A method for constructing copper nanocluster electrocatalyst based on amyloid fibers and application thereof in chlorophenol wastewater

Abstract

The application discloses a method for constructing a copper nanocluster electrocatalyst based on amyloid fibers and application of the copper nanocluster electrocatalyst in chlorophenol wastewater, and comprises the following steps: dissolving lysozyme powder into water, adjusting the pH of the solution to 2 to prepare a lysozyme solution; taking titanium suboxide TiSO as a substrate, immersing the substrate into the lysozyme solution, heating and stirring to obtain an amyloid fiber AFs solution and a TiSO-AFs electrode; taking out the TiSO-AFs electrode, adding the amyloid fiber solution, adding a copper metal ion solution and a reducing agent, allowing the copper ions to be immobilized on the surface of the electrode and converted into copper single elements, cleaning the electrode with deionized water after standing, and drying to obtain a TiSO-AFs-Cu electrode; and the material is used to build an electrochemical reactor, so that chlorophenol wastewater can be efficiently purified.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of sewage treatment materials, and particularly relates to a method for constructing a copper nanocluster electrocatalyst based on amyloid fibers and application of the method in chlorophenol wastewater. BACKGROUND

[0002] The main pollutants in industrial wastewater are mainly three kinds: pathogen pollutants, metal pollutants and organic pollutants. Among them, the water environmental pollution accidents caused by organic pollutants account for half of the total water pollution accidents, and they are the most harmful to the water environment compared with other pollutants. These organic pollutants can cause serious pollution to the water environment, making the composition of industrial wastewater more complex, the concentration and salinity higher, the pH change greater, and the degradation more difficult. Some of them also have "three effects" (i.e. carcinogenic, teratogenic, and mutagenic) and biological accumulation, which pose a serious threat to human health and the ecological environment. Therefore, it is urgent to solve the problem of organic pollution.

[0003] Chlorophenol compounds are a common organic pollutant, which are produced in industries such as petroleum coking, papermaking and dyeing, plastic manufacturing, and are widely used as organic solvents in industries such as wood preservatives, pesticides and herbicides, production of antirust agents and paint coatings. They are mainly distributed in soil and groundwater. The unique structure of chlorophenol compounds makes them difficult to degrade, semi-volatile, highly toxic, and can persist in the environment for a long time.

[0004] Therefore, effective treatment and pollution control of phenolic wastewater have become a key problem that needs to be solved urgently.

[0005] At present, the main methods for treating chlorophenol wastewater at home and abroad are physical and chemical methods (such as adsorption, extraction, membrane treatment), chemical oxidation methods (such as ozone oxidation method, Fenton method, photocatalytic method, ultrasonic degradation method) and biological methods. However, these methods have their respective shortcomings. Physical and chemical methods are only suitable for specific pollutant concentrations and are prone to secondary pollution; biological treatment takes a long time, occupies a large area, and has toxic effects on microorganisms, with low treatment efficiency; chemical oxidation method has high requirements for wastewater and reaction environment, and is also prone to secondary pollution. In comparison, electrocatalytic reduction technology is considered to be one of the most effective methods for degrading chlorophenol wastewater because of its green and efficient, non-production of secondary pollutants, short treatment time, small occupation area, wide applicability in a wide concentration range, and mild operating conditions.

[0006] However, the traditional electrocatalytic reduction technology has some problems that are difficult to solve in practical application due to the size of the electrocatalyst. If the size is too large, it is easy to cause uneven reaction and low efficiency, and if the size is too small, it is easy to cause migration-aggregation behavior, resulting in low active area and uncontrollable dispersion. SUMMARY

[0007] This section is intended to summarize some aspects of the embodiments of the present application and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the summary of the specification and the title of the application in order to avoid obscuring the purpose of this section, the summary of the specification and the title of the application, and such simplifications or omissions are not to be construed as limiting the scope of the present application.

[0008] In view of the above and / or problems existing in the prior art, the present application is proposed.

[0009] Therefore, the purpose of the present application is to overcome the deficiencies in the prior art, and to provide a method for constructing copper nanocluster electrocatalyst based on amyloid fibrils.

