Preparation and application of ferrovanadium bimetallic sulfide nano material for oxidative removal of endocrine disrupters in water body

Abstract

The invention discloses a preparation method of a ferrovanadium bimetallic sulfide nano-material for oxidative removal of endocrine disrupters in a water body and application of the ferrovanadium bimetallic sulfide nano-material in advanced oxidation. The preparation method comprises the following steps: firstly, mixing a precursor solution of vanadium disulfide with a precursor solution of ferrous disulfide to obtain a precursor of ferrovanadium bimetallic sulfide; the precursor is subjected to water bath ultrasonic treatment and then subjected to a hydrothermal reaction, washing and vacuum drying are conducted after the reaction is completed, and then the powdery ferrovanadium bimetallic sulfide is obtained. Due to the synergistic effect between bimetals, the prepared iron-vanadium bimetallic sulfide nano material has stronger persulfate catalytic activation capacity than independent ferrous disulfide and vanadium disulfide, and the degradation reaction rate constant under the same reaction condition is 43 times or 2.1 times of that of independent iron or vanadium sulfide; and meanwhile, the ferrovanadium bimetallic sulfide has good pH adaptability and reusability.

Description

Technical Field

[0001] This invention relates to the preparation and application of iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water, belonging to the field of advanced oxidation nanocatalysts. Background Technology

[0002] In recent years, the widespread use of endocrine disruptors (BPA) has led to their extensive diffusion in the environment, with frequent detections in surface water and soil. BPA can cause a range of health problems, particularly harming the reproductive and immune systems, such as triggering diabetes, cancer, and neurodevelopmental disorders in children. Therefore, the development of efficient BPA degradation technologies is urgently needed. Compared to biological and physical methods, advanced oxidation processes (AOPs) can generate strong oxidants to completely decompose BPA and have been proven to be an effective BPA removal technology.

[0003] Among numerous advanced oxidation technologies, those based on sulfate radicals (SO4) are particularly promising. •− Advanced oxidation processes (SR-AOPs) utilize persulfate (PMS, HSO5) to break down persulfate (PMS, HSO5). − ) and persulfate (PDS, S2O8) 2− SO4 is produced by the OOO bond of SO4. •− Its properties have led to its recognition as an effective method for removing endocrine disruptors from wastewater. Compared to other advanced oxidation processes (such as the Fenton process and ozonation), SO42-... •− It boasts multiple advantages: higher redox potential, longer half-life, wider pH adaptability, higher generation rate, and greater selectivity and degradation efficiency for pollutants containing unsaturated bonds or aromatic rings. This technology can effectively convert organic pollutants in water into low-toxicity or even non-toxic molecules (such as H2O and CO2).

[0004] In recent years, various persulfate activation methods have emerged, including thermal activation, ultraviolet irradiation, alkali activation, and ultrasonic activation. However, these methods often require complex equipment and consume a lot of energy. To meet the demands of sustainable development and low cost, researchers have explored carbon-based materials such as activated carbon, biochar, and asphaltene as PMS activators for the degradation of endocrine disruptors. However, pure carbon materials have poor catalytic performance due to the limited variety of surface functional groups and weak anti-interference ability. Transition metals (such as iron, cobalt, nickel, copper, zinc, etc.) are widely used for persulfate activation due to their simple operation, mild temperature and pressure conditions, and high activation efficiency. However, homogeneous reactions have drawbacks such as the difficulty in controlling the release rate of metal ions, which greatly limits their practical application. In contrast, heterogeneous systems that rely on the active sites of solid supports to initiate the decomposition of persulfate and form reactive oxygen species are attracting increasing attention. Among them, iron-based catalysts stand out due to their wide availability, low price, and high efficiency. Pyrite (FeS2) has attracted extensive research due to its low toxicity, abundant reserves, rich ferrous structure, and controllable release of divalent iron. However, its catalytic activity and the regeneration rate of ferrous iron are slow, making it difficult to meet the needs of practical applications.

