An adsorbing material for treating antibiotics in wastewater and a preparation method and application thereof
The composite material prepared by the hydrothermal reaction of phenylacetylene copper with nano-peryleneimide solves the problems of cumbersome preparation and poor stability of existing carbon-based adsorbent materials, and achieves efficient and stable antibiotic adsorption effect, which is suitable for wastewater treatment.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-25
- Publication Date
- 2026-03-24
AI Technical Summary
Existing carbon-based adsorbent materials are cumbersome, time-consuming, and labor-intensive to prepare, and their adsorption performance is unstable and easily affected by external environmental factors such as pH and light, making it difficult to effectively remove antibiotics from wastewater.
A composite material was formed by hydrothermal reaction of phenylacetylene copper and nano-peryleneimide, simplifying the preparation process and forming a phenylacetylene copper/peryleneimide composite material with high specific surface area and abundant active sites. The π-π stacking force was used to achieve efficient adsorption of antibiotics.
The prepared composite material is unaffected by external environmental factors such as light and pH, exhibits excellent adsorption performance and stability, significantly improves the adsorption capacity and removal efficiency of antibiotics, and is suitable for large-scale production.
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Figure CN119075957B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of antibiotic adsorption materials, in particular to an adsorption material for treating antibiotics in wastewater and a preparation method and application thereof. BACKGROUND
[0002] The widespread use and even abuse of antibiotics has led to a variety of antibiotics in the environment, which are highly polluting and complex in composition and extremely difficult to degrade naturally. Antibiotics can enter the food chain through enrichment. It poses a great threat to humans and other organisms and has strong ecological hazards. Long-term discharge of low-dose antibiotics into the environment can also enhance the drug resistance of sensitive bacteria. Moreover, drug-resistant genes can spread and evolve in the environment, posing a potential threat to the ecological environment and human health. Therefore, removing antibiotic pollutants has become a very urgent task.
[0003] At present, common methods for removing antibiotics include adsorption, membrane separation, photocatalysis and biodegradation. Among them, the adsorption method is considered to be one of the most promising methods for removing antibiotics due to its low cost, simple operation, wide applicability and no secondary pollution.
[0004] High-performance adsorbents are the key to removing antibiotic pollutants in water environments by adsorption. However, the adsorbents used in the prior art are mainly carbon-based adsorption materials, and the prior art mainly uses high-temperature pyrolysis to prepare carbon-based adsorption materials, i.e. through a series of treatments such as activation, modification and pyrolysis of the carbon source, the carbon-based adsorption material is prepared. The above preparation method can improve the surface functional groups, pores and specific surface area of the carbon material, and thus improve the adsorption of antibiotics. However, the above preparation method has a complicated processing procedure, which is time-consuming and labor-intensive, and is not conducive to large-scale production and use. Moreover, the prepared carbon-based adsorption material is easily affected by external environmental factors such as pH and light, and has poor adsorption performance stability. SUMMARY
[0005] To solve the above technical problems, the present application provides an adsorption material for treating antibiotics in wastewater and a preparation method and application thereof.
[0006] The adsorption material for treating antibiotics in wastewater and the preparation method and application thereof of the present application are realized by the following technical solutions:
[0007] This invention recognizes the crucial role of perylene imide in pollutant removal. However, current technologies primarily utilize perylene imide composites with other materials as photocatalytic agents. For instance, the existing technology "Incorporating Fe,Co co-doped graphene with PDI supermolecular for promoted photocatalytic activity: A story of electron transfer, DOI:10.1016 / j.jcis.2022.12.145" proposes a method that combines Fe and Co co-doped graphene with perylene imide supramolecularly. This anchors the iron-cobalt dual single atoms on the nitrogen-doped graphene, improving the migration and separation efficiency of photogenerated carriers. Furthermore, π-π interactions enable self-assembly with perylene imide to form a composite material. While this method improves pollutant removal, the composite material primarily achieves synergistic interactions through the Fe-Co dual active sites, promoting electron transfer in the catalytic reaction and thus achieving photocatalytic degradation of pollutants. Therefore, the materials prepared by this method are still limited by external environmental factors such as light exposure.
[0008] To provide an adsorbent material that is not limited by external environmental factors such as light, this invention proposes a method for preparing an adsorbent material for antibiotic treatment in wastewater, specifically including the following steps:
[0009] Phenylacetylene copper and nano-perylene imide were dispersed in an organic solvent and then subjected to a hydrothermal reaction at a temperature of 80℃~220℃ to obtain a phenylacetylene copper / perylene imide composite material, which was then used as an adsorbent for treating antibiotics in wastewater.
