A method of enhancing adsorption of intermediate species to improve removal of endocrine disrupting compounds from wastewater

Abstract

The present application relates to wastewater treatment technical field, specifically to a kind of method for improving endocrine disruptor removal in wastewater by strengthening intermediate species adsorption, it includes the following steps: providing Ce-Co3S 4‑x Nano catalyst and peroxymonosulfate;Ce-Co3S 4‑x Nano catalyst and peroxymonosulfate are added to the wastewater containing endocrine disruptor to be treated, and Fenton-like catalytic reaction is carried out under stirring condition, and endocrine disruptor in wastewater to be treated is degraded.The method can efficiently and stably remove endocrine disruptor in wastewater, and can achieve almost 99.9% removal rate of bisphenol A within 9min, and 99.6% removal rate of pentachloronitrobenzene within 12min.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, and in particular to a method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater. Background Technology

[0002] Endocrine disrupting chemicals (EDCs) are an emerging class of toxic substances defined as exogenous substances or mixtures that cause harmful health effects on organisms by interfering with the function of the endocrine system. EDCs enter the aquatic environment through multiple pathways, with higher concentrations found in ports near seas and lakes, as well as in industrially and agriculturally developed areas. Furthermore, accidental spills of industrial waste and chemicals during transportation threaten aquatic environments and marine animals. EDCs can cause certain endocrine disorders, and even at trace concentrations, their persistence in water is sufficient to induce endocrine disturbances in many species. Therefore, effective management of endocrine disrupting chemicals in wastewater before discharge is crucial.

[0003] Peroxymonosulfate (PMS) advanced oxidation processes (AOPs) are one of the most effective methods for removing recalcitrant organic pollutants such as endocrine disruptors from wastewater, and the efficient generation of highly reactive intermediates is crucial. This involves interaction with reactive free radicals (such as SO42-). ·- Unlike ·OH, high-valence metals have advantages such as long lifespan, high steady-state concentration, and are not easily removed by coexisting substances (such as natural organic matter). At the same time, high-valence metals play an important role in enzyme catalysis in life processes and selective oxidation in organic synthesis. IV =O compared to Fe IV =O and Mn IV =O has a stronger oxidizing ability. According to the "oxygen wall" rule, when the number of electrons in the 3d orbitals of transition metals is greater than 4, it will hinder their binding with terminal oxygen groups, while Co... IV The number of electrons in the 3d orbital is 5, making it difficult to generate Co. IV =O. Summary of the Invention

[0004] Given the need to overcome the limitations of existing AOPs technologies in removing endocrine disruptors, Co IV To address the bottleneck of difficult O generation, this invention proposes an asymmetric Ce-Co3S... 4-x Strategies to enhance the delocalization of Co3d orbital electrons through configuration: via Co3S 4-x The surface is constructed with Co sites that have unique defective S coordination, thereby promoting electron delocalization, reducing the number of electrons filling the Co3d orbitals, making them easier to coordinate with terminal oxygen, and thermodynamically more favorable for PMS activation and Co. IV = *O-Ce V The purpose of this invention is to provide a method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater, aiming to solve the problem of poor removal efficiency of endocrine disruptors from wastewater by existing processes.

[0005] The technical solution of the present invention is as follows:

[0006] A method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater, comprising the following steps:

[0007] Provide Ce-Co3S 4-x Nanocatalysts and peroxymonosulfate, where x is 1-3;

[0008] The Ce-Co3S 4-x Nanocatalysts and peroxymonosulfate are added to wastewater containing endocrine disruptors and mixed to carry out a Fenton-like catalytic reaction to degrade the endocrine disruptors in the wastewater.

[0009] In some embodiments of the present invention, the Ce-Co3S 4-x The mass ratio of nanocatalyst to peroxymonosulfate is 1-20:5-25.

[0010] In some embodiments of the present invention, the concentration of endocrine disruptors in the wastewater to be treated is 1-50 mg / L.

[0011] In some embodiments of the present invention, the endocrine disruptor is one or both of pentachloronitrobenzene and bisphenol A.

