3,4,9,10-perylenetetracarboxylic diimide / cupric iodide composite material, preparation method and application in photocatalytic water splitting to produce hydrogen and oxygen

Abstract

The application relates to a preparation method of a 3,4,9,10-perylenetetracarboxylic diimide / cuprous iodide composite material: 3,4,9,10-perylenetetracarboxylic diimide is ultrasonically dispersed in N,N-dimethylformamide, cuprous iodide (CuI) solid is dissolved in acetonitrile, the above solutions are mixed, the mixed solution is refluxed and stirred at 80-140 DEG C for 12-36 h, is cooled to room temperature, and is subjected to centrifugal separation, washing and vacuum drying, and the composite material is obtained. The composite material exhibits a wide light response range, realizes efficient water decomposition to produce hydrogen and oxygen under visible light driving, through gas chromatography determination, the hydrogen and oxygen production rates can be kept at 203.2 and 34.8 mu mol / g / h after 12 hours of illumination, and the production rate of an optimized sample decreases by less than 12% in a 7-time cycle experiment.

Description

Technical Field

[0001] This invention belongs to the field of composite material preparation and photocatalytic water splitting technology, specifically relating to a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material, its preparation method, and its application in photocatalytic water splitting to produce hydrogen and oxygen. Background Technology

[0002] With the rapid development of society and industry, environmental pollution and the depletion of fossil fuels have become major challenges threatening human survival and development. Photocatalysis technology, due to its high efficiency, low cost, and environmental friendliness, has gradually attracted widespread attention.

[0003] Furthermore, hydrogen energy is a secondary clean energy source, hailed as the "ultimate energy of the 21st century." At the same time, hydrogen is also an important chemical raw material, but its current conversion cost is relatively high. Photocatalytic decomposition to produce hydrogen and oxygen can significantly promote carbon neutrality, making it one of the ideal alternatives to industrial electrolysis of water in the future.

[0004] The key to photocatalysis technology lies in the development of efficient and stable photocatalysts. While existing commercially available photocatalytic materials like P25(TiO2) exhibit good photocatalytic performance, their light response range is too narrow, especially when dealing with stable water molecules, resulting in low solar energy utilization. Therefore, further research and development of catalysts for photocatalytic water splitting is still necessary. Based on this, this application was developed. Summary of the Invention

[0005] The purpose of this invention is to overcome the defects of the prior art and provide a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material. This composite material can significantly improve the utilization rate of solar energy, has high photocatalytic water splitting activity and stable structure, and has broad application prospects in the energy field.

[0006] The present invention also provides a method for preparing the above-mentioned 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material and its application in photocatalytic water splitting to produce hydrogen and oxygen.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material involves mixing a 3,4,9,10-perylenetetracarboxydiimide dispersion and a cuprous iodide dispersion, refluxing the mixture for 12 to 36 hours, cooling it to room temperature after the reaction, and then centrifuging, washing, and drying the mixture to obtain the final product.

[0008] Specifically, the mass ratio of 3,4,9,10-perylenetetracarboxydiimide to cuprous iodide can be 1:0.3 to 15, such as 1:0.3, 1:2, 1:3, 1:5, 1:15, etc.

[0009] Furthermore, the preparation method of the above-mentioned 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material includes the following steps: 1) 3,4,9,10-peryleneimide was uniformly dispersed in N,N-dimethylformamide to obtain a 3,4,9,10-peryleneimide dispersion; 2) Disperse cuprous iodide powder uniformly in acetonitrile to obtain a cuprous iodide dispersion; 3) Mix the 3,4,9,10-perylenetetracarboxydiimide dispersion obtained in step 1) and the cuprous iodide dispersion obtained in step 2), then heat to 80~140℃ for reflux reaction. After the reaction is completed, cool to room temperature, centrifuge, wash and dry to obtain the final product.

[0010] Specifically, in step 1), 0.1 to 1.0 g of 3,4,9,10-peryleneimide can be uniformly dispersed in 10 to 100 mL of N,N-dimethylformamide.

[0011] Specifically, in step 2), 0.3~1.5 g of cuprous iodide powder can be uniformly dispersed in 10~50 mL of acetonitrile.

