Method for generating hydrogen peroxide by using perylene bisimide / indium zinc sulfide composite photocatalyst

Abstract

The invention provides the preparation method of the efficient photocatalyst which is simple and convenient, does not contain noble metals or toxic metals and does not need a cocatalyst. In the invention, a strategy for synergistically improving the catalytic performance of the zinc indium sulfide by introducing the perylene diimide polymer is provided. The preparation method comprises the following steps: firstly, obtaining Lysine-PDI in a manner of polymerizing perylene diimide and lysine, and successfully preparing N%-Lysine-PDI-ZIS by adding the Lysine-PDI in a synthesis process of a zinc indium sulfide (ZIS) solvothermal method. Pure water is used as a solution to carry out photocatalytic hydrogen peroxide generation reaction. When the compounding ratio is 3%, the catalytic activity reaches the highest, is 9.956 mmol.g.h (5 min), and is 5.8 times of that of an original ZIS catalyst. The prepared catalyst is high in activity and good in stability, and a new way is provided for developing efficient and stable photocatalytic hydrogen peroxide production materials.

Description

Technical Field

[0001] This invention belongs to the field of energy materials, specifically relating to a simple method for preparing a highly efficient and non-toxic photocatalyst based on visible light. Background Technology

[0002] Since the Industrial Revolution, the consumption of fossil fuels has been increasing daily, accounting for the majority of global energy consumption. However, the problem with fossil fuels is that they are the result of millions of years of biomass accumulation and transformation, with an excessively long generation cycle and a regeneration rate far slower than the rate of human consumption, making them non-renewable energy sources. In addition to energy shortages, the use of fossil fuels also causes serious pollution problems, with greenhouse gases and various pollutants being generated during the process. Therefore, it is imperative to take measures to find renewable energy sources that can replace fossil fuels.

[0003] Among numerous renewable energy sources, solar energy receives the most attention due to its green and pollution-free advantages. It is also the source of the vast majority of global energy, and direct utilization of solar energy can reduce losses in various processes. Among all methods of utilizing solar energy, photocatalytic production of hydrogen peroxide is a particularly noteworthy approach because hydrogen peroxide also possesses the advantages of being green, pollution-free, and sustainable, while also exhibiting high redox activity.

[0004] Perylene diimide (PDI), a derivative of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), is a unique n-type organic semiconductor exhibiting broad visible light absorption and photochemical stability. PDI materials have historically been used as light-harvesting sensitizers in photocatalysis and solar cell devices. Due to its high positive valence band potential, photogenerated holes in PDI can act as strong oxidants in organic conversion reactions. Therefore, combining PDI molecules with ZnIn₂S₄ represents a highly promising method for modifying photocatalysts.

[0005] Among all photocatalysts, sulfides have the advantages of smaller band gaps and higher energy utilization efficiency, with CdS and Zn being the most prominent. x Cd 1-x S is the representative. However, due to Cd 2+ It is one of the main culprits behind the ten major public health disasters, and its development and utilization are greatly restricted. Therefore, Cd... 2+ Change to In 3+ The resulting ZnIn2S4 has been extensively studied. It is low in cost, exhibits good photocatalytic efficiency, and also possesses excellent processability. However, pure zinc indium sulfide exhibits drawbacks such as a wide band gap and low charge energy utilization. Therefore, we modified it by introducing PDI polymer to address its short photoresponse range, low charge separation efficiency, and poor energy utilization efficiency.

[0006] In view of the deficiencies of the prior art and the research and application needs in the field, the project aims to provide a simple, non-noble metal, non-toxic metal and non-assisted catalyst efficient photocatalyst preparation method.

[0007] The technical solution for achieving the purpose of the application is: first, Lysine-PDI polymer is obtained by polymerization of PDI and lysine, then a one-step solvothermal method is used to realize the compounding of Lysine-PDI and ZIS in the catalyst by adjusting the ratio of Lysine-PDI and ZIS in the reaction precursor. Then, the composite catalyst is used to realize the photocatalytic production of hydrogen peroxide under the condition of pure water and visible light irradiation.

[0008] To achieve the above purpose, the application provides the following scheme: 1 mmol of perylene diimide, 1 mmol of lysine, 0.5 mmol of zinc acetate dihydrate, and 25 g of imidazole are placed in a 50 ml Schlenk tube, three suction three-way connections are ensured after nitrogen filling, and then heated to 150 DEG C to melt the imidazole, stirred and stored for 24 h. After the reaction is completed, water, dichloromethane, and tetrahydrofuran are used for Soxhlet extraction to purify the polymer, and Lysine-PDI is obtained.