[0010] It should be noted that, in order to further improve the removal efficiency of perylene imide for pollutants, this invention uses copper phenylacetylene as a raw material. Through supramolecular bonding of copper phenylacetylene and nano-perylene imide during a hydrothermal reaction, a copper phenylacetylene / perylene imide composite material with a high specific surface area is formed. The preparation method is simple and easy to operate. This invention, by composite with copper phenylacetylene based on perylene imide, significantly improves the adsorption capacity of copper phenylacetylene for antibiotics in wastewater. Furthermore, the resulting copper phenylacetylene / perylene imide composite material is not limited by external environmental factors such as light, exhibits excellent adsorption performance and stability, and can directly achieve efficient removal of antibiotics from wastewater through its own adsorption, making it suitable as an adsorbent material for antibiotic treatment in wastewater.
[0011] In some preferred embodiments of the present invention, the mass ratio of copper phenylacetylene to nano-peryleneimide is 1:0.1 to 10 to ensure that the added copper phenylacetylene and nano-peryleneimide can react fully and combine to form a copper phenylacetylene / peryleneimide composite material, and to make the obtained copper phenylacetylene / peryleneimide composite material have the best adsorption effect and stable performance at different pH levels.
[0012] In some preferred embodiments of the present invention, the organic solvent is one or more selected from alcohol solvents and N,N-dimethylformamide. This ensures that the organic solvent used has good solubility or dispersibility for both phenylacetylene copper and nano-peryleneimide, thereby facilitating sufficient contact and reaction between phenylacetylene copper and nano-peryleneimide in the organic solvent. In some more preferred embodiments of the present invention, the alcohol solvent is one or more selected from ethanol, methanol, and ethylene glycol.
[0013] In some preferred embodiments of the present invention, the ratio of the organic solvent to the copper phenylacetylene is 10 mL to 100 mL: 15 mg to 120 mg, so that the added organic solvent can fully dissolve or disperse the copper phenylacetylene and the nano-peryleneimide.
[0014] In some preferred embodiments of the present invention, the phenylacetylene copper and nano-peryleneimide are dispersed in an organic solvent by first stirring and then ultrasonicating, so as to achieve rapid and uniform dispersion or dissolution of the phenylacetylene copper and nano-peryleneimide in the organic solvent. In some preferred embodiments of the present invention, the ultrasonication power is 50W to 300W, and the ultrasonication time is 2min to 100min. In other preferred embodiments of the present invention, the stirring time is 20min to 180min.
[0015] In some preferred embodiments of the present invention, the hydrothermal reaction time is 1h to 16h, so as to make the reaction between copper phenylacetylene and peryleneimide more complete.
[0016] The present invention also provides an adsorbent material prepared by the above-described preparation method.
[0017] The present invention also provides an application of the adsorbent material prepared by the above preparation method of the present invention in the adsorption of antibiotics in wastewater.
[0018] It should be noted that when the adsorbent material prepared by the above preparation method of the present invention is used to adsorb antibiotics in wastewater, the adsorbent material of the present invention is placed in the wastewater to be treated and then treated by ultrasound, so that the adsorbent material can fully contact and adsorb the antibiotics in the wastewater to be treated through ultrasound, thereby achieving the removal of antibiotics in the wastewater to be treated.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] This invention utilizes a simple one-step hydrothermal method to successfully composite phenylacetylene copper with perylene imide. During the hydrothermal reaction, phenylacetylene copper and nano-perylene imide undergo supramolecular bonding, forming a high specific surface area adsorbent material for antibiotic treatment in wastewater—the phenylacetylene copper / perylene imide composite material. The preparation method of this invention is simple and easy to operate, simplifying the process flow and reducing the difficulty of preparation, thus facilitating its widespread adoption and large-scale production.
[0021] The phenylacetylene copper / peryleneimide composite material prepared by this invention possesses abundant active sites, strong π-π stacking forces, and high adsorption capacity. Furthermore, this composite material is unaffected by external environmental factors such as pH and light, exhibiting excellent adsorption performance stability. Compared to single phenylacetylene copper and single peryleneimide, this invention, by combining phenylacetylene copper and peryleneimide, effectively improves the adsorption capacity of the material for antibiotics in wastewater. Moreover, the resulting phenylacetylene copper / peryleneimide composite material is not limited by external environmental factors such as light and can directly achieve efficient removal of antibiotics from wastewater through its own adsorption, making it suitable as an adsorbent material for antibiotic treatment in wastewater. Furthermore, a new basic copper carbonate was generated during the hydrothermal reaction of phenylacetylene copper and nano-peryleneimide. The formation of basic copper carbonate enabled the successful composite of peryleneimide and phenylacetylene copper. On the one hand, this greatly increased the specific surface area, pore size and pore volume of the peryleneimide / phenylacetylene copper composite material. On the other hand, the introduction of Cu element also provided more active sites for the phenylacetylene copper / peryleneimide composite material, further improving its adsorption performance.
