Method for degrading phenolic substances by using imitated laccase nano material and application

Abstract

The invention discloses a method for degrading phenolic substances by using a laccase-imitating nano material and application of the laccase-imitating nano material. The method for degrading the phenolic substances by using the imitated laccase nano-material comprises the following steps: adding the imitated laccase nano-material into a medium containing the phenolic substances, and degrading the phenolic substances through catalytic oxidation reaction of the imitated laccase nano-material on the phenolic substances under optional oscillation treatment, the imitated laccase nano material is selected from Cu2O. According to the invention, the nano material Cu2O is found to be used as the imitated laccase, so that the degradation of phenolic substances, especially Cu2O (c-Cu2O) of a cubic structure, can be realized, and the degradation effect on the phenolic substances is better. The simulated laccase nano material developed by the invention overcomes the defects of poor stability, high preparation cost, difficult recovery and the like of natural laccase, and shows a higher degradation rate in actual wastewater treatment. Through the innovation, higher catalytic activity and catalytic stability than natural laccase are realized, and a new solution is provided for efficient degradation of phenolic pollutants.

Description

Technical Field

[0001] The present invention relates to the technical field of sewage treatment, and further relates to a method and application of degrading phenolic substances by utilizing laccase-like nanomaterials. Background Art

[0002] With the continued growth of the population and the rapid development of the economy and society, the types of pollutants discharged into the aquatic environment by human production and daily life activities are increasing, and the composition is becoming increasingly complex, posing a huge challenge to the safety of the aquatic environment. Chlorophenol pollutants are common toxic pollutants widely used in wood preservatives, pesticides, and disinfectants. These chlorophenol pollutants are carcinogenic, reproductive toxic, neurotoxic, and endocrine disrupting, posing a serious threat to human health and have been widely detected in underground soil and water bodies. Therefore, the development of efficient methods for the removal of chlorophenol pollutants is particularly important.

[0003] Currently, a variety of treatment methods have been developed, including biological treatment, physical separation, chemical conversion, and enzyme and enzyme-mimicking catalysis. Enzyme and enzyme-mimicking catalysis are chemical methods. Enzyme catalysis utilizes enzymes produced by microorganisms to catalyze substrates for biochemical reactions, while enzyme-mimicking catalysis mimics the properties of natural enzymes to design and synthesize non-protein molecules or nanomaterials to achieve efficient catalysis of chemical reactions. Enzyme and enzyme-mimicking catalysis primarily converts difficult-to-degrade organic pollutants into easily degradable substances rather than completely mineralizing them, thereby reducing treatment difficulty, reducing the consumption of oxidants and energy, and saving treatment costs. It is a green and sustainable technology with mild conditions, high catalytic efficiency, and a green approach.

[0004] Enzymes and enzyme-mimicking catalysis can degrade macromolecular organic pollutants, particularly phenolic pollutants, into low- or non-toxic small-molecule products, making them suitable pretreatment steps for cost-effective bioremediation methods. Laccase is an enzyme that can be used to degrade phenolic pollutants. It primarily catalyzes oxidation using O₂, which is then reduced to water without producing any other byproducts. However, natural enzymes suffer from high preparation costs, poor stability, and difficulty in recycling, limiting their practical application. Consequently, enzyme-mimicking materials have emerged. In recent years, research on enzyme-mimicking materials has attracted considerable attention, as they overcome the inherent shortcomings of natural enzymes and have become a research hotspot.

