High-entropy alloy sulfide for activating persulfate and preparation and application methods of high-entropy alloy sulfide and carbon composite material
By preparing high-entropy alloy sulfide and carbon composite materials, the problem of low catalytic activity of existing catalysts was solved, achieving efficient degradation of organic pollutants and making it suitable for water environment remediation.
Patent Information
- Application Number
- CN202511160137.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-19
- Publication Date
- 2025-11-07
AI Technical Summary
Existing catalysts exhibit low catalytic activity when activating persulfate and suffer from self-decomposition and performance degradation, making them difficult to effectively degrade organic pollutants.
High-entropy alloy sulfides and their carbon composites are prepared by hydrothermal reaction. Carbon materials such as acetylene black, carbon nanotubes or graphene oxide are added to form high-entropy alloy sulfides and carbon composites, which are used to activate persulfate to degrade organic pollutants.
It improves the degradation rate and degradation speed of organic pollutants, exhibits excellent catalytic activity and stability, and is suitable for water environment remediation.
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Figure CN120900665A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of environmental pollutant degradation, and particularly relates to a high-entropy alloy sulfide for activating persulfate and a preparation and application method of a carbon composite material thereof. BACKGROUND
[0002] Agriculture is the foundation of China's national economy and is a pillar industry that guarantees people's lives. Pesticides are an important unit of agricultural development and are indispensable. However, according to statistics, nearly 6 million tons of pesticides are applied in China every year, of which only 1% plays a role, and the rest enters the environment. Through biological enrichment and food chain effects, pesticides in water and soil environments can enter the human body and may cause diseases, cancers, and deformities, which are extremely harmful. Therefore, in order to ensure people's health and achieve sustainable ecological development, it is necessary to strengthen the research on organic pesticide wastewater degradation technology.
[0003] Organic pollutants usually have certain resistance, and it is usually difficult to effectively remove them by biological and physical treatment methods. Based on this, researchers have developed advanced oxidation technology based on strong oxidizing active oxygen species to attack toxic and harmful and refractory pollutants, which can decompose organic pollutants into less toxic products or even mineralize them into H2O and CO2. Persulfate oxidation technology based on sulfate radicals (SO4· - ) has shown excellent application prospects due to its high oxidation potential, wide pH range, and long half-life. SO4· - is usually generated by the decomposition of peroxymonosulfate (PMS, HSO5 - ) or peroxodisulfate (PDS, S2O8 2- ). Common activation methods include alkaline activation, thermal activation, ultrasonic activation, ultraviolet light activation, metal ion activation, and heterogeneous catalyst activation. Among them, the heterogeneous catalyst activation method does not require energy consumption, has a wide pH range, and can be used in various water treatment scenarios, and has attracted more attention in recent years
[0004] So far, researchers have developed a variety of heterogeneous catalysts that can be used to activate persulfate, such as metal organic framework materials (MOFs), carbon materials, metal oxides and metal sulfides, etc. Among them, MOFs materials show excellent catalytic activity, but most MOFs are poor in water sensitivity, and may self-decompose during the reaction process, with the risk of a large amount of metal ions dissolving out, which may cause secondary pollution. When carbon materials activate persulfate, the surface of the catalyst is easily oxidized by the active substances generated, resulting in deactivation of the catalyst surface, and the performance of the catalyst after recycling use decreases significantly. Compared with metal oxides, metal sulfides show more excellent activity in activating persulfate. However, although metal sulfides have good application prospects in the activation of persulfate, there are still problems in the actual application and industrialization process. Among them, low catalytic activity is one of the key problem factors.
[0005] Therefore, it is urgent to develop a high-catalytic-activity heterogeneous catalyst for activating persulfate to protect and restore the water environment ecology. SUMMARY
[0006] The technical solutions adopted by the present application are as follows:
[0007] In a first aspect, the present application provides a preparation method of a high-entropy alloy sulfide for activating persulfate, the high-entropy alloy sulfide containing five kinds of transition metal elements, the types of the transition metal elements being any five of molybdenum, iron, cobalt, zinc, manganese and nickel, and the method specifically comprising the following steps:
[0008] S1: Dissolving soluble metal salts of the transition metal elements in water to obtain a solution A;
[0009] The concentration of each metal element in the solution A is 0.01-0.05 mol / L;
[0010] S2: Dissolving a sulfur source in water to obtain a solution B; the concentration of the sulfur source in the solution B is 0.1-0.5 mol / L;
[0011] The sulfur source is any one of sulfur-containing compounds such as thioacetamide, thiourea and L-cysteine;
[0012] S3: Mixing the solution A obtained in step S1 with the solution B obtained in step S2, and then performing a hydrothermal reaction at 150-200 DEG C; the volume ratio of the solution A to the solution B is 1:1-1:1.5;
[0013] S4: Collecting the solid product obtained in the hydrothermal reaction in step S3 to obtain the high-entropy alloy sulfide.
