Preparation method of Cu / PDI composite material

Abstract

The application discloses a preparation method of Cu / PDI composite material, which comprises the following steps: step 1, 0.3993g Cu(CH3COO)2.H2O is added into 21mL DMF aqueous solution with a volume fraction of 14%-100%, and stirring is conducted to completely dissolve the Cu(CH3COO)2.H2O, so as to obtain solution A; step 2, 1g PVP is added into the solution A, initial stirring is conducted, then 3.993-35.937mg PDI is added, and continuous stirring is conducted, so as to obtain solution B; and step 3, the solution B is transferred into a polytetrafluoroethylene reaction kettle, the reaction kettle is placed into a drying box, reaction is carried out at 140-180 DEG C for 5-8h, the reaction kettle is cooled to room temperature, and the product C is collected, and then washing and vacuum drying are sequentially conducted, so as to obtain the Cu / PDI composite material, the near-infrared light absorption intensity of the Cu / PDI composite material is enhanced, and the Cu / PDI composite material has excellent photocatalytic activity.

Description

Technical Field

[0001] This invention relates to photocatalysts, specifically a method for preparing a Cu / PDI composite material. Background Technology

[0002] With social development, increasingly serious water pollution has greatly affected human life. Water pollutants mainly include dye molecules such as methyl orange, malachite green (Mg) and rhodamine B (Rh B), as well as heavy metal ions (Cr(VI)) and antibiotics (TC). These substances are difficult to remove effectively through biological self-purification. Therefore, it is particularly important to find efficient and environmentally friendly water pollution treatment methods. Among them, photocatalytic degradation technology, as a new type of water purification technology, has many advantages such as mild conditions, no secondary pollution, and deep degradation. The core of photocatalytic degradation technology lies in the selection of photocatalysts.

[0003] Zero-valent copper exhibits excellent stability, and its modification into photocatalysts can impart higher catalytic activity. Therefore, it has attracted widespread attention from researchers in the field of photocatalysis both domestically and internationally. For example, zero-valent copper-decorated boron-carbon-nitrogen hybrid layers (Cu-BCN) can efficiently oxidize molybdenum (MO) under ultrasonic treatment and direct sunlight, and this process is reproducible. Furthermore, Cu / N-doped TiO2 nanotubes (Cu / N-TNT) produced 7.3 mmol·g⁻¹ CO and 8.5 mmol·g⁻¹ H₂ after 8 hours of illumination. -1 It is 9.1 times and 70.8 times the CO and H2 production of TiO2 photocatalysts, respectively.

[0004] Organic semiconductor PDI has a controllable molecular structure, diverse microstructures, easily modulated electronic structure, and a deep valence band potential, exhibiting strong oxidation and mineralization capabilities. Furthermore, most organic semiconductors demonstrate a wide light absorption range. However, organic semiconductors suffer from two main drawbacks: first, their relatively poor crystallinity leads to poor charge mobility; second, the presence of large conjugated benzene rings in the PDI structure results in low solubility in aqueous media and a low density of surface active sites. These drawbacks limit their application as photocatalysts in water purification.

[0005] Since zero-valent copper in micro- and nano-structures exhibits surface plasmon resonance, it is hoped that PDI can be used to modify zero-valent copper in micro- and nano-structures to broaden the photoresponse range of the material and obtain photocatalysts with high catalytic activity. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing Cu / PDI composite materials. This method is not only simple, but also produces Cu / PDI composite materials with enhanced near-infrared light absorption intensity and excellent photocatalytic activity.

[0007] To achieve the above objectives, the present invention employs the following technical solution:

[0008] A method for preparing a Cu / PDI composite material includes the following steps:

[0009] Step 1: Take 0.3993g Cu(CH3COO)2·H2O and add it to 21mL of DMF aqueous solution with a volume fraction of 14%~100%. Stir until it is completely dissolved to obtain solution A.

[0010] Step 2: Add 1g PVP to solution A, stir initially, then add 3.993-35.937mg PDI, continue stirring to obtain solution B;

[0011] Step 3: Transfer solution B to a polytetrafluoroethylene reactor, place the reactor in a drying oven, and react at 140~180℃ for 5~8 hours. After the reactor cools to room temperature, collect product C, wash and vacuum dry it sequentially to obtain Cu / PDI composite material.