[0005] However, there are few enzyme-mimicking materials that can be used to degrade phenolic pollutants. How to develop more effective enzyme-mimicking materials is a technical problem that needs to be solved at present. Summary of the Invention

[0006] To address the problems encountered in the prior art, the present invention proposes a method and application for degrading phenolic substances using laccase-mimicking nanomaterials. The present invention discovers that the nanomaterial Cu2O, as a laccase-mimicking enzyme, can degrade phenolic substances, particularly Cu2O with a cubic structure (c-Cu2O), which is more effective in degrading phenolic substances. The laccase-mimicking nanomaterial developed by the present invention overcomes the shortcomings of natural laccase, such as poor stability, high preparation cost, and difficult recycling. In particular, the cubic Cu2O (c-Cu2O) is superior to natural laccase in removing phenolic pollutants and exhibits a higher degradation rate in actual wastewater treatment. Through this innovation, the present invention achieves higher catalytic activity and catalytic stability than natural laccase, providing a new solution for the efficient degradation of phenolic pollutants.

[0007] One of the purposes of the present invention is to provide a method for degrading phenolic substances using laccase-like nanomaterials, comprising the following steps:

[0008] adding the laccase-mimicking nanomaterial to a medium containing phenolic substances, and achieving degradation of the phenolic substances through a catalytic oxidation reaction of the laccase-mimicking nanomaterial on the phenolic substances under an optional oscillation treatment;

[0009] The laccase-mimicking nanomaterial is selected from Cu2O.

[0010] In the method for degrading phenolic substances using laccase-like nanomaterials of the present invention, preferably,

[0011] The laccase-mimicking nanomaterial is selected from Cu2O with a cubic structure; and / or,

[0012] The laccase-mimicking nanomaterial is selected from Cu2O with a short hexapod structure; and / or,

[0013] The laccase-mimicking nanomaterial is selected from Cu2O with a rhombic dodecahedron structure.

[0014] In this study, we creatively used Cu2O as a laccase-mimicking material to degrade phenolic pollutants. This is a finding previously unexplored in the prior art. Furthermore, we discovered that the three different Cu2O morphologies described above all function as laccase-mimicking materials for the degradation of phenolic pollutants, but the effectiveness is structure-dependent. Cubic Cu2O exhibited the best laccase-like activity, followed by short hexapods, and the worst by rhombic dodecahedrons. It is noteworthy that cubic Cu2O exhibited significantly better catalytic activity than natural laccase, suggesting promising application prospects.

[0015] In the method for degrading phenolic substances using laccase-like nanomaterials of the present invention, preferably,

[0016] The particle size of the cubic structured Cu2O is in the range of 600-850 nm; and / or,

[0017] The particle size of the short hexapod Cu2O is in the range of 650-800 nm; and / or,

[0018] The particle size of the Cu2O with the rhombic dodecahedron structure ranges from 650 to 800 nm.

[0019] In the method for degrading phenolic substances using laccase-like nanomaterials of the present invention, preferably,

[0020] The medium containing phenolic substances is water containing phenolic substances;

[0021] Preferably, the water containing phenolic substances is wastewater containing phenolic substances;

[0022] More preferably,

[0023] The phenolic substance is selected from at least one of 2,4-dichlorophenol, 2-chlorophenol, hydroquinone, p-nitrophenol, 2-aminophenol or phenol; and / or,

[0024] In wastewater containing phenolic substances, the concentration of phenolic substances is 0.1 mg / mL-1 mg / mL; and / or,

[0025] The salt concentration of the wastewater containing phenolic substances is 0-500mmol / L; and / or,

[0026] The pH of wastewater containing phenolic substances is 4-10.

[0027] In the method for degrading phenolic substances using laccase-like nanomaterials of the present invention, preferably,

[0028] The mass volume ratio of the laccase-mimicking nanomaterial to the medium containing phenolic substances is 0.1 mg-1 mg:1 mL; and / or,

[0029] The temperature of the catalytic oxidation reaction is 30-90°C; and / or,

[0030] The catalytic oxidation reaction time is 1h-10h.

[0031] The laccase-mimicking nanomaterial of the present invention can achieve efficient degradation of phenolic substances at a relatively small amount of the laccase-mimicking nanomaterial added and a relatively low reaction temperature (such as 30° C.).

