Preparation and application of high-entropy alloy micro-electrolysis filler for water treatment

Abstract

The application discloses a kind of high-entropy alloy micro-electrolysis fillings for water treatment preparation and application, the preparation method includes: 1) organic solution preparation carbon dot;2) preparation of molybdenum boride;3) the preparation of high-entropy alloy FeAlNiCuZn-CDs;4) post-processing.The application is synthesized by citric acid and ethylenediamine carbon dot, and it is mixed with the metal salt of metal such as Fe, Ni, Cu, Zn and molybdenum boride precursor, alloy is formed by reduction sintering, a kind of carbon dot doped high-entropy alloy micro-electrolysis fillings is prepared, the micro-battery system of multiple metal construction and the catalytic characteristics of carbon dot are used in this filling, strong oxidizing free radicals are generated synergistically, and the life is long, and it is suitable for high concentration organic wastewater treatment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of micro-electrolysis filler preparation, and particularly relates to a high-entropy alloy micro-electrolysis filler for water treatment and a preparation and application thereof. BACKGROUND

[0002] Micro-electrolysis technology, also known as internal electrolysis method or iron-carbon method, is widely used in the treatment of industrial wastewater such as printing and dyeing, pharmaceutical, pesticide, chemical and landfill leachate as an efficient and economical wastewater pretreatment and advanced treatment method. The basic principle is that metal and carbon materials form a micro galvanic cell in an electrolyte solution, and active substances such as nascent hydrogen, Fe 2+ and hydroxyl radicals (·OH) are generated by electrochemical corrosion, thereby realizing the reduction and oxidation degradation of organic pollutants.

[0003] However, this technology has inherent and insurmountable defects:

[0004] Limited electrochemical efficiency: The traditional filler relies on the limited potential difference between iron and carbon, the number of formed galvanic cells is small, and the potential is single, which leads to low electron transfer efficiency and limited reaction activity, especially for the treatment of stable and refractory macromolecular organic matter.

[0005] Easy passivation and caking: During operation, iron surface is easily oxidized to form passivation film such as iron hydroxide, which hinders electron transfer and continuous reaction; at the same time, due to the uneven physical mixing and low structural strength of carbon materials, caking and caking easily occur, causing water flow channel blockage, quick failure of filler, frequent replacement and other problems.

[0006] Insufficient catalytic activity: The traditional iron-carbon system mainly relies on Fe 2+ / Fe 3+ catalytic Fenton reaction, but the catalytic efficiency is greatly limited by pH, and lacks multi-metal synergistic catalytic mechanism, and has limited degradation capacity for some characteristic pollutants such as azo dyes and polycyclic aromatic hydrocarbons.

[0007] Poor structural stability: The conventional filler is mainly mechanical mixing of iron filings and activated carbon particles, and the carbon material is easy to be lost and the structure is collapsed during long-term use, which leads to reduction of reaction interface and decline of treatment effect.

[0008] These problems together lead to rapid efficiency decay, short service life, unstable operation of traditional micro-electrolysis filler, and frequent replacement or backwashing, which greatly increases the operation and maintenance cost and restricts its large-scale application efficiency.

[0009] Although researchers have tried to improve the performance of micro-electrolysis filler by alloying, porous structure regulation and non-metallic doping in recent years, they have not solved the core contradiction of easy passivation and easy caking from the essence of the material. SUMMARY

[0010] The application aims at providing a high-entropy alloy micro-electrolysis filler for water treatment and a preparation and application method thereof to solve the problems in the prior art.

