Copper peroxide composite material and preparation method and application thereof

Abstract

The present application belongs to the technical field of copper peroxide material, and particularly relates to a copper peroxide composite material, a preparation method and application thereof. The copper peroxide composite material comprises copper peroxide and copper hydroxide. In the copper peroxide composite material, the content of copper peroxide is high, pollutants are adsorbed to the surface of the copper peroxide composite material by adsorption, and then through the action of electron transfer and superoxide anion, efficient oxidation degradation of various pollutants in water is directly realized. In addition, the pH range of the copper peroxide composite material is wide, and in the pH range of 5-9, the removal rate of pollutants can reach nearly 100%, the reagent addition in the acid adjusting process is reduced, and the defects of traditional Fenton-like process, i.e. narrow pH range and strict pH control (pH<4) required for effective degradation of pollutants, are solved.

Description

Technical Field

[0001] This invention belongs to the technical field of copper peroxide materials, and specifically relates to a copper peroxide composite material, its preparation method, and its application. Background Technology

[0002] Industrial sectors such as papermaking, paint production, chemical manufacturing, and biopharmaceuticals discharge numerous organic pollutants into natural waterways without proper treatment. In agricultural production, the extensive use of pesticides also leachs into water bodies, severely impacting the aquatic environment. These pollutants are highly toxic in water, posing serious threats to aquatic life and human health, and disrupting stable food chains. Furthermore, as carcinogens, even low concentrations can damage red blood cells and the liver in organisms.

[0003] Currently, Fenton-like reactions and photocatalysis are commonly used to remove pollutants from water bodies. The generation of reactive oxygen species through Fenton-like reactions is an effective means of treating organic pollutants. Catalysts are used to promote the redox reaction of Fe(III) / Fe(II), driving the decomposition of hydrogen peroxide to produce a large number of hydroxyl radicals or superoxide anions. For example, carbon nanotubes can accelerate the reduction reaction of Fe(III), meaning that hydrogen peroxide can efficiently transfer electrons to Fe(III) to generate Fe(II) through carbon nanotubes, promoting the activation of hydrogen peroxide. Currently, much work has been dedicated to improving the coupling mechanism with ferric iron. For example, compared to the Fe(III) / Fe(II)-ethylenediaminetetraacetic acid (EDTA) complex, the Fe(III) / Fe(II)-S,S-ethylenediaminedisuccinic acid (EDDS) complex can more efficiently drive the Fenton reaction through photocatalysis. However, due to the flammable and explosive nature of liquid hydrogen peroxide and its tendency to decompose easily when heated, it is difficult to store in large quantities, and there are also serious risks and hazards during transportation. Meanwhile, the Fenton reaction has extremely strict pH requirements, consumes a large amount of acid and alkali, increases processing costs, and has drawbacks such as large production of iron sludge requiring secondary treatment.

[0004] Therefore, it is of great significance to provide a material with a wide pH range that can efficiently remove pollutants from water by direct addition without the need for catalysts or acids / bases. Summary of the Invention

[0005] The present invention aims to solve one or more technical problems existing in the prior art, and at least provide a beneficial solution. Specifically, the present invention provides a copper peroxide composite material with high copper peroxide content and a wide pH range, which can efficiently remove various pollutants in water by direct addition without the need to add large amounts of acid or alkali to adjust the pH.

[0006] The inventive concept of this invention: The copper peroxide composite material of this invention comprises copper peroxide and copper hydroxide. Divalent copper ions (Cu...) 2+ The electron configuration of ) is 3d 9 This makes it an electron-deficient center and a strong Lewis acid, readily adsorbing pollutants through coordination with electron-rich groups, thus achieving interfacial enrichment of pollutants. The interfacial complexed pollutants and the peroxide bonds in the copper peroxide composite material achieve "enrichment-oxidation" of various new pollutants in water, such as bisphenol A, dichlorophenol, and ofloxacin, through an interfacial oxidation reaction pathway, simultaneously and efficiently removing them (approximately 99%). Meanwhile, the residual metal ions in the water are far below existing water quality standards (the national standard for copper ion content in drinking water is 1 ppm).

