阅读说明：本技术 一种均相芬顿助催化剂及其制备方法与应用 (Homogeneous Fenton cocatalyst, and preparation method and application thereof ) 是由 时悦悦 胡勇有 肖纯 李贤� 于 2021-08-20 设计创作，主要内容包括：本发明公开了一种均相芬顿助催化剂及其制备方法与应用,属于水处理技术领域。本发明的技术方案要点为：以钼源和硫源为原料,通过简单的溶剂热法一步合成了均相芬顿助催化剂。本发明所制备的助催化剂(MoS-(2))可以有效促进Fe～(3+)/Fe～(2+)的循环速率,且该助催化芬顿体系,仅需在添加0.1mmol的H-(2)O-(2)和1mg/L的FeSO-(4)的条件下,就能对水中的罗丹明B、对氯苯酚、四环素和/或双氯芬酸钠较好的去除效果,分别为92％、73％、87％和83％,且该体系没有铁泥的产生。(The invention discloses a homogeneous Fenton cocatalyst, and a preparation method and application thereof, and belongs to the technical field of water treatment. The technical scheme provided by the invention has the key points that: the homogeneous Fenton cocatalyst is synthesized by taking a molybdenum source and a sulfur source as raw materials through a simple solvothermal method in one step. Cocatalyst (MoS) prepared according to the invention 2 ) Can effectively promote Fe 3+ /Fe 2+ The co-catalytic Fenton system only needs to add 0.1mmol of H 2 O 2 And 1mg/L of FeSO 4 Under the condition, the system has good removal effects on rhodamine B, parachlorophenol, tetracycline and/or diclofenac sodium in water, namely 92 percent, 73 percent, 87 percent and 83 percent respectively, and no iron mud is generated in the system.)

1. A preparation method of a homogeneous Fenton cocatalyst is characterized by comprising the following steps:

adding a molybdenum source and a sulfur source into 30-60 mL of deionized water or N, N-dimethylformamide or a mixed solution of the two, and carrying out ultrasonic treatment on the mixture at room temperature for 10-50 min to obtain a uniformly mixed solution; and then transferring the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating the reaction kettle in an oven at 180-220 ℃ for 18-24 h, cooling the reaction kettle to room temperature, washing the sample with deionized water and absolute ethyl alcohol, and drying the sample in the oven at 40-60 ℃ to obtain the polytetrafluoroethylene fiber reinforced polypropylene composite material.

2. The method of claim 1, wherein the molybdenum source is Na₂MoO₄、(NH₄)₂MoO₄、(NH₄)₆Mo₇O₂₄·4H₂O or MoO₃One kind of (1).

3. A method of making a homogeneous fenton co-catalyst according to claim 1 wherein the sulphur source is one of thiourea, thioacetamide, sodium sulphide or L-cysteine.

4. The method of preparing a homogeneous Fenton's co-catalyst according to claim 1, wherein the molar ratio of the molybdenum source to the sulfur source in the method is 1:1 to 1: 30; in the mixed solution of the deionized water and the N, N-dimethylformamide, the volume ratio of the deionized water to the N, N-dimethylformamide is 1: 1-1: 3.

5. A homogeneous Fenton co-catalyst prepared by the method of any one of claims 1 to 4.

6. Use of a homogeneous Fenton's cocatalyst according to claim 5, characterised in that it consists in reacting 0.02g of the synthetic cocatalyst MoS₂Respectively adding the mixture into 50mL of solutions of rhodamine B, parachlorophenol, tetracycline and diclofenac sodium with the concentration of 15mg/L, adjusting the pH value of the solution to be 3-4.5 by using 1mol/L HCl, and adding 0.05mg of FeSO into the solution₄And 0.1mmol of H₂O₂After that, Fenton reaction was started, and the reaction was continued for 2 hours.

7. The use according to claim 6, wherein (NH) is present in the cocatalyst of the homogeneous Fenton system₄)₂MoO₄When the molar ratio of the N-acetyl thioacetamide to the N-acetyl thioacetamide is 1: 1-1: 30, only not more than 0.1mmol of H needs to be added under the condition that the pH is 3-4.5₂O₂And not more than 0.05mg/L of FeSO₄The cocatalyst (MoS)₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of 15mg/L rhodamine B is 92%, and the system does not generate iron mud.

