High-entropy alloy sulfide and preparation method and application thereof

Abstract

The invention relates to the technical field of environmental pollutant degradation and discloses a high-entropy alloy sulfide as well as a preparation method and application thereof. The metal elements in the high-entropy alloy sulfide are any five of molybdenum, iron, manganese, nickel, zinc and cobalt; according to the method, molybdenum disulfide, ferrous sulfide, manganese sulfide, trinickel disulfide, zinc sulfide and cobalt sulfide are used as raw materials, and the high-entropy alloy sulfide is prepared in one step through ball milling under the protection of argon atmosphere. The high-entropy alloy sulfide is mainly used for activating peroxymonosulfate to degrade organic pollutants in an aqueous solution. Experimental comparison shows that compared with a monometal sulfide, the high-entropy alloy sulfide prepared by the preparation method disclosed by the invention shows more efficient degradation capability on organic pollutants in an aqueous solution when cooperating with peroxymonosulfate. The preparation method disclosed by the invention is simple to operate, mild in reaction condition and capable of realizing large-scale production.

Description

Technical Field

[0001] The invention belongs to the technical field of environmental pollutant degradation, and specifically relates to a high entropy alloy sulfide and a preparation method and application thereof. Background Art

[0002] With the continuous development of science and technology and the gradual expansion of human activities, the types and quantities of pollutants in the environment are also increasing. Among them, organic pollutants in medical and pharmaceutical wastewater can remain in the water environment for a long time, and may enter the human body through the enrichment effect of the food chain, damaging various important organs of the body, thereby endangering human health. Therefore, it is very necessary and of great practical significance to study efficient degradation technology and deeply treat wastewater containing organic pollutants.

[0003] In recent years, researchers have developed advanced oxidation technologies such as photocatalysis, electro-Fenton, ozone oxidation and persulfate oxidation. Among them, persulfate oxidation technology has shown good application prospects due to its high degradation ability and has received widespread attention. At present, common activation methods of persulfate include thermal activation, alkali activation, transition metal activation and ultraviolet activation. Among them, transition metal sulfides can activate persulfate at room temperature and greatly reduce the metal ion pollution caused by homogeneous activation of persulfate by transition metal ions, which is a hot topic of research in recent years. So far, related reports have mostly focused on mono- and di-transition metal sulfides.

[0004] High entropy alloy sulfide refers to a single solid solution sulfide composed of five or more metal elements with close or equal molar ratios. Thanks to the lattice distortion caused by element substitution and the cocktail effect of multiple elements, high entropy alloy sulfide has higher stability and catalytic activity. At present, the application research of high entropy alloy sulfide is mainly concentrated in the fields of electrocatalysis and energy storage, while no reports have been seen in the field of activated persulfate degradation of organic pollutants.

[0005] At present, the reported high entropy alloy sulfides are usually prepared by high temperature solid phase sintering, hydrothermal method or solvothermal method. However, when preparing high entropy alloy sulfides by the above methods, it is impossible to accurately control the molar ratio between the metal elements and the metal elements and sulfur elements. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide a high entropy alloy sulfide and a preparation and application method thereof, which can accurately control the molar ratios between the metal elements and between the metal elements and the sulfur element, and the preparation method is simple to operate, the reaction conditions are mild, and it can be scaled up for production. The obtained high entropy alloy sulfide can effectively activate persulfate to degrade organic pollutants in aqueous solutions.

[0007] The technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a method for preparing a high entropy alloy sulfide, which specifically comprises the following steps:

[0009] S1: Mix any five of molybdenum disulfide, ferrous sulfide, manganese sulfide, nickel disulfide, zinc sulfide and cobalt sulfide and transfer them into a ball mill;

[0010] S2: After replacing the air in the ball mill with an inert gas, the ball mill is sealed and ball milled to obtain a high entropy alloy sulfide;

[0011] The molar number of each metal element in the added molybdenum disulfide, ferrous sulfide, manganese sulfide, nickel disulfide, zinc sulfide and cobalt sulfide is the same.