[0032] In the method for degrading phenolic substances using laccase-like nanomaterials of the present invention, preferably, the method for preparing Cu2O comprises the following steps:

[0033] 1) adding a copper salt solution to water and mixing once, then adding an alkaline solution and mixing twice; then adding a surfactant and mixing three times; finally adding a reducing agent solution and mixing four times, followed by standing and aging to obtain an aged solution;

[0034] 2) Discarding the supernatant in the aging solution, adding an alcohol substance to the remaining material for ultrasonic dispersion, and then centrifuging to obtain a precipitate, and vacuum drying the precipitate to obtain the Cu2O.

[0035] In the method for degrading phenolic substances using laccase-like nanomaterials of the present invention, preferably,

[0036] In step 1),

[0037] The copper salt in the copper salt solution is selected from CuCl2; and / or,

[0038] The concentration of the copper salt solution is 0.1 mol / L-10 mol / L; and / or,

[0039] The volume ratio of the water (the water here refers to the water initially added in step 1, and the same meaning shall apply hereinafter and will not be described in detail here) to the copper salt solution is (94-96):1 or (90-91):1; preferably (95-96):1; and / or,

[0040] The alkaline solution is a NaOH solution; and / or,

[0041] The concentration of the alkaline solution is 1 mol / L-10 mol / L; and / or,

[0042] The volume ratio of water to alkaline solution is (45-48):1; preferably (46-48):1; more preferably (47-48):1; and / or,

[0043] The second mixing was performed by shaking for 10s-1min.

[0044] In the method for degrading phenolic substances using laccase-like nanomaterials of the present invention, preferably,

[0045] In step 1),

[0046] The surfactant is sodium lauryl sulfate; and / or,

[0047] The mass ratio of water to surfactant is (108-110):1 or (104-105):1; preferably (109.5-110):1; and / or,

[0048] The three times of mixing are vigorous stirring until the surfactant is dissolved, and then standing for 5-15 minutes, such as 5 minutes, 10 minutes, and 15 minutes; and / or,

[0049] The reducing agent solution is NH2OH·HCl solution;

[0050] The concentration of the reducing agent solution is 0.18-0.22 mol / L; and / or,

[0051] The volume ratio of water to reducing agent solution is (62-65):1 or (13-14):1; preferably (63.5-64):1; and / or,

[0052] Four times of mixing are shaking for 10s-1min; and / or,

[0053] The static aging time is 1.9h-2.1h.

[0054] In the method for degrading phenolic substances using laccase-like nanomaterials of the present invention, preferably,

[0055] In step 2),

[0056] The alcohol substance is anhydrous ethanol; and / or,

[0057] The volume ratio of the alcohol substance to the aging liquid is (0.0675-0.075):1; and / or,

[0058] The power of the ultrasonic dispersion is 150-500W; and / or,

[0059] The ultrasonic dispersion time is 4 min to 6 min; and / or,

[0060] The above-mentioned preparation method of the present invention is used to prepare Cu2O with a cubic structure and Cu2O with a short hexapod structure. In particular, the present invention unexpectedly discovered that in the post-processing step of obtaining Cu2O, ultrasonic dispersion is first performed, and then the number, time, and speed of centrifugation are strictly controlled to obtain Cu2O with significantly improved degradation effect. Preferably, the number of centrifugation is 1; further preferably, the speed of the centrifugation is 7500rpm-8500rpm; and / or, the centrifugation time is 4.5min-5min; for example, 4.5min, 4.6min, 4.7min, 4.8min, 4.9min, 5min; further preferably, the speed of the centrifugation is 8000rpm; the centrifugation time is 5min; and / or,

[0061] The vacuum drying temperature is 60-80°C.

[0062] The second object of the present invention is to provide an application of the method for degrading phenolic substances using laccase-like nanomaterials as described in one of the objects of the present invention in sewage treatment.

[0063] The substances and parameters not limited in the present invention can be selected according to the existing technology and belong to the conventional technical means in this field.