[0007] Therefore, a first aspect of the present invention provides a copper peroxide composite material.

[0008] Specifically, the copper peroxide composite material includes copper peroxide and copper hydroxide.

[0009] Preferably, the mass ratio of copper peroxide to copper hydroxide is 1:(1.77-4).

[0010] Preferably, the copper peroxide composite material is in sheet form.

[0011] A second aspect of the present invention provides a method for preparing the copper peroxide composite material described in the first aspect of the present invention.

[0012] Specifically, the preparation method of the copper peroxide composite material includes the following steps: (1) The copper salt is pretreated, and then an alkaline solution is added to react and a mixture is obtained; (2) Add hydrogen peroxide solution to the mixture obtained in step (1), react, and dry under vacuum to obtain the product; In step (1), the pretreatment temperature is 0-25℃, and the alkaline solution is added at a rate of 0.45-5.5 mL / min. In step (2), the hydrogen peroxide solution is added at a rate of 0.45-5.5 mL / min; the vacuum drying temperature is 30-65 °C.

[0013] Specifically, in order to obtain a high content of copper peroxide, the reaction system in the preparation process of this invention is carried out in a cold water bath (0-25°C) at a specific temperature, so that the formed copper hydroxide is more dispersed and can fully combine with hydrogen peroxide to generate copper peroxide, thereby greatly increasing the content of copper peroxide in the product.

[0014] Preferably, in step (1), the alkaline solution is added at a rate of 0.5-5 mL / min.

[0015] Preferably, in step (2), the hydrogen peroxide solution is added at a rate of 0.5-5 mL / min.

[0016] Preferably, in step (1), the copper salt includes copper sulfate.

[0017] Preferably, in step (1), the alkaline solution includes at least one of potassium hydroxide solution, sodium hydroxide solution, and ammonia water.

[0018] Preferably, in step (1), the reaction time is 4.5-22 min; more preferably, in step (1), the reaction time is 5-20 min.

[0019] Preferably, in step (2), the reaction time is 4.5-33 min; more preferably, in step (2), the reaction time is 5-30 min.

[0020] Preferably, the molar ratio of copper ions in the copper salt, hydroxide ions in the alkaline solution, and peroxide ions in the hydrogen peroxide solution is 1:2:(3-8); more preferably, the molar ratio of copper ions in the copper salt, hydroxide ions in the alkaline solution, and peroxide ions in the hydrogen peroxide solution is 1:2:6 or 1:2:8.

[0021] A third aspect of the present invention provides the application of the copper peroxide composite material described in the first aspect of the present invention in the removal of pollutants in water.

[0022] Preferably, the contaminant includes at least one of persistent organic compounds, endocrine disruptors, and antibiotics; the persistent organic compounds include at least one of dichlorophenol and nitrobenzene.

[0023] Preferably, the endocrine disruptor includes at least one of bisphenol A and dopamine.

[0024] Preferably, the antibiotic includes at least one of ofloxacin and sulfadiazine.

[0025] Compared with the prior art, the beneficial effects of the technical solution provided by the present invention are as follows: (1) The copper peroxide composite material of the present invention can utilize the adsorption effect of copper hydroxide to adsorb pollutants onto the surface of the material. At the interface of the copper peroxide composite material, peroxide ions are activated to generate a variety of active oxygen species or metal peroxide bonds that directly act on the pollutants, thereby directly achieving efficient oxidation and degradation of pollutants in water.

