A CoAlCuFeNiB-based high-entropy amorphous alloy capable of degrading sewage and evolving hydrogen and oxygen, and its application

Abstract

A CoAlCuFeNiB series high entropy amorphous alloy capable of degrading sewage and performing dual hydrogen and oxygen evolution and its application, which relates to a high entropy amorphous alloy and its application. The present invention aims to solve the problems that the existing catalyst materials have low degradation efficiency and are difficult to be applied to sewage degradation in medium and alkaline environments, and amorphous materials cannot simultaneously meet the dual-effect requirements of sewage degradation and hydrogen and oxygen evolution. The CoAlCuFeNiB series high entropy amorphous alloy capable of degrading sewage and performing dual hydrogen and oxygen evolution has a chemical formula of Co in terms of atomic percentage. a Al b Cu c Fe d Ni e B f ; Application: Using CoAlCuFeNiB series high entropy amorphous alloy as a catalyst, the organic matter in organic wastewater is degraded in the persulfate system; using CoAlCuFeNiB series high entropy amorphous alloy as a catalyst, the electrolysis of water in the electrolyte is used to release hydrogen and oxygen.

Description

Technical Field

[0001] The invention relates to a high-entropy amorphous alloy and its application. Background Art

[0002] In recent years, the rapid development of industries such as the chemical and pharmaceutical industries has generated a large amount of difficult-to-degrade industrial organic wastewater. Effectively addressing this issue of water pollution is a crucial step in achieving the goal of "green development." Researchers have conducted extensive research in the field of water treatment, exploring a range of water treatment technologies. Currently, the most commonly used and effective method is the advanced oxidation process, which can rapidly degrade and effectively remove pollutants from water. However, it is primarily suitable for acidic environments and is less effective in neutral and alkaline environments.

[0003] In addition to water pollution, the energy crisis is also a major issue facing us today. Water electrolysis for hydrogen and oxygen evolution is considered a clean and efficient energy regeneration pathway, leading to a surge in research on water electrolysis. Combining wastewater degradation with water electrolysis for hydrogen and oxygen production can, on the one hand, address the increasingly serious problem of water pollution and alleviate water shortages, and on the other hand, produce hydrogen and oxygen, providing essential energy for daily use. The development and utilization of dual-action catalysts is crucial for achieving both environmental protection and the goal of "green hydrogen."

[0004] Amorphous alloys have become a popular material in recent years. Compared to crystalline structures, their metastable structures offer structural and chemical uniformity, lacking defects such as dislocations and grain boundaries. They also possess excellent corrosion resistance and abundant surface active sites, demonstrating excellent performance in wastewater degradation. However, research on their use as dual-function catalysts for water treatment and water electrolysis is relatively limited. Most existing catalysts are designed for one catalytic function and are unable to simultaneously address the needs of both wastewater degradation and hydrogen and oxygen evolution from water electrolysis. Summary of the Invention

[0005] The present invention aims to solve the problems that existing catalyst materials have low degradation efficiency and are difficult to apply to the degradation of sewage in neutral and alkaline environments, and amorphous materials cannot simultaneously meet the dual-effect requirements of sewage degradation and hydrogen and oxygen evolution. Instead, it provides a CoAlCuFeNiB series high-entropy amorphous alloy and its application that can degrade sewage and evolve hydrogen and oxygen.

[0006] A CoAlCuFeNiB high entropy amorphous alloy capable of degrading wastewater and evolving hydrogen and oxygen. Calculated by atomic percentage, its general chemical formula is Co a Al b Cu c Fe d Ni e B f, where 15≤a≤30, 0≤b≤30, 0≤c≤30, 0≤d≤30, 15≤e≤30, 0≤f≤20, and a+b+c+d+e+f=100.

[0007] The invention discloses an application of a CoAlCuFeNiB series high-entropy amorphous alloy capable of degrading wastewater and evolving hydrogen and oxygen. The CoAlCuFeNiB series high-entropy amorphous alloy is used as a catalyst to degrade organic matter in organic wastewater in a persulfate system; and the CoAlCuFeNiB series high-entropy amorphous alloy is used as a catalyst to electrolyze water in an electrolyte to evolve hydrogen and oxygen.

[0008] The beneficial effects of the present invention are:

[0009] (1) The CoAlCuFeNiB high entropy amorphous fibers prepared by melt drawing were used in a persulfate system for catalytic degradation experiments. The fibers can effectively degrade rhodamine B, sulfamethazine or aniline in organic wastewater. Moreover, the degradation efficiency is very good in both acidic and alkaline pH ranges (pH 2-11). They can be basically completely degraded within 100 seconds and can be reused 25-35 times.