[0010] To solve the above technical problems, the present application provides the following technical scheme: a method for constructing copper nanocluster electrocatalyst based on amyloid fibrils, comprising,

[0011] Dissolve lysozyme powder into water, adjust the pH of the solution to 2, and prepare a lysozyme solution;

[0012] Using titanium suboxide TiSO as a substrate, immerse it in the lysozyme solution, heat and stir to obtain an amyloid fibril AFs solution and a TiSO-AFs electrode;

[0013] Take out the TiSO-AFs electrode, add an amyloid fibril solution, add a copper metal ion solution and a reducing agent, so that the copper ions are immobilized on the surface of the electrode and converted into copper single element, then wash with deionized water after standing, and dry to obtain a TiSO-AFs-Cu electrode.

[0014] As a preferred scheme of the method of the present application, wherein: the mass fraction of the lysozyme solution is 1.8-2.2wt%.

[0015] As a preferred scheme of the method of the present application, wherein: the heating and stirring, wherein the heating temperature is 90℃, the stirring speed is 180-200rpm, and the stirring time is 5-12h.

[0016] As a preferred scheme of the method of the present application, wherein: the copper metal ion solution comprises a CuSO4 solution with a concentration of 0.1M.

[0017] As a preferred scheme of the method of the present application, wherein: the reducing agent comprises an ascorbic acid solution with a concentration of 0.01M.

[0018] As a preferred scheme of the method of the present application, wherein: the volume ratio of the amyloid fibril solution, the copper metal ion solution and the reducing agent is 5:1:100.

[0019] Still another object of the present application is to provide a copper nanocluster electrocatalyst to overcome the deficiencies in the prior art.

[0020] Another object of the present application is to provide an application of the copper nanocluster electrocatalyst in treating chlorophenol wastewater to overcome the deficiencies in the prior art.

[0021] As a preferred scheme of the application, the reactor is separated into a cathode cell and an anode cell by a proton exchange membrane.

[0022] Titanium suboxide is used as the anode, and the TiSO-AFs-Cu electrode is used as the cathode.

[0023] During the entire reduction process, a constant potential is controlled, and the voltage is 5V.

[0024] The electrolyte is a 0.1M Na2SO4 solution.

[0025] The cathode chamber contains 10mg / L of p-chlorophenol contaminated liquid, the anode chamber contains 0.1M Na2SO4 electrolyte, and the action time is 60min.

[0026] As a preferred scheme of the application, the proton exchange membrane is a nafion membrane with a size of 2cm*2cm, and the volume of the cathode cell and the anode cell is each 200mL.

[0027] The electrode geometry size of the cathode and the anode is 2.5cm*4cm.

[0028] The present application has the following beneficial effects:

[0029] (1) The present application provides a preparation method of a copper nanoelectrocatalyst constructed by amyloid fibers for efficiently purifying p-chlorophenol wastewater. Titanium suboxide TiSO is used as a substrate, lysozyme is used to self-assemble amyloid fibers on the surface of the substrate, copper ion solution and a reducing agent are added to in-situ induce the preparation of a TiSO-AFs-Cu cathode electrocatalyst, and an electrochemical reactor is built by using the material to realize efficient purification of p-chlorophenol wastewater.

[0030] (2) The amyloid fiber surface in the present application is rich in amino acids, which can make the copper clusters uniformly distributed and maximize the effective surface area, thereby ensuring the utilization efficiency of copper cluster atoms. The amyloid fiber is used as a template to construct small-size copper clusters on the surface of the substrate electrode as a cathode catalyst for electrocatalytic reduction, and high-efficiency catalytic effect that macroscopic bulk electrodes do not have is obtained based on size effect. The reticular substrate electrode realized by the present application can avoid the mass transfer limitation in the electrochemical reduction process, and high-efficiency operation of the system is realized from macroscopic and microscopic aspects.

[0031] (3) In the traditional electrocatalytic reduction system, noble metal catalysts are often used, and the product selects Cu as the catalytic cathode of the system, which is rich in materials and low in cost, and can achieve a catalytic effect comparable to noble metals such as palladium. In view of the disadvantages of the traditional catalyst, such as difficult solid-liquid separation and uncontrollable distribution, the amyloid fiber is used as a template to realize the stable solid loading of the catalyst on the base electrode. At the same time, the AFs with high aspect ratio can be cross-linked into a three-dimensional network structure on the surface of the base electrode, ensuring high solid loading and high electrochemical active area of the catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0032] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiment description. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor. Among them:

[0033] Figure 1 The AFM characterization diagram of the electrode material of the present application;

[0034] Figure 2 The cycle period removal effect diagram in the embodiment of the present application;

[0035] Figure 3 The effect comparison diagram of adding tert-butyl alcohol in the embodiment of the present application. DETAILED DESCRIPTION

[0036] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail in the following combined with the embodiment of the specification.