[0005] Bimetallic composite transition metal sulfides have attracted considerable attention in advanced oxidation processes due to their enhanced physicochemical properties, synergistic effects among multiple components, and the synergistic effect between the bimetals, which can improve catalytic activity and stabilize metal leaching. Vanadium disulfide, as one of the transition metal sulfides, has gained widespread attention in lithium-ion and sodium-ion batteries due to its unique interlayer spacing (0.57 nm) and metal-insulator transition characteristics. More interestingly, the different phase compositions of vanadium disulfide (metallic 1T phase and semiconducting 2H phase) significantly affect its catalytic activity. The 1T phase of vanadium disulfide has abundant catalytic sites on the basal plane and edges, with strong adsorption energy at the sulfur sites on the layer edges. Therefore, the transition from the semiconducting 2H phase to the metallic 1T phase can promote electron transport. However, to date, research on the use of ferrous disulfide and vanadium disulfide composites for persulfate activation is still scarce. Therefore, the preparation of iron-vanadium bimetallic composites for persulfate activation via a simple synthetic method shows great promise. By leveraging the bridging effect and synergistic effect between the two, it is hoped that various environmental sustainability challenges can be addressed, such as reducing iron leaching and improving the reusability of materials.

[0006] It should be noted that the information disclosed in the background section above is only used to enhance the understanding of the background of this disclosure, and therefore may include information that does not constitute prior art known to those skilled in the art. Summary of the Invention

[0007] The purpose of this invention is to provide a method for preparing iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water and its application in the removal of endocrine disruptors (bisphenol A) from water using activated persulfate.

[0008] The technical solution steps of this invention are as follows: (1) Dissolve ammonium metavanadate, thioacetamide and 30% ammonia in deionized water by stirring, then add an appropriate amount of L-ascorbic acid and stir to dissolve to prepare solution A. The molar ratio of ammonium metavanadate and thioacetamide is 1:5, and the amount of 30% ammonia is 2~4 mL. (2) Dissolve ferrous sulfate heptahydrate, sodium thiosulfate pentahydrate and sulfur powder in deionized water to prepare solution B, wherein the molar ratio of ferrous sulfate heptahydrate, sodium thiosulfate pentahydrate and sulfur powder is 1:1:1; (3) Mix solutions A and B to obtain a precursor solution of iron-vanadium bimetallic sulfide, transfer it to a Teflon liner for ultrasonic treatment, and then put it into a stainless steel autoclave for hydrothermal reaction. After the reaction is completed, the product is washed and vacuum dried to obtain the iron-vanadium bimetallic sulfide nanomaterials used for the oxidation and removal of endocrine disruptors in water. The iron-vanadium bimetallic sulfide nanomaterials prepared in this invention for the oxidative removal of endocrine disruptors in water are applied to the preparation of persulfate catalyst materials, featuring a high metal 1T phase, large specific surface area, and abundant microporous structure.

[0009] The iron-vanadium bimetallic sulfide nanomaterials prepared in this invention for the oxidative removal of endocrine disruptors in water can also be applied to the preparation of electro-Fenton electrode materials.

[0010] Compared with the prior art, the present invention has the following beneficial effects: (1) The iron-vanadium bimetallic sulfide nanomaterial prepared by the present invention through a simple one-step hydrothermal reaction for the oxidation and removal of endocrine disruptors in water has high metal 1T phase characteristics. At the same time, as a catalyst material, its high specific surface area can provide more active sites. Its ability to activate persulfate to remove pollutants in water is far higher than that of common catalysts on the market, such as ferrous disulfide or vanadium disulfide alone, and even higher than the sum of the two in terms of reaction rate constant.

[0011] (2) The iron-vanadium bimetallic sulfide nanomaterial prepared by hydrothermal reaction of the present invention for the oxidation and removal of endocrine disruptors in water is less affected by solution pH than single metal materials and can effectively activate persulfate to produce active oxides in a wide pH range. It is simple, convenient and efficient to use. (3) The iron-vanadium bimetallic sulfide nanomaterials prepared by the present invention through hydrothermal reaction for the oxidation and removal of endocrine disruptors in water can improve the problems of slow iron circulation, poor leaching and reusability of ferrous disulfide in water. Attached Figure Description

[0012] Figure 1The image shows the XRD pattern of the iron-vanadium bimetallic sulfide nanomaterials obtained in Example 1 of this invention for the oxidative removal of endocrine disruptors in water.