[0010] (2) CoAlCuFeNiB high entropy amorphous fibers can simultaneously catalyze the electrolysis of water for hydrogen and oxygen evolution in both acidic and alkaline electrolyte environments, and can be used as a dual-effect catalyst.

[0011] The invention is used for a CoAlCuFeNiB series high entropy amorphous alloy capable of degrading sewage and evolving hydrogen and oxygen, and its application. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20 XRD test pattern of high entropy amorphous alloy fiber;

[0013] Figure 2 The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20 Degradation curves of high entropy amorphous alloy fibers at different pH values;

[0014] Figure 3 The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20Ultraviolet spectrum absorbance curve of high entropy amorphous alloy fiber degrading sulfamethazine;

[0015] Figure 4 The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20 UV spectra absorbance curve of aniline degradation by high entropy amorphous alloy fibers;

[0016] Figure 5 The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20 High entropy amorphous alloy fiber reuse diagram, column A is degradation for 80s, column B is degradation for 100s;

[0017] Figure 6 is the hydrogen evolution performance of high entropy amorphous alloy in alkaline environment, 1 is the Co 20 Cu 20 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 2 is the Co 20 Al 20 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 3 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 4 is the Co 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 The hydrogen evolution curve of high entropy amorphous alloy fiber, 5 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 6 is the Al in the comparative experiment 3 20 Cu 20 Fe 20 Ni 20 Si 10 B10 Hydrogen evolution curve of high entropy amorphous alloy fiber;

[0018] Figure 7 is the oxygen evolution performance of high entropy amorphous alloy in alkaline environment, 1 is the Co 20 Cu 20 Fe 20 Ni 20 B 20 Oxygen evolution curve of high entropy amorphous alloy fiber, 2 is the Co 20 Al 20 Fe 20 Ni 20 B 20 High entropy amorphous alloy fiber oxygen evolution curve, 3 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 Oxygen evolution curve of high entropy amorphous alloy fiber, 4 is the Co 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 Oxygen evolution curve of high entropy amorphous alloy fiber, 5 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 Oxygen evolution curve of high entropy amorphous alloy fiber, 6 is the Al in comparison experiment 3 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 Oxygen evolution curve of high entropy amorphous alloy fiber;

[0019] Figure 8 is the LSV curve of high entropy amorphous fiber in acidic environment, 1 is the Co 20 Cu 20 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 2 is the Co 20 Al 20 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 3 is the Co 20 Al10 Cu 10 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 4 is the Co 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 The hydrogen evolution curve of high entropy amorphous alloy fiber, 5 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 6 is the Al in the comparative experiment 3 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 Hydrogen evolution curve of high entropy amorphous alloy fiber. DETAILED DESCRIPTION

[0020] Specific embodiment 1: This embodiment is a CoAlCuFeNiB series high entropy amorphous alloy that can degrade sewage and evolve hydrogen and oxygen. Its chemical formula is Co a Al b Cu c Fe d Ni e B f , where 15≤a≤30, 0≤b≤30, 0≤c≤30, 0≤d≤30, 15≤e≤30, 0≤f≤20, and a+b+c+d+e+f=100.

[0021] The beneficial effects of this embodiment are:

[0022] (1) The CoAlCuFeNiB high entropy amorphous fibers prepared by melt drawing were used in a persulfate system for catalytic degradation experiments. The fibers can effectively degrade rhodamine B, sulfamethazine or aniline in organic wastewater. Moreover, the degradation efficiency is very good in both acidic and alkaline pH ranges (pH 2-11). They can be basically completely degraded within 100 seconds and can be reused 25-35 times.

[0023] (2) CoAlCuFeNiB high entropy amorphous fibers can simultaneously catalyze the electrolysis of water for hydrogen and oxygen evolution in both acidic and alkaline electrolyte environments, and can be used as a dual-effect catalyst.

[0024] Specific embodiment 2: This embodiment differs from the specific embodiment 1 in that the CoAlCuFeNiB series high entropy amorphous alloy capable of degrading wastewater and producing hydrogen and oxygen evolution is prepared according to the following steps:

[0025] According to the chemical formula Co a Al b Cu c Fe d Ni e B f Weigh each elemental raw material with an atomic percentage of , where 15≤a≤30, 0≤b≤30, 0≤c≤30, 0≤d≤30, 15≤e≤30, 0≤f≤20, and a+b+c+d+e+f=100, to obtain the weighed raw materials; place the weighed raw materials and titanium in a vacuum arc melting furnace, evacuate the furnace, and fill it with protective gas; first, arc-smelt the titanium, then arc-smelt the weighed raw materials to obtain a master alloy ingot; arc-smelt the master alloy ingot and suction-cast it to obtain an alloy rod; place the alloy rod in a high-vacuum precision melt pulling device, evacuate the furnace, fill it with protective gas, set the copper wheel speed and start it, induction heat the alloy rod, and start feeding the master alloy to obtain a CoAlCuFeNiB series high-entropy amorphous alloy. Other aspects are the same as those in the first embodiment.