8. The use according to claim 6, wherein (NH) is present in the cocatalyst of the homogeneous Fenton system₄)₂MoO₄When the molar ratio of the N-acetyl thioacetamide to the N-acetyl thioacetamide is 1: 1-1: 30, only not more than 0.1mmol of H needs to be added under the condition that the pH is 3-4.5₂O₂And not more than 0.05mg/L of FeSO₄The cocatalyst (MoS)₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of 15mg/L p-chlorophenol was 73%, and the system did not generate iron mud.

9. The use according to claim 6, wherein (NH) is present in the cocatalyst of the homogeneous Fenton system₄)₂MoO₄When the molar ratio of the N-acetyl thioacetamide to the N-acetyl thioacetamide is 1: 1-1: 30, only not more than 0.1mmol of H needs to be added under the condition that the pH is 3-4.5₂O₂And not more than 0.05mg/L of FeSO₄The cocatalyst (MoS)₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of tetracycline of 15mg/L was 87%, and the system did not generate iron mud.

10. The use according to claim 6, wherein (NH) is present in the cocatalyst of the homogeneous Fenton system₄)₂MoO₄When the molar ratio of the N-acetyl thioacetamide to the N-acetyl thioacetamide is 1: 1-1: 30, only not more than 0.1mmol of H needs to be added under the condition that the pH is 3-4.5₂O₂And not more than 0.05mg/L of FeSO₄The cocatalyst (MoS)₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of diclofenac sodium with 15mg/L is 83%, and the system does not generate iron mud.

Technical Field

The invention relates to preparation of a homogeneous Fenton cocatalyst and water treatment application, and belongs to the technical field of water treatment.

Background

The industrial wastewater has complex components and a large amount of organic pollutants, and more synthetic substances which are difficult to degrade exist, and harmful ecotoxicological effects can be generated if the synthetic substances are not properly treated. At present, industrial wastewater is treated by adopting a biochemical treatment method, but the method has low treatment efficiency on refractory organic pollutants and is difficult to ensure that tail water is discharged after reaching the standard. Therefore, it is necessary to develop a novel advanced wastewater/sewage treatment technology with high efficiency and low energy consumption to rapidly remove the refractory organics.

The Fenton reaction is a typical advanced oxidation process for degrading organic pollutants, and Fe is generated in the process of the Fenton reaction²⁺Or other reduced transition metals with H₂O₂The reaction generates strong oxidizing OH which can degrade organic pollutants by indiscriminate oxidation and reduce the chemical oxygen demand in water so as to achieve the aim of water quality purification. However, the conventional Fenton reaction needs to be carried out under a strongly acidic condition of pH about 3.5, the degradation efficiency of organic pollutants is low under a neutral condition, and H is low₂O₂The consumption of the iron mud is large, and the generation amount of the iron mud is large. These problems are mainly due to the limitation of electron circulation and H₂O₂Is caused by the ineffective decomposition of (c). Thus how to achieve rapid cycling of electrons, Fe²⁺/Fe³⁺Redox cycling for further improving OH yield and H in Fenton reaction system₂O₂The utilization rate and the reduction of the iron mud generation amount are particularly important.

In recent years, researchers found that the introduction of a cocatalyst in the Fenton reaction process can remarkably promote the electron transfer and H₂O₂And (4) activating. At present, most studies on the promoted Fenton reaction have been conducted using an organic compound as a promoter, for example, quinone-hydroquinone analog, cysteine, protocatechuic acid, etc., and adding a promoter capable of promoting Fe³⁺/Fe^{2 +}Circulating to reduce the production of iron mud; increase H₂O₂Utilization ratio of (1), reduction of H₂O₂The amount of addition of (c). However, some organic cocatalysts are themselves difficult to degrade and prone to secondary contamination. Therefore, the development of inorganic co-catalysts with higher chemical stability than organic compounds has great economic and environmental significance.