[0013] Figure 2 The image shows the Raman spectrum of the iron-vanadium bimetallic sulfide nanomaterials obtained in Example 1 of this invention for the oxidative removal of endocrine disruptors in water.

[0014] Figure 3 This is a SEM image of the iron-vanadium bimetallic sulfide nanomaterial obtained in Example 1 of the present invention for the oxidative removal of endocrine disruptors in water.

[0015] Figure 4 This is the BET spectrum of the iron-vanadium bimetallic sulfide nanomaterial obtained in Example 1 of the present invention for the oxidative removal of endocrine disruptors in water.

[0016] Figure 5 The bisphenol A removal efficiency of the iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water obtained in Example 2 of this invention is compared with that of single metal sulfide materials (ferrous disulfide and vanadium disulfide) under the same conditions.

[0017] Figure 6 The degradation effect of the iron-vanadium bimetallic sulfide nanomaterials obtained in Example 3 of the present invention on different pollutants under the same conditions.

[0018] Figure 7 The degradation effect of iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water obtained in Example 4 of this invention on the removal of bisphenol A under different pH conditions.

[0019] Figure 8 This demonstrates the reusability of the iron-vanadium bimetallic sulfide nanomaterials obtained in Example 5 of the present invention for the oxidative removal of endocrine disruptors in water. Detailed Implementation

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] It should be noted that: Unless otherwise specified in the examples, conditions should be followed according to standard conditions or the manufacturer's recommendations. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0022] In this invention, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are used only for simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0023] The features mentioned in this invention can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification, provided that there is no contradiction in the combination of these features. Each feature disclosed in the specification can be replaced by any alternative feature that provides the same, equivalent, or similar purpose. Therefore, unless otherwise specified, the disclosed features are merely general examples of equivalent or similar features.

[0024] This invention provides a method for preparing iron-vanadium composite bimetallic sulfides through a simple one-step hydrothermal reaction. The introduction of iron induces a transformation of vanadium disulfide from a low metallic 1T phase to a high metallic 1T phase. At the same time, the introduction of vanadium disulfide can also reduce the leaching of iron ions in the material and improve the reusability of the material.

[0025] The following detailed description, through examples, illustrates the preparation and application method of a powdered iron-vanadium bimetallic sulfide provided by the present invention. Example

[0026] A method for preparing an iron-vanadium bimetallic sulfide nanomaterial for the oxidative removal of endocrine disruptors in water is as follows: (1) Dissolve 5 mmol of ammonium metavanadate in 25 mL of deionized water, then add 2-4 mL of 30% ammonia solution and stir continuously until the solution turns pale yellow. Then, add 20 mmol of thioacetamide to the solution and stir again until the solution turns brownish-yellow to obtain solution A; (2) Dissolve 2.5 mmol of ferrous sulfate heptahydrate, sodium thiosulfate pentahydrate and sulfur powder in 15 mL of deionized water to prepare solution B; add 3 mmol of L-ascorbic acid and stir. After stirring, subject the mixed solution to ultrasonic treatment in a water bath at a power of 100 W, a frequency of 49 KHz and a temperature of 25±2℃ to obtain the precursor solution. (2) After mixing and stirring solutions A and B for 15 min, a precursor solution is obtained. The precursor solution is placed in a 100 mL Teflon liner and subjected to ultrasonic treatment in a water bath at a power of 100 W, a frequency of 49 KHz, and a temperature of 25±2℃. Then, it is placed in a stainless steel autoclave for hydrothermal reaction at a hydrothermal temperature of 160℃ and a hydrothermal time of 20 h. (The vanadium disulfide and ferrous disulfide are obtained by directly performing ultrasonic treatment on solutions A and B separately and then hydrothermally treating them.)