[0012] Preferably, in step S1, the mass ratio of the total mass of the added metal sulfide and sulfur to the mass of the ball milling balls in the ball milling jar is 1:11 to 1:44.

[0013] Preferably, in step S2, the ball milling speed is 400-600 rpm, and the ball milling time is 24-96 h; during the ball milling process, the ball is milled for 30-50 minutes and then left to cool for 10-30 minutes.

[0014] Preferably, in step S1, the ball mill is made of corundum.

[0015] Preferably, in step S2, the inert gas is argon.

[0016] In a second aspect, the present invention provides a high entropy alloy sulfide prepared by the method described in the first aspect; the metal elements in the high entropy alloy sulfide are any five of molybdenum, iron, manganese, nickel, zinc and cobalt.

[0017] Preferably, the ratio of the total molar number of the metal elements to the molar number of the sulfur element is 1:1.1 to 1:4.

[0018] In a third aspect, the present invention provides the use of the high entropy alloy sulfide described in the second aspect to activate persulfate to catalyze the degradation of organic pollutants.

[0019] Preferably, the catalytic degradation of organic pollutants specifically includes the following steps: adding the catalyst and persulfate to the organic pollutant wastewater to be treated, and then stirring to start degradation; the amount of the high entropy alloy sulfide catalyst is 0.05-0.2 g / L, and the amount of persulfate added is 0.05-0.2 g / L.

[0020] Furthermore, the persulfate is any one of hydrogen persulfate and sodium persulfate, or a mixture of the two.

[0021] The beneficial effects achieved by the present invention are as follows: compared with the currently commonly used high-temperature solid-phase sintering method and hydrothermal method, the high-entropy alloy sulfide preparation method provided by the present invention can more accurately control the molar ratios between different metal elements and between metal elements and sulfur elements in the high-entropy alloy sulfide; compared with the reported single metal sulfides and binary metal sulfides, the high-entropy alloy sulfide provided by the present invention has higher catalytic activity due to the cocktail effect and lattice distortion effect; when the high-entropy alloy sulfide activates persulfate to degrade organic pollutants, it shows a higher degradation efficiency, and shows good application prospects in the field of organic pollutants in aquatic environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 (a) is the high entropy alloy sulfide (MoFeMnNiZn) prepared in Example 1 1.1 Scanning electron microscope image at 1um scale;

[0023] Figure 1 (b) is the high entropy alloy sulfide (MoFeMnNiZn) prepared in Example 1 1.1 Scanning electron microscope image at 500nm scale.

[0024] Figure 2 The high entropy alloy sulfide (MoFeMnNiZn)S prepared in Example 2 1.1 XRD spectrum of .

[0025] Figure 3 The high entropy alloy sulfide (MoFeMnNiCo)S prepared in Examples 3 to 7 1.3 、(MoFeMnZnCo)S 1.4 、(MoFeNiZnCo)S 1.3 、(MoMnNiZnCo)S 1.3 and (FeMnNiZnCo)S 1.1 XRD spectrum of .

[0026] Figure 4 is (MoFeMnNiCo)S in Example 8 1.3 Schematic diagram of the degradation effect of activated persulfate on acetaminophen.

[0027] Figure 5 is (MoFeMnNiCo)S in Example 9 1.3 Schematic diagram of the degradation effect of activated persulfate on acetaminophen.

[0028] Figure 6 (MoFeMnNiCo)S in Example 10 1.3 Schematic diagram of the degradation effect of activated persulfate on acetaminophen.

[0029] Figure 7 This is a diagram showing the effect of six single metal sulfides activating persulfate to degrade acetaminophenol in Comparative Example 1. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solution and advantages of the present invention more clear, the present invention is further described in detail in conjunction with the following examples. It should be noted that the present invention is not limited to the following examples.

[0031] In the embodiments of the present invention, acetaminophen is used as a typical organic pollutant, but the method is not limited to this pollutant.