[0011] To achieve the above-mentioned purpose, the application adopts the following technical scheme:

[0012] The application first provides a preparation method of the high-entropy alloy micro-electrolysis filler for water treatment, comprising the following steps:

[0013] S1, preparation of carbon dots from an organic solution

[0014] S1.1, preparation of an organic solution:

[0015] Dissolve citric acid and ethylenediamine in deionized water, heat at 200 DEG C for 5 h; after cooling to room temperature, filter the solution to remove solid impurities to obtain an organic solution;

[0016] S1.2, preparation of carbon dots CDs:

[0017] Use a dialysis bag with a molecular weight cut-off of 3500 Da to dialyze the organic solution, and after dialysis, dry the solution to obtain solid CDs;

[0018] Citric acid (carbon source) and ethylenediamine (nitrogen source) undergo dehydration, polymerization and carbonization reactions at 200 DEG C to form nanocarbon material CDs with surface passivation but good water solubility and surface functional groups such as -COOH and -NH2. In subsequent steps, the functional groups of CDs can chelate metal ions, allowing them to be uniformly dispersed in the alloy precursor. In the final product, CDs can enhance the electrical conductivity of the material, provide more active sites for reaction, and possibly inhibit the excessive sintering and agglomeration of alloy particles.

[0019] S2, preparation of molybdenum boride

[0020] Mix molybdenum and boron carbide powder uniformly, then add aluminum powder, put into an alumina crucible, heat to 1250 DEG C under N2 atmosphere, keep for 4 h, take out the sample after cooling to room temperature, crush into powder to obtain aluminum powder with molybdenum boride;

[0021] Aluminum powder acts as a reducing agent to generate molybdenum boride MoB. MoB acts as a reinforcing phase and a hydrogen evolution reaction catalyst to improve the hardness, wear resistance and stability of the final alloy filler, prolonging its service life in a turbulent or stirred water treatment environment.

[0022] S3, preparation of high-entropy alloy FeAlNiCuZn-CDs

[0023] S3.1, preparation of a metal salt solution:

[0024] Dissolve ferrous sulfate, copper sulfate, nickel sulfate, aluminum sulfate, zinc sulfate with deionized water, add dilute sulfuric acid and aluminum powder with boron molybdenum, stir until all salts are completely dissolved and aluminum powder is completely reacted, to obtain a mixed metal salt solution;

[0025] Dissolve aluminum powder with boron molybdenum, expose MoB particles and uniformly disperse them in the solution, and at the same time provide Al 3+ ions;

[0026] S3.2, mixing:

[0027] Dissolve CDs in deionized water, ultrasonic treatment for 30 minutes to make them fully dispersed, slowly drop into the mixed metal salt solution, stir for 12 hours, mix completely, dry to obtain a precursor powder;

[0028] Mix the CDs solution with the metal salt solution, the -COOH, -OH, -NH2 and other functional groups on the surface of the CDs capture various metal ions in the solution through complexation to form a uniform "metal-CDs" precursor. MoB particles are also wrapped or adsorbed in it.

[0029] S3.3, pyrolysis and reduction

[0030] Put the dried powder into a tube pusher kiln, heat to 200℃ at a rate of 2℃ / min under N2 atmosphere, and keep for 2h; switch the atmosphere to a mixture of 5% H2 and 95% N2, and push the sample into the preheated to 400℃ furnace heating zone, and reduce at 400℃ for 2h, after the reaction is completed, the final high-entropy alloy FeAlNiCuZn-CDs is obtained;

[0031] Pyrolysis of the precursor, decomposition of the salt into metal oxides, and partial functional groups of the CDs begin to carbonize, followed by reduction of the metal oxides to metal elements by H2, under the induction and stabilization of the CDs, the newly generated Fe, Cu, Ni, Zn, Al metal atoms diffuse with each other at a temperature much lower than their melting points, forming a single solid solution phase by high-entropy effect, rather than independent metal particles.

[0032] MoB particles are wrapped in high-entropy alloy HEA as inert phase, most of the CDs will be carbonized into amorphous carbon at this temperature, wrapped outside the HEA particles or filled in the gaps, playing a role in preventing HEA particles from sintering and growing.

[0033] S4, post-processing

[0034] The sintered high-entropy alloy will have slight adhesion, use ball milling to disperse, then pass through a vibrating screen, screen out 3-6mm particles to obtain the product, and the high-entropy alloy micro-electrolysis filler for water treatment.