[0037] In the following description, many specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from those described herein, and those skilled in the art can make similar generalizations without departing from the connotation of the present application, therefore the present application is not limited by the specific embodiments disclosed below.

[0038] Secondly, the "one embodiment" or "embodiment" referred to herein means that the specific features, structures or characteristics can be included in at least one implementation of the present application. "In one embodiment" appearing in different places in the specification does not mean the same embodiment, nor is it an independent or alternative embodiment that excludes other embodiments.

[0039] Embodiment 1

[0040] (1) Take 2g lysozyme powder, first dissolve it in 95g water, then slowly add 1M HCl solution, and measure the pH value of the solution at the same time, until pH=2;

[0041] (2) The TiSO electrode was inserted into the prepared lysozyme solution, and then placed in an oil bath at 90°C for 8h with continuous stirring to allow sufficient reaction;

[0042] (3) The prepared TiSO-AFs electrode was taken out and placed in a new container, 5mL of the amyloid fibril solution prepared in step (2) was added, and then 1mL of 0.1M CuSO4 solution was slowly added dropwise under low-speed shaking;

[0043] (4) The shaking speed of the shaker was adjusted to medium (580r / min) and continuously shaken for 24h;

[0044] Under low-speed shaking (100r / min) of the shaker, 100mL of 0.01M ascorbic acid solution was slowly added dropwise, and then the temperature was set to 60°C, the shaking speed of the shaker was adjusted to medium (580r / min), and shaken for 24h.

[0045] The AFM characterization chart of the prepared electrode material is shown in Figure 1 .

[0046] Example 2

[0047] (1) 4g of lysozyme powder was dissolved in 190g of water, and then 1M HCl solution was slowly added dropwise, and the pH value of the solution was measured synchronously until pH=2;

[0048] (2) The TiSO electrode was inserted into the prepared lysozyme solution, and then placed in an oil bath at 90°C for 8h with continuous stirring to allow sufficient reaction;

[0049] (3) The prepared TiSO-AFs electrode was taken out and placed in a new container, 5mL of the amyloid fibril solution prepared in step (2) was added, and then 1mL of 0.1M CuSO4 solution was slowly added dropwise under low-speed shaking;

[0050] (4) The shaking speed of the shaker was adjusted to medium (580r / min) and continuously shaken for 24h;

[0051] Under low-speed shaking (100r / min) of the shaker, 100mL of 0.01M ascorbic acid solution was slowly added dropwise, and then the temperature was set to 60°C, the shaking speed of the shaker was adjusted to medium (580r / min), and shaken for 24h.

[0052] Example 3

[0053] (1) Take 2 g of lysozyme powder, first dissolved in 95 g of water, then slowly add 1M HCl solution, measure the pH value of the solution simultaneously, until pH = 2;

[0054] (2) Insert the TiSO electrode into the prepared lysozyme solution, and then place it in an oil bath at 90℃, continuously stirring for 12h to make it fully react;

[0055] (3) Take out the constructed TiSO-AFs electrode and place it in a new container, first add 5mL of amyloid fibril solution prepared in step (2) to it, then slowly add 1mL of 0.1M CuSO4 solution to it under low-speed shaking in a shaking bed;

[0056] (4) Adjust the shaking speed of the shaking bed to medium (580r / min) and continuously shake for 24h;

[0057] Slowly add 100mL of 0.01M ascorbic acid solution to the solution under low-speed (100r / min) shaking of the shaking bed, then set the temperature to 60℃, adjust the shaking speed of the shaking bed to medium (580r / min), and shake for 24h.

[0058] Application Example 1

[0059] Separate the reactor into a cathode cell (200mL) and an anode cell (200mL) by a proton exchange membrane (2cm×2cm);

[0060] Use titanium suboxide with a length of 4cm and a width of 2.5cm as the anode; use TiSO-AFs-Cu electrode (prepared in Example 1) with a length of 4cm and a width of 2.5cm as the cathode;

[0061] During the entire reduction experiment, use the current technology of switching power supply to control the constant potential on the cathode, with a voltage of 5V and 0.1M Na2SO4 as the background electrolyte;

[0062] Reaction voltage condition: constant 5V voltage;

[0063] Reaction solution volume requirement: 200mL of 10mg / L 4-CP contaminated solution in the cathode chamber, and 200mL of 0.1M Na2SO4 electrolyte in the anode chamber;

[0064] Reaction time requirement: 60min;

[0065] The contaminated wastewater is added to the cathode chamber of the reactor in advance before the reaction, and the removal rate of the pollutants is 99.5%.