So far, relatively few studies have been made on the acceleration of the fenton reaction by the inorganic co-catalyst, and the prior art related to the present invention was searched as follows:

patent publication No. CN 111217429A introduces a method for efficiently removing organic wastewater by molybdenum disulfide-assisted catalysis of heterogeneous electro-Fenton of zero-valent iron. The method takes DSA and modified carbon felt as an anode and a cathode respectively, and can generate enough H in situ₂O₂Effectively avoid H₂O₂Troubles in the transportation and storage processes, and the added molybdenum disulfide powder and zero-valent iron powder in the system can effectively promote Fe in the reaction system³⁺/Fe²⁺Maintaining a high concentration of Fe in the system²⁺Thereby further improving the reaction rate of the system and overcoming the defect that the zero-valent iron catalyst is easy to be activated in the reaction process to a certain extent, but the system is relatively complex to operate and needs higher energy consumption.

The patent with publication number CN 112958117 a prepares a fenton co-catalyst of copper sulfide by using copper chloride and thioacetamide, and is used for promoting the fenton reaction to degrade rhodamine B, but the preparation process of the material needs to be under a strong acid environment (pH is 0.2-1), and the material only has a good effect of removing rhodamine B.

Patent publication No. CN 111732181A provides a method for preparing a composite material comprising FeS₂、H₂O₂And transition metal sulfide, transition metal sulfide (MoS)₂、ZnS、WS₂) The FeS can be increased as a cocatalyst₂Surface Fe²⁺The generation efficiency and stability of Fe can be improved in time³⁺Reduction to Fe²⁺Continue to decompose H₂O₂OH is generated to degrade contaminants. However, to achieve a better contaminant removal effect, FeS₂The concentration in the contaminants is up to 5 g/L.

The invention adopts a simple solvothermal method to prepare a homogeneous Fenton cocatalyst (MoS)₂) Construction of MoS₂The co-catalysis Fenton system only needs to add not more than 0.1mmol of H under the condition that the pH value is 3-4.5₂O₂And not more than 0.05mg/L of FeSO₄The system can be implementedThe removal effect on rhodamine B, parachlorophenol, tetracycline and/or diclofenac sodium in the aqueous solution is high and can reach 92%, 73%, 87% and 83% respectively, and the system does not generate iron mud.

Disclosure of Invention

The invention aims to provide a homogeneous Fenton cocatalyst, and a preparation method and application thereof, so as to overcome the defect that a large amount of iron mud and H are generated in the classical homogeneous Fenton reaction₂O₂The shortage of low utilization rate, thereby promoting Fe in the Fenton reaction system^{3 +}/Fe²⁺The rapid and efficient conversion is realized, and the generation amount of iron mud is reduced; and further improve the yield of OH and H₂O₂Utilization ratio of (1), reduction of H₂O₂The amount of addition of (c).

The invention is characterized in that the invention adopts a simple solvothermal method to prepare the homogeneous Fenton cocatalyst (MoS)₂) Construction of MoS₂In the co-catalysis Fenton system, when the pH value is 3-4.5, only H not more than 0.1mmol needs to be added₂O₂And 1mg/L of FeSO₄The system can realize high removal effects on rhodamine B, parachlorophenol, tetracycline and/or diclofenac sodium in the aqueous solution, which can respectively reach 92%, 73%, 87% and 83%, and the system does not generate iron mud.

The key technical problem solved by the invention is to prepare a cocatalyst (MoS)₂) And used in homogeneous Fenton system to accelerate Fe³⁺/Fe²⁺Increase H₂O₂The utilization ratio of (2).

Another technical problem solved by the invention is to construct MoS₂The cocatalyst system only needs to add 0.1mmol of H₂O₂And 1mg/L of FeSO₄The system can realize high removal effects on rhodamine B, parachlorophenol, tetracycline and/or diclofenac sodium in the aqueous solution, and the removal effects can respectively reach 92%, 73%, 87% and 83%.

The technical scheme of the invention is as follows.

A preparation method of a homogeneous Fenton cocatalyst is realized by the following steps:

adding a molybdenum source and a sulfur source into 30-60 mL of deionized water or N, N-dimethylformamide or a mixed solution of the two, and carrying out ultrasonic treatment on the mixture at room temperature for 10-50 min to obtain a uniformly mixed solution; and then transferring the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating the reaction kettle in an oven at 180-220 ℃ for 18-24 h, cooling the reaction kettle to room temperature, washing the sample with deionized water and absolute ethyl alcohol, and drying the sample in the oven at 40-60 ℃ to obtain the polytetrafluoroethylene fiber reinforced polypropylene composite material.