[0012] In some embodiments of the present invention, the Ce-Co3S 4-x The preparation of nanocatalysts includes the following steps:

[0013] Cobalt salt, 2-methylimidazole and surfactant were dissolved in a solvent and reacted to obtain ZIF-67 nanocubes;

[0014] The ZIF-67 nanocubes and the vulcanizing agent were dispersed in a solvent and reacted to obtain an intermediate product;

[0015] The intermediate product was calcined to prepare Co3S. 4-x Porous nanobox catalysts;

[0016] The Co3S 4-x Porous nanobox catalyst and cerium salt are dispersed in ethanol and thoroughly mixed, magnetically stirred, then a reducing agent is added, and the Ce-Co3S is collected by centrifugation. 4-x Nanocatalysts.

[0017] In an embodiment of the present invention, the reaction conditions for preparing ZIF-67 nanocubes are: room temperature stirring reaction, and centrifugation, with a centrifugation speed of 2000-8000 rpm and a centrifugation time of 3-10 min.

[0018] In some embodiments of the present invention, the surfactant is one of polyvinylpyrrolidone, sodium dodecylbenzenesulfonate, triethanolamine, and hexadecyltrimethylammonium bromide.

[0019] In some embodiments of the present invention, the reaction conditions during the preparation of the intermediate product are: reaction at 25-160°C for 1-18 hours; the process also includes separating, purifying and drying the product after the reaction; the drying temperature is 50-70°C.

[0020] In some embodiments of the present invention, the calcination treatment is carried out under an inert atmosphere at 260–500°C (more preferably 200–500°C) for 0.5–5 h (more preferably 1–5 h); the treatment also includes pulverizing the product.

[0021] In some embodiments of the present invention, the calcination process is carried out in a vacuum tube furnace.

[0022] In some embodiments of the present invention, the vulcanizing agent is one of thiourea, sodium sulfide, sublimed sulfur, thioacetamide, and sulfur powder.

[0023] In some embodiments of the present invention, the cobalt salt is selected from one or more of nitrates, sulfates and chlorides.

[0024] In some embodiments of the present invention, the reducing agent is one or more of oxalic acid, potassium borohydride, sodium borohydride and hydrogen; the concentration of the reducing agent is 0.1 to 1 mol / L.

[0025] In some embodiments of the present invention, the cerium salt is cerium nitrate and / or cerium chloride.

[0026] Beneficial effects: This invention will utilize Ce-Co3S 4-x Nanocatalysts and peroxymonosulfate (PMS) are used to remove endocrine disruptors from wastewater. The strong chemical coordination coupling between rare earth metal Ce single atoms and nano-cobalt sulfide facilitates the removal of endocrine disruptors via Co. II / III With Ce III / IV The repeated redox cycles between multiple valence states lead to the formation of Ce-S-Co chemical coordination, which enhances the electron delocalization of Co atoms, strengthens the Bader charge transfer at the cobalt center, increases the PMS adsorption energy, and reduces the generation of key intermediate species of reactive oxygen species (intermediates refer to: Co(IV) = *The energy barrier of O-Ce(V) conforms to the Sabatier principle, a well-established theory of heterogeneous catalysis that reveals the optimal activity of a catalyst should be achieved by having a moderate binding strength with the key adsorbate to balance the coverage of the adsorbed product and promote adsorption-desorption efficiency. This invention enhances the catalytic activity by optimizing the adsorption / desorption energy barrier of reaction intermediate species during the catalytic process, thereby increasing the formation rate of intermediates that form key reactive oxygen species. This Ce-Co3S… 4-x Nanocatalysts incorporate Ce single atoms into Co3S 4-x In the crystal lattice, asymmetric defects S vacancies are formed, taking advantage of Ce's relatively low electronegativity, as well as Co and defect sulfur (S). 4-x The dpf orbital coupling effect between the Ce and Co (IV) atoms promotes the formation of a dual-reaction active center system with electron-rich Co(IV)-S-Ce(V) centers. Furthermore, the presence of Ce-Co metal ions in the system results in a positively charged catalyst surface, which is beneficial for the adsorption of PMS anions under neutral conditions. Therefore, this invention can utilize electrostatic attraction and the synergistic effect of the dual-reaction centers to enable key intermediates on the catalyst surface to act as electron transfer stations, facilitating rapid electron transfer between the Ce-Co active centers and persulfate, and promoting the adsorption of Ce-Co anions. 3+ / 4+ With Co 2+ / 3+ The multivalent cycle fully activates PMS, rapidly decomposing endocrine disruptors. This invention's method can efficiently and stably remove endocrine disruptors from wastewater, achieving a removal rate of almost 99.9% for bisphenol A within 9 minutes and a removal rate of 99.6% for pentachloronitrobenzene within 12 minutes. Attached Figure Description