[0066] Application Example 2

[0067] The reactor was separated into a cathode cell (200 mL) and an anode cell (200 mL) by a proton exchange membrane (2 cm x 2 cm);

[0068] Titanium suboxide with a length of 4 cm and a width of 2.5 cm was used as the anode; and a TiSO-AFs-Cu electrode (prepared in Example 2) with a length of 4 cm and a width of 2.5 cm was used as the cathode;

[0069] During the entire reduction experiment, a constant potential on the cathode was controlled by using the current technology of a switching power supply, and the voltage was 10 V, and 0.1 M Na2SO4 was used as the background electrolyte;

[0070] The cathode chamber was 200 mL, and the 4-CP contaminated solution was 10 mg / L; the anode chamber was 200 mL, and the electrolyte was 0.1 M Na2SO4;

[0071] The reaction time requirement was 60 min;

[0072] The contaminated wastewater was added in the cathode chamber of the reactor in advance before the reaction, and the removal rate of the pollutants was 99.6%.

[0073] Application Example 3

[0074] The reactor was separated into a cathode cell (200 mL) and an anode cell (200 mL) by a proton exchange membrane (2 cm x 2 cm);

[0075] Titanium suboxide with a length of 4 cm and a width of 2.5 cm was used as the anode; and a TiSO-AFs-Cu electrode (prepared in Example 3) with a length of 4 cm and a width of 2.5 cm was used as the cathode;

[0076] During the entire reduction experiment, a constant potential on the cathode was controlled by using the current technology of a switching power supply, and the voltage was 10 V, and 0.1 M Na2SO4 was used as the background electrolyte;

[0077] The reaction solution volume requirement was that the cathode chamber was 200 mL, and the 4-CP contaminated solution was 10 mg / L;

[0078] The anode chamber was 200 mL, and the electrolyte was 0.05 M Na2SO4; the reaction time requirement was 60 min;

[0079] The contaminated wastewater was added in the cathode chamber of the reactor in advance before the reaction, and the removal rate of the pollutants was 98.2%.

[0080] Application Example 4

[0081] The same conditions as in Application Example 1 were set, and a continuous circulation reaction was performed for 60 min as a reaction period;

[0082] The reaction was performed for 10 periods, and the experimental results are recorded in Table 1. Figure 2 ;

[0083] The experimental results show that the removal effect is consistent for each cycle, and the pollutant removal rate is close to 100% for 60 min, indicating that the material prepared in the experiment has stability.

[0084] Comparative Example 1

[0085] (1) Take 2 g of lysozyme powder, first dissolve it in 70 g of water, then slowly add 1M HCl solution, and measure the pH value of the solution at the same time, until pH = 2;

[0086] (2) Insert the TiSO electrode into the prepared lysozyme solution, and then place it in an oil bath, under the condition of 90℃, continuously stirring for 8h, so that it can fully react;

[0087] (3) Take out the constructed TiSO-AFs electrode, and place it in a new container, first add 5mL of amyloid fibril solution prepared in step (2) to it, then place it in a shaker, and slowly add 1mL of 0.1M CuSO4 solution to it under low-speed shaking;

[0088] (4) Adjust the shaking speed of the shaker to medium (580r / min), and continuously shake for 24h;

[0089] Under the condition of low-speed shaking (100r / min) of the shaker, slowly add 100mL of 0.01M ascorbic acid solution to the solution, then set the temperature to 60℃, adjust the shaking speed of the shaker to medium (580r / min), and shake for 24h.

[0090] Comparative Example 2

[0091] (1) Take 2 g of lysozyme powder, first dissolve it in 95 g of water, then slowly add 1M HCl solution, and measure the pH value of the solution at the same time, until pH = 2.

[0092] (2) Insert the TiSO electrode into the prepared lysozyme solution, and then place it in an oil bath, under the condition of 60℃, continuously stirring for 8h, so that it can fully react.