[0026] (2) This invention solves the defects of traditional Fenton-like processes, which have a narrow pH range and require strict pH control (pH<4) to effectively degrade pollutants. It can remove pollutants at a wide pH range, and can achieve a near 100% removal rate of pollutants in the pH range of 5-9. It reduces the amount of reagents added during the acidification process and has excellent pH adjustment capabilities. At the same time, after the reaction, the material can adjust the pH of the reaction system to slightly neutral (7.0±0.5), which is environmentally friendly. Attached Figure Description

[0027] Figure 1 This is a scanning electron microscope image of the copper peroxide composite material of Example 1 of the present invention; Figure 2 This is a scanning electron microscope image of the copper peroxide composite material of Comparative Example 1 of the present invention; Figure 3 This is the Raman spectrum of the copper peroxide composite material in Example 1 of the present invention; Figure 4 This is the Raman spectrum of copper hydroxide of the present invention; Figure 5 The removal efficiency of bisphenol A by copper hydroxide and copper peroxide composite material from Example 1 is shown in the graph. Figure 6 The graph shows the removal efficiency of bisphenol A by copper hydroxide and copper peroxide composite material from Example 1 after acidification treatment. Figure 7 The graph shows the removal efficiency of bisphenol A by the copper peroxide composite material in Example 1 at different pH ranges. Figure 8 The graph shows the results of removing bisphenol A from water using copper peroxide composite material in different pH ranges, as shown in Example 1. Figure 9 The graph shows the removal efficiency of the copper peroxide composite material in Example 1 for various pollutants. Detailed Implementation

[0028] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0029] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0030] Example 1 This embodiment provides a method for preparing copper peroxide composite material, the steps of which are as follows: Dissolve 1.25 g of CuSO4·5H2O in 50 mL of high-purity water and pour the solution into a 100 mL Erlenmeyer flask. Place the flask in a 25 °C constant temperature water bath. Then, add 20 mL of 0.5 M potassium hydroxide aqueous solution dropwise into the Erlenmeyer flask at a rate of 2 mL / min while stirring continuously with a magnetic stirrer. After the addition is complete, wait 5 min for the reaction to obtain the mixture. At a rate of 2 mL / min, 30 mL of 1 M hydrogen peroxide aqueous solution was added dropwise to the mixture; after the addition was complete, wait for 15 min to allow for a full reaction; then collect by centrifugation, wash the solid three times with anhydrous ethanol, and dry the solid in a vacuum drying oven at 35 °C for 12 h to obtain a yellowish-brown copper peroxide composite material.

[0031] Example 2 This embodiment provides a method for preparing copper peroxide composite material, the steps of which are as follows: Dissolve 1.25 g of CuSO4·5H2O in 50 mL of high-purity water and pour the solution into a 100 mL Erlenmeyer flask. Place the flask in a 25 °C constant temperature water bath. Then, add 20 mL of 0.5 M potassium hydroxide aqueous solution dropwise into the Erlenmeyer flask at a rate of 2 mL / min while stirring continuously with a magnetic stirrer. After the addition is complete, wait 5 min for the reaction to obtain the mixture. Add 40 mL of 1 M hydrogen peroxide aqueous solution dropwise to the mixture at a rate of 2 mL / min; wait 15 min after the addition is complete to allow for a full reaction; then collect by centrifugation, wash the solid three times with anhydrous ethanol, and dry the solid in a vacuum drying oven at 35 °C for 12 h to obtain a yellowish-brown copper peroxide composite material.

[0032] Comparative Example 1: The only difference between Comparative Example 1 and Example 1 is that the vacuum drying temperature of Comparative Example 1 is 70°C, while the rest is the same as Example 1.

[0033] The preparation method of the copper peroxide composite material in Comparative Example 1 is as follows: Dissolve 1.25 g of CuSO4·5H2O in 50 mL of high-purity water and pour the solution into a 100 mL Erlenmeyer flask. Place the flask in a 25 °C constant temperature water bath. Then, add 20 mL of 0.5 M potassium hydroxide aqueous solution dropwise into the Erlenmeyer flask at a rate of 2 mL / min while stirring continuously with a magnetic stirrer. After the addition is complete, wait 5 min for the reaction to obtain the mixture. At a rate of 2 mL / min, 30 mL of 1 M hydrogen peroxide aqueous solution was added dropwise to the mixture; after the addition was complete, wait another 15 min to allow for a full reaction; then collect by centrifugation, wash the solid three times with anhydrous ethanol, and dry the solid in a vacuum drying oven at 70 °C for 12 h to obtain a greenish copper peroxide composite material.