[0009] Zinc acetate dihydrate, indium trichloride tetrahydrate and thioacetamide are dissolved in a 40 ml solution of water: ethanol = 1:1 in a ratio of 1:2:4, denoted as solution A. After ultrasonic treatment for 10 min, stir for 4 h. Introduce it into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and heat the oven to 180 DEG C for 24 h. Then remove the supernatant, wash with deionized water and ethanol alternately, and dry at 60 DEG C overnight, and grind into powder. Finally, the zinc indium sulfide catalyst (ZIS) is obtained.

[0010] Further change the solute ratio in the original reaction solution to achieve modification. Configure B solution of water: ethanol = 1:1 with Lysine-PDI suspended in it, and add it to solution A according to the compounding ratio, and extend the stirring time to 24 h. The rest of the steps are the same and finally N%-Lysine-PDI-ZIS (N is the compounding ratio of PDI monomer to ZIS) composite photocatalyst is obtained.

[0011] The application also provides an application mode of the above-mentioned photocatalyst, which catalyzes the generation of hydrogen peroxide under visible light irradiation.

[0012] The specific steps are as follows: ① take pure water as the solvent; ② add the catalyst to the aqueous solution in ① and form a uniform suspension by ultrasonic treatment; ③ transfer the reaction solution to a quartz reactor and assemble it completely sealed, pass oxygen for 30 min to completely fill oxygen, and then seal with a balloon. ④ select a 300 W xenon lamp as the visible light source, the irradiation area is about 38.48 cm 2, the reactor keeps the reaction temperature at room temperature by circulating water. ⑤ During the reaction, the sampling is carried out by using a syringe, and the sampling liquid is filtered by using a 0.22 μm filter head, and an equal volume of 0.4M KI solution and 0.1M potassium hydrogen phthalate solution are added as a chromogenic solution, and then the content of elemental iodine is detected by absorption spectroscopy to detect the production of hydrogen peroxide. ⑥ After the reaction, the solution is centrifuged, and the supernatant is taken, and the catalyst is recovered.

[0013] Preferably, in step ①, the total volume of the mixed aqueous solution is 100 mL.

[0014] Preferably, in step ②, the amount of catalyst added is 10 mg.

[0015] Preferably, in step ②, the catalyst added is ZIS, 3%-Lysine-PDI-ZIS, respectively.

[0016] Preferably, in step ④, the visible light refers to light with a wavelength ≥420 nm.

[0017] Preferably, in step ⑤, the sampling time is 5 min, 10 min, 15 min, 20 min, 30 min, and 60 min, respectively.

[0018] The present application has the beneficial effects that the performance of the indium zinc sulfide-based photocatalyst is improved by a simple and feasible hydrothermal method, and a high-efficiency photocatalyst is obtained by using a method with few synthesis steps and low cost. Since no noble metal and toxic metal are used as components, the photocatalyst material is relatively economical and environmentally friendly, and has great significance for the popularization and use of the catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0019] The present application will be further described below in combination with the drawings and examples; Figure 1 is the time-dependent curve of the production of hydrogen peroxide by photocatalysis of 3%-Lysine-PDI-ZIS under three atmospheres in Examples 1-3; Figure 2 is the time-dependent curve of the production of hydrogen peroxide by photocatalysis of ZIS under three atmospheres used in Examples 4-6; Figure 3 is the photocatalysis 6-time cycle stability test carried out in Example 1; Figure 4 is the bar chart of the production of hydrogen peroxide by photocatalysis in Examples 7-9; Figure 5 is the time-dependent curve of the production of hydrogen by photocatalysis in Example 9; DETAILED DESCRIPTION

[0020] Example 1: ①Take 100 ml of pure water as solvent; ②Add 10 mg of 3%-Lysine-PDI-ZIS to the aqueous solution in ①, and form a uniform suspension by ultrasonic; ③Transfer the reaction solution to a quartz reactor and completely seal it, and pass oxygen for 30 min to completely oxygenate, and then seal it with a balloon. ④Select a 300 W xenon lamp (>420 nm) as the visible light source, and the irradiation area is about 38.48 cm 2 , and the reactor is kept at room temperature by circulating water. ⑤During the reaction, use a syringe to take samples, filter them with a 0.22 μm filter, and add an equal volume of 0.4 M KI solution and 0.1 M potassium hydrogen phthalate solution to the sample solution as a chromogenic solution, and then detect the iodine content by absorption spectroscopy to obtain a hydrogen peroxide production rate of 9.956 mmol·g⁻¹·h⁻¹ (5 min). ⑥After the reaction, centrifuge the solution and take the supernatant, and recover the catalyst.

[0021] Example 2: The steps ①, ②, ④, ⑤ of this example are the same as those of Example 1, except that in step ③, the oxygen is changed to air when adjusting the reaction atmosphere. Analysis by absorption spectrometer shows that the hydrogen peroxide production rate is 2.99 mmol·g -1 ·h -1 .

[0022] Example 3: The steps ①, ②, ④, ⑤ of this example are the same as those of Example 1, except that in step ③, the oxygen is changed to nitrogen when adjusting the reaction atmosphere. Analysis by absorption spectrometer shows that the hydrogen peroxide production rate is 0.11 mmol·g -1 ·h -1 .