[0093] (3) Take out the constructed TiSO-AFs electrode, and place it in a new container, first add 5mL of amyloid fibril solution prepared in step (2) to it, then place it in a shaker, and slowly add 1mL of 0.1M CuSO4 solution to it under low-speed shaking.

[0094] (4) Adjust the shaking speed of the shaker to medium, and continuously shake for 24h; under the condition of low-speed shaking of the shaker, slowly add 100mL of 0.01M ascorbic acid solution to the solution, then set the temperature to 60℃, adjust the shaking speed of the shaker to medium, and shake for 24h.

[0095] Comparative Example 3

[0096] (1) 2 g of lysozyme powder was dissolved in 95 g of water, and then 1 M HC1 solution was slowly added thereto while measuring the pH of the solution, until the pH was 2.

[0097] (2) A TiSO electrode was inserted into the prepared lysozyme solution, and then was placed in an oil bath, and was continuously stirred at 90°C for 8 h to allow a reaction to be sufficiently performed.

[0098] (3) The prepared TiSO-AFs electrode was taken out and was placed in a new container, 5 mL of the amyloid fibril solution prepared in step (2) was added thereto, and then 1 mL of 0.1 M CuSO4 solution was slowly added thereto while the container was shaken at a low speed.

[0099] (4) The shaking speed of the shaker was adjusted to a medium speed, and was continuously shaken for 24 h, 1 mL of 0.056 M sodium borohydride solution was slowly added thereto while the container was shaken at a low speed, and then the temperature was set to 60°C, and the shaking speed of the shaker was adjusted to a medium speed, and was shaken for 24 h.

[0100] Comparative Example 4

[0101] (1) 2 g of camel milk was dissolved in 95 g of water, and then 1 M HC1 solution was slowly added thereto while measuring the pH of the solution, until the pH was 2.

[0102] (2) A TiSO electrode was inserted into the prepared lysozyme solution, and then was placed in an oil bath, and was continuously stirred at 90°C for 8 h to allow a reaction to be sufficiently performed.

[0103] (3) The prepared TiSO-AFs electrode was taken out and was placed in a new container, 5 mL of the amyloid fibril solution prepared in step (2) was added thereto, and then 1 mL of 0.1 M CuSO4 solution was slowly added thereto while the container was shaken at a low speed.

[0104] (4) The shaking speed of the shaker was adjusted to a medium speed, and was continuously shaken for 24 h.

[0105] 1 mL of 0.01 M ascorbic acid solution was slowly added thereto while the container was shaken at a low speed, and then the temperature was set to 60°C, and the shaking speed of the shaker was adjusted to a medium speed, and was shaken for 24 h.

[0106] Comparative Example 5

[0107] (1) 2 g of lysozyme powder was dissolved in 95 g of water, and then 1 M HC1 solution was slowly added thereto while measuring the pH of the solution, until the pH was 2.

[0108] (2) Insert the TiSO electrode into the prepared lysozyme solution, and then place it in an oil bath at 100°C, continuously stirring for 8h to allow it to fully react;

[0109] (3) Take out the constructed TiSO-AFs electrode, and place it in a new container. First, add 5mL of the amyloid fibril solution prepared in step (2) to the container, and then slowly add 1mL of a 0.1M CuSO4 solution dropwise to the container while shaking at a low speed in a shaker;

[0110] (4) Adjust the shaking speed of the shaker to medium, and continuously shake for 24h;

[0111] Slowly add 100mL of a 0.01M ascorbic acid solution dropwise to the solution while shaking at a low speed in a shaker, and then set the temperature to 60°C, adjust the shaking speed of the shaker to medium, and shake for 24h.

[0112] The 10mg / L 4-CP contaminated solution was treated according to the treatment method of Example 1, and the test results are shown in Table 1.

[0113] Table 1

[0114]

[0115] As can be seen from Table 1, the mass fraction of the lysozyme solution in Comparative Example 1 was changed from 2% to 2.8%, and the 60min removal rate of the pollutant was 99.4%.

[0116] In Comparative Example 2, the temperature during oil bath heating was changed from 90°C to 60°C, and the 60min removal rate of the pollutant was 99.1%;

[0117] In Comparative Example 3, the reducing agent added during the reduction of the electrode was changed from 100mL of a 0.01M ascorbic acid solution to 1mL of a 0.056M sodium borohydride solution, and the 60min removal rate of the pollutant was 78.2%

[0118] In Comparative Example 4, the lysozyme was replaced with camel milk, and the 60min removal rate of the pollutant was only 0.3%;

[0119] In Comparative Example 5, the temperature during oil bath heating was changed from 90°C to 100°C, and the 60min removal rate of the pollutant was 31.9%.

