersed in 10 mL of toluene and stirred in an anaerobic environment until completely dissolved. Then, 1,1-dioxobenzothiophene-3(2H)-one (546.0 mg, 3.0 mmol) and diphenyl phosphate (DPP) (3.0 g, 12.0 mmol) were added and stirred. The resulting solution was heated to 110 °C and reacted for 16 hours. After the reaction was completed, it was cooled to room temperature, and a mixture of 10 mL of methanol and 70 mL of triethylamine was added. The solid was collected by filtration and recrystallized from ethanol. After drying at 60 °C, photocatalyst B22 was obtained. The structural characterization data of the obtained photocatalyst B22 are shown below. Figure 4 and Figure 7 .

[0044] Example 5

[0045]

[0046] 4,6-Dibenzoyl-1,3-m-phenylenediamine (316.0 mg, 1.0 mmol) was dispersed in 10 mL of toluene and stirred in an anaerobic environment until completely dissolved. Then, benzofuran-3(2H)-one (402.0 mg, 3.0 mmol) and diphenyl phosphate (DPP) (3.0 g, 12.0 mmol) were added and stirred. The resulting solution was heated to 110 °C and reacted for 16 hours. After the reaction was completed, it was cooled to room temperature, and a mixture of 10 mL of methanol and 70 mL of triethylamine was added. The solid was collected by filtration and recrystallized from ethanol. After drying at 60 °C, photocatalyst A33 was obtained. The structural characterization data of the obtained photocatalyst A33 are shown below. Figure 5 and Figure 7 .

[0047] Example 6

[0048]

[0049] 2,5-Dibenzoyl-1,4-p-phenylenediamine (316.0 mg, 1.0 mmol) was dispersed in 10 mL of toluene and stirred in an anaerobic environment until completely dissolved. Then, benzofuran-3(2H)-one (402.0 mg, 3.0 mmol) and diphenyl phosphate (DPP) (3.0 g, 12.0 mmol) were added and stirred. The resulting solution was heated to 110 °C and reacted for 16 hours. After the reaction was completed, it was cooled to room temperature, and a mixture of 10 mL of methanol and 70 mL of triethylamine was added. The solid was collected by filtration and recrystallized from ethanol. After drying at 60 °C, photocatalyst B33 was obtained. The structural characterization data of the obtained photocatalyst B33 are shown below. Figure 6 and Figure 7 .

[0050] Example 7

[0051] The photocatalytic hydrogen peroxide production performance of photocatalysts A11, B11, A22, B22, A33, and B33 prepared in Examples 1-6 above was tested. The specific method was as follows: 20.0 mg of photocatalyst was weighed and placed in a beaker, 20.0 mL of deionized water was added, and the beaker was placed in an ultrasonic bath and sonicated for 10 minutes to ensure uniform mixing and dispersion of the reaction system. At room temperature, a flow rate of 100.00 mL / min was continuously introduced into the resulting dispersion. -1 The air was continuously stirred, and then the beaker was placed under a light intensity of 100.0 mW / cm². -2 Irradiate the solution under a xenon lamp with an external 420nm cutoff filter for 4 hours. Take 1.0 mL of the reaction solution every hour and filter it through a 0.45 μm filter membrane to remove the catalyst.

[0052] Hydrogen peroxide concentration testing method: Prepare aqueous solutions of 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, and 0.5 mM Ce(SO4)2, and determine the Ce concentration at different concentrations using a UV-Vis spectrophotometer. 4+ The absorbance of the solution at 316 nm was used to establish a standard curve (see...). Figure 8 The standard curve relationship was obtained as Y = 4.8510X + 0.0098, where Y represents absorbance and X represents Ce. 4+ Concentration, unit: mmol / L -1 R 2 =0.9992. Take 100 μL of the above filtrate and add 2.0 mL of 0.5 mM Ce(SO4)2 aqueous solution. Shake well and wait 10 min to allow the reaction solution to react completely with Ce(SO4)2. Place the reaction solution in a quartz cuvette and use a UV-Vis spectrophotometer to detect the corresponding absorbance at a wavelength of 316 nm. Calculate the Ce content of the reaction solution by comparing it with the standard curve relationship. 4+ The concentration was then used to calculate the hydrogen peroxide concentration in the reaction solution.