[0064] The endpoints and any values of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and a separate point value, and the separate point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be considered as specifically disclosed in this article.

[0065] Compared with the prior art, the present invention has at least the following advantages:

[0066] This invention proposes a laccase-mimicking process based on Cu2O nanomaterials, specifically a process that utilizes cubic Cu2O (c-Cu2O) for the efficient degradation of phenolic pollutants. This process leverages the advantages of Cu2O, such as high stability, low cost, reusability, and ease of preparation, to demonstrate superior degradation efficiency in actual wastewater. Furthermore, this process allows for flexible adjustment of material addition volume and concentration based on market demand, fully achieving efficient resource utilization and possessing broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 This is the crystal phase spectrum of Cu2O prepared in Example 1;

[0068] Figure 2 This is an electron microscope image of Cu2O prepared in Example 1;

[0069] Figure 3 The degradation effect of Cu2O prepared in Example 1 on various phenolic substances;

[0070] Figure 4 Cyclic stability of Cu2O prepared in Example 1;

[0071] Figure 5 Comparison of the relative catalytic activities of Cu2O prepared in Example 1 and natural laccase at different temperatures;

[0072] Figure 6 Comparison of the relative catalytic activities of Cu2O prepared in Example 1 and natural laccase at different pH values;

[0073] Figure 7 This is the crystal phase spectrum of Cu2O prepared in Example 2;

[0074] Figure 8 This is an electron microscope image of Cu2O prepared in Example 2;

[0075] Figure 9 This is the crystal phase spectrum of Cu2O prepared in Example 3;

[0076] Figure 10 This is an electron microscope image of Cu2O prepared in Example 3;

[0077] Figure 11 Comparison of the degradation effects of Cu2O prepared in Example 1 and Comparative Example 1;

[0078] Figure 12 Comparison of the degradation effects of Cu2O prepared in Example 1 and Comparative Example 2;

[0079] Figure 13 Comparison of the degradation effects of Cu2O prepared in Examples 1, 2 and 3 and natural laccase. DETAILED DESCRIPTION

[0080] The present invention will be described in detail below with reference to specific drawings and embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art to the present invention based on the contents of the present invention still fall within the scope of protection of the present invention.

[0081] It should also be noted that the various specific technical features described in the following specific embodiments can be combined in any appropriate manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0082] In addition, the various embodiments of the present invention may be arbitrarily combined as long as they do not violate the concept of the present invention. The technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the scope of protection of the present invention.

[0083] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0084] Example 1

[0085] The present invention provides a method for preparing cubic Cu2O, comprising the following steps:

[0086] 1) Add 382 ml of pure water to a large container; add 4 ml of 0.1 M CuCl2 solution to the pure water; add 8 ml of 1 M NaOH solution to the mixture from the previous two steps and shake for 10 seconds; then add 3.48 g of sodium lauryl sulfate powder to the mixture, stir vigorously until the powder dissolves, and let it stand for 5 minutes; finally, add 6 ml of 0.2 M hydroxylamine hydrochloride (NH2OH·HCl) to the mixture, mix, and shake for 10 seconds to obtain a final solution of 400 ml, which is then aged for 2 hours;

[0087] 2) After aging, a portion of the supernatant was discarded, and 30 ml of anhydrous ethanol was added to the remaining precipitate and solution, and ultrasonic dispersion and washing were performed at a power of 100 W for 5 minutes until the precipitate was completely dispersed. The mixture was then centrifuged at 8000 rpm for 5 minutes, and the centrifuge was discarded to obtain a precipitate. The precipitate was vacuum dried at 60°C for 12 hours to obtain cubic Cu2O (c-Cu2O).

[0088] The particle size of the cubic structure Cu2O prepared in Example 1 is about 600-850nm. The crystal phase spectrum and electron microscope image of the Cu2O prepared in Example 1 are as follows: Figure 1 and Figure 2 shown.