[0120] Comparative Example 6

[0121] (1) Take 2g of lysozyme powder, dissolve it in 95g of water, and then slowly add a 1M HCl solution, while simultaneously measuring the pH value of the solution, until the pH value is 2;

[0122] (2) The TiSO electrode was inserted into the prepared lysozyme solution, and then was placed in an oil bath at 90°C for 8h with continuous stirring to allow the reaction to proceed completely;

[0123] (3) The prepared TiSO-AFs electrode was taken out and placed in a new container. 5mL of the amyloid fibril solution prepared in step (2) was added to the container, and then 1mL of 0.1M CuSO4 solution was slowly added dropwise to the container under low-speed shaking in a shaker;

[0124] (4) The shaking speed of the shaker was adjusted to medium, and the solution was continuously shaken for 24h;

[0125] Under low-speed shaking in a shaker, 100mL of 0.01M ascorbic acid solution was slowly added dropwise to the solution, and then the temperature was set to 60°C, the shaking speed of the shaker was adjusted to medium, and the solution was shaken for 24h.

[0126] Three TiSO-AFs-Cu electrodes were prepared according to the above steps (1), (2), (3) and (4), and were sequentially placed in a reactor for reaction. 1mL of 10mM, 0.1mL of 10mM and 0mL of 10mM tert-butyl alcohol solution were added to the pollutant solution in the reactor, respectively, and were reacted for 60min. The removal rates were 18.9%, 62.5% and 99.4%, respectively. Tert-butyl alcohol is a free radical quencher, and the experimental results show that the electrode can treat 4-cp by generating free radicals. Figure 3

[0127] It should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the present application, and all should be covered in the scope of the present application.​

Claims

1. A method for constructing a copper nanocluster electrocatalyst based on amyloid fibrils, characterized by: The method comprises the steps of: dissolving lysozyme powder into water, adjusting pH of the solution to 2 to obtain a lysozyme solution; immersing titanium suboxide TiSO into the lysozyme solution and heating and stirring to obtain a amyloid fibril AFs solution and a TiSO-AFs electrode; taking out the TiSO-AFs electrode, adding the amyloid fibril AFs solution, adding a copper metal ion solution and a reducing agent, allowing the copper ions to be immobilized on the surface of the electrode and converted into copper element, and then cleaning the TiSO-AFs-Cu electrode with deionized water and drying to obtain the TiSO-AFs-Cu electrode.

2. The method of claim 1, wherein: The mass fraction of the lysozyme solution is 1.8-2.2 wt%.

3. The method of claim 1 or 2, wherein: The heating and stirring are performed at a heating temperature of 90°C, a stirring speed of 180-200 rpm and a stirring time of 5-12 h.

4. The method of claim 1, wherein: The copper metal ion solution comprises a CuSO4 solution with a concentration of 0.1 M.

5. The method of claim 1, wherein: The reducing agent comprises an ascorbic acid solution with a concentration of 0.01 M.

6. The method of any one of claims 1, 2, 4, or 5, wherein: The volume ratio of the amyloid fibril solution, the copper metal ion solution and the reducing agent is 5:1:

100.

7. The copper nanocluster electrocatalyst prepared by the method of any one of claims 1-6.

8. The application of the copper nanocluster electrocatalyst of claim 7 in treating chlorophenol wastewater.

9. Use according to claim 8, wherein: The method comprises the steps of: separating the reactor into a cathode cell and an anode cell by a proton exchange membrane; adopting titanium suboxide as the anode and the TiSO-AFs-Cu electrode as the cathode; controlling a constant potential during the whole reduction process, and the voltage is 5 V; wherein the electrolyte is a 0.1 M Na2SO4 solution; the cathode chamber is filled with 10 mg / L of p-chlorophenol pollution liquid, the anode chamber is filled with 0.1 M Na2SO4 electrolyte, and the action time is 60 min.

10. Use according to claim 9, wherein: The proton exchange membrane is a nafion membrane with a size of 2 cm×2 cm, and the volume of the cathode cell and the anode cell is 200 mL respectively; the electrode geometry size of the cathode and the anode is 2.5 cm×4 cm.

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