A multiphase high-entropy alloy, a preparation method and application thereof

Abstract

The application discloses a kind of multiphase high-entropy alloy and preparation method and application thereof, belong to the technical field of catalyst efficient activation PMS removes organic pollutants;The metal atom composition of the multiphase high-entropy alloy includes five or more in Co, Cu, Mn, Al, La or Cr;The atomic ratio in the multiphase high-entropy alloy is equimolar, and according to the above-mentioned metal atom composition and the hydrate nitrate of ratio relationship is added into solvent, and precursor solution is prepared;The precursor solution is sequentially pyrolyzed, dried, ground and calcined, and finally the multiphase high-entropy alloy is prepared.The application provides a kind of can reach excellent activation effect and catalyst stability under the condition of no external energy input, and still provides the removal thought of always existing small amount of overflow metal ions and part of not completely mineralized material existing in advanced oxidation process under normal temperature and pressure condition, solves the effect evaluation problem of high-entropy alloy CoCuMnAlLaCr in activation PMS and degradation removal organic pollutants.

Description

Technical Field

[0001] This invention belongs to the field of high-efficiency catalyst activation of PMS for the removal of organic pollutants, and particularly relates to a multiphase high-entropy alloy, its preparation method and application. Background Technology

[0002] Advanced oxidation processes (AOPs) are a promising technology that uses highly oxidizing free radicals to disrupt the chemical structure of pollutants, promoting their transformation and mineralization into harmless substances. Peroxymonosulfate (PMS), with the chemical formula HSO5, has attracted considerable attention due to its superior oxidizing power. - It usually exists in the form of sodium salt (NaHSO5) or potassium salt (KHSO5). It can release sulfate free radicals (SO42-) in water. - PMS generates highly oxidizing free radicals such as hydroxyl radicals (·) and hydroxyl radicals (∙OH), which rapidly degrade pollutants in water through oxidation reactions. Activated PMS, as an emerging environmental remediation technology, has broad application potential due to its ability to generate sulfate radicals with high redox potentials (2.5-3.1 V) and whose byproducts are mostly non-polluting sulfates. By studying different activation pathways, its pollutant removal efficiency can be greatly improved.

[0003] Methods for directly activating persulfate include thermal activation, alkaline activation, radiation activation, transition metal activation, and carbon-based material activation. Transition metal activation can be further subdivided into homogeneous activation and heterogeneous activation. While homogeneous activation generally has high efficiency, its practical value is limited due to difficulties in recycling and potential secondary pollution risks. However, through in-depth research on the structure of metallic materials, transition metal catalysts such as single-atom catalysts, metal-organic frameworks, metal oxides, and layered double hydroxides (LDHs) have been developed, effectively improving the activation efficiency of heterogeneous catalysis. Nevertheless, the antagonistic relationship between catalytic activity and stability remains a significant constraint, making it difficult for single-metal or bimetallic materials to simultaneously exhibit satisfactory performance in both dimensions.

[0004] High-entropy alloys (HEAs) are a new type of alloy material, typically composed of five or more main elements in approximately equal atomic proportions. These alloys are unique in that they possess high entropy values, which enhance their stability when forming solid solutions. Furthermore, due to their compositional diversity, they exhibit unique cocktail effects and synergistic effects between different elements, providing more possible pathways and unexpected results for catalytic processes. Currently, the application of HEAs in PMS activation is limited. However, considering the constituent elements of HEAs and the different alloy structures resulting from their influence, HEAs possess significant room for adjustment and development potential to achieve highly efficient PMS activation.

[0005] From the perspective of PMS activation, the first issue is energy consumption: thermal activation, radiation activation, photocatalysis, electrocatalysis, and ultrasonic catalysis can all effectively activate PMS without considering energy consumption, but these require very high external energy input, making them difficult to implement in actual production. The second issue is that the most important aspect of PMS activation is balancing the activation effect with catalyst stability (i.e., preventing secondary metal contamination). The aforementioned single-atom catalysts, metal-organic frameworks, metal oxides, and layered double hydroxides are limited by their relatively singular metal atom composition, resulting in either limited activation capacity, limited free radical generation capacity, or inability to rapidly and effectively degrade target pollutants, or strong activity but with significant metal spillage. In summary, the development of high-entropy alloys has limited application in PMS activation. Furthermore, existing high-entropy alloy PMS activation schemes are limited to single-phase structures, possessing certain activity and stability, but in the absence of energy input, while they can control metal ion spillage within a certain range, they cannot further reduce it.