[0035] Preferably, in the S1.1, the molar ratio of citric acid and ethylenediamine is 1:1; the solid content of the organic solution is 45±5%.

[0036] Preferably, in the S1.2, the dried solid CDs are fluffy brown or black powder.

[0037] Preferably, in the S2, the molar ratio of molybdenum, boron carbide and aluminum is 1:0.25:3.

[0038] Preferably, in the S3.1, the metal ions in the mixed metal salt solution include 30% Fe 2+ , 20% Cu 2+ , 15% Ni 2+ , 15% Al 3+ , 20% Zn 2+ ; the molybdenum boride accounts for 0.5%-2% of the mass of the mixed metal salt solution.

[0039] Preferably, in the S3.2, the concentration of CDs in the configured mixed solution is 5-10 mg / mL.

[0040] The high-entropy alloy micro-electrolysis filler for water treatment obtained by the preparation method is filled in a micro-electrolysis reactor, used for removing refractory organic matter in wastewater, reducing water body color and COD; and is suitable for pollutant treatment of dyeing wastewater, pharmaceutical, pesticide, chemical wastewater, landfill leachate and the like.

[0041] Preferably, the application comprises the following steps:

[0042] The filler is filled in the micro-electrolysis reactor to form a micro-electrolysis system, and the basic components of the system include a reactor, a filler layer, a water inlet system, a gas-water mixing system and a subsequent treatment unit.

[0043] If the wastewater contains a large amount of suspended solids, the wastewater needs to be pretreated by precipitation and filtration, the pH of the wastewater is adjusted to 3-5, the wastewater is pumped into the reactor, and passes through the filler layer.

[0044] The hydraulic retention time is determined according to the pollution condition, and is 0.5-2 h; the filler surface should continuously and uniformly precipitate micro-bubbles, i.e. H2, indicating that the reaction is active.

[0045] The effluent enters a neutralization tank to adjust the pH to 7-8, is precipitated and then enters a biochemical system or is directly discharged or reused.

[0046] Preferably, the subsequent treatment unit includes a neutralization and precipitation tank and a biochemical treatment tank.

[0047] Compared with the prior art, the present application has the following beneficial effects:

[0048] 1. Constructing an efficient and stable micro-electrolysis primary cell system

[0049] Traditional iron-carbon filler relies on the potential difference between iron and carbon to form countless micro primary cells. The present application greatly optimizes and enhances this system through high-entropy alloying and carbon dot (CD) doping. The high-entropy alloy FeAlNiCuZn contains a variety of metals from active to less active, which will form more, more significant potential difference, and more diverse micro primary cell pairs in wastewater, far exceeding the traditional Fe-C two-element system, significantly improving the efficiency and breadth of electrochemical reactions.

[0050] CDs have excellent electrical conductivity and huge specific surface area, which as a doping phase, builds countless high-activity micro-cathodes inside the alloy, greatly increasing the effective reaction area and promoting the progress of cathode reduction reactions.

[0051] 2. Significantly enhance the catalytic degradation efficiency

[0052] The core of micro-electrolysis treatment of wastewater is not only electrochemical corrosion, but also the catalytic degradation of organic matter by active substances (such as ·OH, H2O2, and nascent [H]) generated.

[0053] CDs themselves have peroxidase-like catalytic activity and can efficiently catalyze Fenton or Fenton-like reactions, promoting the generation of strong oxidizing hydroxyl radicals (·OH), thereby non-selectively and efficiently decomposing refractory organic matter. The multiple metal elements in the high-entropy alloy may have a synergistic catalytic effect. For example, Cu and Ni are excellent catalysts for various redox reactions, which can accelerate electron transfer and the generation of active substances. The coexistence of Fe and Cu can construct a more efficient Fenton-like reaction system. This multi-element synergistic effect makes its catalytic activity and selectivity much higher than single or double metal systems.

[0054] 3. Strong anti-passivation ability

[0055] In use, the traditional iron-carbon filler is easy to form an oxide film passivation layer on the surface of iron, and carbon plate closure will also cause rapid failure.