[0027] To make the content of this invention easier to understand, the invention will be further described in detail below with reference to specific embodiments and accompanying drawings, wherein...

[0028] Figure 1 The catalysts prepared in Example 1 and Comparative Examples 1-3 of this invention are used in the removal of bisphenol A by activated PMS. t / C0.

[0029] Figure 2 The catalysts prepared in Example 1 and Comparative Examples 1-3 of this invention are used in the removal of pentachloronitrobenzene by activated PMS. t / C0.

[0030] Figure 3 This is a theoretical adsorption model image of the catalyst prepared in the embodiments of the present invention with peroxymonosulfate (PMS).

[0031] Figure 4 This refers to the cycling of high-valence metals involved in the catalyst prepared in the embodiments of the present invention. Detailed Implementation

[0032] This invention provides a method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0033] Peroxymonosulfate (PMS) is thermodynamically considered a strong oxidant, but its direct reaction kinetics with most pollutants are too slow. Therefore, developing efficient catalysts to activate PMS and generate reactive species (ROS) is crucial for accelerating the oxidation of organic pollutants. In homogeneous catalytic systems, metal ions in aqueous solutions can react effectively with PMS, but certain limitations hinder its practical application. As an alternative, heterogeneous PMS activators have been extensively studied. However, the spatial packing of traditional cobalt oxide particles limits the number of interfacial active sites and electron transfer efficiency in the catalyst, making the actual catalytic performance of heterogeneous catalysts in advanced oxidation processes (AOPs) less than ideal.

[0034] Based on this, the present invention provides a method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater, such as... Figure 1 As shown, it includes the following steps:

[0035] S10, provides Ce-Co3S 4-x Nanocatalysts and peroxymonosulfate; x is 1-3;

[0036] S20, the Ce-Co3S 4-x Nanocatalysts and peroxymonosulfate were added to wastewater containing endocrine disruptors and carried out a Fenton-like catalytic reaction under stirring conditions to degrade the endocrine disruptors in the wastewater.

[0037] In this invention, the Ce-Co3S 4-x (Sulfur-rich defective cerium single-atom anchored cobalt sulfide nanobox) nanocatalysts possess a unique electronic structure and maximum atom utilization efficiency, exhibiting excellent effects on the selective generation of free radicals through PMS activation. This invention utilizes Ce-Co3S... 4-x Nanocatalysts and peroxymonosulfate (PMS) are used to remove endocrine disruptors from wastewater. The strong chemical coordination coupling between rare earth metal Ce single atoms and nano-cobalt sulfide facilitates the removal of endocrine disruptors via Co. II / III With Ce III / IVThe repeated redox cycles between multiple valence states lead to the formation of Ce-S-Co chemical coordination, which enhances the electron delocalization of Co atoms, strengthens the Bader charge transfer at the cobalt center, increases the PMS adsorption energy, and reduces the generation of key intermediates of reactive oxygen species (intermediate refers to: Co(IV) = * The energy barrier of O-Ce(V) conforms to the Sabatier principle, a well-established theory of heterogeneous catalysis that reveals the optimal activity of a catalyst should be achieved by having a moderate binding strength with the key adsorbate to balance the coverage of the adsorbed product and promote adsorption-desorption efficiency. This invention enhances the catalytic activity by optimizing the adsorption / desorption energy barrier of reaction intermediate species during the catalytic process, thereby increasing the formation rate of intermediates that form key reactive oxygen species. This Ce-Co3S… 4-x Nanocatalysts incorporate Ce single atoms into Co3S 4-x In the crystal lattice, asymmetric defects S vacancies are formed, taking advantage of Ce's relatively low electronegativity, as well as Co and defect sulfur (S). 4-x The dpf orbital coupling effect between the Ce and Co (IV) atoms promotes the formation of a dual-reaction active center system with electron-rich Co(IV)-S-Ce(V) centers. Furthermore, the presence of Ce-Co metal ions in the system results in a positively charged catalyst surface, which is beneficial for the adsorption of PMS anions under neutral conditions. Therefore, this invention can utilize electrostatic attraction and the synergistic effect of the dual-reaction centers to enable key intermediates on the catalyst surface to act as electron transfer stations, facilitating rapid electron transfer between the Ce-Co active centers and persulfate, and promoting the adsorption of Ce-Co anions. 3+ / 4+ With Co 2+ / 3+ The multivalent cycle fully activates PMS, rapidly decomposing endocrine disruptors. This invention's method can efficiently and stably remove endocrine disruptors from wastewater, achieving a removal rate of almost 99.9% for bisphenol A within 9 minutes and a removal rate of 99.6% for pentachloronitrobenzene within 12 minutes.