[0012] Furthermore, the initial stirring time in step 2 is 10 minutes.

[0013] Furthermore, the PDI in step 2 is prepared by the following method:

[0014] 1.3760 g of perylene-3,4,9,10,-tetracarboxylic acid dianhydride, 2.5 g of β-alanine and 18 g of imidazole were added to a four-necked flask. The mixture was reacted at 110 °C for 4 h under an argon atmosphere. After the reaction was completed, 100 mL of anhydrous ethanol and 300 mL of 2 M HCl solution were added to the four-necked flask while it was still hot. The mixture was stirred for 24 h, filtered and washed until the pH of the supernatant was 7. After vacuum drying, a purple-red solid PDI was obtained.

[0015] Furthermore, the stirring time in step 2 is 20 minutes.

[0016] Furthermore, the drying oven in step 3 is an electrically heated forced-air drying oven.

[0017] Furthermore, the washing in step 3 involves washing three times each with anhydrous ethanol and deionized water.

[0018] Furthermore, the vacuum drying temperature in step 3 is 60°C.

[0019] Compared with the prior art, the present invention has the following technical effects:

[0020] This invention employs low-temperature solvothermal preparation of Cu / PDI composite materials, eliminating the need for high temperature and high pressure. It offers advantages such as simple and easy operation, readily available raw materials, low cost, and no pollution.

[0021] This invention uses PDI as an electron storage medium and combines it with the stable catalytic activity of elemental Cu to prepare a Cu / PDI composite material that exhibits good light absorption performance in the ultraviolet, visible, and near-infrared regions. In particular, the light absorption intensity in the near-infrared region is significantly enhanced, endowing it with photocatalytic performance in dark environments. It can be used as an all-weather photocatalyst, and its photocatalytic activity is stable and reusable.

[0022] The Cu / PDI composite material prepared by this invention is a spherical body with a micro / nano hierarchical structure and dispersed particles. The micro / nano hierarchical structure has a higher specific surface area, providing more reactive sites. Moreover, after absorbing light, the micro / nano hierarchical structure on the surface easily undergoes a local surface plasmon resonance effect, forming electrons and holes through damped attenuation, which are further converted into ·OH and ·O2. - The active groups enable the Cu / PDI composite material to exhibit excellent catalytic performance.

[0023] The Cu:NC bond in the Cu / PDI composite prepared by this invention facilitates the rapid transfer of electrons generated at the phase interface to the material surface, improves the separation efficiency of electrons and holes, and further enhances the photocatalytic activity of the composite material. Attached Figure Description

[0024] Figure 1 XRD patterns of PDI and Cu / PDI composite materials prepared in Example 1 of this invention and elemental Cu prepared in Comparative Example 1;

[0025] Figures 2(a) to 2(b): Electron micrographs of Cu element prepared in Comparative Example 1 of the present invention at different magnifications;

[0026] Figure 2(c): SEM image of PDI prepared in Example 1 of the present invention;

[0027] Figures 2(d) to 2(e): SEM images of the Cu / PDI composite material prepared in Example 1 of the present invention at different magnifications;

[0028] Figures 2(f) to 2(g): TEM images of the Cu / PDI composite material prepared in Example 1 of the present invention;

[0029] Figure 3 The ultraviolet-visible-near-infrared absorption spectra of the Cu / PDI composite material prepared in Example 1 of this invention and the Cu element prepared in Comparative Example 1;

[0030] Figure 4(a): Degradation curves of Cu / PDI composite material prepared in Example 1 of the present invention and Cu element prepared in Comparative Example 1 on methyl orange under light irradiation.

[0031] Figure 4(b): Degradation curves of Cu / PDI composite material prepared in Example 1 of the present invention and Cu element prepared in Comparative Example 1 for methyl orange under dark conditions;

[0032] Figures 5(a) to 5(b): XPS spectra of the Cu / PDI composite material prepared in Example 1 of the present invention. Detailed Implementation

[0033] The specific content of the present invention will be further explained in detail below with reference to the embodiments.

[0034] Example 1

[0035] Step 1: Take 1.3760g of perylene-3,4,9,10,-tetracarboxylic acid dianhydride (PTCDA), 2.5g of β-alanine, and 18g of imidazole and add them to a four-necked flask. Under an argon atmosphere, react at 110℃ for 4 hours. While still hot, add 100mL of anhydrous ethanol and 300mL of 2M HCl solution to the four-necked flask, stir for 24 hours, filter and wash until the pH of the supernatant is 7. After vacuum drying, a purple-red solid N,N-2(L-alanine-based)perylene diimide, abbreviated as PDI, is obtained.