[0012] This invention provides a preferred method for preparing the above-mentioned 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material, which includes the following steps: 1) Add 0.1-1.0 g of 3,4,9,10-perylenetetracarboxydiimide to 10-100 mL of N,N-dimethylformamide (DMF), stir for 15-45 minutes, and then sonicate at room temperature for 60-90 minutes to obtain a 3,4,9,10-perylenetetracarboxydiimide dispersion; 2) Add 0.3-1.5 g of cuprous iodide (CuI) powder to 10-50 mL of acetonitrile, sonicate at room temperature for 15-45 minutes, and then stir for 30-120 minutes to obtain a cuprous iodide dispersion; 3) Mix the 3,4,9,10-perylenetetracarboxydiimide dispersion obtained in step 1) and the cuprous iodide dispersion obtained in step 2) by sonication at room temperature for 15-45 minutes, then heat to 80-140℃ and reflux with stirring for 12-36 hours. After the reaction is completed, cool to room temperature, centrifuge, wash, and vacuum dry to obtain the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material.

[0013] The present invention provides a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material prepared by the above preparation method.

[0014] This invention provides the application of the above-mentioned 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material in photocatalytic water splitting to produce hydrogen and oxygen.

[0015] Furthermore, in the above application, the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material can be dispersed in deionized water, and a 300 W Xe arc lamp can be used as the light source for photocatalytic water splitting to produce hydrogen and oxygen.

[0016] In this invention, 3,4,9,10-perylenetetracarboxydiimide is a semiconductor material that can effectively absorb solar energy in the visible light region. Its band structure can effectively achieve photocatalytic water splitting for oxygen production, making it an ideal photocatalyst. However, the thermodynamic contradiction between optical absorption and redox potential severely limits the overall water splitting performance of a single 3,4,9,10-perylenetetracarboxydiimide catalyst. Cuprous iodide (CuI), as an inexpensive and readily available visible light-driven material, possesses excellent electron transfer capabilities, especially after micro-nanoization, which significantly enhances its catalytic performance. Furthermore, by controlling the composition of the composite material in the face of structurally stable water molecules, it helps improve carrier separation, effectively enhancing the photocatalytic hydrogen and oxygen production activities of the material. This invention designs a one-step heterogeneous reaction synthesis method for preparing 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite materials. This composite material significantly improves solar energy utilization, exhibits high photocatalytic water splitting activity, and demonstrates structural stability, showing broad application prospects in energy, chemical, and other fields.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: 1) This invention employs a heterogeneous reaction method to prepare and construct 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite materials. This method fully utilizes the directional reaction between interfaces, forming an interaction force between the 3,4,9,10-perylenetetracarboxydiimide surface and CuI nanoclusters, thus forming an effective 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide heterojunction, thereby achieving rapid and efficient transfer and separation of charge carriers; 2) The 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material of the present invention exhibits a wide light response range, realizing efficient hydrogen and oxygen production by full water splitting under visible light. According to gas chromatography, after 12 hours of light irradiation, the hydrogen and oxygen yields can be maintained at 203.2 μmol / g / h and 34.8 μmol / g / h, respectively. After 7 cycles of optimized sample, the yield decrease is less than 12%. Attached Figure Description

[0018] Figure 1 The XRD patterns are of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material samples prepared in Examples 1-3(a), 4-6(b), and 7-8(c) of the present invention. Figure 2XPS images of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite materials prepared in Examples 1 and 3 of this invention are shown (in the figures, a is the high-resolution energy spectrum of Cu in Examples 1 and 3; b is the high-resolution energy spectrum of I in Examples 1 and 3). Figure 3 The images show the photocatalytic activity of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material samples prepared in Examples 1-8; in the images, A refers to P25, B refers to 3,4,9,10-perylenetetracarboxydiimide, C refers to CuI, and DK refers to Examples 1-8 respectively. Figure 4 The image shows the cyclic catalytic activity of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material sample prepared in Example 8. Detailed Implementation

[0019] The technical solution of the present invention will be further described in detail below with reference to the embodiments, but the scope of protection of the present invention is not limited thereto.