[0089] Example 2

[0090] 1) Add 362 ml of deionized water to beaker a;

[0091] 2) Then add 4 ml of 0.1 M CuCl2 solution into beaker a;

[0092] 3) Add 8 ml of 1 M NaOH solution to beaker a and shake for 10 seconds;

[0093] 4) Add 3.48g of sodium lauryl sulfate powder to beaker a, stir vigorously until the powder dissolves, and let it stand for 5 minutes;

[0094] 5) Then, add 26 ml of 0.2 M NH2OH·HCl to beaker a, mix, and shake for 10 seconds;

[0095] 6) Obtain 400 ml of final solution;

[0096] 7) After aging for 2 hours, pour off the supernatant, leaving only the precipitate and part of the solution, and transfer the precipitate in beaker a to a centrifuge tube;

[0097] 9) Centrifuge at 8000 rpm for 5 min and discard the centrifuge; add anhydrous ethanol and ultrasonically disperse and wash, that is, centrifuge at 8000 rpm for 5 min to remove unreacted chemicals and sodium lauryl sulfate surfactant, and discard the centrifuge after centrifugation;

[0098] 8) After centrifugation, vacuum dry at 60°C for 12 hours to obtain Cu2O with a short hexapod structure.

[0099] The particle size of the short hexapod structure Cu2O prepared in Example 2 is about 650-800nm. The crystal phase spectrum and electron microscope image of the Cu2O prepared in Example 2 are as follows: Figure 7 and Figure 8 shown.

[0100] Example 3

[0101] Dissolve 0.25g of copper sulfate pentahydrate in 40ml of water to form a clear solution. Add 20ml of anhydrous ethanol to the solution. Pour the mixture into a three-necked round-bottom flask and stir vigorously at 500 rpm with a stirrer.

[0102] 1) Add 4 ml of oleic acid while stirring vigorously, then heat;

[0103] 2) After heating to 100°C, 10 ml of NaOH (0.8 M) was added to the mixture;

[0104] 3) After 5 minutes, add 30 ml of D-glucose aqueous solution (0.63 M) to the blue suspension and continue stirring for 60 minutes. A brick red color gradually appears.

[0105] 4) After the reaction, cool naturally for 40 minutes, transfer the solution to a 50 ml round-bottom centrifuge tube, centrifuge at 8000 rpm for 5 minutes, discard the centrifuge, wipe the blue oil on the tube wall with paper, add anhydrous ethanol for ultrasonic washing, centrifuge at 8000 rpm for 5 minutes, and discard the centrifuge.

[0106] 5) The precipitate was dried in a vacuum drying oven at 60° C. for 12 h to obtain Cu2O with a short hexapod structure.

[0107] The particle size of Cu2O prepared in Example 3 with a rhombic dodecahedral structure is about 650-800 nm. The crystal phase spectrum and electron microscope image of Cu2O prepared in Example 3 are as follows: Figure 9 and Figure 10 shown.

[0108] Comparative Example 1

[0109] The preparation method was identical to that of Example 1 of the present invention, with the only difference being that, in step 2), the aged solution was centrifuged at 3500 rpm for 2 minutes, and the supernatant was removed. Subsequently, the precipitate was centrifuged twice more using ethanol.

[0110] Comparative Example 2

[0111] The preparation method is the same as that of Example 1 of the present invention, with the only difference being that in step 2), in Comparative Example 2, centrifugation is performed twice under the same conditions as in Example 1.

[0112] Application Example 1

[0113] The Cu2O prepared in Example 1 was used to degrade phenolic pollutants in sewage, specifically:

[0114] The laccase-mimicking nanomaterials are added into wastewater containing phenolic substances, and the phenolic substances are degraded through the catalytic oxidation reaction of the laccase-mimicking nanomaterials.