[0036] Step 2: Take 0.3993g Cu(CH3COO)2·H2O and add it to 21mL of 14% DMF aqueous solution. Stir until it is completely dissolved to obtain solution A.

[0037] Step 3: Add 1g of polyvinylpyrrolidone (PVP) to solution A, stir for 10 minutes initially, then add 3.993mg of PDI and continue stirring for 20 minutes to obtain solution B;

[0038] Step 4: Transfer solution B to a 30 mL polytetrafluoroethylene reaction vessel, place the reaction vessel in an electric heating drying oven, and react at 170 °C for 8 h. After the reaction vessel cools to room temperature, collect product C, wash it three times with anhydrous ethanol and deionized water respectively, and dry it under vacuum at 60 °C to obtain Cu / PDI composite material.

[0039] Example 2

[0040] Step 1: Take 1.3760g of perylene-3,4,9,10,-tetracarboxylic acid dianhydride (PTCDA), 2.5g of β-alanine, and 18g of imidazole and add them to a four-necked flask. Under an argon atmosphere, react at 110℃ for 4 hours. While still hot, add 100mL of anhydrous ethanol and 300mL of 2M HCl solution to the four-necked flask, stir for 24 hours, filter and wash until the pH of the supernatant is 7. After vacuum drying, a purple-red solid N,N-2(L-alanine-based)perylene diimide, abbreviated as PDI, is obtained.

[0041] Step 2: Take 0.3993g Cu(CH3COO)2·H2O and add it to 21mL of 43% DMF aqueous solution. Stir until it is completely dissolved to obtain solution A.

[0042] Step 3: Add 1g of polyvinylpyrrolidone (PVP) to solution A, stir for 10 minutes initially, then add 11.979mg of PDI and continue stirring for 20 minutes to obtain solution B;

[0043] Step 4: Transfer solution B to a 30 mL polytetrafluoroethylene reactor, place the reactor in an electric heating drying oven, and react at 140 °C for 8 h. After the reactor cools to room temperature, collect product C, wash it three times with anhydrous ethanol and deionized water respectively, and dry it under vacuum at 60 °C to obtain Cu / PDI composite material.

[0044] Example 3

[0045] Step 1: Take 1.3760g of perylene-3,4,9,10,-tetracarboxylic acid dianhydride (PTCDA), 2.5g of β-alanine, and 18g of imidazole and add them to a four-necked flask. Under an argon atmosphere, react at 110℃ for 4 hours. While still hot, add 100mL of anhydrous ethanol and 300mL of 2M HCl solution to the four-necked flask, stir for 24 hours, filter and wash until the pH of the supernatant is 7. After vacuum drying, a purple-red solid N,N-2(L-alanine-based)perylene diimide, abbreviated as PDI, is obtained.

[0046] Step 2: Take 0.3993g Cu(CH3COO)2·H2O and add it to 21mL of 57% DMF aqueous solution. Stir until it is completely dissolved to obtain solution A.

[0047] Step 3: Add 1g of polyvinylpyrrolidone (PVP) to solution A, stir for 10 minutes initially, then add 19.965mg of PDI and continue stirring for 20 minutes to obtain solution B.

[0048] Step 4: Transfer solution B to a 30 mL polytetrafluoroethylene reactor, place the reactor in an electric heating drying oven, and react at 150 °C for 7 h. After the reactor cools to room temperature, collect product C, wash it three times with anhydrous ethanol and deionized water respectively, and dry it under vacuum at 60 °C to obtain Cu / PDI composite material.

[0049] Example 4

[0050] Step 1: Take 1.3760g of perylene-3,4,9,10,-tetracarboxylic acid dianhydride (PTCDA), 2.5g of β-alanine, and 18g of imidazole and add them to a four-necked flask. Under an argon atmosphere, react at 110℃ for 4 hours. While still hot, add 100mL of anhydrous ethanol and 300mL of 2M HCl solution to the four-necked flask, stir for 24 hours, filter and wash until the pH of the supernatant is 7. After vacuum drying, a purple-red solid N,N-2(L-alanine-based)perylene diimide, abbreviated as PDI, is obtained.