[0026] Specific embodiment 3: This embodiment differs from specific embodiment 1 or 2 in that the protective gas is argon. Other aspects are the same as specific embodiment 1 or 2.

[0027] Specific embodiment 4: This embodiment uses a CoAlCuFeNiB series high-entropy amorphous alloy that can degrade sewage and evolve hydrogen and oxygen. The CoAlCuFeNiB series high-entropy amorphous alloy is used as a catalyst to degrade organic matter in organic wastewater in a persulfate system; and the CoAlCuFeNiB series high-entropy amorphous alloy is used as a catalyst to electrolyze water in an electrolyte to evolve hydrogen and oxygen.

[0028] Specific embodiment 5: This embodiment differs from specific embodiment 4 in that the organic compound is rhodamine B, sulfamethazine or aniline. Other aspects are the same as specific embodiment 4.

[0029] Specific embodiment 6: This embodiment differs from either specific embodiment 4 or 5 in that: a CoAlCuFeNiB-based high entropy amorphous alloy is used as a catalyst to degrade organic matter in organic wastewater in a persulfate system, specifically by the following steps:

[0030] Adjusting the pH of the organic wastewater to 2-11, adding a sodium persulfate solution until the concentration of sodium persulfate in the organic wastewater is 1 mmol / L-15 mmol / L, and then adding a CoAlCuFeNiB series high entropy amorphous alloy, and degrading it at a speed of 2000 r / min-2800 r / min and room temperature for 1 min-10 min;

[0031] The amount of the CoAlCuFeNiB high entropy amorphous alloy added is 0.1 g / L to 1 g / L. Other aspects are the same as those of the fourth or fifth embodiment.

[0032] Specific embodiment 7: This embodiment differs from any one of specific embodiments 4 to 6 in that 2 mol / L dilute hydrochloric acid or 1 mol / L dilute sodium hydroxide solution is added dropwise to the organic wastewater until the pH is 2 to 11. Other aspects are the same as specific embodiments 4 to 6.

[0033] Specific embodiment 8: This embodiment differs from Specific embodiments 4 to 7 in that a CoAlCuFeNiB-based high-entropy amorphous alloy is used as a catalyst to degrade organic matter in organic wastewater in a persulfate system, with a reuse frequency of 25 to 35 times. Other aspects are the same as Specific embodiments 4 to 7.

[0034] Specific embodiment 9: This embodiment differs from specific embodiments 4 to 8 in that the concentration of organic matter in the organic wastewater is 10 mg / L to 100 mg / L. Other aspects are the same as specific embodiments 4 to 8.

[0035] Specific embodiment 10: This embodiment differs from specific embodiments 4 to 9 in that a CoAlCuFeNiB-based high-entropy amorphous alloy is used as a catalyst, and when water is electrolyzed in an electrolyte for hydrogen and oxygen evolution, the electrolyte is a 1.0 mol / L KOH solution or a 0.5 mol / L H2SO4 solution. Other aspects are the same as specific embodiments 4 to 9.

[0036] The following examples are used to verify the beneficial effects of the present invention:

[0037] Example 1:

[0038] A CoAlCuFeNiB high entropy amorphous alloy capable of degrading wastewater and evolving hydrogen and oxygen. Calculated by atomic percentage, its general chemical formula is Co a Al b Cu c Fe d Ni e B f , where a=20, b=0, c=20, d=20, e=20, and f=20.