[0038] In some embodiments, the Ce-Co3S 4-x The mass ratio of nanocatalyst to peroxymonosulfate is 1-20:5-25. This example demonstrates through experiments that when Ce-Co3S... 4-x When the mass ratio of nanocatalyst to peroxymonosulfate is 1-20:5-25, Ce-Co3S 4-x Nanocatalysts can fully activate peroxymonosulfate, thereby inducing PMS to acquire a high redox potential, thus achieving more efficient degradation and removal of secretion interferences.

[0039] In some embodiments, the concentration of endocrine disruptors in the wastewater to be treated is 1-50 mg / L, but is not limited thereto.

[0040] In some embodiments, the endocrine disruptor is one or both of pentachloronitrobenzene and bisphenol A, but is not limited thereto.

[0041] In some embodiments, the Ce-Co3S 4-x The preparation of the nanocatalyst includes the following steps: dissolving cobalt salt, 2-methylimidazole, and a surfactant in deionized water, stirring the reaction at room temperature, and collecting the product ZIF-67 nanocubes by centrifugation; dispersing the ZIF-67 nanocubes and a sulfiding agent in ethanol, reacting at 25-160℃ for 1-18 hours, separating, purifying, and drying the reaction product to obtain an intermediate product; and calcining the intermediate product in an inert atmosphere in a vacuum tube furnace to prepare Co3S. 4-x Porous nanobox catalyst; the Co3S 4-x Porous nanobox catalyst and cerium salt are dispersed in ethanol and thoroughly mixed, magnetically stirred, then a reducing agent is added, and the Ce-Co3S is collected by centrifugation. 4-x Nanocatalysts.

[0042] The Ce-Co3S provided by this invention 4-x The preparation method of nanocatalysts is low-cost, reproducible, and stable, and the catalytic materials exhibit excellent catalytic performance, good reusability, and are environmentally friendly. This invention utilizes anions (O2) to... - -S2 - ) and cations (Co) 2+ -Ce 3+ A two-step exchange procedure anchors single cerium atoms in situ within a cobalt sulfide nanobox catalyst rich in sulfur vacancy defects. This single-site embedding method generates abundant asymmetric defect structures, effectively increasing the exposure of metal active sites and activating their catalytic (redox) performance by altering the electron delocalization and energy distribution of cobalt sites. Furthermore, the constructed hierarchical, ordered hollow porous structure significantly improves the utilization efficiency of catalytic active sites, enhances the mass transfer rate between reaction substrates and catalytic products at the catalyst interface, and solves the problem of deeply buried active centers within the catalyst being unable to participate in catalytic reactions, further improving catalytic performance.