In the method, the molybdenum source is Na₂MoO₄、(NH₄)₂MoO₄、(NH₄)₆Mo₇O₂₄·4H₂O or MoO₃One kind of (1).

In the method, the sulfur source is one of thiourea, thioacetamide, sodium sulfide or L-cysteine.

In the method, the molar ratio of the molybdenum source to the sulfur source is 1: 1-1: 30.

In the method, the volume ratio of the deionized water to the N, N-dimethylformamide in the mixed solution of the deionized water and the N, N-dimethylformamide is 1: 1-1: 3.

The application of the homogeneous Fenton cocatalyst comprises the following method that the cocatalyst MoS is added into a homogeneous Fenton system₂，Fe²⁺Activation of H₂0₂Production of 0H to degrade rhodamine B, parachlorophenol, tetracycline and/or diclofenac sodium, and Fe^{2 +}Is oxidized into Fe³⁺Mo exposed on the surface of the cocatalyst after the cocatalyst is added into the system⁴⁺Can be mixed with Fe³⁺Reaction occurs to promote Fe²⁺/Fe³⁺Redox cycling with Mo⁶⁺Is then H₂O₂Mo is mixed with⁶⁺Reduction to Mo⁴⁺To ensure the recycling of the cocatalyst, thus reducing FeSO₄The dosage of the iron mud is not more than 1mg/L, and the generation amount of the iron mud is reduced.

In the above application, MoS₂The co-catalysis homogeneous Fenton system can reduce H to the maximum extent₂O₂In an amount ofNot more than 0.1 mmol.

In the above application, in the cocatalyst (NH) of the homogeneous Fenton system₄)₂MoO₄When the molar ratio of the N-acetyl thioacetamide to the N-acetyl thioacetamide is 1: 1-1: 30, only not more than 0.1mmol of H needs to be added under the condition that the pH is 3-4.5₂O₂And not more than 0.05mg/L of FeSO₄The cocatalyst (MoS)₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of 15mg/L rhodamine B is 92%, and the system does not generate iron mud.

In the above application, in the cocatalyst (NH) of the homogeneous Fenton system₄)₂MoO₄When the molar ratio of the N-acetyl thioacetamide to the N-acetyl thioacetamide is 1: 1-1: 30, only not more than 0.1mmol of H needs to be added under the condition that the pH is 3-4.5₂O₂And not more than 0.05mg/L of FeSO₄The cocatalyst (MoS)₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of p-chlorophenol with the concentration of 15mg/L is 73%, and the system does not generate iron mud.

In the above application, in the cocatalyst (NH) of the homogeneous Fenton system₄)₂MoO₄When the molar ratio of the N-acetyl thioacetamide to the N-acetyl thioacetamide is 1: 1-1: 30, only not more than 0.1mmol of H needs to be added under the condition that the pH is 3-4.5₂O₂And not more than 0.05mg/L of FeSO₄The cocatalyst (MoS)₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of tetracycline with the concentration of 15mg/L is 87%, and the system does not generate iron mud.

In the above application, in the cocatalyst (NH) of the homogeneous Fenton system₄)₂MoO₄When the molar ratio of the N-acetyl thioacetamide to the N-acetyl thioacetamide is 1: 1-1: 30, only not more than 0.1mmol of H needs to be added under the condition that the pH is 3-4.5₂O₂And not more than 0.05mg/L of FeSO₄The cocatalyst (MoS)₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) To pairThe 50mL of diclofenac sodium with the concentration of 15mg/L has the removal rate of 83 percent, and the system does not generate iron mud.

The invention relates to a homogeneous phase Fenton cocatalyst (MoS)₂) The constructed cocatalyst Fenton system has good removal effects on rhodamine B, parachlorophenol, tetracycline and/or diclofenac sodium in water, and the removal effects respectively reach 92%, 73%, 87% and 83%.

Preferably, the homogeneous Fenton co-catalyst is (NH)₄)₂MoO₄With a molar ratio of thioacetamide of 1:10, a cocatalyst (MoS) was prepared₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of rhodamine B with the concentration of 15mg/L is 92%.