[0039] The CoAlCuFeNiB series high entropy amorphous alloy capable of degrading sewage and evolving hydrogen and oxygen is specifically prepared according to the following steps:

[0040] According to the chemical formula Co a Al b Cu c Fe d Ni e B f , weigh Co particles, Al particles, Cu particles, Fe particles, Ni particles and B particles, where a=20, b=0, c=20, d=20, e=20, f=20, and obtain weighed raw materials; place the weighed raw materials and titanium in a vacuum arc melting furnace, evacuate to 6.6×10 -3 Pa, and then filled with argon, first arc-melted titanium for 1 min, then arc-melted the weighed raw materials, and turned over more than 5 times to obtain a master alloy ingot, which was arc-melted and suction-cast to obtain an alloy rod with a length of 9.0 cm and a diameter of 10 mm; the alloy rod was placed in a high vacuum precision melt pulling equipment and vacuumed to 6.0×10 -3 Pa, then filled with protective gas, and the vacuum degree was 6.0×10 -3 Pa, power supply heating power of 20kW, Cu roller linear speed of 25m / s, master alloy feeding speed of 30μm / s and roller angle of 60°, the CoAlCuFeNiB high entropy amorphous alloy, namely Co 20 Cu 20 Fe 20 Ni 20 B 20 High entropy amorphous alloy fiber, diameter 35μm.

[0041] The total weight of the granular raw materials weighed during the preparation process is 40g, and the purity of the granular raw materials is above 99.9%. After the raw materials are cleaned, they are mixed using an analytical balance with an accuracy of one ten-thousandth. Light, volatile components or low-melting-point raw materials are placed under large pieces of high-melting-point components to reduce volatilization.

[0042] Example 2: This example is different from Example 1 in that: a CoAlCuFeNiB high entropy amorphous alloy capable of degrading wastewater and evolving hydrogen and oxygen is used. Its general chemical formula is Co a Al b Cu c Fe d Ni e B f , where a=20, b=20, c=0, d=20, e=20, f=20; Co 20 Al20 Fe 20 Ni 20 B 20 High entropy amorphous alloy fiber. Other aspects are the same as those of Example 1.

[0043] Example 3: This example is different from Example 1 in that: a CoAlCuFeNiB high entropy amorphous alloy capable of degrading wastewater and evolving hydrogen and oxygen is used. Its general chemical formula is Co a Al b Cu c Fe d Ni e B f , where a=20, b=10, c=10, d=20, e=20, f=20; Co 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 High entropy amorphous alloy fiber. Other aspects are the same as those of Example 1.

[0044] Comparative Example 1: The difference between this comparative example and Example 1 is that the high entropy amorphous alloy, in terms of atomic percentage, has the chemical formula Co a Cu b Fe c Ni d Si e B f , where a=20, b=20, c=20, d=20, e=10, f=10; Co 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 High entropy amorphous alloy fiber. Other aspects are the same as those of Example 1.

[0045] Comparative Example 2: This comparative example differs from Example 1 in that the high entropy amorphous alloy, in terms of atomic percentage, has the general chemical formula Co a Al b Cu c Fe d Ni e Si f , where a=20, b=10, c=10, d=20, e=20, f=20; Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20High entropy amorphous alloy fiber. Other aspects are the same as those of Example 1.

[0046] Comparative Example 3: This comparative example differs from Example 1 in that the high entropy amorphous alloy, in terms of atomic percentage, has the general chemical formula Al a Cu b Fe c Ni d Si e B f , where a=20, b=20, c=20, d=20, e=10, f=10; Al 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 High entropy amorphous alloy fiber. Other aspects are the same as those of Example 1.

[0047] (1) The high entropy amorphous alloys prepared in Examples 1 to 3 and Comparative Experiments 1 to 3 were used as catalysts to degrade rhodamine B in organic wastewater in a persulfate system. Specifically, the following steps were followed:

[0048] (1) According to the experimental content, weigh 5 mg of rhodamine B and use deionized water to prepare a rhodamine B solution with a concentration of 25 mg / L in a 200 mL volumetric flask; weigh sodium persulfate powder and use deionized water to prepare it into a 1 mol / L sodium persulfate solution; use deionized water to prepare a 2 mol / L HCl solution (dilute hydrochloric acid) and a 1 mol / L NaOH solution (dilute sodium hydroxide solution); weigh 0.05 g of a high-entropy amorphous alloy with a length of 40 mm.

[0049] (2) Dilute hydrochloric acid or dilute sodium hydroxide solution was added dropwise to 100 mL of organic wastewater (Rhodamine B solution with a concentration of 25 mg / L) until the pH value was 3, 5, 7, 9, and 11, respectively. Then, sodium persulfate solution was added until the concentration of sodium persulfate in the organic wastewater was 10 mmol / L. Then, 0.05 g of high entropy amorphous alloy was added and degraded at a rotation speed of 2600 r / min and room temperature.