[0051] Step 2: Take 0.3993g Cu(CH3COO)2·H2O and add it to 21mL of 86% DMF aqueous solution. Stir until it is completely dissolved to obtain solution A.

[0052] Step 3: Add 1g of polyvinylpyrrolidone (PVP) to solution A, stir for 10 minutes initially, then add 27.951mg of PDI and continue stirring for 20 minutes to obtain solution B.

[0053] Step 4: Transfer solution B to a 30 mL polytetrafluoroethylene reaction vessel, place the reaction vessel in an electric heating drying oven, and react at 160 °C for 6 h. After the reaction vessel cools to room temperature, collect product C, wash it three times with anhydrous ethanol and deionized water respectively, and dry it under vacuum at 60 °C to obtain Cu / PDI composite material.

[0054] Example 5

[0055] Step 1: Take 1.3760g of perylene-3,4,9,10,-tetracarboxylic acid dianhydride (PTCDA), 2.5g of β-alanine, and 18g of imidazole and add them to a four-necked flask. Under an argon atmosphere, react at 110℃ for 4 h. While hot, add 100mL of anhydrous ethanol and 300mL of 2M HCl solution to the four-necked flask, stir for 24 h, filter and wash until the pH of the supernatant is 7. After vacuum drying, a purple-red solid N,N-2(L-alanine-based)perylene diimide, abbreviated as PDI, is obtained.

[0056] Step 2: Take 0.3993g Cu(CH3COO)2·H2O and add it to 21mL DMF. Stir until it is completely dissolved to obtain solution A;

[0057] Step 3: Add 1g of polyvinylpyrrolidone (PVP) to solution A, stir for 10 minutes initially, then add 35.937mg of PDI and continue stirring for 20 minutes to obtain solution B.

[0058] Step 4: Transfer solution B to a 30 mL polytetrafluoroethylene reaction vessel, place the reaction vessel in an electric heating drying oven, and react at 180 °C for 5 h. After the reaction vessel cools to room temperature, collect product C, wash it three times with anhydrous ethanol and deionized water respectively, and dry it under vacuum at 60 °C to obtain Cu / PDI composite material.

[0059] Comparative Example 1

[0060] Step 1: Take 0.3993g Cu(CH3COO)2·H2O and add it to 21mL of 14% DMF aqueous solution. Stir until it is completely dissolved to obtain solution A.

[0061] Step 2: Add 1g of polyvinylpyrrolidone (PVP) to solution A and stir for 10 minutes to obtain solution D;

[0062] Step 3: Transfer solution D to a 30 mL polytetrafluoroethylene reaction vessel, place the reaction vessel in an electric heating drying oven, and react at 170 °C for 8 h. After the reaction vessel cools to room temperature, collect product E, wash it three times with anhydrous ethanol and deionized water respectively, and dry it under vacuum at 60 °C to obtain elemental Cu.

[0063] from Figure 1 It can be seen that 43.3, 50.4, and 74.1° correspond to the (111), (200), and (220) crystal planes of Cu, respectively, and the (111) peak is the sharpest and strongest, indicating that the diffraction peak of the (111) crystal plane is the main orientation crystal plane, proving that zero-valent copper was successfully prepared in Comparative Example 1. The appearance of a small peak of Cu2O (PDF Card No. 05-0667) at 36.41° indicates the presence of Cu. 2+ This demonstrates that the Cu / PDI composite material prepared in Example 1 contains zero-valent copper and Cu. 2+ .

[0064] Referring to Figure 2, Figures 2(a) to 2(b) are electron microscope images of elemental Cu prepared in Comparative Example 1. It can be seen that Cu is a relatively smooth, chamfered hexahedral particle with a particle size of 12 μm and a particle cluster size of 40 μm. Figure 2(c) is a scanning electron microscope image of PDI prepared in Example 1. It can be seen that PDI has a filamentous structure. Figures 2(d) and 2(e) are scanning electron microscope images of Cu / PDI prepared in Example 1 at different magnifications. It can be seen that compared with Cu, Cu / PDI has a regular spherical structure. The surface of the sphere is composed of nanostructures. The entire microsphere exhibits a micro-nano hierarchical structure. The diameter of the microsphere is 15 μm and it is uniformly dispersed. Figures 2(f) and 2(g) are high-resolution transmission electron microscope images of Cu / PDI prepared in Example 1. It can be seen that the particle size of Cu / PDI is 100 nm.