[0022] The phenylacetylene copper / peryleneimide composite material prepared in this invention, when used as an adsorbent, can adsorb target antibiotic pollutants in wastewater without requiring specific light or pH conditions, and is unaffected by external environmental factors such as light or pH. Furthermore, under ultrasonic treatment for 30 minutes, the maximum adsorption capacity of the adsorbent material of this invention for tetracycline reaches 238.33 mg / g, which is 21.96 times and 12.36 times the maximum adsorption capacity of phenylacetylene copper alone and peryleneimide alone for tetracycline, respectively. The adsorbent material prepared in this invention also achieves an adsorption removal rate of 81.97% for ciprofloxacin, indicating that the phenylacetylene copper / peryleneimide composite material prepared in this invention has good versatility in adsorbing antibiotics in wastewater. Attached Figure Description
[0023] Figure 1 This is a scanning electron microscope image of phC2Cu in Comparative Example 1.
[0024] Figure 2 This is a PDI scanning electron microscope image of Comparative Example 2.
[0025] Figure 3 The image shown is a scanning electron microscope image of phC2Cu / PDI from Example 1.
[0026] Figure 4 The following is an EDS energy spectrum of phC2Cu / PDI from Example 1. In the figure, figure a is the total elemental distribution of phC2Cu / PDI from Example 1, figure b is the distribution of C element in figure a, figure c is the distribution of O element in figure a, figure d is the distribution of Cu element in figure a, and figure e is the distribution of N element in figure a.
[0027] Figure 5 The XRD patterns are of phC2Cu in Comparative Example 1, PDI in Comparative Example 2, and phC2Cu / PDI in Example 1.
[0028] Figure 6 The XPS spectra of phC2Cu / PDI in Example 1 are shown below. In the figure, a is the C 1s spectrum of phC2Cu / PDI, b is the N 1s spectrum of phC2Cu / PDI, c is the O 1s spectrum of phC2Cu / PDI, and d is the Cu 2p spectrum of phC2Cu / PDI.
[0029] Figure 7 The N2 adsorption-desorption isotherms are for phC2Cu in Comparative Example 1, PDI in Comparative Example 2, and phC2Cu / PDI in Example 1.
[0030] Figure 8 The pore size distribution curves are for phC2Cu of Comparative Example 1, PDI of Comparative Example 2, and phC2Cu / PDI of Example 1.
[0031] Figure 9 The cumulative pore volume distribution curves are for phC2Cu of Comparative Example 1, PDI of Comparative Example 2, and phC2Cu / PDI of Example 1.
[0032] Figure 10 The results show the adsorption performance of phC2Cu / PDI for tetracycline and ciprofloxacin in Example 1.
[0033] Figure 11 The images show the FTIR spectra of phC2Cu before and after adsorption in Example 1. Detailed Implementation
[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below.
[0035] Example 1
[0036] This embodiment provides an adsorbent material for treating antibiotics in wastewater, which is prepared through the following steps:
[0037] Step 1, Preparation of nano-peryleneimide:
[0038] 1.1) Under nitrogen protection, 1.376 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2.5 g of 3-aminopropionic acid and 16 g of imidazole were mixed and reacted at 100 °C for 4 h. After the reaction was completed, the mixture was cooled to room temperature, 100 mL of ethanol and 300 mL of 2 M hydrochloric acid were added, and the mixture was then reacted for 12 h under stirring to obtain a red solution.
[0039] 1.2) The obtained red solution was filtered through a 0.45 μm filter membrane and washed with distilled water until the pH value was neutral. The solid was collected and dried in a vacuum drying oven at 60 °C for 12 h to obtain crude perylene imide.
[0040] 1.3) Disperse 0.54 g of crude perylene imide in 200 mL of deionized water, add 800 μL of triethylamine and stir for 1 h; then add 35 mL of 2 M hydrochloric acid and stir for 3 h to obtain a dark red solution.
[0041] 1.4) The obtained dark red solution was filtered through a 0.45 μm filter membrane and washed with distilled water until the pH value was neutral. The solid was collected and dried in a vacuum drying oven at 60 °C for 12 h to obtain nano-peryleneimide.
[0042] Step 2, Preparation of Copper Phenylacetylene
[0043] 2.1) Mix 0.365 g of copper chloride dihydrate with 40 mL of methanol to obtain a methanol solution of copper chloride.
[0044] 2.2) Add 1.12 mL of triethylamine to the above-mentioned methanol solution of copper chloride and stir until homogeneous; then add 0.44 mL of phenylacetylene and mix well, then transfer to a 65°C water bath and stir for 30 min.
