Method for treating organic pollutant wastewater by using tourmaline-molybdenum disulfide piezoelectric composite material to activate peracetic acid
By preparing tourmaline-molybdenum disulfide piezoelectric composite materials and constructing a stable 1T/2H heterostructure, the problems of poor stability and low catalytic activity of molybdenum disulfide materials in the prior art are solved. This enables efficient activation of peracetic acid and rapid degradation of organic pollutants, and has the advantages of simple process, convenient operation and green environmental protection.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HUNAN UNIV
- Filing Date
- 2026-02-10
- Publication Date
- 2026-05-15
AI Technical Summary
In the existing technology, the preparation method of molybdenum disulfide materials is complicated and the 1T phase has poor stability, resulting in low catalytic activity, difficulty in efficiently activating peracetic acid, difficulty in efficiently degrading organic pollutants, and poor reusability. Furthermore, tourmaline pretreatment may damage its crystal structure and affect the piezoelectric properties of the composite material.
A tourmaline-molybdenum disulfide piezoelectric composite material was used as a catalyst and prepared via a hydrothermal reaction. Tourmaline powder was used as an inducer and stabilizer, and its dosage was optimized to 20%–40% to construct a stable 1T/2H heterostructure. The thermoelectric effect of tourmaline was used to directionally induce the growth of the 1T phase of molybdenum disulfide, forming a highly efficient piezoelectric catalyst. Under ultrasonic treatment, peracetic acid was activated to generate strong oxidizing free radicals.
It achieves the degradation of organic pollutants with simple process, convenient operation, high treatment efficiency, good removal effect, strong adaptability, and green environmental protection, and is suitable for treating organic pollutant wastewater.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of piezoelectric catalytic material preparation and environmental pollution control technology, and relates to a method for treating organic pollutant wastewater by activating peracetic acid using tourmaline-molybdenum disulfide piezoelectric composite material. Background Technology
[0002] Piezoelectric catalysis provides a novel approach for the efficient activation of peracetic acid without external light or electrical excitation, but its performance is fundamentally limited by the charge dynamics efficiency of the piezoelectric material itself. Molybdenum disulfide (MoS2) possesses intrinsic piezoelectricity due to its non-centrosymmetric 2H phase structure; however, the single 2H phase is a semiconductor, exhibiting a fundamental drawback of rapid piezoelectric-induced charge recombination and slow migration, resulting in limited catalytic activity. Research indicates that constructing a 1T (metallic phase) / 2H (semiconductor phase) heterostructure with a built-in electric field can effectively promote the spatial separation of piezoelectric charges: the metallic 1T phase acts as a high-speed electron channel and forms a Schottky junction with the 2H phase, driving the directional transfer of electrons from the 2H phase to the 1T phase, thereby significantly improving piezoelectric catalytic efficiency.
[0003] However, existing mainstream methods for achieving 1T / 2H mixed phases (such as chemical lithiation intercalation or intense hydrothermal methods) have significant bottlenecks. These methods are typically complex and demanding, and the introduced 1T phase is in a thermodynamically metastable state, making it prone to irreversible phase transitions in practical applications, reverting to the stable 2H phase (which lacks piezoelectric catalytic advantages) or a disordered structure, leading to rapid degradation of material performance. Furthermore, these methods struggle to precisely control the ratio, distribution, and interfacial coupling of the two phases, resulting in poor reproducibility of material performance and severely hindering their application prospects in practical water treatment engineering.