[0006] Therefore, there is an urgent need to provide a multiphase high-entropy alloy (CoCuMnAlLaCr) that can be used to rapidly and efficiently activate persulfate (PMS) and simultaneously generate MnO2 for coagulation and removal of organic pollutants, as well as its preparation method. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention proposes a multiphase high-entropy alloy, its preparation method, and its applications.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] One of the technical solutions of this invention:

[0010] A multiphase high-entropy alloy having a metallic atomic composition including five or more of Co, Cu, Mn, Al, La, or Cr;

[0011] The atomic ratio in the multiphase high-entropy alloy is equimolar.

[0012] Preferably, the metal atomic composition of the multiphase high-entropy alloy includes: CoCuMnAlLaCr, CuMnAlLaCr, CoCuMnAlCr, CoCuAlLaCr, CoCuMnAlLaCr, CoCuMnAlLa, or CoCuMnLaCr.

[0013] Furthermore, the atomic composition of the multiphase high-entropy alloy is CoCuMnAlLaCr.

[0014] Beneficial effects: This invention utilizes a high-entropy structure to adjust the elemental composition of a high-entropy alloy and find suitable metal combinations. First, Cu is identified as the basis for forming the FCC structure. Cr and La are incorporated into the composition to enrich the phase composition of the material. Cr, as the most stable element in the material, significantly enhances the overall catalytic ability while achieving zero spillage during the reaction. Co is introduced as the most effective element for activating PMS, providing active sites. Furthermore, this invention incorporates Mn into the high-entropy alloy composition and utilizes the reaction of Mn and PMS to generate MnO2 flocs. During the activation of PMS, organic pollutants are oxidized and degraded, and incompletely mineralized small-molecule organic matter and a small amount of metal ions spilled during the reaction are removed through coagulation.

[0015] Preferably, the phase structure of the multiphase high-entropy alloy includes: an FCC phase structure and an R-3c phase structure.

[0016] The second technical solution of this invention:

[0017] The preparation method of the above-mentioned multiphase high-entropy alloy includes the following steps:

[0018] A precursor solution was prepared by adding hydrated nitrates according to the above metal atomic composition and ratio into a solvent.

[0019] The precursor solution was subjected to pyrolysis, drying, grinding and calcination in sequence to finally prepare the multiphase high-entropy alloy.

[0020] Preferably, the solvent is a synthetic solvent, including citric acid and anhydrous ethanol, and the ratio of the two is: citric acid : anhydrous ethanol = 4.18 mmol : 50 mL.

[0021] Beneficial effects: Citric acid in the synthesis solvent acts as a complexing agent in the prepared precursor solution, forming stable complexes with metal ions, which helps to maintain the uniform dispersion of metal ions; it adjusts the pH value to prevent the metal ions from hydrolyzing or precipitating in the solution; during calcination, citric acid acts as a carbon source to reduce the metal and reduce the formation of metal oxides; and the gas generated during the pyrolysis of citric acid helps to generate gas phase protection during sintering, preventing particle agglomeration, forming a more uniform particle distribution, and simultaneously introducing microporous or porous structures.

[0022] Preferably, the molar ratio of citric acid to each (metal) atom is 10:1.

[0023] Preferably, the conditions during the pyrolysis process are: direct pyrolysis in a water bath at 90°C for 1 hour; and / or

[0024] The drying conditions are: drying in an oven at 80°C for 2 hours; and / or

[0025] The conditions for the calcination process are: calcination at 800~1100℃ for 3 hours under an argon atmosphere.

[0026] Beneficial effects: By adjusting the synthesis process and changing the ratio of the synthesis solvent, water bath temperature, oxygen and temperature during metal firing (calcination), this invention synthesizes a hexa-element high-entropy alloy with optimal performance.