[0034] Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that in Comparative Example 2, potassium hydroxide aqueous solution was added to the conical flask all at once, and hydrogen peroxide aqueous solution was added to the mixture all at once. Otherwise, they are the same as in Example 1.

[0035] The preparation method of the copper peroxide composite material in Comparative Example 2 is as follows: Dissolve 1.25 g of CuSO4·5H2O in 50 mL of high-purity water and pour it into a 100 mL Erlenmeyer flask. Place the flask in a 25 °C constant temperature water bath. Then, add 20 mL of 0.5 M potassium hydroxide aqueous solution to the Erlenmeyer flask all at once and stir continuously with a magnetic stirrer. Wait for the reaction to proceed for 5 min to obtain a mixture. Add 30 mL of 1 M hydrogen peroxide aqueous solution to the mixture all at once, wait 15 min to allow it to react fully; finally, collect by centrifugation, wash the solid three times with anhydrous ethanol, and dry it in a vacuum drying oven at 35 °C for 12 h to obtain green solid particles.

[0036] Comparative Example 3: The only difference between Comparative Example 3 and Example 1 is that in Comparative Example 3, 30 mL of 0.45 M hydrogen peroxide aqueous solution was added dropwise to the mixture, that is, the molar ratio of copper salt, alkaline solution and hydrogen peroxide aqueous solution was 1:2:2.7, which is not within the range of 1:2:(3-8). Otherwise, it was the same as Example 1.

[0037] The preparation method of the copper peroxide composite material in Comparative Example 3 is as follows: Dissolve 1.25 g of CuSO4·5H2O in 50 mL of high-purity water and pour it into a 100 mL Erlenmeyer flask. Place the flask in a 25 °C constant temperature water bath. Then, add 20 mL of 0.5 M potassium hydroxide aqueous solution dropwise into the Erlenmeyer flask at a rate of 2 mL / min. Stir continuously with a magnetic stirrer and wait for 5 min to obtain a mixture. Add 30 mL of 0.45 M hydrogen peroxide aqueous solution dropwise to the mixture at a rate of 2 mL / min; wait 15 min again to allow for complete reaction; finally, collect by centrifugation, wash three times with anhydrous ethanol, and dry in a vacuum drying oven at 35 °C for 12 h to obtain greenish solid particles.

[0038] Comparative Example 4: The only difference between Comparative Example 4 and Example 1 is that in Comparative Example 4, 30 mL of 1.66 M hydrogen peroxide aqueous solution was added dropwise to the mixture, that is, the molar ratio of copper salt, alkaline solution and hydrogen peroxide aqueous solution was 1:2:10, which is not within the range of 1:2:(2-8). Otherwise, it is the same as Example 1.

[0039] Dissolve 1.25 g of CuSO4·5H2O in 50 mL of high-purity water and pour it into a 100 mL Erlenmeyer flask. Place the flask in a 25 °C constant temperature water bath. Then, add 20 mL of 0.5 M potassium hydroxide aqueous solution dropwise into the Erlenmeyer flask at a rate of 2 mL / min. Stir continuously with a magnetic stirrer and wait for 5 min to obtain a mixture. Add 30 mL of 1.66 M hydrogen peroxide aqueous solution dropwise to the mixture at a rate of 2 mL / min, wait 15 min again to allow for complete reaction; finally, collect by centrifugation, wash three times with anhydrous ethanol, and dry in a vacuum drying oven at 35 °C for 12 h to obtain a yellowish-brown copper peroxide composite material.