[0032] Example 1

[0033] This embodiment provides a high entropy alloy sulfide (MoFeMnNiZn)S 1.1 The preparation method comprises the following specific steps:

[0034] Step 1: Take 0.312g of molybdenum disulfide, 0.172g of ferrous sulfide, 0.170g of manganese sulfide, 0.156g of nickel disulfide and 0.190g of zinc sulfide and transfer them to a 50mL zirconia ball mill.

[0035] Step 2: Use a glove box to replace the air in the ball mill with argon, then seal it and place it in a ball mill. Mill it at a speed of 510 rpm for 72 hours to obtain a high entropy alloy sulfide (MoFeMnNiZn)S 1.1 During the ball milling process, in order to prevent overheating, the ball was milled for 40 minutes and then left to cool for 20 minutes.

[0036] Example 2

[0037] Similar to Example 1, this example provides a high entropy alloy sulfide (MoFeMnNiZn)S 1.1 The method for preparing the present invention is as follows, except that, in this embodiment, the raw materials added in step 1 are 0.156 g of molybdenum disulfide, 0.086 g of ferrous sulfide, 0.085 g of manganese sulfide, 0.078 g of nickel disulfide and 0.095 g of zinc sulfide, the ball milling time in step 2 is 96 hours, and the remaining steps and the addition of raw materials are the same as those in embodiment 1.

[0038] Example 3

[0039] This embodiment provides a high entropy alloy sulfide (MoFeMnNiCo)S 1.3 The preparation method, the specific steps are as follows:

[0040] Step 1: Take 0.297g of molybdenum disulfide, 0.163g of ferrous sulfide, 0.162g of manganese sulfide, 0.149g of nickel disulfide and 0.229g of cobalt sulfide and transfer them to a 50mL zirconia ball mill.

[0041] Step 2: Use a glove box to replace the air in the ball mill with argon, then seal it and place it in a ball mill. Mill it at 510 rpm for 72 hours to obtain high entropy alloy sulfide (MoFeMnNiCo)S 1.3 During the ball milling process, in order to prevent overheating, the ball was milled for 40 minutes and then left to cool for 20 minutes.

[0042] Example 4

[0043] This embodiment provides a high entropy alloy sulfide (MoFeMnZnCo)S 1.4 The preparation method, the specific steps are as follows:

[0044] Step 1: Take 0.288g of molybdenum disulfide, 0.158g of ferrous sulfide, 0.157g of manganese sulfide, 0.175g of zinc sulfide and 0.222g of cobalt sulfide and transfer them to a 50mL zirconia ball mill.

[0045] Step 2: Use a glove box to replace the air in the ball mill with argon, then seal it and place it in a ball mill. Mill it at 510 rpm for 72 hours to obtain high entropy alloy sulfide (MoFeMnZnCo)S 1.4 During the ball milling process, in order to prevent overheating, the ball was milled for 40 minutes and then left to cool for 20 minutes.

[0046] Example 5

[0047] This embodiment provides a high entropy alloy sulfide (MoFeNiZnCo)S 1.3 , and its preparation method is:

[0048] Step 1: Take 0.292g of molybdenum disulfide, 0.160g of ferrous sulfide, 0.146g of nickel disulfide, 0.178g of zinc sulfide and 0.224g of cobalt sulfide and transfer them to a 50mL zirconia ball mill.

[0049] Step 2: Use a glove box to replace the air in the ball mill with argon, then seal it and place it in a ball mill. Mill it at a speed of 510 rpm for 72 hours to obtain high entropy alloy sulfide (MoFeNiZnCo)S 1.3 During the ball milling process, in order to prevent overheating, the ball was milled for 40 minutes and then left to cool for 20 minutes.

[0050] Example 6

[0051] This embodiment provides a high entropy alloy sulfide (MoMnNiZnCo)S 1.3 , and its preparation method is:

[0052] Step 1: Take 0.292g of molybdenum disulfide, 0.159g of manganese sulfide, 0.146g of nickel disulfide, 0.178g of zinc sulfide and 0.225g of cobalt sulfide and transfer them to a 50mL zirconia ball mill.