[0056] In step S2, aluminum powder with molybdenum boride is prepared. The aluminum powder acts as a strong reducing agent, effectively protecting the metal from oxidation in the reducing atmosphere during subsequent sintering. The introduction of boron elements can refine the grain size, occupy the grain boundaries, and change the structure of the oxide layer on the alloy surface, making it more dense but not easy to peel off, and improving its electrical conductivity, thereby significantly inhibiting the passivation of the alloy filler and maintaining sustained reactivity.

[0057] The unique "cocktail effect" and severe lattice distortion of high-entropy alloy make the surface more easily form a layer of dense, stable and strong adhesion mixed oxide passivation film; this film is fundamentally different from the loose passivation film of Fe(OH)3: it is extremely thin and dense, can prevent further corrosion of the matrix, but does not hinder the penetration of electrons, has semiconductor properties, so that the alloy anode is protected by the passivation film while still able to continuously transmit electrons, changing from a "consumable anode" to a "catalytic anode".

[0058] The traditional cathode is a physical mixture of carbon particles, and the present application is a three-dimensionally interconnected porous carbon skeleton, which is an integral conductive network rather than loose particles. It cannot be dispersed by water flow, and its macroscopic and microscopic pores are permanently interconnected, providing a rapid escape channel for reaction products and preventing their accumulation inside, and the solid carbon skeleton prevents the bed from hardening and ensures uniform water flow, fundamentally avoiding physical blockage.

[0059] 4. Widening the application range and improving the treatment efficiency

[0060] Based on the above-mentioned enhanced electrochemical activity and catalytic activity, the filler is suitable for various refractory wastewater. The abundant micro-battery reaction and catalytic ·OH can quickly break the chromophore groups such as azo bond and benzene ring structure, effectively reducing the colority and chemical oxygen demand of the water body. It has better adaptability and treatment effect for complex composition, high toxicity and difficult biodegradation of printing and dyeing wastewater, pharmaceutical and pesticide wastewater, chemical wastewater and landfill leachate.

[0061] In summary, the present application synergistically enhances the electrochemical activity, catalytic performance and structural stability of the micro-electrolysis filler through the three core innovations of high-entropy alloy design, carbon point doping and boron element modification, thereby realizing efficient, durable and stable treatment effect of refractory organic wastewater, and is particularly suitable for pretreatment and advanced treatment of high-concentration industrial wastewater. DETAILED DESCRIPTION

[0062] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments.

[0063] The purity and manufacturers of each drug used in the experiment are shown in Table 1:

[0064] Table 1. Raw material drug information

[0065]

[0066] Example 1:

[0067] A preparation method of a high-entropy alloy micro-electrolysis filler for water treatment, comprising the following steps:

[0068] S1, preparation of carbon dots from organic solution

[0069] S1.1, preparation of organic solution:

[0070] Dissolve citric acid and ethylenediamine in deionized water, heat at 200℃ for 5h; after cooling to room temperature, filter the solution to remove solid impurities to obtain an organic solution;

[0071] S1.2, preparation of carbon dots CDs:

[0072] Use a dialysis bag with a molecular weight cut-off of 3500Da to dialyze the organic solution, after dialysis, dry the solution to obtain solid CDs;

[0073] S2, preparation of molybdenum boride

[0074] Mix molybdenum and boron carbide powder uniformly, then add aluminum powder, put into an alumina crucible, heat to 1250℃ under N2 atmosphere, keep for 4h, cool to room temperature, take out the sample, crush into powder, get the aluminum powder with molybdenum boride;

[0075] S3, preparation of high-entropy alloy FeAlNiCuZn-CDs

[0076] S3.1, preparation of metal salt solution:

[0077] Dissolve ferrous sulfate, copper sulfate, nickel sulfate, aluminum sulfate, zinc sulfate with deionized water, add dilute sulfuric acid and aluminum powder with molybdenum boride, stir until all salts are completely dissolved and aluminum powder is completely reacted, get mixed metal salt solution;