[0043] This invention utilizes a Ce-Co bimetallic center formed through a two-step ion exchange process, which facilitates the adsorption of PMS anions. Ce has relatively low electronegativity, and the electron compensation effect between Co and sulfide ions leads to the formation of cobalt electron-rich centers. PMS molecules are contacted on the catalyst surface through vacancy adsorption and reduction, inducing the breaking and activation of PMS oxygen-oxygen bonds to form O-Co-S. v -Ce, then forms *OO, which further desorbs to generate a large amount of O2· -This differs from traditional Co-based catalysts that activate PMS via a non-radical (singlet oxygen) pathway. This invention primarily utilizes a radical pathway to produce superoxide radicals. Furthermore, its nanoscale cavities provide a suitable environment for the catalytic reaction, fully exposing sites and enhancing mass transfer. This facilitates improved host-guest contact and tandem radical catalysis, enabling the free radicals generated from the catalytic PMS reaction to oxidize organic pollutants locally.

[0044] In some embodiments, the cobalt salt is one or more of cobalt nitrate, cobalt sulfate, and cobalt chloride, but is not limited thereto; the concentration of the cobalt salt is 0.1 mM-3 mM.

[0045] In some embodiments, the surfactant is one or more of polyvinylpyrrolidone, sodium dodecylbenzenesulfonate, triethanolamine, and hexadecyltrimethylammonium bromide, but is not limited thereto.

[0046] In some embodiments, the step of stirring the reaction under a preset temperature condition and centrifuging to collect the product ZIF-67 nanocubes, wherein the preset temperature condition is 20-160°C, but not limited to this; the centrifugation speed is 1000-8000 rpm, and the centrifugation time is 1-10 min. In this embodiment, since nanocubes of different sizes can be synthesized at different reaction temperatures, and the longer the reaction time, the smaller the particle size, the more likely the nanocrystals are to agglomerate. This is because, as the reaction time increases, the particle size of the already formed metal nanoparticles gradually decreases, which easily leads to the agglomeration of nanocrystals; and when the temperature rises, the mixture and cobalt compound are reduced simultaneously, causing the formed cobalt nanocubes and cobalt nanoparticles to separate. Therefore, by using a simple solvent reaction and selecting a specific temperature and time in a dimethylimidazole system, uniformly grown ZIF-67 nanocubes of different sizes can be prepared.

[0047] In some embodiments, the vulcanizing agent is one of thiourea, sodium sulfide, sublimed sulfur, thioacetamide, and sulfur powder, but is not limited thereto. The amount of vulcanizing agent used is 1.0 mM-20.0 mM. In this embodiment, the crystal type and hollow structure of cobalt sulfide can be further controlled by controlling the amount of vulcanizing agent and the time. The amount of vulcanizing agent is used to control the O 2- -S 2- Degree of ion exchange. The more sulfiding agent, the more oxygen is exchanged. Based on the gradual increase of sulfur content, it can be divided into CoS, CoS2, Co3S4 and Co9S8 in sequence.

[0048] In some embodiments, the intermediate product is calcined in a vacuum tube furnace under an inert atmosphere at a temperature of 260-500°C for 1-5 hours. The inert atmosphere is one or more of nitrogen, helium, or argon; nitrogen is preferred due to its availability and cost. In this embodiment, the calcination temperature and time affect crystal formation and control the porosity of the nanobox; excessively high or low temperatures will not yield the desired material. The formation mechanism of the porous nanobox catalyst is attributed to the non-equilibrium shrinkage and adhesion forces generated during the thermal decomposition of the solid precursor due to a large temperature gradient. Specifically, the newly formed outermost shell attempts to maintain its outer diameter and resist further shrinkage, while the inner precursor shrinks rapidly due to the loss of organic components at gradually increasing temperatures. This is called heterogeneous shrinkage. The core-shell interface is subjected to two opposing forces: cohesive forces (σco) from the core and adhesive forces (σad) from the rigid shell. The former promotes inward shrinkage of the core, while the latter prevents it. When σco < σad, the inner core contracts outward to the pre-formed outer shell, thus forming a hollow structure. As the heating temperature increases, σco exceeds σad. Therefore, the inner core contracts inward, separating from the hard shell, forming an eggshell structure. When the heating temperature increases further, the ultrafine structural units aggregate together, thus forming a porous structure. This embodiment experimentally demonstrates that porous nanobox catalysts can be prepared when the calcination temperature is between 260-500℃ and the calcination time is between 1-5 hours.