[0027] (3) After the hydrothermal reaction is completed, the product is washed three times with deionized water and three times with anhydrous ethanol, then vacuum dried at 60°C, and then ground through a 10-mesh sieve to obtain the iron-vanadium bimetallic sulfide nanomaterials used for the oxidation and removal of endocrine disruptors in water. Example

[0028] (1) Weigh 10 mg each of the iron-vanadium bimetallic sulfide nanomaterials, ferrous disulfide and vanadium disulfide obtained in Example 1 for the oxidation and removal of endocrine disruptors in water, weigh 3 portions of 1 mmol potassium persulfate, measure 100 mL of 20 mg / L bisphenol A solution and transfer them to 250 mL Erlenmeyer flasks respectively, and label them.

[0029] (2) Place the conical flasks containing pollutants and marked in a constant temperature shaker. Set the temperature to 25°C and the rotation speed to 150 rpm / min. After adding the weighed potassium persulfate to each conical flask, immediately add the corresponding iron-vanadium bimetallic sulfide nanomaterials, ferrous disulfide, and vanadium disulfide catalyst according to the markings to activate the potassium persulfate to generate active oxides to remove bisphenol A from the solution. Take samples at the set time points, test and record the pollutant concentration, and process the data results. Example

[0030] (1) Weigh 5 portions of 10 mg of the iron-vanadium bimetallic sulfide nanomaterials obtained in Example 1 for the oxidation and removal of endocrine disruptors in water, weigh 1 mmol of potassium persulfate of the corresponding amount, measure 100 mL of 20 mg / L solutions of bisphenol A, tetracycline, methyl orange, rhodamine B, benzoic acid and 4-nitrobenzoic acid and transfer them to 250 mL conical flasks respectively, and label them.

[0031] (2) Place the conical flasks containing pollutants and marked in a constant temperature shaker. Set the temperature to 25℃ and the rotation speed to 150 rpm / min. After adding the weighed potassium persulfate to each conical flask, immediately add the corresponding iron-vanadium bimetallic sulfide nanomaterials according to the markings to activate the potassium persulfate and generate active oxide species to remove bisphenol A from the solution. Take samples at the set time points, test and record the concentration of bisphenol A, and process the data results. Example

[0032] (1) Weigh 4 portions of 10 mg of the iron-vanadium bimetallic sulfide nanomaterials obtained in Example 1 for the oxidation and removal of endocrine disruptors in water, weigh 1 mmol of potassium persulfate of the corresponding amount, measure 100 mL of 20 mg / L bisphenol A solution of the corresponding amount and adjust to different pH values, then transfer them to 250 mL conical flasks and label them.

[0033] (2) Place the conical flasks containing pollutants and marked in a constant temperature shaker. Set the temperature to 25℃ and the rotation speed to 150 rpm / min. After adding the weighed potassium persulfate to each conical flask, immediately add the corresponding iron-vanadium bimetallic sulfide nanomaterials according to the markings to activate the potassium persulfate and generate active oxide species to remove bisphenol A from the solution. Take samples at the set time points, test and record the concentration of bisphenol A, and process the data results. Example

[0034] (1) Weigh 10 mg of the iron-vanadium bimetallic sulfide nanomaterial obtained in Example 1 for the oxidation and removal of endocrine disruptors in water, weigh 2 mmol of potassium persulfate, measure 100 mL of 20 mg / L bisphenol A and transfer it to a 250 mL conical flask, and label it.

[0035] (2) Place the conical flasks containing pollutants and marked in a constant temperature shaker. Set the temperature to 25℃ and the rotation speed to 150 rpm / min. After adding the weighed potassium persulfate to each conical flask, add iron-vanadium bimetallic sulfide nanomaterials to activate the potassium persulfate to generate active oxides to remove bisphenol A from the solution. Take samples at the set time points, test and record the concentration of bisphenol A, and process the data results.