Preferably, the homogeneous Fenton co-catalyst is (NH)₄)₂MoO₄With a molar ratio of thioacetamide of 1:10, a cocatalyst (MoS) was prepared₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of p-chlorophenol at 15mg/L was 73%.

Preferably, the homogeneous Fenton co-catalyst is (NH)₄)₂MoO₄With a molar ratio of thioacetamide of 1:10, a cocatalyst (MoS) was prepared₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of tetracycline at 15mg/L was 87%.

Preferably, the homogeneous Fenton co-catalyst is (NH)₄)₂MoO₄With a molar ratio of thioacetamide of 1:10, a cocatalyst (MoS) was prepared₂) Constructed assisted Fenton System (MoS)₂/Fe²⁺/H₂O₂) The removal rate of 50mL of diclofenac sodium with 15mg/L is 83 percent.

Compared with the prior art, the invention has the following excellent effects:

(1) by adding MoS₂As a cocatalyst, Fe in a reaction system can be effectively promoted³⁺/Fe²⁺The circulation rate of (2) is such that Fe in the system²⁺The concentration is maintained to be higher, the system basically has no generation of iron mud, and when the pH value of the cocatalyst Fenton system is 3-4.5, only no more than 0.1mmol of H needs to be added₂O₂And 1mg/L of FeSO₄Can reduce Fe to the maximum²⁺And H₂O₂The amount of addition of (c).

(2) Under the conditions, the cocatalyst prepared by the invention can cooperate with Fe²⁺Degrading rhodamine B, parachlorophenol, tetracycline and/or diclofenac sodium, wherein the degrading effect reaches 92%, 73%, 87% and 83% respectively, and the system does not generate iron mud.

Drawings

FIG. 1 shows a co-promoted Fenton System (MoS)₂/Fe²⁺/H₂O₂) And (3) removing the rhodamine B, the parachlorophenol, the tetracycline and the diclofenac sodium.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

Example 1

Homogeneous Fenton cocatalyst (MoS)₂) The preparation method comprises the following steps:

30mg of MoO₃And 83mg of thiourea were dissolved in 30mL of N, N-dimethylformamide, and the mixture was sonicated at room temperature for 30min to give a homogeneous solution. The solution was then transferred to a 100mL reaction kettle with a teflon liner and heated in an oven at 200 ℃ for 20h, after cooling to room temperature, the sample was washed with deionized water and absolute ethanol and dried in an oven at 40 ℃.

Comparative example 1: commercial MoS for direct purchase₂(particle size 100 nm).

Application of example 1: 0.02g of the cocatalyst synthesized above was added to 50mL of 15mg/L rhodamine B solution, the pH of the solution was adjusted to 4.5 with 1mol/L HCl, and 0.05mg of FeSO was added to the solution₄(concentration 1mg/L) and 0.1mmol of H₂O₂And then starting the reaction, wherein the system has a rhodamine B removal rate of 85% after the reaction is carried out for 1 h. With 1mol/L HC without cocatalystL adjusting the pH value of 50mL of 15mg/L rhodamine B solution to be 4.5, and adding 0.05mg of FeSO into the solution₄And 0.1mmol of H₂O₂And then, starting the reaction, wherein the removal rate of rhodamine B by the homogeneous Fenton system is 31% after the reaction is carried out for 1 h. Namely, the addition of the cocatalyst into the homogeneous Fenton system can effectively promote Fe in the reaction system³⁺/Fe²⁺The cycle rate of (2), and thus the yield of 0H.

Application of comparative example 1: 0.02g of commercial MoS purchased directly₂The cocatalyst is added into 50mL of 15mg/L rhodamine B solution, the pH value of the solution is adjusted to 4.5 by using 1mol/L HCl, and 0.05mg of FeSO is added into the solution₄(concentration 1mg/L) and 0.1mmol of H₂O₂And then the reaction is started, and after the reaction is carried out for 1h, the system has the rhodamine B removal rate of 58%.