[0014] Preferably, in the step S1, the soluble metal salt of transition metal element is any of molybdenum chloride, iron chloride, zinc acetate, cobalt chloride, manganese chloride and nickel chloride; the adding amount of the five metal elements is equimolar ratio.
[0015] Preferably, in the step S3, the hydrothermal reaction time is 6h-48h.
[0016] Preferably, in the step S4, the solid is washed by alternately washing with ethanol and deionized water for 5-20 times.
[0017] Further, in the step S4, after washing, drying is performed by air blowing or vacuum drying at a temperature of 60-80℃ for 12-24h.
[0018] Preferably, the high-entropy alloy sulfide composite material further contains a carbon material, and the carbon material is one or a mixture of two or more of acetylene black, carbon nanotube and graphene oxide.
[0019] The difference lies in that, in the step S2, a certain amount of carbon material is dispersed in the solution B obtained in the step S2 to obtain a solution C; the concentration of the carbon material is 0.05-1.875g / L.
[0020] In the step S3, the volume ratio of the solution A to the solution C is 1:1-1:1.5.
[0021] In a second aspect, the application provides a high-entropy alloy sulfide for activating persulfate, which is prepared by the method of the first aspect.
[0022] In a third aspect, the application provides a high-entropy alloy sulfide-carbon composite material for activating persulfate, which is prepared by the method of the first aspect.
[0023] In a fourth aspect, the application provides a method for catalytically degrading organic pollutants by using the high-entropy alloy sulfide for activating persulfate of the second aspect and the high-entropy alloy sulfide-carbon composite material for activating persulfate of the third aspect, which specifically comprises the following steps: adding the high-entropy alloy sulfide or the high-entropy alloy sulfide-carbon composite material into wastewater containing organic pollutants to be degraded, adding persulfate after stirring to start degradation; the amount of the high-entropy alloy sulfide or the high-entropy alloy sulfide-carbon composite material is 0.1-0.3g / L, and the adding amount of persulfate is 0.1-0.5g / L.
[0024] Preferably, the reaction temperature is 5-45℃, and the reaction time is 1-30min.
[0025] Preferably, the persulfate is any one or a mixture of two or more of potassium persulfate, potassium monopersulfate, sodium persulfate and sodium monopersulfate.
[0026] The application provides the high-entropy alloy sulfide and the carbon composite material thereof, and the synergistic effect and the high-entropy effect based on multiple elements are beneficial to the improvement of catalytic activity; through comparison by experiments, compared with single metal sulfide, the high-entropy alloy sulfide improves the degradation rate and the degradation rate constant of organic matter when activating the degradation of aqueous organic pollutants by persulfate, and has a good application prospect in the field of water environment remediation. BRIEF DESCRIPTION OF DRAWINGS
[0027] Figure 1 (a) is a scanning electron microscope image of the high-entropy alloy sulfide (MoCoZnMnNi) S prepared in example 1 under a scale of 2um; x
[0028] Figure 1 (b) is a scanning electron microscope image of the high-entropy alloy sulfide (MoCoZnMnNi) S prepared in example 1 under a scale of 1um. x
[0029] Figure 2 is an XRD spectrum of the high-entropy alloy sulfide (MoCoZnMnNi) S prepared in example 1. x
[0030] Figure 3 is an XRD spectrum of the high-entropy alloy sulfide and carbon composite material (MoFeZnMnNi) S-AB prepared in example 3. x
[0031] Figure 4 (a) is a scanning electron microscope image of the high-entropy alloy sulfide and carbon composite material (MoFeZnMnNi) S-CNT prepared in example 4 under a scale of 1um. x
[0032] Figure 4 (b) is a scanning electron microscope image of the high-entropy alloy sulfide and carbon composite material (MoFeZnMnNi) S-CNT prepared in example 4 under a scale of 500nm. x
[0033] Figure 5 is a degradation effect diagram of potassium persulfate activated by the high-entropy alloy sulfide (MoFeCoMnNi) S prepared in example 2 on atrazine. x
[0034] Figure 6 is a degradation effect of potassium persulfate activated by the high-entropy alloy sulfide and carbon composite material (MoFeZnMnNi) S-CNT prepared in example 4 on atrazine. x
[0035] Figure 7 is a graph of the degradation effect of six single metal sulfide activated potassium persulfate on atrazine in Comparative Example 1.