[0036] (3) Collect the iron-vanadium bimetallic sulfide nanomaterials after step (2) of Example 5, and wash them three times with ultrapure water and anhydrous ethanol, and then vacuum dry them at 60°C to obtain iron-vanadium bimetallic sulfide nanomaterials after one use; perform steps (1) and (2) on the used iron-vanadium bimetallic sulfide nanomaterials.

[0037] (4) Collect the iron-vanadium bimetallic sulfide nanomaterials after step (3) of Example 5, and wash them three times with ultrapure water and anhydrous ethanol, and then vacuum dry them at 60°C to obtain iron-vanadium bimetallic sulfide nanomaterials after secondary use; perform steps (1) and (2) on the used iron-vanadium bimetallic sulfide nanomaterials.

[0038] (5) Collect the iron-vanadium bimetallic sulfide nanomaterials obtained at the end of step (2) of Example 5, and wash them three times with ultrapure water and anhydrous ethanol, and then vacuum dry them at 60°C to obtain iron-vanadium bimetallic sulfide nanomaterials after three uses; perform steps (1) and (2) on the used iron-vanadium bimetallic sulfide nanomaterials.

[0039] The above description is merely a partial embodiment of the present invention and is not intended to limit the invention in any way. After reading the above, those skilled in the art will readily understand various modifications and substitutions to the present invention. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. A bimetallic iron-vanadium sulfide nanomaterial for the oxidative removal of endocrine disruptors in water, characterized in that: It has a large specific surface area, a high proportion of vanadium disulfide phase with 1T metal content, and good reusability.

2. The method for preparing iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water, as described in claim 1, is characterized by: cold water bath ultrasonic treatment of the precursor solution, hydrothermal reaction, and vacuum drying.

3. A method for preparing iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water, characterized in that, The preparation method includes the following steps: (1) Dissolve ammonium metavanadate, thioacetamide and 30% ammonia in deionized water by stirring, then add an appropriate amount of L-ascorbic acid and stir to dissolve to prepare solution A. The molar ratio of ammonium metavanadate and thioacetamide is 1:5, and the amount of 30% ammonia is 2~4 mL. (2) Dissolve ferrous sulfate heptahydrate, sodium thiosulfate pentahydrate and sulfur powder in deionized water to prepare solution B, wherein the molar ratio of ferrous sulfate heptahydrate, sodium thiosulfate pentahydrate and sulfur powder is 1:1:1; (3) Mix solutions A and B to obtain a precursor solution of iron-vanadium bimetallic sulfide, transfer it to a Teflon liner for ultrasonic treatment, and then put it into a stainless steel autoclave for hydrothermal reaction. After the reaction is completed, the product is washed and vacuum dried to obtain the iron-vanadium bimetallic sulfide nanomaterial for the oxidation removal of endocrine disruptors in water.

4. The method for preparing iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water according to claim 3, characterized in that, In steps (1) and (2), the stirring time is 15 to 30 minutes.

5. The method for preparing iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water according to claim 3, characterized in that, In step (3), the ultrasonic treatment has a power of 100~200 W, a frequency of 49KHz, a temperature of 25±2℃, and a treatment time of 15±2 min.

6. The method for preparing iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water according to claim 1, characterized in that, In step (3), the temperature of the hydrothermal reaction is 160±0.5 ℃ and the reaction time is 20±0.5 h.

7. The method for preparing iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water according to claim 1, characterized in that, In step (3), the product is washed three times each with deoxygenated deionized water and anhydrous ethanol, and the vacuum drying temperature is 60±5 ℃ and the vacuum drying time is 10±2 h.

8. The method for preparing iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water according to claim 1, characterized in that, In step (3), the product is washed three times each with deionized water and anhydrous ethanol.

9. The method for preparing iron-vanadium bimetallic sulfide nanomaterials for the oxidative removal of endocrine disruptors in water according to claim 1, characterized in that, In step (3), the vacuum drying temperature is 60±5 ℃ and the vacuum drying time is 10±2 h.

10. The application of the iron-vanadium bimetallic sulfide nanomaterial for the oxidative removal of endocrine disruptors in water as described in any one of claims 1 to 8, characterized in that: Catalyst materials used in the advanced oxidation of persulfates.

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