[0053] Step 2: Use a glove box to replace the air in the ball mill with argon, then seal it and place it in a ball mill. Mill it at 510 rpm for 72 hours to obtain high entropy alloy sulfide (MoMnNiZnCo)S 1.3 During the ball milling process, in order to prevent overheating, the ball was milled for 40 minutes and then left to cool for 20 minutes.

[0054] Example 7

[0055] This embodiment provides a high entropy alloy sulfide (FeMnNiZnCo)S 1.1 , and its preparation method is:

[0056] Step 1: Take 0.185g of ferrous sulfide, 0.183g of manganese sulfide, 0.168g of nickel disulfide, 0.205g of zinc sulfide and 0.259g of cobalt sulfide and transfer them to a 50mL zirconia ball mill.

[0057] Step 2: Use a glove box to replace the air in the ball mill with argon, then seal it and place it in a ball mill. Mill it at 510 rpm for 72 hours to obtain high entropy alloy sulfide (FeMnNiZnCo)S 1.1 During the ball milling process, in order to prevent overheating, the ball was milled for 40 minutes and then left to cool for 20 minutes.

[0058] Example 8

[0059] 4 mg of the high entropy alloy sulfide (MoFeMnNiCo)S in Example 4 was added to 50 mL of 20 mg / L acetaminophen aqueous solution. 1.3 and 5 mg potassium persulfate. The mechanical stirring was turned on to start the degradation of acetaminophenol in the aqueous solution. The reaction time was 15 min. After the reaction, the removal rate of acetaminophenol in the solution reached 63.8%. The results are as follows Figure 4 shown.

[0060] Example 9

[0061] As in Example 8, in 50 mL of a 20 mg / L acetaminophen aqueous solution, a high entropy alloy sulfide (MoFeMnNiCo)S 1.3Replaced with the high entropy alloy sulfide (MoFeNiZnCo)S prepared in Example 6 of the same mass 1.3 The remaining steps were the same as the addition amount of potassium persulfate. After 15 minutes of reaction, the removal rate of acetaminophen in the solution was 62.9%, as Figure 5 shown.

[0062] Example 10

[0063] As in Example 8, in 50 mL of a 20 mg / L acetaminophen aqueous solution, a high entropy alloy sulfide (MoFeMnNiCo)S 1.3 The addition amount was changed to 2, 4, 6, 8 and 10 mg respectively, and the addition amount of potassium persulfate was adjusted from 5 mg to 15 mg, and the other experimental steps remained unchanged. After 15 minutes of reaction, the removal rates of acetaminophen in the solution were 60.3%, 88.4%, 93.3%, 94.1% and 94.3% respectively. Figure 6 shown.

[0064] Comparative Example 1

[0065] The difference from Example 8 is that in this comparative example, (MoFeMnNiCo)S 1.3 The samples were replaced with 6 mg of MoS2, FeS, MnS, Ni3S2, ZnS and CoS2 in turn, and the remaining steps were the same as the addition amount of potassium persulfate. After 15 min of reaction, the removal rate of acetaminophen was as follows: Figure 7 As shown in the figure, it can be seen that after adding MoS2 and CoS2, the removal rates of acetaminophen were 17.4% and 47.6%, respectively. However, after adding FeS, MnS, Ni3S2 and ZnS, the concentration of acetaminophen did not change significantly.

[0066] The comparison results show that compared with single metal sulfides, the high entropy alloy sulfide (MoFeMnNiCo)S prepared by the patented method 1.3 The activation effect on persulfate is more obvious, and the removal of organic pollutants is also more significant, increasing from 47.6% to 93.3%.

[0067] Comparative Example 2

[0068] The hydrothermal method is one of the commonly used methods previously reported to prepare high entropy alloy sulfides. In order to investigate the problem of element loss, the hydrothermal method was used to prepare high entropy alloy sulfides as a comparative example.