[0078] S3.2, mixing:

[0079] Dissolve CDs in deionized water, ultrasonic treatment for 30 minutes to make them fully dispersed, slowly add to the mixed metal salt solution, stir for 12h, mix completely, dry to get precursor powder;

[0080] S3.3, pyrolysis and reduction

[0081] Put the dried powder into a tube push plate kiln, heat to 200℃ at a rate of 2℃ / min under N2 atmosphere, and keep for 2h; switch the atmosphere to 5%H2 / N2 mixed gas, and push the sample into the preheated to 400℃ furnace heating zone, and reduce at 400℃ for 2h, after the reaction is completed, get the final high-entropy alloy FeAlNiCuZn-CDs;

[0082] S4, post-processing

[0083] The sintered high-entropy alloy has slight adhesion, which is dispersed by ball milling, and then screened by a vibrating screen to obtain 3-6 mm particles as the product, the high-entropy alloy micro-electrolysis filler for water treatment.

[0084] In S1.1, the molar ratio of citric acid and ethylenediamine is 1:1; the solid content of the organic solution is 45±5%.

[0085] In S1.2, the dried solid CDs are fluffy brown or black powder.

[0086] In S2, the molar ratio of molybdenum, boron carbide and aluminum is 1:0.25:3.

[0087] In S3.1, the metal ions in the mixed metal salt solution include 30% Fe 2+ , 20% Cu 2+ , 15% Ni 2+ , 15% Al 3+ , 20% Zn 2+ ; and the mass fraction of molybdenum boride in the mixed metal salt solution is 0.5%.

[0088] In S3.2, the concentration of CDs in the prepared mixed solution is 10 mg / mL.

[0089] Example 2:

[0090] The implementation method is the same as that of Example 1, but

[0091] In S3.1, the mass fraction of molybdenum boride in the mixed metal salt solution is 1.25%.

[0092] In S3.2, the concentration of CDs in the prepared mixed solution is 7.5 mg / mL.

[0093] Example 3:

[0094] The implementation method is the same as that of Example 1, but

[0095] In S3.1, the mass fraction of molybdenum boride in the mixed metal salt solution is 2%.

[0096] In S3.2, the concentration of CDs in the prepared mixed solution is 5 mg / mL.

[0097] Accordingly, the following is also designed:

[0098] Comparative Example 1: The same as Example 2 in terms of formula and experimental method, but in S3.1, the mass fraction of molybdenum boride in the mixed metal salt solution is 0.1%.

[0099] Comparative Example 2: The same as Example 2 in terms of formula and experimental method, but in S3.1, the mass fraction of molybdenum boride in the mixed metal salt solution is 5%.

[0100] Comparative Example 3: Same as Example 2 in formulation and experimental method, but in S3.2, the concentration of CDs in the mixed solution is 1 mg / mL.

[0101] Comparative Example 4: Same as Example 2 in formulation and experimental method, but in S3.2, the concentration of CDs in the mixed solution is 20 mg / mL.

[0102] The filler is loaded into the micro-electrolysis reactor to form a micro-electrolysis system. The basic components of the system include a reactor, a filler layer, a water inlet system, a gas-water mixing system, and a subsequent treatment unit (neutralization and precipitation tank, biochemical treatment tank).

[0103] If the wastewater contains a large amount of suspended solids, it needs to be pretreated by precipitation and filtration, and the pH of the wastewater is adjusted to 3-5. The wastewater is pumped into the reactor and passes through the filler layer.

[0104] The hydraulic retention time is determined by the pollution condition and is 0.5-2 h. The filler surface should continuously and uniformly precipitate micro-bubbles, i.e. H2, indicating active reaction.

[0105] The effluent enters the neutralization tank to adjust the pH to 7-8, and then enters the biochemical system after precipitation or is directly discharged or reused.