[0004] In addition, a method for preparing a molybdenum disulfide-tourmaline composite material has been proposed in the prior art. This method utilizes a natural mineral (tourmaline) and molybdenum disulfide to effectively composite via a microwave hydrothermal method, improving the severely agglomerated flower-like structure of molybdenum disulfide microspheres into uniformly dispersed nanosheets. These nanosheets grow regularly on the tourmaline, resulting in a novel molybdenum disulfide-tourmaline composite material. In this preparation method, to promote the bonding between tourmaline and molybdenum disulfide, the tourmaline needs to be pretreated. However, during the pretreatment process, high-temperature calcination (500-900℃) may damage the crystal structure of tourmaline, significantly reducing or even eliminating its spontaneous polarization ability. This means that during the composite material synthesis process, tourmaline primarily functions as a carrier, and its spontaneous polarization's influence on the content of the 1T phase of molybdenum disulfide in the composite material lacks in-depth research. Consequently, the composite material struggles to possess both excellent piezoelectric charge generation capabilities and high charge separation efficiency, making it difficult to efficiently activate peracetic acid and rapidly form more strong oxidizing free radicals, ultimately hindering the rapid degradation of organic pollutants.
[0005] To address the above problems, this invention is proposed. Summary of the Invention
[0006] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a method for treating organic pollutant wastewater by activating peracetic acid with tourmaline-molybdenum disulfide piezoelectric composite material, which is simple in process, convenient in operation, high in treatment efficiency, good in removal effect, good in adaptability, and environmentally friendly.
[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A method for treating organic pollutant wastewater using tourmaline-molybdenum disulfide piezoelectric composite material to activate peracetic acid. The method uses the tourmaline-molybdenum disulfide piezoelectric composite material as a catalyst to degrade the organic pollutant wastewater. The tourmaline-molybdenum disulfide piezoelectric composite material is prepared by hydrothermal reaction using molybdenum source and sulfur source as raw materials, and tourmaline powder as an inducing agent and stabilizer. The amount of tourmaline powder used is 20%–40% of the total mass of the molybdenum source, sulfur source, and tourmaline powder.
[0008] In a further improvement to the above method, the amount of tourmaline powder used is 25% to 35% of the total mass of the molybdenum source, sulfur source, and tourmaline powder; the molar ratio of the molybdenum source to the sulfur source is 1:2.
[0009] In a further improvement to the above method, the molybdenum source is one of ammonium molybdate, magnesium molybdate, or sodium molybdate; and the sulfur source is thiourea or thioacetamide.
[0010] A further improvement to the above method, the preparation method of the tourmaline-molybdenum disulfide piezoelectric composite material includes the following steps: S1. Mix the molybdenum source, sulfur source, and water, and stir to obtain a mixed solution; S2. Mix the tourmaline powder with the mixed solution obtained in step S1, stir, and sonicate to obtain a precursor solution; S3. Perform a hydrothermal reaction on the precursor solution obtained in step S2 to obtain a tourmaline-molybdenum disulfide piezoelectric composite material.
[0011] In a further improvement to the above method, the stirring time in step S1 is 30 minutes.
[0012] In a further improvement to the above method, in step S2, the stirring time is 30 minutes; the ultrasonication time is 30 minutes.
[0013] In a further improvement to the above method, in step S3, the hydrothermal reaction is carried out at a temperature of 200°C; the hydrothermal reaction time is 12 hours; after the hydrothermal reaction is completed, the process further includes: filtration, washing, and drying to obtain a tourmaline-molybdenum disulfide piezoelectric composite material; the drying is carried out under vacuum conditions; the drying temperature is 60°C; and the drying time is 12 hours.
[0014] In a further improvement to the above method, in step S3, the tourmaline-molybdenum disulfide piezoelectric composite material includes molybdenum disulfide and tourmaline, with the molybdenum disulfide growing on the surface of the tourmaline.
[0015] A further improvement to the above method, using a tourmaline-molybdenum disulfide piezoelectric composite material as a catalyst for activating peracetic acid to degrade organic pollutant wastewater, includes the following steps: Tourmaline-molybdenum disulfide piezoelectric composite material and organic pollutant wastewater are mixed, peracetic acid is added, and a piezoelectric catalytic degradation reaction is carried out under ultrasonic conditions to complete the degradation treatment of organic pollutant wastewater.
[0016] In a further improvement to the above method, the amount of tourmaline-molybdenum disulfide piezoelectric composite material added is 0.1 g to 0.5 g per liter of the organic pollutant wastewater; and the initial concentration of peracetic acid in the piezoelectric catalytic degradation reaction system is ≤2 mmol / L.