[0045] 2.3) After filtering the reaction solution obtained in 2.2), wash it with deionized water and anhydrous ethanol, collect the solid and dry it in a vacuum drying oven at 60°C for 12 h to obtain copper phenylacetylene.
[0046] Step 3, hydrothermal reaction:
[0047] 3.1) Place 0.1g of nano-peryleneimide obtained in step 1.4) and 0.02g of phenylacetylene copper obtained in step 2.3) into 40mL of ethanol, stir for 120min to obtain a stirred mixture.
[0048] 3.2) The obtained stirred mixture was ultrasonically treated at an ultrasonic power of 200W for 30 minutes to obtain an ultrasonic mixture.
[0049] 3.3) Transfer the above ultrasonic mixture to a 50 mL polytetrafluoroethylene liner, seal it in the reactor, place the reactor in an oven, and perform a hydrothermal reaction at 120 °C for 12 h.
[0050] 3.4) The reaction solution obtained in 3.3) above was washed three times by centrifugation with anhydrous ethanol. The washed material was placed in a vacuum drying oven and dried at 60°C for 12 hours to obtain the phenylacetylene copper / peryleneimide composite material, denoted as phC2Cu / PDI.
[0051] Example 2
[0052] This embodiment provides an adsorbent material for treating antibiotics in wastewater, which is prepared through the following steps:
[0053] Step 1, Preparation of nano-peryleneimide:
[0054] 1.1) Under nitrogen protection, 1.376 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2.5 g of 3-aminopropionic acid and 16 g of imidazole were mixed and reacted at 100 °C for 4 h. After the reaction was completed, the mixture was cooled to room temperature, 100 mL of ethanol and 300 mL of 2 M hydrochloric acid were added, and the mixture was then reacted for 12 h under stirring to obtain a red solution.
[0055] 1.2) The obtained red solution was filtered through a 0.45 μm filter membrane and washed with distilled water until the pH value was neutral. The solid was collected and dried in a vacuum drying oven at 60 °C for 12 h to obtain crude perylene imide.
[0056] 1.3) Disperse 0.54 g of crude perylene imide in 200 mL of deionized water, add 800 μL of triethylamine and stir for 1 h; then add 35 mL of 2 M hydrochloric acid and stir for 3 h to obtain a dark red solution.
[0057] 1.4) The obtained dark red solution was filtered through a 0.45 μm filter membrane and washed with distilled water until the pH value was neutral. The solid was collected and dried in a vacuum drying oven at 60 °C for 12 h to obtain nano-peryleneimide.
[0058] Step 2, Preparation of Copper Phenylacetylene
[0059] 2.1) Mix 0.365 g of copper chloride dihydrate with 40 mL of methanol to obtain a methanol solution of copper chloride.
[0060] 2.2) Add 1.12 mL of triethylamine to the above-mentioned methanol solution of copper chloride and stir until homogeneous; then add 0.44 mL of phenylacetylene and mix well, then transfer to a 65°C water bath and stir for 30 min.
[0061] 2.3) After filtering the reaction solution obtained in 2.2), wash it with deionized water and anhydrous ethanol, collect the solid and dry it in a vacuum drying oven at 60°C for 12 h to obtain copper phenylacetylene.
[0062] Step 3, hydrothermal reaction:
[0063] 3.1) Place 0.006 g of nano-peryleneimide obtained in step 1.4) and 0.06 g of phenylacetylene copper obtained in step 2.3 into 10 mL of ethanol, stir for 180 min, and obtain a stirred mixture.
[0064] 3.2) The obtained stirred mixture was ultrasonically treated at an ultrasonic power of 50W for 100 minutes to obtain an ultrasonic mixture.
[0065] 3.3) Transfer the above ultrasonic mixture into a polytetrafluoroethylene liner, seal it in the reactor, place the reactor in an oven, and perform a hydrothermal reaction at 80°C for 8 hours.
[0066] 3.4) The reaction solution obtained in 3.3) above was washed three times by centrifugation with anhydrous ethanol. The washed material was placed in a vacuum drying oven and dried at 60°C for 12 hours to obtain the phenylacetylene copper / peryleneimide composite material.
[0067] Example 3
[0068] This embodiment provides an adsorbent material for treating antibiotics in wastewater, which is prepared through the following steps:
[0069] Step 1, Preparation of nano-peryleneimide:
[0070] 1.1) Under nitrogen protection, 1.376 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2.5 g of 3-aminopropionic acid and 16 g of imidazole were mixed and reacted at 100 °C for 4 h. After the reaction was completed, the mixture was cooled to room temperature, 100 mL of ethanol and 300 mL of 2 M hydrochloric acid were added, and the mixture was then reacted for 12 h under stirring to obtain a red solution.