[0036] Figure 8 is a schematic diagram of the preparation process of high-entropy alloy sulfide for activating persulfate.
[0037] Figure 9 is a schematic diagram of the preparation process of high-entropy alloy sulfide and carbon composite material for activating persulfate. DETAILED DESCRIPTION
[0038] In order to make the purpose, technical scheme and advantages of the present application more clear and definite, the present application is further described in detail in combination with the following examples. It should be noted that the present application is not limited to the following examples.
[0039] Although the embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to the embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.
[0040] The preparation process schematic diagram of high-entropy alloy sulfide for activating persulfate in the following Examples 1-2 is shown in Figure 9 .
[0041] The preparation process schematic diagram of high-entropy alloy sulfide and carbon composite material for activating persulfate in the following Examples 3-5 is shown in Figure 9 .
[0042] Example 1
[0043] The present example provides a high-entropy alloy sulfide (MoCoZnMnNi)S for activating persulfate, x which contains transition metal elements Mo, Co, Zn, Mn and Ni, and the preparation method is:
[0044] Step 1: 0.2732 g of molybdenum chloride, 0.2379 g of cobalt chloride, 0.2195 g of zinc acetate, 0.1258 g of manganese chloride and 0.1296 g of nickel chloride were dissolved in 30 mL of deionized water, respectively, and stirred by magnetic stirring until completely dissolved to obtain solution A.
[0045] Step 2: 1.216 g of L-cysteine was weighed and dissolved in 40 mL of deionized water to obtain solution B.
[0046] Step 3: Mix solution A and solution B, then transfer to a hydrothermal reactor, seal and react at 150°C for 20 h.
[0047] Step 4: The hydrothermal product is cooled, the supernatant is filtered off, the precipitate is washed with ethanol and water alternately for 10 times, and then is transferred to 80℃ for vacuum drying for 12h to obtain high-entropy alloy sulfide (MoCoZnMnNi)S x .
[0048] The scanning electron microscope image and the XRD spectrum of the prepared high-entropy alloy sulfide (MoFeZnMnNi)S x are shown in Figure 1 、 Figure 2 .
[0049] Example 2
[0050] The present example provides a high-entropy alloy sulfide (MoFeCoMnNi)S x containing transition metal elements Mo, Fe, Co, Mn and Ni for activating persulfate, and a preparation method thereof is as follows:
[0051] Step 1: 0.2732g of molybdenum chloride, 0.2703g of iron chloride, 0.2379g of cobalt chloride, 0.1258g of manganese chloride and 0.1296g of nickel chloride are respectively dissolved in 30mL of deionized water, and are magnetically stirred until completely dissolved to obtain solution A.
[0052] Step 2: 1.216g of L-cysteine is weighed and dissolved in 40mL of deionized water to obtain solution B.
[0053] Step 3: Solution A and solution B are mixed, and then are transferred to a hydrothermal reactor, which is sealed and reacted at 150℃ for 20h.
[0054] Step 4: The hydrothermal product is cooled, the supernatant is filtered off, the precipitate is washed with ethanol and water alternately for 10 times, and then is transferred to 80℃ for vacuum drying for 12h to obtain high-entropy alloy sulfide (MoFeCoMnNi)S x .
[0055] Example 3
[0056] The present example provides a high-entropy alloy sulfide and carbon composite material (MoFeZnMnNi)S x -AB for activating persulfate, wherein the high-entropy alloy sulfide contains transition metal elements Mo, Fe, Co, Mn and Ni, and the carbon material is acetylene black, and a preparation method thereof is as follows:
[0057] Step 1: 0.2732g of molybdenum chloride, 0.2703g of iron chloride, 0.2195g of zinc acetate, 0.1258g of manganese chloride and 0.1296g of nickel chloride are respectively dissolved in 30mL of deionized water, and are magnetically stirred until completely dissolved to obtain solution A.
[0058] Step 2: 1.216 g L-cysteine was weighed and dissolved in 40 mL deionized water to obtain solution B.
[0059] Step 3: 5.7 mg acetylene black was weighed and added to solution B, and stirred and ultrasonically dispersed to obtain solution C.
[0060] Step 4: Solution A and solution C were mixed, and then transferred to a hydrothermal reactor, sealed and reacted at 150°C for 20 h.