[0017] The above method is further improved in that the organic pollutant in the wastewater is at least one of bisphenol A, tetracycline, rhodamine B, and carbamazepine; and the initial concentration of the organic pollutant in the wastewater is ≤20 mg / L.
[0018] In a further improvement to the above method, the piezoelectric catalytic degradation reaction time is 30 min.
[0019] Compared with the prior art, the advantages of the present invention are as follows: (1) In view of the shortcomings of existing molybdenum disulfide materials, such as complicated preparation methods, poor 1T phase stability, and low catalytic activity, as well as the resulting defects such as difficulty in efficiently activating peracetic acid, difficulty in efficiently degrading organic pollutants and poor reuse effect, this invention creatively proposes a method for treating organic pollutant wastewater by activating peracetic acid with tourmaline-molybdenum disulfide piezoelectric composite material. The tourmaline-molybdenum disulfide piezoelectric composite material is used as a catalyst for activating peracetic acid to degrade organic pollutant wastewater. The tourmaline-molybdenum disulfide piezoelectric composite material is prepared by hydrothermal reaction with molybdenum source and sulfur source as raw materials and tourmaline powder as inducing and stabilizing agent. The amount of tourmaline powder is 20% to 40% of the total mass of molybdenum source, sulfur source and tourmaline powder. In this invention, molybdenum and sulfur sources are used as raw materials. Tourmaline powder is introduced into the hydrothermal reaction system, which acts as an inducing agent and stabilizer. The localized electrostatic field formed around tourmaline under heating conditions (or more broadly, spontaneous electrode effect) directionally induces and stabilizes the formation and growth of the metallic 1T phase in molybdenum disulfide crystals. Simultaneously, by optimizing the amount of tourmaline powder to 20%–40% of the total mass of the molybdenum, sulfur, and tourmaline powders, the content of the 1T phase in the material can be controlled. This ensures that the molybdenum disulfide particles are uniformly and firmly loaded onto the tourmaline, and also allows the 1T and 2H phases of molybdenum disulfide to bond tightly and form a heterostructure. This gives the tourmaline-molybdenum disulfide piezoelectric composite material excellent piezoelectric charge generation energy. The invention leverages the high charge separation efficiency of tourmaline, and more importantly, the continuous electric field of tourmaline may help stabilize the 1T phase structure and inhibit its transformation to the 2H phase, thereby obtaining a stable and high-performance piezoelectric catalyst. Ultimately, a tourmaline-molybdenum disulfide piezoelectric composite material with stable structure and excellent piezoelectric catalytic performance is prepared. Furthermore, since the piezoelectric properties of tourmaline itself are weaker than those of molybdenum disulfide, excessive use of tourmaline can lead to a deterioration in piezoelectric performance. Therefore, the tourmaline-molybdenum disulfide piezoelectric composite material is used as a catalyst to activate peracetic acid. Under ultrasonic irradiation, peracetic acid is efficiently activated to rapidly generate more strong oxidizing free radicals (such as hydroxyl radicals and organic oxygen radicals), which are then used to achieve rapid degradation of organic pollutants. This invention utilizes the tourmaline-molybdenum disulfide piezoelectric composite material to activate peracetic acid for treating organic pollutant wastewater. This method has advantages such as simple process, convenient operation, high treatment efficiency, good removal effect, good adaptability, and environmental friendliness, achieving efficient removal of organic pollutants from wastewater.
[0020] (2) In this invention, by combining the permanent spontaneous electrode effect of tourmaline with the hydrothermal synthesis process, the crystal phase of molybdenum disulfide is controlled in a green and mild manner to construct a stable 1T / 2H heterostructure. It has the advantages of simple process, mild reaction conditions and environmental friendliness, and eliminates the high-risk reagents and complex post-processing required by the traditional chemical intercalation method. Attached Figure Description
[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.
[0022] Figure 1 The images show SEM and EDS images of the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) prepared in Example 1 of this invention and the molybdenum disulfide piezoelectric material (MoS2) prepared in Comparative Example 1.