[0023] Example 4: The steps ①, ③, ④, ⑤ of this example are the same as those of Example 1, except that in step ②, the catalyst type is changed from 3%-Lysine-PDI-ZIS to ZIS when preparing the catalyst suspension, and a uniform suspension is formed by ultrasonic. Analysis by absorption spectrometer shows that the hydrogen peroxide production rate is 27.43 mmol·g -1 ·h -1 .

[0024] Example 5: The steps ①, ②, ④, ⑤ of this example are the same as those of Example 4, except that in step ③, the oxygen is changed to air when adjusting the reaction atmosphere. Analysis by absorption spectrometer shows that the hydrogen peroxide production rate is 1.1 mmol·g -1 ·h -1 .

[0025] Example 6: The steps 1, 2, 4, 5 of this example are the same as those of Example 4, except that the oxygen in step 3 is changed to nitrogen. Analysis by the absorption spectrometer shows that the hydrogen peroxide production rate is 0.09 mmol·g -1 ·h -1 .

[0026] Example 7: The steps 2, 3, 4, 5 of this example are the same as those of Example 1, except that 200 mg of 1, 4-benzoquinone is further added in step 1. Analysis by the absorption spectrometer shows that the hydrogen peroxide production rate is 0.64 mmol·g -1 ·h -1 .

[0027] Example 8: The steps 2, 3, 4, 5 of this example are the same as those of Example 1, except that 200 mg of FeCl3·6H2O is further added in step 1. Analysis by the absorption spectrometer shows that the hydrogen peroxide production rate is 0.59 mmol·g -1 ·h -1 .

[0028] Example 9: The steps 2, 3, 4, 5 of this example are the same as those of Example 1, except that 1 ml of benzyl alcohol is further added in step 1. Analysis by the absorption spectrometer shows that the hydrogen peroxide production rate is 27.3 mmol·g-1·h-1.

[0029] The above examples show that the method provided in the present application can achieve efficient hydrogen production under visible light by using a photocatalyst. The process does not use high temperature and does not introduce noble metal co-catalysts, and does not contain harmful metal ions, which meets the requirements of green chemistry.

[0030] The above examples 1-9 are only representative examples of the present application, and do not limit the present application in any form. Any person skilled in the art can easily implement the present application according to the drawings and the above description. However, any equivalent changes, modifications and evolution of the above examples made by those skilled in the art without departing from the scope of the technical solutions of the present application are also equivalent embodiments of the present application. Meanwhile, any equivalent changes, modifications and evolution of the above examples made by those skilled in the art according to the implementation technology of the present application are also within the protection scope of the technical solutions of the present application.

Claims

1. A method for the preparation of a simple and efficient photocatalyst for the production of hydrogen peroxide based on indium zinc sulfide, characterized by: The hydrogen peroxide is generated by photocatalytic reaction under the action of zinc indium sulfide catalyst with Lysine-PDI in pure water, and has the following steps: The zinc indium sulfide catalyst is added into pure water to form a suspension under ultrasonic; The reaction solution is transferred into a quartz reactor and completely sealed, and oxygen is passed for 30 min to completely oxygenate, and then sealed with a balloon; A 300 W xenon lamp was selected as the visible light source, and the irradiation area was about 38.48 cm 2 The reactor maintained the reaction temperature at room temperature by circulating water During the reaction, the sample is taken by a syringe, filtered by a 0.22 μm filter head, and an equal volume of 0.4 M KI solution and 0.1 M potassium hydrogen phthalate solution are added into the sample solution as a chromogenic solution, and then the iodine content is detected by absorption spectrum to determine the hydrogen peroxide yield.

2. The solution after reaction is taken, and the catalyst is recovered after centrifugation.

3. The method for preparing a simple and efficient hydrogen-producing photocatalyst based on indium zinc sulfide according to claim 1, characterized by: The total volume of the aqueous solution in step ① is 100 mL.

4. The method for preparing a simple and efficient hydrogen-producing photocatalyst based on indium zinc sulfide according to claim 1, characterized by: The catalyst in step ① is ZIS, 3%-Lysine-PDI-ZIS respectively.

5. The method for preparing a simple and efficient hydrogen-evolving photocatalyst based on indium zinc sulfide according to claim 1, characterized by: The catalyst dosage in step ① is 10 mg.

6. The method for preparing a simple and efficient hydrogen-evolving photocatalyst based on indium zinc sulfide according to claim 1, characterized by: The visible light in step ③ refers to light with a wavelength of ≥420 nm.

7. The method for preparing a simple and efficient hydrogen-evolving photocatalyst based on indium zinc sulfide according to claim 1, characterized by: The detection wavelength of the absorption spectrum in step ④ is 325 nm-500 nm.

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