[0061] Step 5: The hydrothermal product was cooled, the supernatant was filtered off, the precipitate was washed with ethanol and water alternately for 10 times, and then transferred to a vacuum drying oven at 80°C for 12 h to obtain a high-entropy alloy sulfide and carbon composite material (MoFeZnMnNi)S x -AB. The XRD spectrum of the prepared high-entropy alloy sulfide and carbon composite material (MoFeZnMnNi)S x -AB is shown in Figure 3
[0062] Example 4
[0063] This example provides a high-entropy alloy sulfide and carbon composite material (MoFeZnMnNi)S x -CNT, wherein the transition metal elements contained in the high-entropy alloy sulfide are Mo, Fe, Co, Mn and Ni, and the carbon material is carbon nanotubes, and the preparation method is as follows:
[0064] Step 1: 0.2732 g of molybdenum chloride, 0.2703 g of iron chloride, 0.2195 g of zinc acetate, 0.1258 g of manganese chloride and 0.1296 g of nickel chloride were respectively dissolved in 30 mL of deionized water, and magnetically stirred until completely dissolved to obtain solution A.
[0065] Step 2: 1.216 g L-cysteine was weighed and dissolved in 40 mL deionized water to obtain solution B.
[0066] Step 3: 23.7 mg of carbon nanotubes was weighed and added to solution B, and stirred and ultrasonically dispersed to obtain solution C.
[0067] Step 4: Solution A and solution C were mixed, and then transferred to a hydrothermal reactor, sealed and reacted at 150°C for 20 h.
[0068] Step 5: The hydrothermal product was cooled, the supernatant was filtered off, the precipitate was washed with ethanol and water alternately for 10 times, and then transferred to a vacuum drying oven at 80°C for 12 h to obtain a high-entropy alloy sulfide and carbon composite material (MoFeZnMnNi)S x CNT. The prepared high-entropy alloy sulfide-carbon composite material (MoFeZnMnNi)S x The scanning electron microscope image of the CNT is shown in FIG. 1. Figure 4
[0069] Example 5
[0070] The present example provides a high-entropy alloy sulfide-carbon composite material (MoFeZnMnNi)S x -CNT, wherein the transition metal elements contained in the high-entropy alloy sulfide are Mo, Fe, Co, Mn and Ni, and the carbon material is graphene oxide, and the preparation method is as follows:
[0071] Step 1: 0.2732 g of molybdenum chloride, 0.2703 g of iron chloride, 0.2195 g of zinc acetate, 0.1258 g of manganese chloride and 0.1296 g of nickel chloride were respectively dissolved in 30 mL of deionized water, and magnetic stirring was performed until complete dissolution to obtain solution A.
[0072] Step 2: 1.216 g of L-cysteine was weighed and dissolved in 40 mL of deionized water to obtain solution B.
[0073] Step 3: 50 mg of graphene oxide was added to solution B, and stirring and ultrasonic dispersion were performed to obtain solution C.
[0074] Step 4: Solution A and solution C were mixed, and then transferred to a hydrothermal reaction kettle, which was sealed and reacted at 150°C for 20 h.
[0075] Step 5: The hydrothermal product was cooled, the supernatant was filtered off, the precipitate was washed with ethanol and water alternately for 10 times, and then transferred to a vacuum drying oven at 80°C for 12 h to obtain the high-entropy alloy sulfide-carbon composite material (MoFeZnMnNi)S x -rGO.
[0076] Example 6
[0077] In 50 mL of 10 mg / L aqueous atrazine solution, 4 mg of high-entropy alloy sulfide (MoFeCoMnNi)S x and 5 mg of potassium persulfate were added. Under the action of magnetic stirring, the degradation of atrazine in the aqueous solution began, and the reaction time was 15 min. After the reaction, the removal rate of atrazine in the solution reached 93.09%, and the results are shown in Figure 5 .
[0078] Example 7
[0079] In 50 mL of 10 mg / L aqueous atrazine solution, 4 mg of high-entropy alloy sulfide (MoFeCoMnNi)S x -CNT and 0.2 g / L potassium persulfate. Under the action of magnetic stirring, the degradation of atrazine in the aqueous solution was started, and the reaction time was 15 min. (MoFeCoMnNi)S x When the amount of CNT was 0.10, 0.15, 0.20, 0.25 and 0.30 g / L, the removal rates of atrazine in the solution after the reaction were 79.78%, 99.75%, 92.00%, 89.29% and 87.30% respectively, and the results were shown in Table 1. Figure 6
[0080] Comparative Example 1
[0081] The difference between Example 7 and the present comparative example was that in the present comparative example, (MoFeCoMnNi)S x -CNT was replaced by 7.5 mg of MoS2, FeS, CoS, ZnS, MnS and Ni3S2 in turn, and the rest of the steps and the amount of potassium persulfate added were the same. After 15 min of reaction, the removal rate of atrazine was shown in Table 2. It can be seen that when MoS2, FeS and CoS were used to activate potassium persulfate, the removal rates of atrazine were 28.91%, 14.12% and 6.79% respectively. When ZnS, MnS and Ni3S2 were used as heterogeneous catalysts, the concentration of atrazine did not change significantly. Figure 7
[0082] The comparison results showed that compared with single metal sulfide, the high-entropy alloy sulfide and carbon composite material (MoFeCoMnNi)S x -CNT had more obvious activation effect on persulfate, and the removal of organic pollutants was also more significant, which increased from 28.91% to 99.75%.