[0071] 1.2) The obtained red solution was filtered through a 0.45 μm filter membrane and washed with distilled water until the pH value was neutral. The solid was collected and dried in a vacuum drying oven at 60 °C for 12 h to obtain crude perylene imide.
[0072] 1.3) Disperse 0.54 g of crude perylene imide in 200 mL of deionized water, add 800 μL of triethylamine and stir for 1 h; then add 35 mL of 2 M hydrochloric acid and stir for 3 h to obtain a dark red solution.
[0073] 1.4) The obtained dark red solution was filtered through a 0.45 μm filter membrane and washed with distilled water until the pH value was neutral. The solid was collected and dried in a vacuum drying oven at 60 °C for 12 h to obtain nano-peryleneimide.
[0074] Step 2, Preparation of Copper Phenylacetylene
[0075] 2.1) Mix 0.365 g of copper chloride dihydrate with 40 mL of methanol to obtain a methanol solution of copper chloride.
[0076] 2.2) Add 1.12 mL of triethylamine to the above-mentioned methanol solution of copper chloride and stir until homogeneous; then add 0.44 mL of phenylacetylene and mix well, then transfer to a 65°C water bath and stir for 30 min.
[0077] 2.3) After filtering the reaction solution obtained in 2.2), wash it with deionized water and anhydrous ethanol, collect the solid and dry it in a vacuum drying oven at 60°C for 12 h to obtain copper phenylacetylene.
[0078] Step 3, hydrothermal reaction:
[0079] 3.1) Place 1.2g of nano-peryleneimide obtained in step 1.4) and 0.12g of copper phenylacetylene obtained in step 2.3 into 100mL of ethanol, stir for 20min, and obtain a stirred mixture.
[0080] 3.2) The obtained stirred mixture was ultrasonically treated at an ultrasonic power of 300W for 20 minutes to obtain an ultrasonic mixture.
[0081] 3.3) Transfer the above ultrasonic mixture into a polytetrafluoroethylene liner, seal it in the reactor, place the reactor in an oven, and perform a hydrothermal reaction at 220°C for 1 hour.
[0082] 3.4) The reaction solution obtained in 3.3) above was washed three times by centrifugation with anhydrous ethanol. The washed material was placed in a vacuum drying oven and dried at 60°C for 12 hours to obtain the phenylacetylene copper / peryleneimide composite material.
[0083] Comparative Example 1
[0084] This comparative example provides an adsorbent material for treating antibiotics in wastewater, which is prepared through the following steps:
[0085] 1) Mix 0.365g of copper chloride dihydrate with 40mL of methanol to obtain a methanol solution of copper chloride.
[0086] 2) Add 1.12 mL of triethylamine to the above-mentioned copper chloride methanol solution and stir until homogeneous; then add 0.44 mL of phenylacetylene and mix well, then transfer to a 65°C water bath and stir for 30 min.
[0087] 3) After filtering the reaction solution obtained in 2), wash it with deionized water and anhydrous ethanol, collect the solid and dry it in a vacuum drying oven at 60°C for 12 hours to obtain copper phenylacetylene, denoted as phC2Cu.
[0088] The only difference between this comparative example and Example 1 is that:
[0089] It does not undergo a hydrothermal reaction with peryleneimide, meaning that copper phenylacetylene is used as the adsorbent material in this comparative example.
[0090] Comparative Example 2
[0091] This comparative example provides an adsorbent material for treating antibiotics in wastewater, which is prepared through the following steps:
[0092] 1) Under nitrogen protection, 1.376 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2.5 g of 3-aminopropionic acid and 16 g of imidazole were mixed and reacted at 100 °C for 4 h. After the reaction was completed, the mixture was cooled to room temperature, 100 mL of ethanol and 300 mL of 2 M hydrochloric acid were added, and the mixture was reacted for 12 h under stirring to obtain a red solution.
[0093] 2) The obtained red solution was filtered through a 0.45 μm filter membrane and washed with distilled water until the pH value was neutral. The solid was collected and dried in a vacuum drying oven at 60 °C for 12 h to obtain crude perylene imide.
[0094] 3) Disperse 0.54 g of crude perylene imide in 200 mL of deionized water, add 800 μL of triethylamine and stir for 1 h; then add 35 mL of 2 M hydrochloric acid and stir for 3 h to obtain a dark red solution.
[0095] 4) The obtained dark red solution was filtered through a 0.45 μm filter membrane and washed with distilled water until the pH value was neutral. The solid was collected and dried in a vacuum drying oven at 60 °C for 12 h to obtain nano-perylene imide, denoted as PDI.
[0096] The only difference between this comparative example and Example 1 is that:
[0097] It does not undergo a hydrothermal reaction with phenylacetylene copper, meaning that this comparative example uses a single perylene imide as the adsorbent.