[0049] In some embodiments, the reducing agent is one or more of oxalic acid, potassium borohydride, sodium borohydride, and hydrogen, but is not limited thereto.

[0050] The present invention will be further explained and illustrated below through specific embodiments:

[0051] Example 1

[0052] Ce-Co3S 4-x The preparation of nanocatalysts includes the following steps:

[0053] Preparation of S1 and ZIF-67 nanocubes:

[0054] First, 0.6 mM Co(NO3)2·6H2O was dissolved in 10 mL of deionized water containing 6 mg of hexadecyltrimethylammonium bromide. Then, this solution was rapidly injected into 70 mL of an aqueous solution containing 51 mM 2-methylimidazole. The mixture was stirred at 25 °C for 30 min. The product was collected by centrifugation at 4000 rpm for 5 min, washed several times with ethanol, and finally dried in a vacuum oven at 60 °C for 12 h to collect the ZIF-67 nanocubes.

[0055] Preparation of S2 and Co3S4 hollow nanocubes:

[0056] The prepared ZIF-67 cubes and 1.8 mM thioacetamide were dispersed in 30 mL of ethanol. The solution was transferred to a Teflon-lined stainless steel autoclave and heated in an oven at 160 °C for 10 h. The precipitate was collected by centrifugation and washed with ethanol. The precipitate was annealed in a N2 atmosphere at 350 °C for 2 h (3 °C / min) to obtain hollow Co3S4 nanocubes.

[0057] S3, Ce-Co3S 4-x Preparation of hollow nanocubes:

[0058] Hollow Co3S4 nanocubes (10 mg dispersed in 50 mL of ethanol) and 0.02 mM Ce(NO3)3·6H2O (dispersed in 50 mL of ethanol) were thoroughly mixed and magnetically stirred at 60 °C for 10 h. Sodium borohydride was then added and reacted for another hour. The Ce-Co3S4 nanocubes were collected by centrifugation. 4-x Wash with ethanol multiple times and then dry.

[0059] Example 2

[0060] Ce-Co3S 4-x The preparation of nanocatalysts includes the following steps:

[0061] Preparation of S1 and ZIF-67 nanocubes:

[0062] First, 1 mM Co(NO3)2·6H2O was dissolved in 30 mL of deionized water containing 4 mg sodium dodecylbenzenesulfonate. Then, this solution was rapidly injected into 70 mL of an aqueous solution containing 55 mM 2-methylimidazole. The mixture was stirred at 25 °C for 30 min. The product was collected by centrifugation at 4200 rpm for 8 min, washed several times with ethanol, and finally dried in a vacuum oven at 60 °C for 12 h to collect the ZIF-67 nanocubes.

[0063] Preparation of S2 and Co3S4 hollow nanocubes:

[0064] The prepared ZIF-67 cubes and 3.0 mM thiourea were dispersed in 30 mL of ethanol. The solution was transferred to a Teflon-lined stainless steel autoclave and heated in an oven at 160 °C for 10 h. The precipitate was collected by centrifugation and washed with ethanol. The precipitate was annealed in a N2 atmosphere at 350 °C for 2 h (3 °C / min) to obtain hollow Co3S4 nanocubes.

[0065] S3, Ce-Co3S 4-x Preparation of hollow nanocubes:

[0066] Hollow Co3S4 nanocubes (10 mg dispersed in 50 mL of ethanol) and 0.05 mM Ce(NO3)3·6H2O (dispersed in 50 mL of ethanol) were thoroughly mixed and magnetically stirred at 60 °C for 10 h. Sodium borohydride was then added and reacted for another hour. The Ce-Co3S4 nanocubes were collected by centrifugation. 4-x Wash with ethanol multiple times and then dry.