[0050] (3) While performing the above steps, start the stopwatch and take samples at different times. During the sampling process, use a syringe to aspirate 3 mL of the reaction solution and add quenchers such as tert-butyl alcohol and anhydrous ethanol to terminate the reaction and maintain the authenticity of the test. During the experiment, the samples were tested using an ultraviolet spectrophotometer. The detection wavelength of the equipment was adjusted to 250 nm to 800 nm. The decay process of the characteristic peak curve of rhodamine B was tested to characterize the catalytic degradation performance of the high-entropy amorphous microfilaments.

[0051] Figure 1The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20 XRD test diagram of high entropy amorphous alloy fiber; it can be seen from the figure that only the amorphous diffuse scattering peak appears at about 45°, and there is no crystallization diffraction peak, which proves that the microwire is purely amorphous.

[0052] Figure 2 The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20 The degradation curve of high entropy amorphous alloy fiber at different pH values ​​shows that when the pH value is 3, Rhodamine B can be completely degraded in about 80s; when the pH value is 5, Rhodamine B can be completely degraded in about 60s; when the pH value is 7, Rhodamine B can be completely degraded in about 60-80s; when the pH value is 9, Rhodamine B can be completely degraded in about 100s; when the pH value is 11, Rhodamine B can be degraded by 80% in 300s. 20 Cu 20 Fe 20 Ni 20 B 20 High-entropy amorphous alloy fibers have excellent degradation properties in the entire pH range, and the degradation time is very short, breaking away from the shackles of being difficult to degrade in alkaline environments in the past.

[0053] Co described in Example 2 20 Al 20 Fe 20 Ni 20 B 20 When the pH value is 3-7, high-entropy amorphous alloy fibers can completely degrade Rhodamine B in about 110s to 180s, showing excellent degradation performance in acidic and neutral environments; when the pH value is 9, Rhodamine B can be completely degraded in about 300s; when the pH value is 11, Rhodamine B is degraded by 70% in 480s.

[0054] Co described in Example 3 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 When the pH value is 3-9, the high-entropy amorphous alloy fiber can completely degrade Rhodamine B in about 80s-120s; when the pH value is 11, Rhodamine B is degraded by 68% in 300s, showing excellent degradation performance in acidic and weakly alkaline environments.

[0055] Co described in Comparative Example 1 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 When the pH value is 3-5, the high-entropy amorphous alloy fiber can completely degrade Rhodamine B in about 120s-180s; when the pH value is 7, Rhodamine B can be completely degraded in about 240s; when the pH value is 9, Rhodamine B can be completely degraded in about 360s; when the pH value is 11, Rhodamine B is degraded by 80% in about 600s.

[0056] Co described in Comparative Example 2 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 When the pH value is 3-5, the high-entropy amorphous alloy fiber can completely degrade Rhodamine B in about 120s to 200s; when the pH value is 7, Rhodamine B can be completely degraded in about 280s; when the pH value is 9, Rhodamine B can be completely degraded in about 420s; when the pH value is 11, Rhodamine B is degraded by 75% in about 600s.

[0057] Al described in Comparative Example 3 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 When the pH value is 3-5, the high-entropy amorphous alloy fiber can completely degrade Rhodamine B in about 180s to 300s; when the pH value is 7, Rhodamine B can be completely degraded in about 400s; when the pH value is 9, Rhodamine B is degraded by 50% in about 600s; when the pH value is 11, Rhodamine B is only degraded by 30% in about 600s.

[0058] It can be seen that the degradation performance of Comparative Examples 1 to 3 in neutral and alkaline environments is relatively poor, among which Comparative Example 3 has the worst degradation efficiency in neutral and alkaline environments.

[0059] (2) Using the high-entropy amorphous alloys prepared in Examples 1 to 3 and Comparative Experiments 1 to 3 as catalysts, sulfamethazine in organic wastewater was degraded in a persulfate system. Specifically, the following steps were followed:

[0060] According to the experimental content, weigh 5 mg of sulfamethazine, use deionized water to prepare a 25 mg / L sulfamethazine solution in a 200 mL volumetric flask, and add dilute hydrochloric acid or dilute sodium hydroxide solution to 100 mL of organic wastewater (25 mg / L sulfamethazine solution) until the pH value is 3. The rest of the preparation work and degradation and detection process are the same as (1).

[0061] Figure 3 The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20 Ultraviolet spectrum absorbance curve of sulfamethazine degradation by high entropy amorphous alloy fiber; the characteristic peaks of sulfamethazine are 245nm and 270nm, and the characteristic peaks disappear after 30s of degradation, proving that sulfamethazine has been completely degraded.