[0023] Figure 2 XPS images of the tourmaline-molybdenum disulfide piezoelectric composite materials (T20-MoS2, T30-MoS2, T40-MoS2) prepared in Example 1 of the present invention and the molybdenum disulfide piezoelectric material (MoS2) prepared in Comparative Example 1.
[0024] Figure 3 This is a comparison chart showing the degradation effects of tourmaline-molybdenum disulfide piezoelectric composite materials (T20-MoS2, T30-MoS2, T40-MoS2) and molybdenum disulfide piezoelectric material (MoS2) piezoelectric activated peracetic acid system on bisphenol A in wastewater in Example 1 of the present invention.
[0025] Figure 4 This is a comparison chart showing the degradation effects of different piezoelectrically activated peracetic acid systems on bisphenol A in wastewater in Example 1 of the present invention.
[0026] Figure 5 This is a comparison chart showing the degradation effect of the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) piezoelectric activated peracetic acid system on bisphenol A in wastewater under different pH conditions in Example 1 of the present invention.
[0027] Figure 6 This is a comparison diagram showing the degradation effect of the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) piezoelectric activated peracetic acid system on bisphenol A in wastewater under the conditions of coexisting inorganic anions and humic acid interference, according to Example 1 of the present invention.
[0028] Figure 7 This is a comparison curve of the degradation and removal rate of different organic pollutants by the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) under the same conditions in Example 1 of the present invention, showing the change over time. Detailed Implementation
[0029] The present invention will be further described below with reference to the accompanying drawings and specific preferred embodiments, but this does not limit the scope of protection of the present invention.
[0030] In the following embodiments of the present invention, unless otherwise specified, the materials and instruments used are commercially available, the equipment used is conventional equipment, and the data obtained are the average values of more than three repeated experiments.
[0031] Example 1 A method for treating organic pollutant wastewater using tourmaline-molybdenum disulfide piezoelectric composite material to activate peracetic acid, specifically using the tourmaline-molybdenum disulfide piezoelectric composite material as a catalyst for activating peracetic acid to degrade organic pollutant wastewater, includes the following steps: The tourmaline-molybdenum disulfide piezoelectric composite material was added at a dosage of 0.5 g per liter of organic pollutant wastewater, i.e., a dosage of 0.5 g / L. Tourmaline-molybdenum disulfide piezoelectric composite materials (T20-MoS2, T30-MoS2, and T40-MoS2) were weighed and added to a bisphenol A aqueous solution with an initial concentration of 20 mg / L. Peracetic acid was added to bring the initial concentration of peracetic acid in the system to 2 mmol / L. The mixture was ultrasonicated at 25℃ for 30 min to carry out a piezoelectric catalytic degradation reaction of the bisphenol A aqueous solution, thus completing the degradation treatment of the bisphenol A wastewater.
[0032] In this embodiment, the tourmaline-molybdenum disulfide piezoelectric composite material is T20-MoS2, T30-MoS2, and T40-MoS2, and the corresponding test groups are numbered sequentially as follows: T20-MoS2 / PAA / US, T30-MoS2 / PAA / US, and T40-MoS2 / PAA / US.
[0033] Control group 1 (MoS2 / PAA / US): molybdenum disulfide piezoelectric material (MoS2) was used instead of tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2), with other conditions remaining the same.
[0034] Control group 2 (T30-MoS2 / PAA): The piezoelectric catalytic degradation reaction was carried out under stirring conditions using tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) as a catalyst, with other conditions being the same.
[0035] Control group 3 (T30-MoS2 / US): using tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) as catalyst, without the addition of peracetic acid, and with other conditions being the same.
[0036] Control group 4 (PAA / US): No tourmaline-molybdenum disulfide piezoelectric composite material was added, and all other conditions were the same.
[0037] Control group 5 (TM / PAA / US): Tourmaline was replaced with tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2), and all other conditions were the same.