[0106] The performance of each example and comparative example is detected in detail, and the detection method and corresponding results are shown as follows:

[0107] 1. Wastewater treatment capacity

[0108] The wastewater treatment capacity of the present application is evaluated according to the test method of GB 8978-1996.

[0109] 2. Harmful substance dissolution

[0110] The concentration of heavy metal ions dissolved by the present application is evaluated according to the test method of GB 8978-1996.

[0111] 3. COD removal rate

[0112] The ability of the present application to degrade organic matter is evaluated according to the test method of HJ 828-2017.

[0113] 4. Hydrogen evolution (anti-passivation) phenomenon

[0114] When treating wastewater under acidic conditions, the filler surface should continuously and uniformly precipitate micro-bubbles (H2), rather than stopping the reaction after a few minutes of operation.

[0115] 5. Stability and service life

[0116] Evaluate the durability of the filler, after 100h continuous operation, COD removal rate compared with the initial efficiency, attenuation should be <20%.

[0117] The performance test data is summarized in Table 2:

[0118] Table 2. Performance test data of high-entropy alloy micro-electrolysis filler for water treatment

[0119]

[0120] Data analysis:

[0121] From the comparison of Example 2, Comparative Example 1 and Comparative Example 2, it can be seen that molybdenum boride as a conductive enhancer and dispersant can promote electron transfer in the micro-electrolysis reaction, improve reaction rate and stability, and appropriate addition can form uniform catalytic centers, promote sustained and uniform hydrogen evolution reaction, and prevent surface passivation. Too low, not enough catalytic centers, uneven reaction, easy passivation, leading to rapid performance decay; too high may lead to local over-catalysis, uneven current distribution, and even metal dissolution (such as Cu, Zn), while bubbles accumulate, and the reaction is unstable.

[0122] From the comparison of Example 2, Comparative Example 3 and Comparative Example 4, it can be seen that CDs have excellent electrical conductivity, can form an electron conduction path between alloy particles, promote electron transfer in the micro-electrolysis reaction, which is the key to improving COD removal rate, and can effectively prevent metal particles from excessive agglomeration during preparation and sintering, so that they form a more uniform and smaller microstructure, thereby exposing more active sites.

[0123] If the concentration of CDs is too low, it cannot form a continuous and effective conductive network, resulting in high electron transfer resistance, low micro-electrolysis reaction efficiency, lack of enough CDs to disperse and support metal particles, making the alloy more prone to sintering and agglomeration, and reducing the active sites. In the reaction, the surface is rapidly covered with oxides or contaminants and passivated, showing unstable hydrogen evolution, large bubbles, and then a sharp decrease in reaction rate (decay rate as high as 27.2%). Although no heavy metals were detected, the unstable structure poses a potential risk of dissolution.

[0124] If the concentration of CDs is too high, it will wrap around the surface of the metal particles, although the conductive network is developed, but physically blocks the contact between the reactants, i.e. wastewater, and the metal active centers, the reaction interface is partially covered by CDs, leading to uneven hydrogen evolution, easy merging into large bubbles and aggregation, which is actually a manifestation of localized reaction, low efficiency, and the covered active sites cannot continuously participate in the reaction in the long-term operation, and the carbonaceous material of CDs may be lost or clogged in the long-term operation, leading to rapid performance decay.