[0062] Co described in Example 2 20 Al 20 Fe 20 Ni 20 B 20 High entropy amorphous alloy fibers can completely degrade sulfamethazine in about 80 seconds;

[0063] Co described in Example 3 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 High entropy amorphous alloy fibers can completely degrade sulfamethazine in about 50 seconds;

[0064] Co described in Comparative Example 1 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 High entropy amorphous alloy fibers can completely degrade sulfamethazine in about 120 seconds;

[0065] Co described in Comparative Example 2 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 High entropy amorphous alloy fibers can completely degrade sulfamethazine in about 150 seconds;

[0066] Al described in Comparative Example 3 20 Cu 20 Fe 20 Ni20 Si 10 B 10 High entropy amorphous alloy fibers can completely degrade sulfamethazine in about 250s.

[0067] (3) Using the high-entropy amorphous alloys prepared in Examples 1 to 3 and Comparative Experiments 1 to 3 as catalysts, aniline in organic wastewater was degraded in a persulfate system. Specifically, the following steps were followed:

[0068] According to the experimental content, weigh 5 mg of aniline and prepare a 25 mg / L aniline solution with deionized water in a 200 mL volumetric flask. Add dilute hydrochloric acid or dilute sodium hydroxide solution to 100 mL of organic wastewater (25 mg / L aniline solution) until the pH reaches 3. The rest of the preparation work and degradation and detection procedures are the same as (1).

[0069] Figure 4 The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20 Ultraviolet spectrum absorbance curve of aniline degradation by high entropy amorphous alloy fiber; the characteristic peaks of aniline are 230nm and 280nm, and the characteristic peaks disappear after 5s of degradation, proving that aniline has been completely degraded.

[0070] Co described in Example 2 20 Al 20 Fe 20 Ni 20 B 20 High entropy amorphous alloy fibers can completely degrade aniline in about 35 seconds;

[0071] Co described in Example 3 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 High entropy amorphous alloy fibers can completely degrade aniline in about 15 seconds;

[0072] Co described in Comparative Example 1 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 High entropy amorphous alloy fibers can completely degrade aniline in about 50 seconds;

[0073] Co described in Comparative Example 2 20 Al 10 Cu 10 Fe 20 Ni20 Si 20 High entropy amorphous alloy fibers can completely degrade aniline in about 80 seconds;

[0074] Al described in Comparative Example 3 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 High entropy amorphous alloy fibers can completely degrade aniline in about 150s.

[0075] (IV) Using the high entropy amorphous alloy prepared in Example 1 as a catalyst, the degradation experiment and detection process described in (I) (at pH = 5) were carried out. After completing one degradation experiment, the high entropy amorphous alloy fibers were collected, rinsed briefly with deionized water, and then placed in an ethanol solution for cleaning and drying to prevent rust. Repeat the solution ratio and experimental process in (I), and continue to put the used fibers into the next degradation experiment. Repeat this process, record the experimental data, and see the results. Figure 5 The experimental conditions were as follows: pH = 5, high entropy amorphous alloy fiber dosage of 0.5 g / L, ambient temperature of 25°C, rhodamine B concentration of 25 mg / L, and rotation speed of 2600 r / min.

[0076] Figure 5 The Co described in Example 1 20 Cu 20 Fe 20 Ni 20 B 20 Reuse diagram of high entropy amorphous alloy fiber, column A is degradation for 80s, column B is degradation for 100s; it can be seen from the figure that the high entropy amorphous fiber can be reused 30 times, and the degradation performance is very stable. In the first 15 degradation experiments, the degradation rate within 80s is above 95%, and Rhodamine B can be completely degraded within 100s; with the increase of the number of reuses, the degradation efficiency decreases slightly, but in the first 25 degradation experiments, the degradation rate within 80s is above 80%, and the degradation rate within 100s can reach above 90%; at the 30th time, the degradation rate within 100s dropped to about 75%, and finally degraded completely in about 120s. From this, it can be seen that Co 20 Cu 20 Fe 20 Ni 20 B 20 High-entropy amorphous fibers can be reused 30 times without a significant decrease in degradation performance, demonstrating excellent degradation performance.

