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CN-122006753-A - Preparation and application of iron-vanadium bimetallic sulfide nano material for removing endocrine disruptors in water body through oxidation

CN122006753ACN 122006753 ACN122006753 ACN 122006753ACN-122006753-A

Abstract

The invention discloses a preparation method of an iron-vanadium bimetallic sulfide nano material for removing endocrine disruptors in a water body by oxidation and application of the iron-vanadium bimetallic sulfide nano material in advanced oxidation, wherein the preparation method comprises the steps of firstly mixing a precursor solution of vanadium disulfide with a precursor solution of ferrous disulfide to obtain a precursor of the iron-vanadium bimetallic sulfide; and carrying out water bath ultrasonic treatment on the precursor, carrying out hydrothermal reaction, and washing and vacuum drying after the reaction is finished to obtain the powdery iron-vanadium bimetallic sulfide. The Fe-V bimetallic sulfide nano material prepared by the method has stronger persulfate catalytic activation capability than that of single ferrous disulfide and vanadium disulfide due to the synergistic effect between the bimetallic, the degradation reaction rate constant under the same reaction condition is 43 times or 2.1 times that of single Fe or V sulfide, and meanwhile, the Fe-V bimetallic sulfide has good pH adaptability and reusability.

Inventors

  • WU LEIXIANG
  • ZHOU YIAN
  • KOU WENJING
  • LIU XIAOBO
  • WANG ZHUOWEI
  • ZHANG PANWEI
  • WANG XIAOLONG
  • CHEN FEI
  • LIU WEIQIAO
  • LIU ZIMENG
  • Xia Minhui

Assignees

  • 中国水利水电科学研究院

Dates

Publication Date
20260512
Application Date
20260205

Claims (10)

  1. 1. The Fe-V bimetallic sulfide nano material for removing endocrine disruptors in water is characterized by large specific surface area, high metal 1T phase vanadium disulfide ratio and good reusability.
  2. 2. The method for preparing the iron-vanadium bimetallic sulfide nano material for removing endocrine disruptors in water body oxidation according to claim 1 is characterized by comprising the steps of precursor solution cold water bath ultrasonic treatment, hydrothermal reaction and vacuum drying.
  3. 3. The preparation method of the iron-vanadium bimetallic sulfide nano material for removing endocrine disruptors in water body by oxidation is characterized by comprising the following steps of: (1) Stirring and dissolving ammonium metavanadate, thioacetamide and 30% ammonia water in deionized water, adding a proper amount of L-ascorbic acid, stirring and dissolving to prepare a solution A, wherein the molar ratio of the ammonium metavanadate to the thioacetamide is 1:5, and the 30% ammonia water is 2-4 mL; (2) Stirring and dissolving ferrous sulfate heptahydrate, sodium thiosulfate pentahydrate and sulfur powder in deionized water to prepare a solution B, wherein the molar ratio of the ferrous sulfate heptahydrate, the sodium thiosulfate pentahydrate and the sulfur powder is 1:1:1; (3) Mixing the solution A and the solution B to obtain an iron-vanadium bimetallic sulfide precursor solution, transferring the precursor solution into a Teflon liner for ultrasonic treatment, then filling the precursor solution into a stainless steel autoclave for hydrothermal reaction, and washing and vacuum drying a product after the reaction is completed to obtain the iron-vanadium bimetallic sulfide nano material for removing endocrine disruptors in a water body.
  4. 4. The method for preparing the iron-vanadium bimetallic sulfide nano material for removing endocrine disruptors in a water body according to claim 3, wherein in the steps (1) and (2), the stirring time is 15-30 min.
  5. 5. The method for preparing iron-vanadium bimetallic sulfide nano-material for removing endocrine disruptors in water according to claim 3, wherein in the step (3), the ultrasonic treatment is performed at a power of 100-200W, a frequency of 49 KHz, a temperature of 25+/-2 ℃ and a treatment time of 15+/-2 min.
  6. 6. The method for preparing iron-vanadium bimetallic sulfide nanomaterial for oxidation removal of endocrine disruptors in a water body according to claim 1, wherein in the step (3), the hydrothermal reaction is performed at 160±0.5 ℃ for 20±0.5 h.
  7. 7. The method for preparing iron-vanadium bimetallic sulfide nanomaterial for oxidation removal of endocrine disruptors in a water body according to claim 1, wherein in step (3), the product is washed three times with deoxygenated deionized water and absolute ethanol, respectively, the vacuum drying temperature is 60±5 ℃, and the vacuum drying time is 10±2h.
  8. 8. The method for preparing iron vanadium bimetallic sulfide nanomaterial for oxidation removal of endocrine disruptors in a water body according to claim 1, wherein in step (3), the product washing is three times each using deionized water and absolute ethanol, respectively.
  9. 9. The method for preparing iron-vanadium bimetallic sulfide nano-material for oxidation removal of endocrine disruptors in a water body according to claim 1, wherein in the step (3), the vacuum drying temperature is 60±5 ℃ and the vacuum drying time is 10±2 h.
  10. 10. The application of the iron-vanadium bimetallic sulfide nano material for removing endocrine disruptors in water body through oxidation according to any one of claims 1-8, which is characterized by being applied to a catalyst material for persulfate advanced oxidation.