[0027] The third technical solution of this invention:

[0028] Application of the multiphase high-entropy alloy in the field of rapid and efficient activation of persulfate (PMS) and simultaneous generation of MnO2 for coagulation and removal of organic pollutants.

[0029] Beneficial Effects: This invention discloses a multiphase high-entropy alloy (CoCuMnAlLaCr) that can be used to rapidly and efficiently activate persulfate (PMS) and simultaneously generate MnO2 for coagulation and removal of organic pollutants. The principle involved is as follows: by utilizing the four significant core effects of high-entropy alloys—lattice distortion effect, high-entropy effect, delayed diffusion effect, and cocktail effect—and adjusting the constituent elements and synthesis process of the high-entropy alloy, a novel multiphase high-entropy alloy was designed. On the one hand, the lattice distortion effect increased the specific surface area and reactive sites of the catalyst, improving the catalytic efficiency. Within 2 minutes after the addition of PMS, the pollutant atrazine was rapidly degraded (degradation rate >95%). On the other hand, the high entropy effect was used to achieve stability in the reaction process. At the same time, the cocktail effect was used to design an integrated oxidation-coagulation degradation and removal system. The generated MnO2 flocs settled to remove atrazine and its degradation intermediates, and the final total organic carbon (TOC) removal rate of the pollutant solution reached 75%. Furthermore, the technical effect of precipitating a small amount of overflowing metal ions with coagulation provides a solution for removing a small amount of overflowing metal ions and some incompletely mineralized substances present in the advanced oxidation process under normal temperature and pressure conditions. This solves the problem of evaluating the effectiveness of high entropy alloy CoCuMnAlLaCr in activating PMS and degrading and removing organic pollutants.

[0030] Preferably, the organic pollutant is atrazine, chemically named 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, an organic compound with the chemical formula C8H10H2O. 14 C l N5.

[0031] Preferably, the process for removing organic pollutants is as follows:

[0032] The multiphase high-entropy alloy was added to a solution containing organic pollutants and subjected to ultrasonic and stirring treatment to obtain a mixed solution.

[0033] Add potassium persulfate (PMS) solution to the mixed solution, stir, and filter.

[0034] Preferably, the amount of the multiphase high-entropy alloy added is 0.0167~0.0333 g / L.

[0035] Compared with the prior art, the present invention has the following advantages and technical effects:

[0036] 1. This invention provides a novel high-entropy alloy composition (CoCuMnAlLaCr).

[0037] 2. This invention provides a novel perspective (multiphase composition) on high-entropy alloy materials in the field of activated persulfate;

[0038] 3. This invention provides a catalyst (SO4) that is highly efficient at activating persulfate and rapidly (10 s) generating various active free radicals. － ·,·OH,O2· － );

[0039] 4. This invention utilizes the high-entropy structure of high-entropy alloys and the synergistic effect between metals to achieve ultra-low catalyst dosage concentration (0.0167 g / L) and actual total metal dosage concentration (<0.006 g / L);

[0040] 5. This invention utilizes the cocktail effect and multi-component characteristics of high-entropy alloys to create an oxidation-coagulation system for removing organic matter, simultaneously recovering metal ions and small-molecule organic byproducts, providing a new solution to the problem of metal spillage in heterogeneous catalysis. Attached Figure Description

[0041] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. In the drawings:

[0042] Figure 1 This is a comparison of the catalytic removal effects of the multiphase high-entropy alloys prepared in Examples 1-7 of the present invention and the mixed reagent prepared in Comparative Example 1 on ATZ.

[0043] Figure 2 This is a comparison of the removal effects of the high-entropy alloy prepared in Example 1 of this invention on 10 ppm ATZ by activating 0-1.2 mM PMS.

[0044] Figure 3 This is a comparison of the catalytic removal effect of multiphase high-entropy alloys prepared in Examples 1 and 8-12 (different firing temperatures) of the present invention on ATZ.