[0053] like Figure 9 As shown, this invention utilizes bis(indenzoanthrazoline) compounds as photocatalysts to catalyze the reaction of oxygen and water to produce hydrogen peroxide without the need for sacrificial agents, achieving a hydrogen peroxide production rate of 2183.61–12310.6 μMh. -1 .

Claims

1. A method for photocatalytic production of hydrogen peroxide using bis(indenzoanthrazoline) compounds, characterized in that, Diindone anthrazoline compounds were dispersed in deionized water, and then air was continuously bubbled into the resulting dispersion while stirring at room temperature. Hydrogen peroxide was prepared by reacting the mixture under visible light irradiation. The bisinanthrazoline compound is any one of the following compounds: In the above structural formula, X1 and X2 each independently represent any one of carbonyl, sulfone, cyano, oxygen, and sulfur; R1, R2, R3, and R4 each independently represent any one of hydrogen, carboxyl, hydroxyl, cyano, and amino.

2. The method for photocatalytic production of hydrogen peroxide using bis(indenzoanthrazoline) compounds according to claim 1, characterized in that, The amount of bisindoanthrazoline compounds added to the deionized water is 0.10–3.00 mg / mL.

3. The method for photocatalytic production of hydrogen peroxide using bis(indenzoanthrazoline) compounds according to claim 1 or 2, characterized in that, The preparation method of the bisinanthrazoline compounds is as follows: 2,5-dibenzoyl-1,4-p-phenylenediamine or 4,6-dibenzoyl-1,3-m-phenylenediamine is dispersed in toluene and stirred in an anaerobic environment until it is completely dissolved. Then, indanone compound I, indanone compound II, and diphenyl phosphate are added and stirred. The resulting solution is heated to 100-120°C and reacted for 5-24 hours. After the reaction is completed, it is cooled to room temperature, and a mixed solution of methanol and triethylamine is added. The solid is collected by filtration and recrystallized with ethanol. The solid is then dried to obtain the bisinanthrazoline compounds. In the above structural formula, X1 and X2 each independently represent any one of carbonyl, sulfone, cyano, oxygen, and sulfur; R1, R2, R3, and R4 each independently represent any one of hydrogen, carboxyl, hydroxyl, cyano, and amino.

4. The method for photocatalytic production of hydrogen peroxide using bis(indenzoanthrazoline) compounds according to claim 3, characterized in that, The molar ratio of 2,5-dibenzoyl-1,4-p-phenylenediamine or 4,6-dibenzoyl-1,3-m-phenylenediamine to indanone compound I, indanone compound II, and diphenyl phosphate is 1:1 to 3:1 to 3:8 to 15.

5. The method for photocatalytic production of hydrogen peroxide using bis(indenzoanthrazoline) compounds according to claim 3, characterized in that, The volume ratio of methanol to triethylamine is 1:5 to 10.

6. The method for photocatalytic production of hydrogen peroxide using bis(indenzoanthrazoline) compounds according to claim 1, characterized in that, The air flow rate is 50.00–150.00 mL / min. -1 .

7. The method for photocatalytic production of hydrogen peroxide using bis(indenzoanthrazoline) compounds according to claim 1, characterized in that, The intensity of the visible light is 50.00–500.0 mW / cm². -2 .

8. The method for photocatalytic production of hydrogen peroxide using bis(indenzoanthrazoline) compounds according to claim 7, characterized in that, The reaction time under visible light irradiation is 1 to 8 hours.

9. The method for photocatalytic production of hydrogen peroxide using bis(indenzoanthrazoline) compounds according to claim 7, characterized in that, The visible light comes from a xenon lamp with an external 420nm cutoff filter.

Images