[0067] Example 3

[0068] Ce-Co3S 4-x The preparation of nanocatalysts includes the following steps:

[0069] Preparation of S1 and ZIF-67 nanocubes:

[0070] First, 2.5 mM Co(NO3)2·6H2O was dissolved in 30 mL of deionized water containing 12 mg polyvinylpyrrolidone. Then, this solution was rapidly injected into 70 mL of an aqueous solution containing 60 mM 2-methylimidazole. The mixture was stirred at 25 °C for 30 min. The product was collected by centrifugation at 4600 rpm for 3 min, washed several times with ethanol, and finally dried in a vacuum oven at 60 °C for 12 h to collect the ZIF-67 nanocubes.

[0071] Preparation of S2 and Co3S4 hollow nanocubes:

[0072] The prepared ZIF-67 cubes and 3.5 mM sodium sulfide were dispersed in 30 mL of ethanol. The solution was transferred to a Teflon-lined stainless steel autoclave and heated in an oven at 160 °C for 10 h. The precipitate was collected by centrifugation and washed with ethanol. The precipitate was annealed in a N2 atmosphere at 350 °C for 2 h (3 °C / min) to obtain hollow Co3S4 nanocubes.

[0073] S3, Ce-Co3S 4-x Preparation of hollow nanocubes:

[0074] Hollow Co3S4 nanocubes (10 mg dispersed in 50 mL of ethanol) and 0.15 mM Ce(NO3)3·6H2O (dispersed in 50 mL of ethanol) were thoroughly mixed and magnetically stirred at 60 °C for 10 h. Sodium borohydride was then added and reacted for another hour. The Ce-Co3S4 nanocubes were collected by centrifugation. 4-x Wash with ethanol multiple times and then dry.

[0075] Comparative Example 1

[0076] Synthesis of Co3S4 Hollow Nanoboxes

[0077] The prepared ZIF-67 cubes and 1.8 mM thioacetamide were dispersed in 80 mL of ethanol. The solution was transferred to a Teflon-lined stainless steel autoclave and heated in an oven at 160 °C for 10 h. The precipitate was collected by centrifugation and washed with ethanol. The precipitate was annealed in a N2 atmosphere at 350 °C for 2 h (3 °C / min) to obtain hollow Co3S4 nanocubes.

[0078] Comparative Example 2

[0079] Synthesis of Co3S4 nanoparticles

[0080] 1 mM Co(NO3)2·6H2O and 3.2 mM thioacetamide were dispersed in 80 mL of ethanol. The solution was transferred to a Teflon-lined stainless steel autoclave and heated in an oven at 160 °C for 10 h. The precipitate was collected by centrifugation and washed with ethanol. The precipitate was annealed at 350 °C in a N2 atmosphere for 2 h (3 °C / min) to obtain hollow Co3S4 nanoparticles.

[0081] Comparative Example 3

[0082] Synthesis of Co3O4 nanoparticles

[0083] First, 0.888 g of sodium hydroxide was dissolved in 14 mL of deionized water, then mixed with a Co(NO3)2·6H2O solution (12.8 g of salt in 30 mL of water), and finally transferred to an 80 mL Teflon-lined stainless steel autoclave. The mixture was then heated at 180 °C for 12 h. A black precipitate was obtained, which was washed repeatedly by centrifugation with deionized water, dried overnight at 60 °C, and finally heat-treated in air at 550 °C for 2 h at a heating rate of 1 °C per minute to obtain Co3O4 nanoparticles.

[0084] Test Example 1

[0085] Catalytic degradation test:

[0086] A catalyst-activated PMS pollutant removal experiment was conducted at 25℃. The method for the catalyst-activated PMS pollutant removal experiment was as follows: 50 mL of pollutant aqueous solution was placed in a 150 mL beaker, with a pollutant concentration of 10 mg / L. 5 mg of catalyst and 1 mM PMS were added to the pollutant aqueous solution at 25℃. The catalyst was one of the sulfur-rich defective cerium single-atom doped cobalt sulfide nanobox catalysts prepared in Example 1. A Fenton-like catalytic reaction was carried out under stirring conditions to ensure the uniformity of contact between the catalyst and organic pollutant molecules. Every once in a while, 1 mL of the reaction solution was taken out, diluted by half, and filtered through a 0.22 μm organic filter. The concentration of residual pollutants in the reaction solution was detected by ultraviolet spectrophotometer. The degradation efficiency of pollutants was calculated according to formula (1).