[0038] In this embodiment, the tourmaline-molybdenum disulfide piezoelectric composite material (T20-MoS2) is prepared by hydrothermal reaction using molybdenum source and sulfur source as raw materials and tourmaline powder as an inducing agent and stabilizer. The amount of tourmaline powder used is 20% of the total mass of molybdenum source, sulfur source and tourmaline powder. The process includes the following steps: S1. Dissolve 0.62g of ammonium molybdate tetrahydrate and 0.53g of thiourea in 35mL of deionized water and stir magnetically for 30min to obtain a mixed solution.
[0039] S2. Mix 0.29g of tourmaline powder (commercially available) with the mixed solution obtained in step S1, stir magnetically for 30min at room temperature, and then sonicate for 30min to make the materials uniformly mixed to obtain the precursor solution.
[0040] S3. The precursor solution obtained in step S2 is placed in a stainless steel autoclave lined with polytetrafluoroethylene and subjected to hydrothermal reaction at 200°C for 12 hours. After natural cooling, the mixture is filtered to obtain a precipitate. The precipitate is washed several times with deionized water and ethanol. The precipitate is then vacuum dried at 60°C for 12 hours to obtain a tourmaline-molybdenum disulfide piezoelectric composite material, denoted as T20-MoS2.
[0041] In this embodiment, the tourmaline-molybdenum disulfide piezoelectric composite material (T20-MoS2) used includes molybdenum disulfide and tourmaline, with molybdenum disulfide growing on the surface of tourmaline.
[0042] In this embodiment, the preparation method of the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) is basically the same as that of the tourmaline-molybdenum disulfide piezoelectric composite material (T20-MoS2), except that in the preparation method of the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2), the amount of tourmaline powder is 30% of the total mass of the molybdenum source, sulfur source and tourmaline powder.
[0043] In this embodiment, the preparation method of the tourmaline-molybdenum disulfide piezoelectric composite material (T40-MoS2) is basically the same as that of the tourmaline-molybdenum disulfide piezoelectric composite material (T20-MoS2), except that in the preparation method of the tourmaline-molybdenum disulfide piezoelectric composite material (T40-MoS2), the amount of tourmaline powder is 40% of the total mass of the molybdenum source, sulfur source and tourmaline powder.
[0044] In this embodiment, the preparation method of the molybdenum disulfide piezoelectric material (MoS2) includes the following steps: (1) Dissolve 0.62g ammonium molybdate tetrahydrate and 0.53g thiourea in 35mL of deionized water, stir magnetically for 30min, and sonicate for 30min to obtain a mixed solution.
[0045] (2) The mixed solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and hydrothermally reacted at 200°C for 12 hours. After natural cooling, the precipitate was obtained by filtration. The precipitate was washed several times with deionized water and ethanol. The precipitate was vacuum dried at 60°C for 12 hours. The molybdenum disulfide piezoelectric material was denoted as MoS2.
[0046] The tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) prepared in Example 1 and the molybdenum disulfide piezoelectric material (MoS2) prepared in Comparative Example 1 were subjected to scanning electron microscopy and energy-dispersive X-ray spectroscopy analysis. The results are as follows: Figure 1 As shown. X-ray photoelectron spectroscopy (XPS) was performed on the tourmaline-molybdenum disulfide piezoelectric composite materials (T20-MoS2, T30-MoS2, T40-MoS2) prepared in Example 1 and the molybdenum disulfide piezoelectric material (MoS2) prepared in Comparative Example 1. The results are as follows. Figure 2 As shown.
[0047] Figure 1 The images show SEM and EDS images of the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) prepared in Example 1 of this invention and the molybdenum disulfide piezoelectric material (MoS2) prepared in Comparative Example 1. Figure 1 In the image, (a) is the SEM image of MoS2, (b) is the SEM image of T30-MoS2, and (c) and (d) are the EDS images of T30-MoS2. Figure 1 It is known that molybdenum disulfide has been successfully grown on the surface of tourmaline in the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) prepared by this invention.