[0115] Among them, the phenolic substances in the wastewater are 2,4-dichlorophenol, 2-chlorophenol, hydroquinone, p-nitrophenol, 2-aminophenol, and phenol;

[0116] In the wastewater containing phenolic substances, the concentration of phenolic substances is 1 mg / ml; the salt concentration of the wastewater containing phenolic substances is 10 mg / ml (the salt is NaCl); and the pH of the wastewater containing phenolic substances is 6.8.

[0117] The mass volume ratio of the laccase-like nanomaterial to the wastewater containing phenolic substances is 1 mg:1 mL; the temperature of the catalytic oxidation reaction is 30° C.; and the time of the catalytic oxidation reaction is 1 h.

[0118] Among them, the degradation effect of Cu2O prepared in Example 1 on various phenolic substances is as follows Figure 3 As shown, Figure 3 The absorbance at the wavelength of 510 nm is calculated. Figure 3 The names of the phenolic substances are shown in Table 1 below:

[0119] Table 1

[0120] English name Chinese name 2,4-Dichlorophenol 2,4-Dichlorophenol 2-Chlorophenol 2-Chlorophenol Hydroquinone hydroquinone p-Nitrophenol p-Nitrophenol 2-Aminophenol 2-Aminophenol phenol phenol Control Control (using water control)

[0121] from Figure 3 It can be seen that the Cu2O prepared in Example 1 has a certain degradation effect on various phenolic substances, especially the best degradation effect on 2,4-dichlorophenol, followed by 2-chlorophenol.

[0122] Figure 4The results of cyclic stability testing of the Cu2O prepared in Example 1 show that the c-Cu2O (cubic Cu2O) catalyst provided by the present invention retained approximately 70% of its initial catalytic activity after four consecutive reuses, demonstrating excellent cyclic stability and reusability. In contrast, natural laccase is difficult to recycle and has poor stability, making it difficult to effectively reuse in practical applications. This comparative result fully demonstrates the significant advantages of the catalyst of the present invention in terms of recyclability and stability.

[0123] Application Example 2

[0124] The Cu2O prepared in Example 1, Comparative Example 1 and Comparative Example 2 were respectively used to degrade phenolic pollutants in sewage. Specifically:

[0125] The reaction method is basically the same as that of Application Example 1, except that the phenolic substance to be degraded is 2,4-dichlorophenol. After the laccase-like nanomaterial is added, the phenolic substance is catalyzed and oxidized under oscillation conditions.

[0126] The comparison results of Example 1 and Comparative Example 1 are as follows Figure 11 As shown, the activity of Cu2O prepared under different post-treatment conditions in the present invention and comparative example 1 is compared. It can be found that the cubic Cu2O prepared according to the post-treatment method of the present invention has higher activity.

[0127] The comparison results of Example 1 and Comparative Example 2 are as follows: Figure 12 As shown in the figure, a comparison of the activities of Cu2O prepared under the post-treatment conditions of the present invention and Comparative Example 2 reveals that the activity of the cubic Cu2O prepared at a speed of 8000 rpm and a centrifugation time of only 5 minutes is higher. Furthermore, the present invention also found that the activity of the cubic Cu2O prepared at a speed of 8000 rpm and a centrifugation time of only 3 minutes is significantly lower than that of the Cu2O prepared under the post-treatment conditions of Example 1.

[0128] The above results fully demonstrate that only the cubic Cu2O prepared by the post-treatment method of the present invention has higher activity and better degradation effect on phenolic substances.

[0129] In addition, by comparing the results of Application Example 2 and Application Example 1, it can be seen that the Cu2O prepared in Example 1 of the present invention has a better effect on the degradation of phenolic substances under oscillation conditions.

[0130] Application Example 3

[0131] The Cu2O prepared in Example 1 and natural laccase were used to degrade phenolic pollutants in sewage, specifically:

[0132] The same reaction method as in Application Example 1 was used, except that the temperature of the catalytic oxidation reaction was 30-90 degrees. The degradation results of the corresponding materials on phenolic pollutants in wastewater were as follows: Figure 5 shown.