[0098] Experimental Section
[0099] (I) Scanning Electron Microscopy Testing
[0100] This invention uses phC2Cu from Comparative Example 1, PDI from Comparative Example 2, and phC2Cu / PDI from Example 1 as examples, and performs scanning electron microscopy tests on them respectively. The test results are as follows: Figures 1-3 As shown.
[0101] Figure 1 The image shows a scanning electron microscope (SEM) image of phC2Cu in Comparative Example 1. It can be seen that the sample grows into a structure of long nanoribbons and is stacked into bundles, which can provide more adsorption sites for the target analyte.
[0102] Figure 2 The image shown is a scanning electron microscope image of PDI in Comparative Example 2, which shows that pure PDI exhibits a one-dimensional microrod morphology.
[0103] Figure 3 The scanning electron microscope (SEM) image of phC2Cu / PDI from Example 1 shows that the samples all exhibit regular rod-like structures with a relatively uniform distribution. Compared to Figure 1 and 2 In the case of phC2Cu / PDI in Example 1, the introduction of Cu element will help provide more active sites, greatly increase the specific surface area of the composite material, and solve the problem of low adsorption capacity of pure nano PDI and copper phenylacetylene.
[0104] (II) EDS energy dispersive spectroscopy test
[0105] This invention takes the phC2Cu / PDI of Example 1 as an example and conducts separate tests on it, and the test results are as follows: Figure 4 As shown in the figure. Figure a is the EDS elemental distribution diagram of phC2Cu / PDI in Example 1, Figure b is the distribution diagram of C element in Figure a, Figure c is the distribution diagram of O element in Figure a, Figure d is the distribution diagram of Cu element in Figure a, and Figure e is the distribution diagram of N element in Figure a.
[0106] from Figure 4 As shown in Figure a, the phC2Cu / PDI prepared in Example 1 is mainly composed of C, O, Cu, and N elements. Figure 4 Figures b-e show that C, O, Cu, and N elements are uniformly distributed on the surface of the phC2Cu / PDI prepared in Example 1, indicating that the phenylacetylene copper / peryleneimide composite material prepared by the method of this invention has a uniform component distribution, which is beneficial to ensuring the stability of the material properties. Furthermore, the uniform doping of Cu element in the phC2Cu / PDI prepared in Example 1 helps to provide more active sites, thereby solving the problem of low adsorption capacity of pure nano-PDI.
[0107] (III) XRD Testing
[0108] This invention uses phC2Cu from Comparative Example 1, PDI from Comparative Example 2, and phC2Cu / PDI from Example 1 as examples, and XRD tests were performed on them respectively. The test results are as follows: Figure 5 As shown.
[0109] Figure 5 The XRD patterns of phC2Cu in Comparative Example 1, PDI in Comparative Example 2, and phC2Cu / PDI in Example 1 are shown below. Figure 5 As can be seen, the peaks between 24° and 28° correspond to the typical π-π stacking between PDI frameworks. Clearly, the intensity of the 14° peak in the phC2Cu / PDI sample is lower than that of the 26° peak. Similar to nano-PDI, the peak intensity ratio of the 26° peak to the 14° peak is greater than 1, proving that phC2Cu / PDI has strong π-π stacking forces. This indirectly proves that the composite adsorbent has good adsorption properties, and π-π stacking also plays a certain role.
[0110] (iv) XPS Test
[0111] This invention takes the phC2Cu / PDI of Example 1 as an example and performs X-ray photoelectron spectroscopy (XPS) testing on it, and the test results are as follows. Figure 6 As shown.
[0112] Figure 6 The XPS spectrum of phC2Cu / PDI in Example 1 is shown below. Figure 6 In the diagram, figure a shows the C1s spectrum of phC2Cu / PDI, figure b shows the N1s spectrum of phC2Cu / PDI, figure c shows the O1s spectrum of phC2Cu / PDI, and figure d shows the Cu 2p spectrum of phC2Cu / PDI.
[0113] Depend on Figure 6 As can be seen from Figures a-d in the table, C, O, Cu and N elements are indeed present in the phC2Cu / PDI of Example 1.
[0114] And by Figure 6 Figure a shows four characteristic peaks with different binding energies: 284.79 eV, 285.42 eV, 287.84 eV, and 288.77 eV. The peaks at 288.77 eV and 285.42 eV correspond to the OC=O bond in PDI and the C≡C bond in phC₂Cu, respectively. The peak at 287.84 eV indicates the presence of a metal carbonate, further confirming the successful binding of phC₂Cu with PDI.
[0115] And by Figure 6Figure b shows three characteristic peaks with binding energies at 399.44, 400.09, and 400.82 eV. The peaks at 400.09 eV and 400.82 eV correspond to the CN in the PDI. X The peak at 399.44 eV corresponds to the NH bond in PDI.