[0020] Unless otherwise specified, all raw materials used in the following examples are commercially available products that can be directly purchased or prepared using conventional methods in the art. For example, the 3,4,9,10-perylenetetracarboxydiimide powder and CuI powder used were purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0021] Room temperature refers to 25±5℃.

[0022] Example 1 A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material, specifically comprising the following steps: 1) Add 1.0 g of 3,4,9,10-perylenetetracarboxydiimide powder to 100 mL of DMF, stir for 30 minutes, and then sonicate at room temperature for 90 minutes to obtain a 3,4,9,10-perylenetetracarboxydiimide dispersion; 2) Add 0.3 g CuI powder to 10 mL acetonitrile, sonicate at room temperature for 30 minutes, and then stir for 30 minutes to obtain an acetonitrile dispersion of CuI. 3) The 3,4,9,10-perylenetetracarboxydiimide dispersion obtained in step 1) and the CuI acetonitrile dispersion obtained in step 2) were mixed and sonicated at room temperature for 30 minutes. The mixture was then heated to 80 °C and refluxed with stirring for 12 h. After the reaction was completed, the mixture was naturally cooled to room temperature and centrifuged at 8000 rpm to obtain a purple-red powder. The powder was washed and centrifuged 5 times each with distilled water and anhydrous ethanol. The powder was then placed in a vacuum oven and dried at 50 °C under a vacuum of 0.8 MPa to obtain the 3,4,9,10-perylenetetracarboxydiimide / CuI composite material.

[0023] Example 2 A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material differs from Example 1 in that step 3) is replaced by a reflow heating temperature of 120 ℃ instead of the reflow heating temperature of 80 ℃ in Example 1, while the other steps are the same as in Example 1.

[0024] Example 3 A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material differs from Example 1 in that step 3) is replaced by a reflow heating temperature of 140 ℃ instead of the reflow heating temperature of 80 ℃ in Example 1, while the other steps are the same as in Example 1.

[0025] Example 4 A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material, specifically comprising the following steps: 1) Add 0.1 g of 3,4,9,10-perylenetetracarboxydiimide powder to 10 mL of DMF, stir for 30 minutes, and then sonicate at room temperature for 90 minutes to obtain a 3,4,9,10-perylenetetracarboxydiimide dispersion; 2) Add 1.5 g of CuI powder to 50 mL of acetonitrile, sonicate at room temperature for 30 minutes, and then stir for 30 minutes to obtain an acetonitrile dispersion of CuI. 3) The 3,4,9,10-perylenetetracarboxydiimide dispersion obtained in step 1) and the CuI acetonitrile dispersion obtained in step 2) were mixed and sonicated at room temperature for 30 minutes. The mixture was then heated to 120 °C and stirred for 18 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and centrifuged at 8000 rpm to obtain a purple-red powder. The powder was washed with distilled water and anhydrous ethanol five times each and centrifuged five times. The powder was then placed in a vacuum oven and dried at 50 °C under a vacuum of 0.8 MPa to obtain the 3,4,9,10-perylenetetracarboxydiimide / CuI composite material.

[0026] Example 5 A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material differs from Example 4 in that step 3) is replaced by a reflux time of 24 hours in Example 4, while the other steps are the same as in Example 4.

[0027] Example 6 A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material differs from Example 4 in that step 3) is replaced by a reflux time of 36 hours in Example 4 with a reflux time of 18 hours, while the other steps are the same as in Example 4.

[0028] Example 7 A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material, specifically comprising the following steps: 1) Add 0.5 g of 3,4,9,10-perylenetetracarboxydiimide powder to 50 mL of DMF, stir for 30 minutes, and then sonicate at room temperature for 90 minutes to obtain a 3,4,9,10-perylenetetracarboxydiimide dispersion; 2) Add 1.5 g of CuI powder to 50 mL of acetonitrile, sonicate at room temperature for 30 minutes, and then stir for 30 minutes to obtain an acetonitrile dispersion of CuI. 3) The 3,4,9,10-perylenetetracarboxydiimide dispersion obtained in step 1) and the CuI acetonitrile dispersion obtained in step 2) were mixed and sonicated at room temperature for 30 minutes. The mixture was then heated to 105 °C and refluxed with stirring for 20 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature and centrifuged at 8000 rpm to obtain a purple-red powder. The powder was washed and centrifuged 5 times each with distilled water and anhydrous ethanol. The powder was then placed in a vacuum oven and dried at 50 °C under a vacuum of 0.8 MPa to obtain the 3,4,9,10-perylenetetracarboxydiimide / CuI composite material.