[0045] Figure 4 In the effect example, the effect of different catalyst (hexa-element high-entropy alloy prepared in Example 1) dosage on ATZ removal efficiency at 0.6 mM MPMS;

[0046] Figure 5 The X-ray diffraction patterns of the multiphase high-entropy alloys (CoCuMnAlLaCr) prepared in Examples 1 and 8-12 of this invention are shown below.

[0047] Figure 6 The infrared spectra of the multiphase high-entropy alloy (CoCuMnAlLaCr) prepared in Example 1 of the present invention before and after the reaction, and the infrared spectra of the flocs generated in the system after the reaction in Comparative Example 1.

[0048] Figure 7XPS image of the multiphase high-entropy alloy (CoCuMnAlLaCr) prepared in Example 1 of this invention. Detailed Implementation

[0049] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0050] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0051] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0052] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0053] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0054] A method for preparing a multiphase high-entropy alloy (CoCuMnAlLaCr) that can be used for rapid and efficient activation of persulfate (PMS) and simultaneous generation of MnO2 for coagulation and removal of organic pollutants includes the following steps:

[0055] (1) Weigh the raw materials: citric acid (CA, C6H8O7·H2O), anhydrous ethanol, Co(NO3)2·6H2O (0.418 mmol), Al(NO3)3·9H2O (0.418 mmol), Mn(NO3)2·4H2O (0.418 mmol), Cr(NO3)3·9H2O (0.418 mmol), La(NO3)3·6H2O (0.418 mmol), Cu(NO3)2·3H2O (0.418 mmol);

[0056] (2) Preparation steps:

[0057] First, 4.18 mmol of citrate monohydrate (CA, C6H8O7·H2O) was added to 50 mL of anhydrous ethanol and stirred for 10 min to form a colorless and transparent solution.

[0058] Then, equimolar amounts of cobalt nitrate hexahydrate (Co(NO3)2·6H2O, 0.418 mmol), aluminum nitrate nonahydrate (Al(NO3)3·9H2O, 0.418 mmol), manganese nitrate tetrahydrate (Mn(NO3)2·4H2O, 0.418 mmol), chromium nitrate nonahydrate (Cr(NO3)3·9H2O, 0.418 mmol), lanthanum nitrate hexahydrate (La(NO3)3·6H2O, 0.418 mmol), and copper nitrate trihydrate (Cu(NO3)2·3H2O, 0.418 mmol) were added to the above solution sequentially. After magnetic stirring for 1 hour, a clear and deep purple precursor solution was obtained.

[0059] (3) The precursor solution was placed in a water bath and directly pyrolyzed at 90°C for 1 hour with slow stirring. Then, the monomer was left to stand at room temperature for 1 hour and then dried in an oven at 80°C for 2 hours. The evaporated crystals were then transferred to a mortar and carefully ground to obtain a light gray powder. Finally, the light gray powder was calcined at 900°C for 3 hours under an argon atmosphere to obtain CoCuMnAlLaCr.

[0060] Unless otherwise specified, "room temperature" in this invention refers to 20-30℃.

[0061] All raw materials used in this invention were purchased from the market.

[0062] The technical solution of the present invention will be further illustrated by the following embodiments.

[0063] Example 1

[0064] Preparation process of a multiphase high-entropy alloy (CoCuMnAlLaCr):

[0065] (1) Selection of raw materials: citric acid (CA, C6H8O7·H2O), anhydrous ethanol, Co(NO3)2·6H2O (0.418 mmol), Al(NO3)3·9H2O (0.418 mmol), Mn(NO3)2·4H2O (0.418 mmol), Cr(NO3)3·9H2O (0.418 mmol), La(NO3)3·6H2O (0.418 mmol), Cu(NO3)2·3H2O (0.418 mmol)

[0066] (2) Preparation method:

[0067] First, 4.18 mmol of citrate monohydrate (CA, C6H8O7·H2O) was added to 50 mL of anhydrous ethanol and stirred for 10 min to form a colorless and transparent solution.