[0116] And by Figure 6 A characteristic peak can be observed in chromatogram c, which can be further decomposed into two peaks. The peak with a binding energy of 533.36 eV is attributed to the C=O group in PDI, while the peak at 531.52 eV confirms the presence of a metal carbonate.
[0117] And by Figure 6 Four characteristic peaks can be observed in the d-plot, located at 933.12 eV, 934.9 eV, 952.88 eV, and 954.42 eV. The peaks at 933.12 eV and 952.88 eV are Cu 2p 3 / 2 and Cu 2p 1 / 2 The main peaks at 934.9 eV and 954.42 eV are consistent with the above findings, suggesting that basic copper carbonate was formed during the bonding process between the two materials. These results fully demonstrate the successful bonding of phC2Cu and PDI.
[0118] (V) BET Test
[0119] This invention uses phC2Cu from Comparative Example 1, PDI from Comparative Example 2, and phC2Cu / PDI from Example 1 as examples to test their pore structures, and the test results are as follows: Figures 7-9 As shown.
[0120] Figure 7 The N2 adsorption-desorption isotherms of phC2Cu (Comparative Example 1), PDI (Comparative Example 2), and phC2Cu / PDI (Example 1) are shown. It can be seen that the isotherms of PDI, phC2Cu, and phC2Cu / PDI all belong to type IV, indicating they are mesoporous materials. Furthermore, the specific surface area of phC2Cu / PDI is 95.6062 m² / g. 2 g -1 It is much larger than PDI (0.4992m). 2 g -1 ) and phC2Cu(51.377m 2 g -1 ).
[0121] Figure 8The pore size distribution curves of phC2Cu in Comparative Example 1, PDI in Comparative Example 2, and phC2Cu / PDI in Example 1 show that, compared with Comparative Example 2, the pore size of phC2Cu / PDI in Example 1 has changed significantly, with a significant increase in pore size, which can effectively improve the specific surface area of the material. This is one of the reasons for the enhanced adsorption performance of the new material.
[0122] Figure 9 The cumulative pore volume distribution curves of phC2Cu in Comparative Example 1, PDI in Comparative Example 2, and phC2Cu / PDI in Example 1 show that the cumulative pore volume is significantly increased, which is one of the reasons for the enhanced adsorption performance of the new material.
[0123] (vi) Adsorption performance test
[0124] 1) Adsorption performance test of tetracycline in solution
[0125] In this invention, the phC2Cu / PDI from Example 1 was used as the adsorbent material, and its adsorption performance was tested. The test method was as follows:
[0126] 20 mg of phC2Cu / PDI from Example 1 was weighed and placed in a 250 mL beaker. 100 mL of an initial tetracycline solution (TC solution) with a mass concentration of 20 mg / L was added. The solution was then transferred to a temperature-controlled sonicator and sonicated at 25°C for 30 min. The supernatant was aspirated every 6 min and filtered through a 0.22 μm mixed cellulose microporous membrane. The resulting filtrate was the TC solution after adsorption equilibrium. The absorbance of the filtrate was measured at the maximum absorption wavelength of 357 nm. The mass concentration of the TC solution after adsorption equilibrium was calculated based on the curve fitting equation between the mass concentration and absorbance of the TC solution. The equilibrium adsorption capacity of phC2Cu / PDI was calculated using Equation 1. The curve fitting equation between the mass concentration and absorbance of the TC solution is y1 = 0.0329x1 - 0.0034, R... 2 =0.999, where x1 is the mass concentration of the TC solution, mg / L; y1 is the absorbance at the maximum absorption wavelength of 357 nm.
[0127]
[0128] In the formula, q e1 The equilibrium adsorption capacity of C2Cu / PDI is given in mg / g; C 01 The initial mass concentration of the TC solution is 20 mg / L; C e1 The concentration of TC in the solution when adsorption reaches equilibrium is mg / L; V1 is the total volume of the solution, 100 mL; m1 is the mass of the adsorbent phC2Cu / PDI, 20 mg.
[0129] 2) Adsorption performance test of ciprofloxacin in solution
[0130] This invention follows the above method, replacing the 20 mg / L tetracycline solution with a 20 mg / L ciprofloxacin solution, i.e., a CIP solution, for testing. The difference in the testing is as follows:
[0131] The absorbance of the obtained filtrate was measured at the maximum absorption wavelength of 272 nm. The mass concentration of the CIP solution after adsorption equilibrium was calculated based on the curve fitting equation between the mass concentration of the CIP solution and the absorbance measurement. The equilibrium adsorption capacity of phC2Cu / PDI was then calculated using Equation 2. The curve fitting equation between the mass concentration of the CIP solution and the absorbance measurement is y2 = 0.0815x2 - 0.0128, where R... 2 =0.9994, where x2 is the mass concentration of the CIP solution, mg / L; y2 is the absorbance at the maximum absorption wavelength of 272 nm.