Example 2

Homogeneous Fenton cocatalyst (MoS)₂) The preparation method comprises the following steps:

1.372g (NH4)₂MoO₄And 1.1418g of thiourea were dissolved in 30mL of deionized water, and the mixture was sonicated at room temperature for 30min to give a homogeneous solution. The solution was then transferred to a 100mL reaction kettle with a teflon liner and heated in an oven at 200 ℃ for 24h, after cooling to room temperature, the sample was washed with deionized water and absolute ethanol and dried in an oven at 40 ℃.

Application of example 2: 0.02g of the cocatalyst synthesized above was added to 50mL of 5mg/L rhodamine B solution, the pH of the solution was adjusted to 4.5 with 1mol/L HCl, and 0.05mg of FeSO was added to the solution₄(concentration 1mg/L) and 0.1mmol of H₂O₂And then the reaction is started, and after the reaction is carried out for 1h, the system has the rhodamine B removal rate of 70%.

Example 3

Homogeneous Fenton cocatalyst (MoS)₂) The preparation method comprises the following steps:

0.144g of MoO₃And 2.2836g of thiourea were dissolved in 30mL of deionized water, and the mixture was sonicated at room temperature for 30min to give a homogeneous solution. Then will beThe solution was transferred to a 100mL autoclave with a teflon liner and heated in an oven at 200 ℃ for 24h, cooled to room temperature, the sample was washed with deionized water and absolute ethanol and dried in an oven at 40 ℃.

Application of example 3: 0.02g of the cocatalyst synthesized above was added to 50mL of 5mg/L rhodamine B solution, the pH of the solution was adjusted to 4.5 with 1mol/L HCl, and 0.05mg of FeSO was added to the solution₄And 0.1mmol of H₂O₂And then starting the reaction, wherein the system has a rhodamine B removal rate of 50% after the reaction is carried out for 1 h.

Example 4

Homogeneous Fenton cocatalyst (MoS)₂) The preparation method comprises the following steps:

1.2358g (NH4)₆Mo₇O₂₄·4H₂O and 1.1418g of thiourea were dissolved in 30mL of deionized water and the mixture was sonicated for 30min at room temperature to give a homogeneous solution. The solution was then transferred to a 100mL reaction kettle with a teflon liner and heated in an oven at 200 ℃ for 24h, after cooling to room temperature, the sample was washed with deionized water and absolute ethanol and dried in an oven at 40 ℃.

Application of example 4: 0.02g of the cocatalyst synthesized above was added to 50mL of 5mg/L rhodamine B solution, the pH of the solution was adjusted to 4.5 with 1mol/L HCl, and 0.05mg of FeSO was added to the solution₄And 0.1mmol of H₂O₂And then the reaction is started, and after the reaction is carried out for 1h, the system has the rhodamine B removal rate of 83 percent.

Example 5

Homogeneous Fenton cocatalyst (MoS)₂) The preparation method comprises the following steps:

adding 41mg (NH)₄)₂MoO₄And 157mg of thioacetamide were dissolved in 30mL of N, N-dimethylformamide, and the mixture was sonicated at room temperature for 30min to obtain a homogeneous solution. The solution was then transferred to a 100mL reaction kettle with a Teflon liner and heated in an oven at 200 deg.C for 20h, cooled to room temperature, and washed with deionized water and absolute ethanolThe samples were washed and dried in an oven at 40 ℃.

Application of example 5: 0.02g of the cocatalyst synthesized above was added to 100mL of 15mg/L rhodamine B solution, the pH of the solution was adjusted to 4.5 with 1mol/L HCl, and 0.05mg of FeSO was added to the solution₄And 0.1mmol of H₂O₂And then starting the reaction, wherein the system has a rhodamine B removal rate of 82% after the reaction is carried out for 1 h.

Example 6

Homogeneous Fenton cocatalyst (MoS)₂) The preparation method comprises the following steps:

adding 41mg (NH)₄)₂MoO₄And 83mg of thiourea were dissolved in 30mL of N, N-dimethylformamide, and the mixture was sonicated at room temperature for 30min to give a homogeneous solution. The solution was then transferred to a 100mL reaction kettle with a teflon liner and heated in an oven at 200 ℃ for 20h, after cooling to room temperature, the sample was washed with deionized water and absolute ethanol and dried in an oven at 40 ℃.