[0040] Performance testing 1. Determination of copper peroxide content in copper peroxide composite materials The copper peroxide content in the copper peroxide composite materials prepared in Examples 1-2 and Comparative Examples 1-4 was tested using the following methods: The peroxide content in the copper peroxide composite material was determined by redox reaction with acidic potassium permanganate. A certain mass of copper peroxide composite material (denoted as m0) was added to 10 mL of 1 mM acidic potassium permanganate solution (denoted as C0). After reacting for 3 min, the concentration of potassium permanganate after the reaction (denoted as C1) was measured at 525 nm using a UV spectrophotometer. The actual content of copper peroxide in the synthesized copper peroxide composite material was then calculated using the following formula.

[0041] The calculation formula is as follows: Copper peroxide content = (C0-C1)×V×2.5×96 / m0×100%; Where: C1 and C0: represent the concentrations of potassium permanganate after the reaction and before the reaction, respectively, in mmol / L; V: Represents the total volume of the reaction, in liters (L); m0: represents the mass of the added copper peroxide composite material, in grams.

[0042] The copper peroxide content in the copper peroxide composite materials prepared in Examples 1-2 and Comparative Examples 1-4 is shown in Table 1.

[0043] Table 1: Copper peroxide content in the copper peroxide composite materials prepared in Examples 1-2 and Comparative Examples 1-4

[0044] As shown in Table 1, the copper peroxide content in the copper peroxide composite material prepared by this invention is relatively high. In contrast, the copper peroxide content in the products of Comparative Examples 1-4 is significantly lower than that of this invention. This indicates that the preparation method of this invention can increase the copper peroxide content in the copper peroxide composite material.

[0045] 2. Scanning electron microscopy observation Scanning electron microscopy (SEM) was performed on the copper peroxide composite materials prepared in Example 1 and Comparative Example 1. The SEM results are as follows: Figure 1 and Figure 2 As shown.

[0046] Depend on Figure 1 and Figure 2 It can be seen that the composite materials of Example 1 and Comparative Example 1 both contain substances with a plate-like morphology, which is different from the synthesized needle-like copper hydroxide and is identified as the morphological characteristics of copper peroxide composite materials.

[0047] 3. Raman spectroscopy test To determine whether a metal peroxide has been synthesized, Raman spectroscopy can be performed on the synthesized material. For example, when performing Raman spectroscopy on magnesium peroxide, the presence of peroxide ions (O2) in magnesium peroxide can be detected. 2- The OO stretching vibration of the ion is at 875 cm⁻¹ -1 An absorption peak appeared at 831.6 cm⁻¹; for example, when lanthanum peroxide was detected by Raman spectroscopy, an absorption peak appeared at 831.6 cm⁻¹. -1 An absorption peak of OO was detected at the point.

[0048] Raman spectroscopy was performed on the copper peroxide composite material of Example 1, and the results are as follows: Figure 3 As shown.

[0049] The Raman spectrum of copper hydroxide is as follows: Figure 4 As shown.

[0050] Depend on Figure 3 , 4 It can be seen that its Raman spectrum differs from that of copper hydroxide at 828 cm⁻¹. -1 An absorption peak was detected at the point, further confirming the synthesis of copper peroxide.

[0051] 4. Pollutant removal capacity test To illustrate the specific removal kinetics of a certain pollutant by the synthesized copper peroxide composite material, bisphenol A was used as the main pollutant in the experiment, specifically: Equivalent amounts of copper hydroxide (0.033 g) and copper peroxide composite material from Example 1 (0.045 g) were added to 50 mL of bisphenol A solution containing 5 μM for comparative experiments. Samples were taken at different time points, and the bisphenol A content in the samples was detected using a high-performance liquid chromatography detector and denoted as C. The initial content was denoted as C0. Finally, the removal rate was calculated according to the removal rate formula (1-C / C0)×100%, where C / C0 represents the ratio of the bisphenol A content in the sample to the initial content at different sampling points.