[0029] Example 8 A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material differs from Example 7 in that step 2) is replaced by adding 1.0 g CuI powder to 25 mL acetonitrile instead of adding 1.5 g CuI powder to 50 mL acetonitrile in step 2) of Example 7, and the other steps are the same as in Example 7.

[0030] Characterization of the composite materials prepared in Examples 1-8 Figure 1 XRD patterns of the 3,4,9,10-perylenetetracarboxylic diimide / cuprous iodide composite materials prepared in Examples 1-8 are presented. Figure 1 It can be seen that the characteristic peaks of the 3,4,9,10-perylenetetracarboxylic diimide / cuprous iodide composite material sample are composed of diffraction peaks from tetragonal CuI and PDI (3,4,9,10-perylenetetracarboxylic diimide) standards. In Examples 1-3, due to the lower amount of CuI, the characteristic peaks of CuI are weaker. Compared to Examples 1, 8, and 4, with the increase of the CuI / 3,4,9,10-perylenetetracarboxylic diimide feeding ratio, the CuI / PDI characteristic peak (located at 25.5) increases. o The diffraction peaks and those located at 27.1 oThe peak intensity ratio of the diffraction peaks increased from 0.46 to 1.02, showing a gradual increase. Compared to Examples 4, 5, and 6, the peak intensity of the CuI characteristic peaks gradually increased with the increase of heating and reflow time. This indicates that increasing the CuI feed amount and increasing the reflow time are beneficial to CuI deposition in the composite material. In addition, compared with Examples 1, 4, 7, and 8, the peak intensity ratio of the 3,4,9,10-perylenetetracarboxylic diimide component in the composite material showed significant differences, indicating that the CuI / 3,4,9,10-perylenetetracarboxylic diimide feed ratio has a certain influence on its self-growth direction.

[0031] Figure 2 XPS spectra of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composites prepared in samples 1 and 3 are presented. Figure 2 As can be seen, the characteristic peaks of Cu(I) can be clearly found in the high-resolution energy dispersive spectroscopy (HEDS) of Cu in Examples 1 and 3; similarly, the characteristic peaks of I(I) also appear in the HEDS of I in Examples 1 and 3. Under the reaction conditions of low CuI feed concentration, high reflux temperature, and short reflux time, the presence of CuI in the composite sample can be confirmed. Therefore, combined with XRD analysis, the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite samples in Examples 1-8 are composed of 3,4,9,10-perylenetetracarboxydiimide and cuprous iodide.

[0032] Photocatalysis test: The specific operation for evaluating photocatalytic performance is as follows: 0.1 g of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material (m0) prepared in Examples 1 to 8 was dispersed in 100 mL of deionized water. After sonication for 30 minutes, the turbid solution was transferred into the CEL-PAEM-D8 photocatalytic activity evaluation system (Beijing Zhongjiao Jinyuan Technology Co., Ltd.). A 300 W Xe arc lamp (CEL-HXF300 Beijing Zhongjiao Jinyuan Co., Ltd.) was used as the light source, and the irradiation light was filtered through an ultraviolet filter (λ>400 nm) to obtain visible irradiation light. After irradiation for a certain period of time (t, hours), the concentrations of hydrogen and oxygen, c, were calculated using the external standard method based on the characteristic peak areas of hydrogen and oxygen in gas chromatography. H2 and c O2 Its product yield is y = c / m0, and its rate is v = c / m o / t.

[0033] Cyclic experiment: After the above test, the solution containing the catalyst was centrifuged at 10,000 rpm for 5 min. The solid catalyst was taken, washed with water 3 times, and without replacing the catalyst, it was added back into distilled water. The catalytic activity of the sample was evaluated according to the above method.