[0048] Figure 2 XPS images of the tourmaline-molybdenum disulfide piezoelectric composite materials (T20-MoS2, T30-MoS2, T40-MoS2) prepared in Example 1 of the present invention and the molybdenum disulfide piezoelectric material (MoS2) prepared in Comparative Example 1. Figure 2 In the given diagram, (a) is MoS2, (b) is T20-MoS2, (c) is T30-MoS2, and (d) is T40-MoS2. (The remaining text appears to be incomplete and requires further context.) Figure 2 It can be seen that in the tourmaline-molybdenum disulfide piezoelectric composite material prepared by the present invention, tourmaline induces the formation of the molybdenum disulfide 1T phase, and the 1T phase content is positively correlated with the tourmaline content.
[0049] During the piezoelectric catalytic degradation reaction, 1 mL of solution was taken every 5 min starting from 0 min, filtered through a 0.22 μm filter membrane, and 20 μL of 0.1 mol / L sodium thiosulfate solution was added as a quencher to terminate the reaction. The solution was stored in a 1.5 mL liquid chromatography vial for determining the concentration of bisphenol A and calculating the degradation rate of bisphenol A in different peracetic acid piezoelectric catalytic systems after 30 min of reaction.
[0050] Table 1. Degradation rate of bisphenol A by peracetic acid systems activated by different catalysts using piezoelectric catalysts
[0051] Table 2 Degradation rates of bisphenol A by different oxidation systems
[0052] The degradation rate in the above experiments ( The calculation formula is: , Where C0 is the initial concentration of organic pollutants, C t Let be the concentration of organic pollutants at time t.
[0053] Figure 3 This is a comparison chart showing the degradation effects of tourmaline-molybdenum disulfide piezoelectric composite materials (T20-MoS2, T30-MoS2, T40-MoS2) and molybdenum disulfide piezoelectric material (MoS2) piezoelectric activated peracetic acid system on bisphenol A in wastewater in Example 1 of the present invention.
[0054] Figure 4 This is a comparison chart showing the degradation effects of different piezoelectrically activated peracetic acid systems on bisphenol A in wastewater in Example 1 of the present invention.
[0055] Depend on Figure 3 As shown in Table 1, the tourmaline-molybdenum disulfide piezoelectric composite material of this invention is superior to molybdenum disulfide as a catalyst for activating the degradation of bisphenol A by peracetic acid. Furthermore, with increasing tourmaline content, the prepared tourmaline-molybdenum disulfide piezoelectric composite material exhibits better activation of peracetic acid and a higher degradation rate for bisphenol A. When the tourmaline content reaches 40%, the degradation effect of bisphenol A decreases. This may be because the piezoelectric properties of tourmaline itself are lower than those of molybdenum disulfide. Therefore, with excessively high tourmaline content, the piezoelectric catalytic performance of the tourmaline-molybdenum disulfide piezoelectric composite material declines, failing to simultaneously possess excellent piezoelectric charge generation capability and high charge separation efficiency. Therefore, considering cost, the tourmaline-molybdenum disulfide piezoelectric composite material T30-MoS2 is more preferred for the same degradation efficiency.
[0056] Depend on Figure 4As shown in Table 2, in the system with only peracetic acid and ultrasound (PAA / US), the degradation rate of bisphenol A was 46.69%; in the condition without ultrasound but with only T30-MoS2 activating peracetic acid (T30-MoS2 / PAA), the degradation rate of bisphenol A was 38.16%; in the system with both peracetic acid and MoS2 and ultrasound (MoS2 / PAA / US), the degradation rate of bisphenol A was 72%; in the system with both peracetic acid and TM and ultrasound (TM / PAA / US), the degradation rate of bisphenol A was only 46.69%; in the system with both peracetic acid and T30-MoS2 and ultrasound (T30-MoS2 / PAA / US), the removal capacity of bisphenol A was the strongest, reaching 100% degradation rate within 25 min, indicating that T30-MoS2 has superior piezoelectric catalytic performance.
[0057] In this embodiment, the piezoelectric catalytic degradation effect of the T30-MoS2 / PAA / US system on bisphenol A under different pH conditions was also investigated. The specific experimental steps were the same as in Experiment 1, except that the pH of the system was 3, 5, 7, 9 and 11, and there was a control group (initial pH).