[0133] like Figure 5 The temperature stability test results shown indicate that the c-Cu2O catalyst prepared in the present invention maintains high catalytic activity under low, medium, and high temperature conditions, demonstrating excellent temperature adaptability and thermal stability. In contrast, the catalytic activity of natural laccase decreases significantly under high temperature conditions. This comparative experimental data fully demonstrates the significant technical advantage of the Cu2O prepared in the present invention over the natural enzyme in terms of high temperature resistance, enabling it to maintain stable catalytic efficiency under a wider range of ambient temperature conditions.

[0134] Application Example 4

[0135] The Cu2O prepared in Example 1 and natural laccase were used to degrade phenolic pollutants in sewage, specifically:

[0136] The same reaction method as in Application Example 1 was used, except that the pH of the catalytic oxidation reaction was 4-10 degrees. The degradation results of the corresponding materials on phenolic pollutants in wastewater were as follows: Figure 6 shown.

[0137] like Figure 6 The pH stability test results shown indicate that the c-Cu2O catalyst prepared in the present invention maintains stable catalytic activity across a wide pH range, demonstrating excellent pH adaptability. In contrast, natural laccase exhibits high activity only under weakly acidic conditions and essentially loses its catalytic function in alkaline environments. This comparative experimental data fully demonstrates the significant improvement in pH tolerance of the Cu2O prepared in the present invention compared to the natural enzyme, enabling it to maintain stable catalytic performance under a wider range of environmental conditions and possessing broader application prospects.

[0138] Application Example 5

[0139] The Cu2O laccase-mimicking nanomaterials and natural laccase prepared in Examples 1, 2 and 3 were used to degrade phenolic pollutants in sewage. Specifically:

[0140] The same reaction method as in Application Example 2 was used, and the specific degradation results were as follows: Figure 13 shown.

[0141] from Figure 13It can be seen from the figure that in terms of catalytic activity comparison, the degradation effects of the short hexapod and rhombic dodecahedron Cu2O prepared in Examples 2 and 3 and natural laccase on phenolic pollutants are lower than that of the cubic Cu2O prepared in Example 1. The cubic Cu2O prepared in Example 1 of the present invention has the best degradation effect on phenolic pollutants.

[0142] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present invention without departing from the spirit and scope of the present invention, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be determined by the appended claims.

[0143] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of conflict, the definitions in this specification shall prevail.

[0144] When this specification uses the prefix "well known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, the objects introduced by the prefix include those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become generally recognized in the art to be suitable for similar purposes.

[0145] In the context of this specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.

Claims

1. A method for degrading phenolic substances using laccase-like nanomaterials, characterized in that: The following steps are involved: adding the laccase-mimicking nanomaterial to a medium containing phenolic substances, and achieving degradation of the phenolic substances through a catalytic oxidation reaction of the laccase-mimicking nanomaterial on the phenolic substances under an optional oscillation treatment; The laccase-mimicking nanomaterial is selected from Cu2O.

2. The method for degrading phenolic substances using laccase-like nanomaterials according to claim 1, characterized in that: The laccase-mimicking nanomaterial is selected from Cu2O with a cubic structure; and / or, The laccase-mimicking nanomaterial is selected from Cu2O with a short hexapod structure; and / or, The laccase-mimicking nanomaterial is selected from Cu2O with a rhombic dodecahedron structure.

3. The method for degrading phenolic substances using laccase-like nanomaterials according to claim 2, characterized in that: The particle size of the cubic structured Cu2O is in the range of 600-850 nm; and / or, The particle size of the short hexapod Cu2O is in the range of 650-800 nm; and / or, The particle size of the Cu2O with the rhombic dodecahedron structure ranges from 650 to 800 nm.