[0065] from Figure 3 It can be seen that the copper prepared in Comparative Example 1 has an absorption effect on ultraviolet-visible-near-infrared light. The Cu / PDI composite material prepared by introducing PDI in Example 1 has significantly enhanced light absorption in the near-infrared region, thus endowing the Cu / PDI composite material with photocatalytic performance under dark conditions. Since the Cu / PDI composite material is smaller than Cu elemental particles and has a micro-nano hierarchical structure on the surface, it is more likely to undergo local surface plasmon resonance effect. Therefore, the catalytic activity of Cu / PDI in the near-infrared region is significantly enhanced.

[0066] The Cu elemental prepared in Comparative Example 1 and the Cu / PDI composite material prepared in Example 1 were mixed with methyl orange solution and tested under light and dark conditions for 60 min, respectively. Samples were taken every 10 min for analysis. The results are shown in Figure 4(a) and Figure 4(b). As can be seen from Figure 4(a), under light irradiation for 60 min, the degradation rate of methyl orange by Cu / PDI composite material reached 97.56%, which is 40% higher than that of Cu. As can be seen from Figure 4(b), under dark conditions, Cu / PDI composite material has a good degradation effect on methyl orange, and the degradation efficiency under dark conditions is lower than that under light conditions.

[0067] As can be seen from the high-resolution Cu 2p spectrum of the Cu / PDI composite material prepared in Example 1 in Figure 5(a), 931.93 and 933.58 eV belong to Cu 2p. 3 / 2 951.67 and 953.20 eV belong to Cu 2p 1 / 2 941.69 eV makes Cu 2+ The satellite peaks, 931.93 and 951.67 eV, belong to Cu. 0 933.58 and 953.20 eV belong to Cu + This indicates that Cu / PDI has a mixed valence state.0 Cu + and Cu 2+ A small amount of Cu 2+ It is Cu + Oxidized by air to form Cu 2+ As can be seen from the N 1s spectrum of the Cu / PDI composite material prepared in Example 1 in Figure 5(b), the binding energies of 399.7 and 397.8 eV belong to CN and Cu:N bonds, respectively, indicating that N in PDI forms Cu:N bonds with Cu, thus indicating that the Cu / PDI composite material was successfully prepared.

Claims

1. A method for preparing a Cu / PDI composite material, characterized in that, Includes the following steps: Step 1: Take 0.3993g Cu(CH3COO)2·H2O and add it to 21mL of DMF aqueous solution with a volume fraction of 14%~100%. Stir until it is completely dissolved to obtain solution A. Step 2: Add 1g of PVP to solution A, stir initially, then add 3.993-35.937mg of PDI, and continue stirring to obtain solution B. The PDI is prepared by the following method: 1.3760 g of perylene-3,4,9,10,-tetracarboxylic acid dianhydride, 2.5 g of β-alanine and 18 g of imidazole were added to a four-necked flask. The mixture was reacted at 110 °C for 4 h under an argon atmosphere. After the reaction was completed, 100 mL of anhydrous ethanol and 300 mL of 2 M HCl solution were added to the four-necked flask while it was still hot. The mixture was stirred for 24 h, filtered and washed until the pH of the supernatant was 7. After vacuum drying, a purple-red solid PDI was obtained. Step 3: Transfer solution B to a polytetrafluoroethylene reactor, place the reactor in a drying oven, and react at 140~180℃ for 5~8 hours. After the reactor cools to room temperature, collect product C, wash and vacuum dry it sequentially to obtain Cu / PDI composite material.

2. The method for preparing the Cu / PDI composite material according to claim 1, characterized in that, The initial stirring time in step 2 is 10 minutes.

3. The method for preparing the Cu / PDI composite material according to claim 1, characterized in that, The stirring time in step 2 is 20 minutes.

4. The method for preparing the Cu / PDI composite material according to claim 1, characterized in that, The drying oven in step 3 is an electric heating forced-air drying oven.

5. The method for preparing the Cu / PDI composite material according to claim 1, characterized in that, The washing in step 3 involves washing three times each with anhydrous ethanol and deionized water.

6. The method for preparing the Cu / PDI composite material according to claim 1, characterized in that, The vacuum drying temperature in step 3 is 60°C.

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