[0083] The above is only a preferred embodiment of the present application and is not intended to limit the present application. Those skilled in the art can understand that various changes, modifications, replacements and variations can be made to the embodiments without departing from the principles and spirits of the present application, and the scope of the present application is defined by the appended claims and their equivalents.
Claims
1. A method for producing a high-entropy alloy sulfide for activation of persulfate salts, characterized by, The high-entropy alloy sulfide contains five transition metal elements, and the transition metal element species is any five of molybdenum, iron, cobalt, zinc, manganese and nickel, and specifically includes the following steps: S1: Dissolve the soluble metal salt of the transition metal element in water to obtain solution A; The concentration of each metal element in the solution A is 0.01-0.05 mol / L; S2: Take the sulfur source and dissolve it in water to obtain solution B; the concentration of the sulfur source in the solution B is 0.1-0.5 mol / L; The sulfur source is any one of sulfur-containing compounds such as thioacetamide, thiourea and L-cysteine; S3: Mix the solution A obtained in step S1 with the solution B obtained in step S2, and then perform hydrothermal reaction at 150-200 DEG C; the volume ratio of the solution A to the solution B is 1:1-1:1.5; S4: Collect the solid product obtained by the hydrothermal reaction in step S3 to obtain the high-entropy alloy sulfide.
2. The method for producing a high-entropy alloy sulfide for activation of persulfates according to claim 1, characterized by, In the step S1, the soluble metal salt of the transition metal element is any five of molybdenum chloride, iron chloride, zinc acetate, cobalt chloride, manganese chloride and nickel chloride; the addition amount of the five metal elements is equimolar ratio.
3. The method of claim 1, wherein the high-entropy alloy sulfide is prepared by a process comprising: mixing a plurality of metal powders to form a mixture; and sintering the mixture to form the high-entropy alloy sulfide. In the step S3, the hydrothermal reaction time is 6-48 h.
4. The method for producing a high-entropy alloy sulfide for activation of persulfates according to claim 1, characterized by, In the step S4, the solid is washed by alternately washing with ethanol and deionized water for 5-20 times; after washing, drying is performed by air blowing or vacuum drying at a temperature of 60-80 DEG C for 12-24 h.
5. The method for producing a high-entropy alloy sulfide for activation of persulfates according to any one of claims 1 to 4, characterized by, The high-entropy alloy sulfide composite material further contains a carbon material, and the carbon material is one or a mixture of two or more of acetylene black, carbon nanotube and graphene oxide; The difference lies in that in step S2, a certain amount of carbon material is dispersed in the solution B obtained in step S2 to obtain solution C; the concentration of the carbon material is 0.05-1.875 g / L; In step S3, the volume ratio of the solution A to the solution C is 1:1-1:1.
5.
6. A high-entropy alloy sulfide for activating persulfate salt, prepared by the method of any one of claims 1-4.
7. A high-entropy alloy sulfide and carbon composite material for activating persulfate salt, prepared by the method of claim 5.
8. A method for the catalytic degradation of organic pollutants using the high-entropy alloy sulfide of claim 6, the high-entropy alloy sulfide-carbon composite material of claim 7, characterized in that, Specifically includes the following steps: the high-entropy alloy sulfide or the high-entropy alloy sulfide and carbon composite material is added to the organic pollutant wastewater to be degraded, and after stirring, the persulfate salt is added to start degradation; the amount of the high-entropy alloy sulfide or the carbon composite material thereof is 0.1-0.3 g / L, and the amount of the persulfate salt is 0.1-0.5 g / L.
9. The method of claim 8, wherein, The reaction temperature is 5-45 DEG C, and the reaction time is 1-30 min.
10. The use according to claim 8, characterized in that, The persulfate salt is any one or a mixture of two or more of potassium persulfate, potassium hydrogen persulfate, sodium persulfate and sodium hydrogen persulfate.