[0034] The photocatalytic activity of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite materials prepared in Examples 1-8 of this invention is as follows: Figure 3 As shown, after 12 hours of visible light irradiation, P25, 3,4,9,10-perylenetetracarboxydiimide (PDI), and CuI exhibited relatively weak photocatalytic water splitting performance. In Examples 1-8, the photocatalytic hydrogen and oxygen production activities of PDI / CuI in water splitting were significantly improved. Among the listed samples, a suitable CuI loading can efficiently enhance catalytic performance. Example 8 exhibited the best photocatalytic hydrogen and oxygen production performance in water splitting; after 12 hours of irradiation, the rates of hydrogen and oxygen products still reached 203.2 mmol / g / h and 34.8 mmol / g / h, respectively.

[0035] Meanwhile, taking the 83,4,9,10-perylenetetracarboxylic acid diimide / cuprous iodide composite material sample of this embodiment as an example, the recycling performance of the material is demonstrated (e.g. Figure 4 (As shown in the figure). The results show that after 7 cycles, the rate of catalytic hydrogen and oxygen production still decreased by less than 12%.

[0036] In summary, the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material of this invention significantly improves solar energy utilization and carrier separation efficiency, exhibits high photocatalytic water splitting activity for hydrogen and oxygen production, and has a stable structure, thus showing broad application prospects in energy, chemical and other fields.

Claims

1. A method for preparing a 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material, characterized in that, After mixing the 3,4,9,10-perylenetetracarboxydiimide dispersion and the cuprous iodide dispersion, the mixture was refluxed for 12 to 36 hours. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, washed, and dried to obtain the final product.

2. The preparation method of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material as described in claim 1, characterized in that, The mass ratio of 3,4,9,10-perylenetetracarboxydiimide to cuprous iodide is 1:0.3~15.

3. The preparation method of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material as described in claim 1, characterized in that, Includes the following steps: 1) 3,4,9,10-perylenetetracarboxydiimide was uniformly dispersed in N,N-dimethylformamide to obtain a 3,4,9,10-perylenetetracarboxydiimide dispersion; 2) Disperse cuprous iodide powder uniformly in acetonitrile to obtain a cuprous iodide dispersion; 3) Mix the 3,4,9,10-perylenetetracarboxydiimide dispersion obtained in step 1) and the cuprous iodide dispersion obtained in step 2), then heat to 80~140℃ for reflux reaction. After the reaction is completed, cool to room temperature, centrifuge, wash and dry to obtain the final product.

4. The method for preparing the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material as described in claim 3, characterized in that, In step 1), 0.1 to 1.0 g of 3,4,9,10-perylenetetracarboxydiimide is uniformly dispersed in 10 to 100 mL of N,N-dimethylformamide.

5. The method for preparing the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material as described in claim 3, characterized in that, In step 2), 0.3~1.5 g of cuprous iodide powder is uniformly dispersed in 10~50 mL of acetonitrile.

6. The method for preparing the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material as described in claim 1, characterized in that, Includes the following steps: 1) Add 0.1-1.0 g of 3,4,9,10-perylenetetracarboxydiimide to 10-100 mL of N,N-dimethylformamide, stir for 15-45 minutes, and then sonicate at room temperature for 60-90 minutes to obtain a 3,4,9,10-perylenetetracarboxydiimide dispersion; 2) Add 0.3-1.5 g of cuprous iodide powder to 10-50 mL of acetonitrile, sonicate at room temperature for 15-45 minutes, and then stir for 30-120 minutes to obtain a cuprous iodide dispersion; 3) Mix the 3,4,9,10-perylenetetracarboxydiimide dispersion obtained in step 1) and the cuprous iodide dispersion obtained in step 2), then heat to 80~140℃ for reflux reaction. After the reaction is completed, cool to room temperature, centrifuge, wash and dry to obtain the final product.

7. The 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material prepared by any one of the preparation methods described in claims 1 to 6.

8. The application of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material of claim 7 in photocatalytic water splitting to produce hydrogen and oxygen.

9. The application of the 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material as described in claim 8 in photocatalytic water splitting to produce hydrogen and oxygen, characterized in that, The 3,4,9,10-perylenetetracarboxydiimide / cuprous iodide composite material was dispersed in deionized water, and a 300 W Xe arc lamp was used as the light source for photocatalytic water splitting to produce hydrogen and oxygen.

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