[0132]
[0133] In the formula, q e2 The equilibrium adsorption capacity of C2Cu / PDI is given in mg / g; C 02 The initial mass concentration of the CIP solution is 20 mg / L; C e2 V2 is the mass concentration of CIP in the solution when adsorption reaches equilibrium, in mg / L; V2 is the total volume of the solution, in 100 mL; m2 is the mass of the adsorbent phC2Cu / PDI, in 20 mg.
[0134] Furthermore, the test results for the adsorption performance of tetracycline in solution and the adsorption performance of tetracycline in solution are as follows: Figure 10 As shown.
[0135] according to Figure 10 The test results show that when the phenylacetylene copper / peryleneimide composite material prepared in this invention is used as an adsorbent, the maximum adsorption capacity of tetracycline can reach 238.33 mg / g after being treated with ultrasound for 30 min, which is 21.96 times and 12.36 times that of phenylacetylene copper and peryleneimide, respectively.
[0136] It can also be seen that when the phenylacetylene copper / peryleneimide composite material prepared by the present invention is used as an adsorbent, the adsorption rate of 20 mg / L ciprofloxacin can also reach 81.97%.
[0137] Furthermore, since the structures of the phenylacetylene copper / peryleneimide composite materials obtained in Examples 2 and 3 are similar to those in Example 1, and tests have shown that the adsorption effect of the phenylacetylene copper / peryleneimide composite materials obtained in Examples 2 and 3 on tetracycline is 97% to 99% of that in Example 1; and the adsorption effect on ciprofloxacin is 95% to 97% of that in Example 1.
[0138] The test results above show that the phenylacetylene copper / peryleneimide composite material prepared in this invention can be used as an adsorbent for antibiotics in wastewater. It has good adsorption performance and versatility for antibiotics in wastewater, providing a new approach and option for the treatment of antibiotic wastewater.
[0139] (vii) FTIR test
[0140] The present invention also performed FTIR tests on phC2Cu of Example 1 before and after the above adsorption performance tests, and the test results are as follows. Figure 11 As shown.
[0141] Figure 11 These are the FTIR spectra of phC2Cu before and after adsorption in Example 1. The upper spectrum is the FTIR spectrum of phC2Cu before adsorption in Example 1, and the lower spectrum is the FTIR spectrum of phC2Cu after adsorption in Example 1. Figure 11 It can be seen from this that 1691cm -1 The peak at 1656 cm⁻¹ is attributed to the stretching vibration of the C=O group in the carboxyl group. -1 The tensile vibration peak at 1344 cm⁻¹ is caused by the ketone functional group in perylene imide. -1 and 1590cm -1 The absorption peak is attributed to the stretching vibration of -COO-. Comparison of the infrared spectra before and after adsorption shows that the functional groups of the adsorbent did not change significantly, indicating that the prepared adsorbent has excellent stability in the degradation of tetracycline residues.
[0142] Obviously, the above embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.
Claims
1. A method for preparing an adsorbent material for treating antibiotics in wastewater, characterized in that, Includes the following steps: Phenylacetylene copper and nano-peryleneimide were dispersed in an organic solvent and then subjected to a hydrothermal reaction at 80℃~220℃ to obtain a phenylacetylene copper / peryleneimide composite material, which was then used as an adsorbent for antibiotic treatment in wastewater.
2. The preparation method according to claim 1, characterized in that, The mass ratio of phenylacetylene copper to nano-peryleneimide is 1:0.1 to 10.
3. The preparation method according to claim 1, characterized in that, The organic solvent is one or more of an alcohol solvent and N,N-dimethylformamide.
4. The preparation method according to claim 1, characterized in that, The ratio of the organic solvent to the copper phenylacetylene is 10 mL to 100 mL: 15 mg to 120 mg.
5. The preparation method according to claim 1, characterized in that, The phenylacetylene copper and nano-peryleneimide were dispersed in an organic solvent by first stirring and then ultrasonic treatment.
6. The preparation method according to claim 5, characterized in that, The ultrasonic treatment time is 2 min to 100 min.
7. The preparation method according to claim 5, characterized in that, The stirring time is 20 min to 180 min.
8. The preparation method according to claim 1, characterized in that, The hydrothermal reaction time is 1 hour to 16 hours.
9. An adsorbent material prepared by the preparation method according to any one of claims 1 to 8.
10. The application of the adsorbent material according to claim 9 in the adsorption of antibiotics in wastewater.
Citation Information
Patent Citations
Novel cuprous oxide and copper phenylacetylene compounded organic wastewater adsorbent
CN114682226A