[0052] The removal efficiency of bisphenol A by copper hydroxide and copper peroxide composite material (Example 1) is as follows: Figure 5 As shown.

[0053] Depend on Figure 5 It can be seen that copper hydroxide was almost saturated with bisphenol A adsorption after 20 minutes, while the copper peroxide composite material in Example 1 continued to remove bisphenol A, and the removal rate reached 95% after 5 hours.

[0054] Because copper hydroxide has a strong adsorption capacity for bisphenol A (BPA), in order to eliminate the influence of the adsorption of copper hydroxide in the copper peroxide composite material on the removal rate and to demonstrate the oxidative degradation effect of copper peroxide in the copper peroxide composite material, the sample solution at different time points was acidified (by adding 10 μL of 4.6M sulfuric acid solution to 1 mL of sample solution to dissolve the copper peroxide composite material, and simultaneously adding 10 μL of 99% methanol). Then, the bisphenol A content in the sample was detected by a high performance liquid chromatography detector and recorded as C, and the initial content was recorded as C0. Finally, the removal rate was calculated according to the removal rate formula (1-C / C0)×100%, where C / C0 represents the ratio of the bisphenol A content in the sample to the initial content at different sampling points.

[0055] The removal efficiency of bisphenol A by copper hydroxide and copper peroxide composite material (Example 1) after acidification treatment is as follows: Figure 6 As shown.

[0056] Depend on Figure 6 It can be seen that when bisphenol A was removed using acid-treated copper hydroxide, the bisphenol A content returned to its initial value, further confirming that copper hydroxide only plays an adsorption role for pollutants. After dissolving the material with acid, the bisphenol A adsorbed on the surface of the copper hydroxide material reappeared in the aqueous solution. In the copper peroxide composite material of Example 1, after acid treatment, the influence of copper hydroxide adsorption was eliminated, but bisphenol A still gradually degraded, and the degradation rate reached 100% within 3-5 hours. This indicates that copper peroxide in the copper peroxide composite material can remove bisphenol A through oxidative degradation.

[0057] 5. Effect of pH range on bisphenol A removal test The removal rate of bisphenol A was tested using the copper peroxide composite material prepared in Example 1 under different pH conditions to study the effect of pH range on the removal rate of bisphenol A.

[0058] The specific testing process is as follows: 50 mL of 5 μM BPA aqueous solution was adjusted to different pH values ​​(3, 5, 7, 9, 11) using 0.1 M sulfuric acid or sodium hydroxide. Then, equal amounts of (2.5 mM) copper peroxide composite material were added to each solution for the experiment, and samples were taken for testing at different time points.

[0059] Example 1: The removal efficiency of copper peroxide composite material for bisphenol A in different pH ranges is as follows: Figure 7 As shown.

[0060] Depend on Figure 7 As can be seen, unlike traditional Fenton-type compounds which have a narrow pH range and require strict pH control (pH < 4) to effectively degrade pollutants, the copper peroxide composite material of this invention can operate in a wide range of pH solutions. Within the pH range of 5-9, it can achieve a near 100% removal rate, reducing the amount of reagents needed for acidification and exhibiting excellent pH adjustment capabilities. Furthermore, the pH of the system can be adjusted to slightly neutral (7.0 ± 0.5) after the reaction, making it more environmentally friendly.

[0061] In addition, after the above-mentioned bisphenol A removal test was completed, the residual metal ions in the water were tested. The test method was as follows: the supernatant after the reaction was filtered through a 22 μM filter membrane and then diluted with 2 wt% nitric acid. The resulting clear and transparent liquid was then tested for copper ion leakage using inductively coupled plasma optical emission spectrometry (ICP-OES).

[0062] The results of copper ion content in water after bisphenol A removal by copper peroxide composite material at different pH ranges are shown in the figure below. Figure 8 As shown.