[0077] (V) The hydrogen and oxygen evolution performance of the high entropy amorphous alloys prepared in Examples 1 to 3 and Comparative Experiments 1 to 3 in an alkaline environment was specifically carried out according to the following steps:

[0078] The electrochemical workstation used in the experiment was a Shanghai Chenhua CHI760E. During the test, the electrolyte was a 1.0 mol / L KOH solution, the reference electrode was a mercury-mercuric oxide electrode, and the counter electrode was a platinum electrode. A high-entropy alloy fiber was placed in a platinum electrode holder. A rubber band was used to almost completely submerge the microfilament in the electrolyte, with the platinum electrode not in contact with the electrolyte. After calculating the surface area of ​​the fiber, the electrochemical workstation software was opened. 100 CV cycles were performed from -0.8V to -1.8V for the hydrogen evolution reaction and 100 CV cycles from 0V to 1.2V for the oxygen evolution reaction before performance testing was performed. The tested microfilament was removed from the platinum electrode holder and the data was processed using the electrochemical workstation data and the specific surface area of ​​the fiber, the pH of the electrolyte, and the standard potential of the reference electrode to obtain the Tafel slope of the high-entropy amorphous alloy fiber catalysis.

[0079] Figure 6 is the hydrogen evolution performance of high entropy amorphous alloy in alkaline environment, 1 is the Co 20 Cu 20 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 2 is the Co 20 Al 20 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 3 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 4 is the Co 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 The hydrogen evolution curve of high entropy amorphous alloy fiber, 5 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 6 is the Al in the comparative experiment 3 20 Cu 20 Fe 20 Ni 20 Si 10 B 10The hydrogen evolution curve of high entropy amorphous alloy fiber. As can be seen from the figure, the horizontal axis is the potential and the vertical axis is the current density. After the hydrogen evolution reaction overpotential is processed, it is found that at 10mA / cm 2 When the Co of Examples 1 to 3 20 Cu 20 Fe 20 Ni 20 B 20 、Co 20 Al 20 Fe 20 Ni 20 B 20 、Co 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 The overpotentials of high entropy amorphous fibers are 412mV, 455mV, and 450mV respectively. 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 、Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 、Al 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 The overpotentials of the high entropy amorphous fibers were 461 mV, 462 mV, and 489 mV, respectively. The greater the overpotential, the worse the performance. Therefore, Example 1 performed best in alkaline hydrogen evolution catalysis, followed by Examples 2 and 3.

[0080] Figure 7 is the oxygen evolution performance of high entropy amorphous alloy in alkaline environment, 1 is the Co 20 Cu 20 Fe 20 Ni 20 B 20 Oxygen evolution curve of high entropy amorphous alloy fiber, 2 is the Co 20 Al 20 Fe 20 Ni 20 B 20 High entropy amorphous alloy fiber oxygen evolution curve, 3 is the Co 20 Al 10 Cu 10 Fe20 Ni 20 B 20 Oxygen evolution curve of high entropy amorphous alloy fiber, 4 is the Co 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 Oxygen evolution curve of high entropy amorphous alloy fiber, 5 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 Oxygen evolution curve of high entropy amorphous alloy fiber, 6 is the Al in comparison experiment 3 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 Oxygen evolution curve of high entropy amorphous alloy fiber. As can be seen from the figure, the horizontal axis is the potential and the vertical axis is the current density. After the oxygen evolution reaction overpotential is processed, it is found that at 10mA / cm 2 When the Co of Examples 1 to 3 20 Cu 20 Fe 20 Ni 20 B 20 、Co 20 Al 20 Fe 20 Ni 20 B 20 、Co 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 The overpotentials of high entropy amorphous fibers are 328mV, 342mV, and 352mV respectively. 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 、Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 、Al 20 Cu 20 Fe 20 Ni 20 Si 10 B 10The overpotentials of the high entropy amorphous fibers are 358 mV, 380 mV, and 746 mV, respectively. The larger the overpotential, the worse the performance. Therefore, Example 1 has the best performance in alkaline oxygen evolution catalysis, followed by Examples 2 and 3.

[0081] (VI) The hydrogen and oxygen evolution performance of the high entropy amorphous alloy prepared in Examples 1 to 3 and Comparative Experiments 1 to 3 in an acidic environment. The specific steps are different from those in (V) except that the electrolyte used is a H2SO4 solution with a concentration of 0.5 mol / L. The rest is the same. The performance test is as follows Figure 8 .