[0125] The above merely describes preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art, according to the technical solution and inventive concept of the present application, makes equivalent replacement or change within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A method for preparing a high-entropy alloy micro-electrolysis filler for water treatment, characterized in that, The method comprises the following steps: S1, organic solution preparation carbon dots S1.1, organic solution preparation: Dissolve citric acid and ethylenediamine in deionized water, heat at 200℃ for 5h; after cooling to room temperature, filter the solution to remove solid impurities to obtain an organic solution; S1.2, preparation of carbon dots CDs: Use a dialysis bag with a molecular weight cut-off of 3500 Da to dialyze the organic solution, after dialysis, dry the solution to obtain solid CDs; S2, preparation of boronized molybdenum Mix molybdenum and boron carbide powder uniformly, then add aluminum powder, put into an alumina crucible, heat to 1250℃ under N2 atmosphere, keep for 4h, take out the sample after cooling to room temperature, crush into powder to obtain boronized molybdenum coated aluminum powder; S3, preparation of high-entropy alloy FeAlNiCuZn-CDs S3.1, preparation of metal salt solution: Dissolve ferrous sulfate, copper sulfate, nickel sulfate, aluminum sulfate and zinc sulfate in deionized water, add dilute sulfuric acid and boronized molybdenum coated aluminum powder, stir until all salts are completely dissolved and aluminum powder is completely reacted to obtain a mixed metal salt solution; S3.2, mixing: Dissolve CDs in deionized water, ultrasonic treat for 30 minutes to make it fully dispersed, slowly add to the mixed metal salt solution, stir for 12h, mix completely, dry to obtain a precursor powder; S3.3, pyrolysis and reduction Put the dried powder into a tube push plate kiln, heat to 200℃ at a rate of 2℃ / min under N2 atmosphere, and keep for 2h; switch the atmosphere to a mixture of 5% H2 and 95% N2, and push the sample into the preheated to 400℃ furnace heating zone, and reduce at 400℃ for 2h, after the reaction is completed, the final high-entropy alloy FeAlNiCuZn-CDs is obtained; S4, post-treatment The sintered high-entropy alloy will have slight adhesion, which is dispersed by ball milling, then screened through a vibrating screen to obtain particles of 3-6mm to obtain the product, a high-entropy alloy micro-electrolysis filler for water treatment.

2. The preparation method of the high-entropy alloy micro-electrolysis filler for water treatment according to claim 1, characterized in that, In S1.1, the molar ratio of citric acid and ethylenediamine is 1:1; the solid content of the organic solution is 45±5%.

3. The preparation method of the high-entropy alloy micro-electrolysis filler for water treatment according to claim 1, characterized in that, In S1.2, the dried solid CDs are fluffy brown or black powder.

4. The preparation method of the high-entropy alloy micro-electrolysis filler for water treatment according to claim 1, characterized in that, In S2, the molar ratio of molybdenum, boron carbide and aluminum is 1:0.25:

3.

5. The method according to claim 1, wherein the method is characterized by, In the S3.1, the metal ions in the mixed metal salt solution include 30% of Fe 2+ , 20% of Cu 2+ , 15% of Ni 2+ , 15% of Al 3 + , 20% of Zn 2+ ; and the molybdenum boride accounts for 0.5%-2% of the mass of the mixed metal salt solution.

6. The preparation method of the high-entropy alloy micro-electrolysis filler for water treatment according to claim 1, characterized in that, In S3.2, the concentration of CDs in the prepared mixed solution is 5-10mg / mL.

7. Use of the microelectrolysis packing produced by the method according to claims 1-6, characterized by the fact that it is used in the treatment of waste water. The high-entropy alloy micro-electrolysis filler is filled in a micro-electrolysis reactor for removing refractory organic matter in wastewater, reducing water color and COD.

8. Use of the microelectrolytic packing according to claim 7, characterised in that, The method comprises the following steps: Load the filler into the micro-electrolysis reactor to form a micro-electrolysis system, which comprises a reactor, a filler layer, a water inlet system, a gas-water mixing system and a subsequent treatment unit; If the wastewater contains a large amount of suspended solids, it needs to be pretreated by precipitation and filtration, and the pH of the wastewater is adjusted to 3-5, then the wastewater is pumped into the reactor through the filler layer; The hydraulic retention time is determined according to the pollution condition, which is 0.5-2h; the surface of the filler should continuously and uniformly generate tiny gas bubbles, i.e. H2, indicating active reaction; The effluent enters a neutralization tank to adjust the pH to 7-8, then is precipitated and enters a biochemical system or is directly discharged or reused.

9. Use of the microelectrolytic packing according to claim 8, characterised in that, The subsequent treatment unit comprises a neutralization and sedimentation tank and a biochemical treatment tank.

Images