[0087] Formula (1): Degradation efficiency (%) = (1-C) t / C0)×100%, where C0 is the initial concentration of pollutants in the water, C t This represents the concentration of residual pollutants in the water after degradation.

[0088] Figure 1 Using bisphenol A (BPA), a common and persistent micropollutant in water, as the research object, the effects of Ce-Co3S on the degradation of bisphenol A (BPA) were investigated. 4-x The catalytic activity of the catalyst for PMS. From Figure 1 The results show that hollow porous Ce-Co3S 4-x The nanobox exhibited the most outstanding catalytic activity, achieving 99.9% BPA removal within 9 minutes. In contrast, the control samples (i.e., Co3O4 NPs in Comparative Example 1, Co3S4 NPs in Comparative Example 2, and Co3S4 NBs in Comparative Example 3) showed lower BPA removal rates.

[0089] Figure 2 Using pentachloronitrobenzene, a common and persistent micropollutant in water, as the research object, the effects of Ce-Co3S on water quality were investigated. 4-x The catalytic activity of the catalyst for PMS. From Figure 2 The results show that hollow porous Ce-Co3S 4-x The nanobox exhibited the most outstanding catalytic activity, achieving a 99.6% removal rate of pentachloronitrobenzene within 12 minutes. In contrast, the control samples (i.e., Co3O4 NPs in Comparative Example 1, Co3S4 NPs in Comparative Example 2, and Co3S4 NBs in Comparative Example 3) showed lower removal rates of pentachloronitrobenzene.

[0090] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater, characterized in that, Includes the following steps: Provide Ce-Co3S 4-x Nanocatalysts and peroxymonosulfate, where x is 1-3; The Ce-Co3S 4-x Nanocatalysts and peroxymonosulfate are added to wastewater containing endocrine disruptors and mixed to carry out a Fenton-like catalytic reaction to degrade the endocrine disruptors in the wastewater. The endocrine disruptor is one or both of pentachloronitrobenzene and bisphenol A; The Ce-Co3S 4-x The preparation of nanocatalysts includes the following steps: Cobalt salt, 2-methylimidazole and surfactant were dissolved in a solvent and reacted to obtain ZIF-67 nanocubes; The obtained ZIF-67 nanocubes and vulcanizing agent were dispersed in a solvent and reacted to obtain an intermediate product; The intermediate product was calcined to prepare Co3S. 4-x Porous nanobox catalysts; The Co3S 4-x The porous nanobox catalyst and cerium salt are dispersed and mixed in a solvent, and a reducing agent is added to react and obtain the Ce-Co3S. 4-x Nanocatalysts.

2. The method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater according to claim 1, characterized in that, The Ce-Co3S 4-x The mass ratio of nanocatalyst to peroxymonosulfate is 1-20:5-25.

3. The method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater according to claim 1, characterized in that, The concentration of endocrine disruptors in the wastewater to be treated is 1-50 mg / L.

4. The method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater according to claim 1, characterized in that, The surfactant is one of polyvinylpyrrolidone, sodium dodecylbenzenesulfonate, triethanolamine, and hexadecyltrimethylammonium bromide.

5. The method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater according to claim 1, characterized in that, The cobalt salt is selected from one or more of nitrates, sulfates and chlorides.

6. The method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater according to claim 1, characterized in that, The vulcanizing agent is one of thiourea, sodium sulfide, sublimed sulfur, thioacetamide, and sulfur powder.

7. The method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater according to claim 1, characterized in that, The calcination conditions are as follows: calcination temperature is 260-500℃, and calcination time is 1-5h.

8. The method for enhancing the adsorption of intermediate species to improve the removal of endocrine disruptors from wastewater according to claim 1, characterized in that, The cerium salt is cerium nitrate and / or cerium chloride; The reducing agent is one or more of oxalic acid, potassium borohydride, sodium borohydride, and hydrogen. The concentration of the reducing agent is 0.1–1 mol / L.

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