[0082] Figure 8 is the LSV curve of high entropy amorphous fiber in acidic environment, 1 is the Co 20 Cu 20 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 2 is the Co 20 Al 20 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 3 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 4 is the Co 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 The hydrogen evolution curve of high entropy amorphous alloy fiber, 5 is the Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 The hydrogen evolution curve of high entropy amorphous alloy fiber, 6 is the Al in the comparative experiment 3 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 The hydrogen evolution curve of high entropy amorphous alloy fiber. The measured curve is as follows Figure 8 As shown, the horizontal axis is the potential and the vertical axis is the current density. After the hydrogen evolution reaction overpotential is processed, it is found that at 10 mA / cm 2 When the Co of Examples 1 to 3 20 Cu20 Fe 20 Ni 20 B 20 、Co 20 Al 20 Fe 20 Ni 20 B 20 、Co 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 The overpotentials of high entropy amorphous fibers are 292mV, 462mV, and 321mV respectively. 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 、Co 20 Al 10 Cu 10 Fe 20 Ni 20 Si 20 、Al 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 The overpotentials of high entropy amorphous fibers are 503mV, 529mV, and 549mV, respectively. 20 Cu 20 Fe 20 Ni 20 B 20 、Co 20 Al 20 Fe 20 Ni 20 B 20 、Co 20 Al 10 Cu 10 Fe 20 Ni 20 B 20 High entropy amorphous fiber at 10mA / cm 2 The oxygen evolution overpotentials are 348mV, 405mV, and 375mV respectively. 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 、Co 20 Al 10 Cu10 Fe 20 Ni 20 Si 20 、Al 20 Cu 20 Fe 20 Ni 20 Si 10 B 10 The oxygen evolution overpotentials of high entropy amorphous fibers are 455mV, 472mV, and 649mV, respectively.

Claims

1. Application of a CoAlCuFeNiB series high entropy amorphous alloy capable of degrading wastewater and evolving hydrogen and oxygen, characterized in that In terms of atomic percentage, its general chemical formula is Co a Al b Cu c Fe d Ni e B f , where a=c=d=e=f=20, b=0; When the CoAlCuFeNiB series high entropy amorphous alloy is used as a catalyst to degrade organic matter in organic wastewater in a persulfate system, the number of repeated uses is 25 to 35 times, specifically according to the following steps: adjusting the pH of the organic wastewater to 2 to 11, adding sodium persulfate solution until the sodium persulfate concentration in the organic wastewater is 1 mmol / L to 15 mmol / L, and then adding the CoAlCuFeNiB series high entropy amorphous alloy, and degrading it at a speed of 2000 r / min to 2800 r / min and room temperature for 1 min to 10 min; the amount of the CoAlCuFeNiB series high entropy amorphous alloy added is 0.1 g / L to 1 g / L; When the CoAlCuFeNiB series high entropy amorphous alloy is used as a catalyst to electrolyze water in an electrolyte to release hydrogen and oxygen, the electrolyte is a KOH solution with a concentration of 1.0 mol / L or a H2SO4 solution with a concentration of 0.5 mol / L.

2. The application of a CoAlCuFeNiB series high entropy amorphous alloy capable of degrading wastewater and performing dual hydrogen and oxygen evolution according to claim 1, characterized in that The CoAlCuFeNiB series high entropy amorphous alloy capable of degrading sewage and evolving hydrogen and oxygen is specifically prepared according to the following steps: According to the chemical formula Co a Al b Cu c Fe d Ni e B f The weighed raw materials are weighed according to the atomic percentage of , wherein a=c=d=e=f=20, and b=0, to obtain the weighed raw materials; the weighed raw materials and titanium are respectively placed in a vacuum arc melting furnace, which is evacuated and filled with protective gas, arc-melted titanium is firstly arc-melted, and then the weighed raw materials are arc-melted to obtain a master alloy ingot, the master alloy ingot is arc-melted and suction-casted to obtain an alloy rod; the alloy rod is placed in a high-vacuum precision melt pulling equipment, which is evacuated and filled with protective gas, the copper wheel speed is set and started, the alloy rod is induction heated, and the master alloy feeding is started to obtain a CoAlCuFeNiB series high-entropy amorphous alloy.

3. The application of a CoAlCuFeNiB series high entropy amorphous alloy capable of degrading wastewater and performing dual hydrogen and oxygen evolution according to claim 2, characterized in that The protective gas is argon.

4. The application of a CoAlCuFeNiB series high entropy amorphous alloy capable of degrading wastewater and performing dual hydrogen and oxygen evolution according to claim 1, characterized in that The organic matter is rhodamine B, sulfamethazine or aniline.

5. The application of a CoAlCuFeNiB series high entropy amorphous alloy capable of degrading wastewater and performing dual hydrogen and oxygen evolution according to claim 1, characterized in that Add 2 mol / L dilute hydrochloric acid or 1 mol / L dilute sodium hydroxide solution to the organic wastewater until the pH is 2~11.

6. The application of a CoAlCuFeNiB series high entropy amorphous alloy capable of degrading wastewater and performing dual hydrogen and oxygen evolution according to claim 1, characterized in that The concentration of organic matter in the organic wastewater is 10 mg / L to 100 mg / L.

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