[0069] Step 1: Accurately weigh 1 mmol each of molybdenum chloride, ferric chloride, zinc acetate, manganese chloride and nickel chloride, then add them to 30 mL of deionized water, and stir magnetically until completely dissolved to obtain solution A;

[0070] Step 2: Weigh 1.216 g of L-cysteine ​​and add it to 40 mL of deionized water, stirring magnetically until completely dissolved to obtain solution B;

[0071] Step 3: Then, under magnetic stirring, solution B was added to solution A, mixed and transferred to a reactor, and then reacted at 150°C for 20 hours;

[0072] Step 4: After the hydrothermal reaction, the hydrothermal product was collected by suction filtration, washed alternately with deionized water and anhydrous ethanol for multiple times, and then transferred to an oven at 80° C. and dried for 12 h to obtain a high entropy alloy (MoFeMnNiZn)S.

[0073] The elemental composition was analyzed by ICP-MS analysis, where the molar ratio of Mo, Fe, Mn, Ni and Zn elements was 2.75:1:0.13:2.08:1.39, and the molar number of each metal element in the starting material was equal. Obviously, when the high entropy alloy sulfide is prepared by the hydrothermal method, the element loss is serious. In contrast, when the high entropy alloy sulfide is prepared by the method in this patent, there is no problem of element loss, and the molar number of each metal element in the obtained high entropy alloy sulfide is equal.

[0074] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. It is understandable to those skilled in the art that various changes, modifications, substitutions and variations may be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing high entropy alloy sulfide, characterized in that: The specific steps include: S1: Mix any five of molybdenum disulfide, ferrous sulfide, manganese sulfide, nickel disulfide, zinc sulfide and cobalt sulfide and transfer them into a ball mill; S2: After replacing the air in the ball mill with an inert gas, the ball mill is sealed and ball milled to obtain a high entropy alloy sulfide; The molar number of each metal element in the added molybdenum disulfide, ferrous sulfide, manganese sulfide, nickel disulfide, zinc sulfide and cobalt sulfide is the same.

2. The method for preparing high entropy alloy sulfide according to claim 1, characterized in that: In the step S1, the mass ratio of the total mass of the added metal sulfide and sulfur to the mass of the ball milling balls in the ball milling jar is 1:11 to 1:

44.

3. The method for preparing high entropy alloy sulfide according to claim 1, characterized in that: In the step S2, the ball milling speed is 400-600 rpm, and the ball milling time is 24-96 hours; during the ball milling process, the ball milling is performed for 30-50 minutes and then left to cool for 10-30 minutes.

4. The method for preparing high entropy alloy sulfide according to claim 1, characterized in that: In the step S1, the ball mill is made of corundum.

5. The method for preparing high entropy alloy sulfide according to claim 1, characterized in that: In step S2, the inert gas is argon.

6. A high entropy alloy sulfide prepared by the method according to any one of claims 1 to 5, wherein the metal elements in the high entropy alloy sulfide are any five of molybdenum, iron, manganese, nickel, zinc and cobalt.

7. The high entropy alloy sulfide according to claim 6, characterized in that: The ratio of the total molar number of the metal elements to the molar number of the sulfur element is 1:1.1 to 1:

4.

8. Use of the high entropy alloy sulfide according to claim 6 or 7 to activate persulfate to catalyze the degradation of organic pollutants.

9. The use of high entropy alloy sulfide activated persulfate to catalyze degradation of organic pollutants according to claim 8, characterized in that: The catalytic degradation of organic pollutants specifically includes the following steps: adding the catalyst and persulfate to the organic pollutant wastewater to be treated, and then stirring to start degradation; the amount of the high entropy alloy sulfide catalyst is 0.05-0.2g / L, and the amount of persulfate added is 0.05-0.2g / L.

10. The use of high entropy alloy sulfide activated persulfate to catalyze degradation of organic pollutants according to claim 9, characterized in that: The persulfate is any one of hydrogen persulfate and sodium persulfate or a mixture of the two.

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