[0068] Then, equimolar amounts of cobalt nitrate hexahydrate (Co(NO3)2·6H2O, 0.418 mmol), aluminum nitrate nonahydrate (Al(NO3)3·9H2O, 0.418 mmol), manganese nitrate tetrahydrate (Mn(NO3)2·4H2O, 0.418 mmol), chromium nitrate nonahydrate (Cr(NO3)3·9H2O, 0.418 mmol), lanthanum nitrate hexahydrate (La(NO3)3·6H2O, 0.418 mmol), and copper nitrate trihydrate (Cu(NO3)2·3H2O, 0.418 mmol) were added to the above solution sequentially. After magnetic stirring for 1 hour, a clear and deep purple precursor solution was obtained.

[0069] Subsequently, the precursor solution was directly pyrolyzed in a water bath at 90°C for 1 hour with slow stirring. Afterward, it was allowed to stand at room temperature for 1 hour, and then dried in an oven at 80°C for 2 hours. The evaporated crystals were then transferred to a mortar and carefully ground to obtain a light gray powder. Finally, the light gray powder was calcined at 900°C for 3 hours under an argon atmosphere to obtain CoCuMnAlLaCr.

[0070] Example 2

[0071] The preparation process of a high-entropy alloy (CoMnAlLaCr)

[0072] The difference from Example 1 is that copper nitrate trihydrate is not added, while the amount of other raw materials and the preparation process are the same as in Example 1.

[0073] Example 3

[0074] The preparation process of a high-entropy alloy (CoCuMnAlCr)

[0075] The difference from Example 1 is that lanthanum nitrate hexahydrate is not added, while the amount of other raw materials and the preparation process are the same as in Example 1.

[0076] Example 4

[0077] The preparation process of a high-entropy alloy (CoCuMnAlLa)

[0078] The difference from Example 1 is that no raw material chromium nitrate nonahydrate is added, while the amount of other raw materials and the preparation process are the same as in Example 1.

[0079] Example 5

[0080] The preparation process of a high-entropy alloy (CoCuMnLaCr)

[0081] The difference from Example 1 is that aluminum nitrate nonahydrate is not added, while the amount of other raw materials and the preparation process are the same as in Example 1.

[0082] Example 6

[0083] The preparation process of a high-entropy alloy (CuMnAlLaCr)

[0084] The difference from Example 1 is that no raw material cobalt nitrate hexahydrate is added, while the amount of other raw materials and the preparation process are the same as in Example 1.

[0085] Example 7

[0086] The preparation process of a high-entropy alloy (CoCuAlLaCr)

[0087] The difference from Example 1 is that no raw material manganese nitrate tetrahydrate is added, while the amount of other raw materials and the preparation process are the same as in Example 1.

[0088] Example 8

[0089] Preparation process of a high-entropy alloy (CoCuMnAlLaCr)

[0090] The difference from Example 1 is that the calcination temperature is 600°C. The amounts of other raw materials and the preparation process are the same as in Example 1.

[0091] Example 9

[0092] Preparation process of a high-entropy alloy (CoCuMnAlLaCr)

[0093] The difference from Example 1 is that the calcination temperature is 700°C. The amounts of other raw materials and the preparation process are the same as in Example 1.

[0094] Example 10

[0095] Preparation process of a high-entropy alloy (CoCuMnAlLaCr)

[0096] The difference from Example 1 is that the calcination temperature is 800°C. The amounts of other raw materials and the preparation process are the same as in Example 1.

[0097] Example 11

[0098] Preparation process of a multiphase high-entropy alloy (CoCuMnAlLaCr)

[0099] The difference from Example 1 is that the calcination temperature is 1000℃. The amounts of other raw materials and the preparation process are the same as in Example 1.

[0100] Example 12

[0101] Preparation process of a multiphase high-entropy alloy (CoCuMnAlLaCr)

[0102] The difference from Example 1 is that the calcination temperature is 1100℃. The amounts of other raw materials and the preparation process are the same as in Example 1.

[0103] Comparative Example 1

[0104] Reagents: Co(NO3)2·6H2O (0.418 mmol), Al(NO3)3·9H2O (0.418 mmol), Mn(NO3)2·4H2O (0.418 mmol), Cr(NO3)3·9H2O (0.418 mmol), Cu(NO3)2·3H2O (0.418mmol).