Example 7

Homogeneous Fenton cocatalyst (MoS)₂) The preparation method comprises the following steps:

adding 30mg of Na₂MoO₄And 55mg of thioacetamide were dissolved in 30mL of N, N-dimethylformamide, and the mixture was sonicated at room temperature for 30min to obtain a homogeneous solution. The solution was then transferred to a 100mL reaction kettle with a teflon liner and heated in an oven at 200 ℃ for 20h, after cooling to room temperature, the sample was washed with deionized water and absolute ethanol and dried in an oven at 40 ℃.

Example 8

0.02g of the cocatalyst synthesized in example 5 was added to 50mL of solutions of rhodamine B, p-chlorophenol, tetracycline and diclofenac sodium each having a concentration of 15mg/L, the pH of the solution was adjusted to 4.5 with 1mol/L of HCl, and 0.05mg of FeSO was added to the solution₄And 0.1mmol of H₂O₂After that, Fenton reaction is started, and after 2 hours of reaction, the system can remove pollutants in four parts as shown in figure 1. Namely, the MoS₂/Fe²⁺/H₂O₂The system has good removal effect on the four pollutants.

Example 9

Homogeneous Fenton cocatalyst (MoS)₂) The preparation method comprises the following steps:

30mg of MoO₃And 83mg of thiourea were dissolved in 30mL of N, N-dimethylformamide, and the mixture was sonicated at room temperature for 30min to give a homogeneous solution. The solution was then transferred to a 100mL reaction kettle with a teflon liner and heated in an oven at 200 ℃ for 20h, after cooling to room temperature, the sample was washed with deionized water and absolute ethanol and dried in an oven at 40 ℃.

Application of example 9: 0.02g of the cocatalyst synthesized above was added to 100mL of 10mg/L rhodamine B solution, the pH of the solution was adjusted to 4.5 with 1mol/L HCl, and 0.05mg of FeSO was added to the solution₄And 0.1mmol of H₂O₂And then the reaction is started, and after the reaction is carried out for 1h, the system has a rhodamine B removal rate of 45%.

Example 10

0.02g of the cocatalyst synthesized in example 5 was added to 50mL of 1mg/L rhodamine B solution, the pH of the solution was adjusted to 4.5 with 1mol/L HCl, and 0.05mg of FeSO was added to the solution₄And 0.1mmol of H₂O₂After that, Fenton reaction was started, and after 0.5h, the MoS was obtained₂/Fe²⁺/H₂O₂The removal rate of the system to rhodamine B is 100%.

Example 11

0.02g of the cocatalyst synthesized in example 5 was added to 50mL of a 1mg/L p-chlorophenol solution, the pH of the solution was adjusted to 4.5 with 1mol/L HCl, and 0.05mg of FeSO was added to the solution₄And 0.1mmol of H₂O₂After that, Fenton reaction was started, and after 0.5h, the MoS was obtained₂/Fe²⁺/H₂O₂The removal rate of p-chlorophenol in the system was 96%.

Example 12

0.02g of the cocatalyst synthesized in example 5 was reactedAdding the preparation into 50mL diclofenac sodium solution with concentration of 1mg/L, adjusting pH value of the solution to 4.5 with 1mol/L HCl, and adding 0.05mg FeSO₄And 0.1mmol of H₂O₂After that, Fenton reaction was started, and after 0.5h, the MoS was obtained₂/Fe²⁺/H₂O₂The removal rate of the system to the diclofenac sodium is 99%.

Example 13

0.02g of the cocatalyst synthesized in example 5 was added to 50mL of a 1mg/L tetracycline solution, respectively, the pH of the solution was adjusted to 4.5 with 1mol/L HCl, and 0.05mg of FeSO was added to the solution₄And 0.1mmol of H₂O₂After that, Fenton reaction was started, and after 0.5h, the MoS was obtained₂/Fe²⁺/H₂O₂The tetracycline removal rate of the system is 100%.

The above-mentioned embodiments are preferred embodiments of the present invention, but the detailed description of the present invention is not limited to the above-mentioned embodiments, and other changes, modifications, simplifications, etc. made by those skilled in the art without departing from the spirit and principle of the present invention should be included in the scope of patent protection defined by the claims of the present invention.