4. The method for degrading phenolic substances using laccase-like nanomaterials according to claim 1, characterized in that: The medium containing phenolic substances is water containing phenolic substances; Preferably, the water containing phenolic substances is wastewater containing phenolic substances; More preferably, The phenolic substance is selected from at least one of 2,4-dichlorophenol, 2-chlorophenol, hydroquinone, p-nitrophenol, 2-aminophenol or phenol; and / or, In wastewater containing phenolic substances, the concentration of phenolic substances is 0.1 mg / mL-1 mg / mL; and / or, The salt concentration of the wastewater containing phenolic substances is 0-500mmol / L; and / or, The pH of wastewater containing phenolic substances is 4-10.

5. The method for degrading phenolic substances using laccase-like nanomaterials according to claim 1, characterized in that: The mass volume ratio of the laccase-mimicking nanomaterial to the medium containing phenolic substances is 0.1 mg-1 mg:1 mL; and / or, The temperature of the catalytic oxidation reaction is 30-90°C; and / or, The catalytic oxidation reaction time is 1h-10h.

6. The method for degrading phenolic substances using laccase-like nanomaterials according to claim 2, characterized in that: The preparation method of Cu2O comprises the following steps: 1) adding a copper salt solution to water and mixing once, then adding an alkaline solution and mixing twice; then adding a surfactant and mixing three times; finally adding a reducing agent solution and mixing four times, followed by standing and aging to obtain an aged solution; 2) Discarding the supernatant in the aging solution, adding an alcohol substance to the remaining material for ultrasonic dispersion, and then centrifuging to obtain a precipitate, and vacuum drying the precipitate to obtain the Cu2O.

7. The method for degrading phenolic substances using laccase-like nanomaterials according to claim 6, characterized in that: In step 1), The copper salt in the copper salt solution is selected from CuCl2; and / or, The concentration of the copper salt solution is 0.1 mol / L-10 mol / L; and / or, The volume ratio of water to copper salt solution is (94-96):1 or (90-91):1; preferably (95-96):1; and / or, The alkaline solution is a NaOH solution; and / or, The concentration of the alkaline solution is 1 mol / L-10 mol / L; and / or, The volume ratio of water to alkaline solution is (45-48):1; preferably (46-48):1; more preferably (47-48):1; and / or, The second mixing was performed by shaking for 10s-1min.

8. The method for degrading phenolic substances using laccase-like nanomaterials according to claim 6, characterized in that: In step 1), The surfactant is sodium lauryl sulfate; and / or, The mass ratio of water to surfactant is (108-110):1 or (104-105):1; preferably (109.5-110):1; and / or, The three-times mixing is vigorous stirring until the surfactant is dissolved, and then standing for 5-15 minutes; and / or, The reducing agent solution is NH2OH·HCl solution; The concentration of the reducing agent solution is 0.18-0.22 mol / L; and / or, The volume ratio of water to reducing agent solution is (62-65):1 or (13-14):1; preferably (63.5-64):1; and / or, Four times of mixing are shaking for 10s-1min; and / or, The static aging time is 1.9h-2.1h.

9. The method for degrading phenolic substances using laccase-like nanomaterials according to claim 6, characterized in that: In step 2), The alcohol substance is anhydrous ethanol; and / or, The volume ratio of the alcohol substance to the aging liquid is (0.0675-0.075):1; and / or, The power of the ultrasonic dispersion is 150-500W; and / or, The ultrasonic dispersion time is 4 min to 6 min; and / or, The number of centrifugation is 1; preferably, the centrifugal speed is 7500 rpm-8500 rpm; and / or, the centrifugal time is 4.5 min-5 min; further preferably, the centrifugal speed is 8000 rpm; the centrifugal time is 5 min; and / or, The vacuum drying temperature is 60-80°C.

10. Use of the method for degrading phenolic substances using laccase-like nanomaterials according to any one of claims 1 to 9 in sewage treatment.

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