[0063] Depend on Figure 8 It can be seen that under different pH conditions, after removing bisphenol A using copper peroxide composite material, the content of copper ions in the water is much lower than the existing water quality standard (the national standard for copper ion content in drinking water is 1 ppm).

[0064] 6. Tests on the removal efficiency of copper peroxide composite materials for various pollutants. The copper peroxide composite material of Example 1 was used to remove various pollutants to study its removal efficiency. The specific test procedure is as follows: The copper peroxide composite material of Example 1 was added to different pollutants, including dopamine (DA), ofloxacin (OFX), 2,4-dichlorophenol (24DCP), sulfadiazine (SDZ), nitrobenzene (NB), 4-chlorophenol (4-CP), norfloxacin (NFX), ciprofloxacin (CIP), phenol (PHENOL), diclofenac (DCF), and enrofloxacin (EN). The following contaminants were removed: R), 2,4-dinitrophenol (DNP), carbamazepine (CBZ), metronidazole (MTZ), DEET, benzotriazole (BZFT), ibuprofen (IBP), caffeine (CAF), chloramphenicol (CAP), atenolol (ATN), and sulfamethoxazole (SMX). Samples were taken at different time points, and the content of different contaminants in the samples was detected by high performance liquid chromatography (HPLC) and recorded as C. The initial content was recorded as C0. Finally, the removal rate was calculated according to the removal rate formula (1-C / C0)×100%.

[0065] The removal efficiency of copper peroxide composite materials for various pollutants, such as Figure 9 As shown.

[0066] Depend on Figure 9 It can be seen that copper peroxide composite materials can adsorb and oxidize various pollutants, making them widely applicable to the treatment of multiple pollutants in wastewater. They have strong practical applicability and can effectively address various types of polluted water bodies.

[0067] In summary, the copper peroxide composite material obtained by this invention through a specific preparation process has a high copper peroxide content. It utilizes adsorption to adsorb pollutants onto the surface of the copper peroxide composite material particles, and then achieves efficient oxidative degradation of various pollutants in water directly through electron transfer and the action of superoxide anions. Furthermore, the copper peroxide composite material of this invention has a wide pH range, achieving near 100% removal rate of pollutants within the pH range of 5-9. This reduces the amount of reagents added during acidification and overcomes the shortcomings of traditional Fenton-like processes, which have a narrow pH range and require strict pH control (pH < 4) for effective pollutant degradation.

[0068] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. Use of a copper peroxide composite material for the oxidative removal of pollutants from water, characterized in that, The contaminant includes at least one of bisphenol A and dopamine; The pH of the application is 5-9; The preparation method of the copper peroxide composite material includes the following steps: (1) The copper salt is pretreated, and then an alkaline solution is added to react and a mixture is obtained; (2) Add hydrogen peroxide solution to the mixture obtained in step (1), react, and dry under vacuum to obtain the product; In step (1), the pretreatment temperature is 0-25℃, and the alkaline solution is added at a rate of 0.45-5.5 mL / min. In step (2), the hydrogen peroxide solution is added at a rate of 0.45-5.5 mL / min; the vacuum drying temperature is 30-65 °C. The molar ratio of copper ions in the copper salt, hydroxide ions in the alkaline solution, and peroxide ions in the hydrogen peroxide solution is 1:2:(3-8). The copper peroxide composite material includes copper peroxide and copper hydroxide; The mass ratio of copper peroxide to copper hydroxide is 1:(1.77-4).

2. Use according to claim 1, characterized in that, The copper peroxide composite material is in sheet form.

3. Use according to claim 1, characterized in that, In step (1), the copper salt includes copper sulfate; and / or, the alkaline solution includes at least one of potassium hydroxide solution, sodium hydroxide solution, and ammonia water.

4. Use according to claim 1, characterized in that, In step (1), the reaction time is 4.5-22 min.

5. The application according to claim 1, characterized in that, In step (2), the reaction time is 4.5-33 min.

Images