[0105] Preparation method: Simply mix the above reagents, and label it homogeneous.

[0106] Effect verification:

[0107] The high-entropy alloy material prepared above was added to a 10 ppm ATZ solution to verify the catalytic effect of the high-entropy alloy.

[0108] Four 60 mL aliquots of 10 ppm atrazine solution were prepared. 1 mg / 2 mg / 6 mg / 10 mg of CoCuMnAlLaCr prepared in Example 1 were added to the solutions, and the mixture was sonicated for 5 min, followed by stirring for 25 min. Then, 0.3 mL of 120 mM PMS solution was added, and stirring continued. At regular intervals, 1 mL of the sample was taken, filtered through a 0.22 μm filter membrane, and collected in a brown liquid chromatography vial. The atrazine concentration was analyzed by HPLC.

[0109] Set up a blank sample without adding any catalyst. Add 0.3 mL of 120 mM PMS directly to 60 mL of 10 ppm atrazine solution, stir continuously, take samples at regular intervals, filter, and analyze the atrazine concentration using HPLC.

[0110] To prepare a control sample, catalysts prepared in Examples 2-7 and Comparative Example 1 were added to seven 60 mL 10 ppm atrazine solutions, respectively. After adding the catalysts according to the same metal molar concentration as in Example 1, the solutions were sonicated for 5 min, stirred for 25 min, and then 0.3 mL 120 mM PMS solution was added. The mixture was stirred continuously, and samples were taken at regular intervals, filtered, and the atrazine concentration was analyzed by HPLC.

[0111] To prepare control samples, 1 mg of the catalyst prepared in Example 1 was added to each of six 60 mL 10 ppm atrazine solutions. The solutions were sonicated for 5 min, then stirred for 25 min, followed by the addition of 0 mL, 0.15 mL, 0.2 mL, 0.3 mL, 0.45 mL, and 0.6 mL of 120 mM PMS solution, respectively. The mixture was stirred continuously, and samples were taken at regular intervals, filtered, and the atrazine concentration was analyzed by HPLC.

[0112] To prepare a control sample, 1 mg of the catalyst prepared in Examples 8-12 was added to each of five 60 mL 10 ppm atrazine solutions. The solutions were sonicated for 5 min, then stirred for 25 min, and 0.3 mL of 120 mM PMS solution was added. The mixture was stirred continuously, and samples were taken at regular intervals, filtered, and the atrazine concentration was analyzed by HPLC.

[0113] Figure 1 The graph shows a comparison of the degradation and removal effects of the multiphase high-entropy alloy (1 mg) prepared in Examples 1-7 of this invention and the mixed reagent (1 mg) prepared in Comparative Example 1 on 10 ppm ATZ (the original ATZ solution had a pH of 7, i.e., the pH of the ATZ solution before the addition of catalyst and PMS, the same below) activated by 0.6 mM PMS. As can be seen from the graph, the multiphase high-entropy alloy prepared in Example 1 of this invention has the best PMS activation effect, and the degradation rate of ATZ reaches more than 95% within 2 minutes after the addition of PMS.

[0114] Figure 2 The graph shows a comparison of the removal effects of the high-entropy alloy (1 mg) prepared in Example 1 of this invention on 10 ppm ATZ (the original ATZ solution has a pH of 7) activated by 0-1.2 mM PMS. It can be seen from the graph that the PMS concentration is the most important factor in the degradation effect. The 1 mg of multiphase high-entropy alloy prepared in Example 1 of this invention has sufficient reaction sites to provide higher concentrations of PMS to achieve 100% ATZ degradation within 2 minutes.

[0115] Figure 3 This is a comparison of the removal effect of the high-entropy alloy (1 mg) prepared in Examples 1 and 8-12 (different calcination temperatures) on 10 ppm ATZ (the original ATZ solution has a pH of 7) after activation with 0.6 mM PMS. As can be seen from the figure, within different calcination temperature ranges, the multiphase high-entropy alloy prepared at 900℃ in Example 1 of this invention has excellent removal effect on organic pollutants, and the removal rate can reach more than 95% within 2 minutes after adding PMS.