Description

Preparation and application of iron-vanadium bimetallic sulfide nano material for removing endocrine disruptors in water body through oxidation Technical Field The invention relates to preparation and application of an iron-vanadium bimetallic sulfide nano material for removing endocrine disruptors in water body by oxidation, belonging to the field of advanced oxidation nano catalysts. Background In recent years, the large-scale use of endocrine disruptors has led to their wide spread in the environment, and frequency has been detected in the environments such as surface water and soil. Endocrine disruptors can cause a range of health problems, particularly damage to the reproductive and immune systems, such as those that cause diabetes, cancer, and childhood neurodevelopmental disorders. Therefore, development of a highly efficient bisphenol a degradation technology is urgent. Advanced Oxidation Processes (AOPs) have been demonstrated to be effective BPA removal techniques that produce strong oxidants to thoroughly decompose BPA, as compared to biological and physical processes. Among the numerous advanced oxidation technologies, advanced oxidation processes (SR-AOPs) based on sulfate radicals (SO 4•−) have been considered as an effective method for removing endocrine disruptors in wastewater due to their characteristic of generating SO 4•− by breaking the O-O bonds of peroxymonosulfate (PMS, HSO 5−) and peroxydisulfate (PDS, S 2O82−). SO 4•− has multiple advantages over other advanced oxidation processes (e.g., fenton and ozonization, etc.), such as higher redox potential, longer half-life, wider pH window, higher rate of formation, and higher selectivity and degradation efficiency for contaminants containing unsaturated bonds or aromatic rings. The technology can effectively convert organic pollutants in the water body into low-toxicity or even nontoxic molecules (such as H 2 O and CO 2). In recent years, various persulfate activation methods including thermal activation, ultraviolet irradiation, alkali activation, ultrasonic activation, and the like have come out successively, but these methods often require complicated equipment and consume high energy. In order to meet the requirements of sustainable development and low cost, researchers have explored carbon-based materials such as activated carbon, biochar and asphaltene as PMS activators for endocrine disruptors degradation. However, pure carbon materials have poor catalytic performance due to limited surface functional group types and weak anti-interference capability. Transition metals (such as iron, cobalt, nickel, copper, zinc and the like) are widely used for persulfate activation due to simple operation, mild temperature and pressure conditions and high activation efficiency, but homogeneous phase reaction has the defects of difficult control of metal ion release rate and the like, so that the practical application is greatly limited. In contrast, heterogeneous systems that rely on solid support active sites to initiate persulfate decomposition and form reactive oxygen species are of increasing interest, where iron-based catalysts are distinguished by their wide availability, low cost and high efficiency. Among them, pyrite (FeS 2) has been widely studied due to its low toxicity, abundant reserves, rich ferrous structure, and controllable release of ferrous iron. However, the catalytic activity and the regeneration rate of ferrous iron are slow, and the practical application requirements are difficult to meet. Transition metal sulfides with bimetal composite structures are attractive in advanced oxidation process application because of the improvement of physical and chemical properties and the synergistic effect among multiple components, and the synergistic effect among the bimetal can improve the catalytic activity and stabilize metal leaching. Vanadium disulfide is one of the transition metal sulfides, and is widely focused in the fields of lithium batteries or sodium batteries due to its unique interlayer spacing (0.57 nm) and metallic insulator transition characteristics. More interestingly, the different phase compositions of vanadium disulphide (metallic 1T phase and semiconducting 2H phase) have a significant impact on their catalytic activity. The 1T-phase vanadium disulfide has rich catalytic sites on the basal plane and the edge, and the layer edge sulfur sites have strong adsorption energy. Therefore, the transition from the semiconducting 2H phase to the metallic 1T phase can promote electron transport. However, so far, researches on the combination of ferrous disulfide and vanadium disulfide for persulfate activation are still reported. Therefore, the preparation of the iron-vanadium bimetallic composite material by a simple synthesis method has a broad prospect in persulfate activation. By utilizing the bridging effect and the synergistic effect between the two, the method is expected to cope with various environmental sustaina