[0116] Figure 4 In the effect example, the effect of different catalyst (Example 1) dosages on the removal efficiency of ATZ (pH 7 of the original ATZ solution) under 0.6 mM PMS conditions was investigated. As can be seen from the figure, at a dosage of 1 mg, the multiphase high-entropy alloy prepared in Example 1 showed the best ATZ removal efficiency, and in terms of dosage, it saved costs.

[0117] Figure 5 The image shows the X-ray diffraction pattern of the multiphase high-entropy alloy (CoCuMnAlLaCr) prepared in Example 1 of this invention. As can be seen from the image, under heating conditions of 600℃, 700℃ and 800℃, the high-entropy alloy CoCuMnAlLaCr mainly exhibits an FCC spatial structure. When the heating temperature rises to 900℃, the R-3c phase structure grows on the basis of the FCC phase structure and coexists stably with the FCC phase structure.

[0118] Figure 6 The images show the infrared spectra of the multiphase high-entropy alloy (CoCuMnAlLaCr) prepared in Example 1 of this invention before and after the reaction, and the infrared spectrum of the flocs generated in the system after the reaction in Comparative Example 1. It can be seen from the figures that the high-entropy alloy CoCuMnAlLaCr material after the degradation reaction basically retains the characteristic peaks of the material before the reaction, which shows the stability of the material from a structural perspective. The material after the reaction under the original ATZ solution was neutral (pH=7) and acidic (pH=3) conditions showed the same characteristic peaks as the flocs in Comparative Example 1, indicating that the oxidation-coagulation system was successfully established under neutral and acidic conditions, and effectively combined the intermediate products of ATZ degradation.

[0119] Figure 7 The image shows an XPS image of the multiphase high-entropy alloy (CoCuMnAlLaCr) prepared in Example 1 of this invention. It can be seen from the image that all six metal elements were successfully loaded onto the carbon material. At the same time, all six metal elements exist in high valence states in the material, with Mn, Co, and Cu having multiple valence states.

[0120] The above are merely preferred embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A method for preparing a multiphase high-entropy alloy, characterized in that, The metal atomic composition includes: CoCuMnAlLaCr, CoCuMnAlCr, CoCuAlLaCr, CoCuMnAlLa, or CoCuMnLaCr; The atomic ratio in the multiphase high-entropy alloy is equimolar. Includes the following steps: A precursor solution was prepared by adding hydrated nitrates according to the metal atom composition and ratio to a solvent; the solvent was a mixed solution of citric acid and anhydrous ethanol; wherein, the ratio of hydrated nitrates of each metal atom to anhydrous ethanol was 0.418 mmol to 4.18 mmol to 50 mL. The precursor solution was subjected to pyrolysis, drying, grinding and calcination in sequence to finally prepare the multiphase high-entropy alloy.

2. The method for preparing a multiphase high-entropy alloy according to claim 1, characterized in that, The conditions for the pyrolysis process are: pyrolysis in a water bath at 90°C for 1 hour; and / or The conditions for the drying process are: drying at 80°C for 2 hours; and / or The conditions for the calcination process are: calcination at 800~1100℃ for 3 hours under an argon atmosphere.

3. The application of the multiphase high-entropy alloy prepared by the preparation method according to any one of claims 1-2 in the field of rapid and efficient activation of persulfate and simultaneous generation of MnO2 for coagulation and removal of organic pollutants, characterized in that, The multiphase high-entropy alloy is used as a catalyst.

4. The application according to claim 3, characterized in that, The organic pollutant is 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine.

5. The application according to claim 3, characterized in that, The process for removing organic pollutants is as follows: The multiphase high-entropy alloy was added to a solution containing organic pollutants and subjected to ultrasonic and stirring treatment to obtain a mixed solution. Add potassium persulfate solution to the mixture, stir, and filter.

6. The application according to claim 5, characterized in that, The amount of the multiphase high-entropy alloy added is 0.0167~0.0333 g / L.

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