[0058] In this embodiment, the piezoelectric catalytic degradation effect of the T30-MoS2 / PAA / US system on bisphenol A under the conditions of coexisting inorganic anions and humic acid interference was also investigated. The specific experimental steps were the same as in Experiment 1, except that the test groups were: humic acid (HA), Cl - NO3 - H2PO4 - and HCO3 - (concentration such as) Figure 6 As shown), and the control group (Blank).
[0059] In this embodiment, the piezoelectric catalytic degradation of bisphenol A (BPA), carbamazepine (CBZ), tetracycline (TC), and rhodamine B (RhB) by the T30-MoS2 / PAA / US system was also investigated, with other conditions the same as in Example 1.
[0060] Figure 5 This is a comparison chart showing the degradation effect of the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) piezoelectric activated peracetic acid system on bisphenol A in wastewater under different pH conditions in Example 1 of the present invention.
[0061] Figure 6 This is a comparison diagram showing the degradation effect of the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) piezoelectric activated peracetic acid system on bisphenol A in wastewater under the conditions of coexisting inorganic anions and humic acid interference, according to Example 1 of the present invention.
[0062] Figure 7 This is a comparison curve of the degradation and removal rate of different organic pollutants by the tourmaline-molybdenum disulfide piezoelectric composite material (T30-MoS2) under the same conditions in Example 1 of the present invention, showing the change over time.
[0063] Depend on Figure 5 It can be seen that the T30-MoS2 / PAA / US system can still maintain its high efficiency in degrading bisphenol A under different pH conditions, and has a wide pH application range.
[0064] like Figure 6 As shown, except for HCO3 - In addition, other anions and HA do not inhibit the piezoelectric catalytic degradation of bisphenol A in the T30-MoS2 / PAA / US system. HCO3 - The inhibition comes from the capture of active free radicals. Nevertheless, the T30-MoS2 / PAA / US piezoelectric catalytic system can still maintain good degradation efficiency.
[0065] Depend on Figure 7 The T30-MoS2 / PAA / US system exhibits significant degradation activity against various organic pollutants, including endocrine disruptors, antibiotics, and dyes. In particular, it demonstrates excellent instantaneous removal capabilities for rhodamine B and tetracycline, and good mineralization potential for the recalcitrant drug carbamazepine. This confirms the broad applicability and high catalytic efficiency of this composite material in water treatment.
[0066] The results above show that the tourmaline-molybdenum disulfide piezoelectric composite material prepared in this invention has advantages such as structural stability and excellent piezoelectric catalytic performance. It is used to activate peracetic acid, and under ultrasonic irradiation, it efficiently activates peracetic acid to rapidly generate more strong oxidizing free radicals (such as hydroxyl radicals and organic oxygen radicals), thereby utilizing these strong oxidizing free radicals to achieve rapid degradation of organic pollutants. This invention's method for treating organic pollutant wastewater by activating peracetic acid with tourmaline-molybdenum disulfide piezoelectric composite material has advantages such as simple process, convenient operation, high treatment efficiency, good removal effect, good adaptability, and environmental friendliness, achieving efficient removal of organic pollutants from wastewater.
[0067] The above embodiments are merely preferred embodiments of the present invention, and the scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, improvements and modifications made without departing from the principles of the present invention should also be considered within the scope of protection of the present invention.
Claims
1. A method for treating organic pollutant wastewater using tourmaline-molybdenum disulfide piezoelectric composite material activated peracetic acid, characterized in that, The method uses a tourmaline-molybdenum disulfide piezoelectric composite material as a catalyst to degrade organic pollutant wastewater by activating peracetic acid. The tourmaline-molybdenum disulfide piezoelectric composite material is prepared by hydrothermal reaction using molybdenum source and sulfur source as raw materials and tourmaline powder as an inducing agent and stabilizer. The amount of tourmaline powder used is 20% to 40% of the total mass of the molybdenum source, sulfur source and tourmaline powder.
2. The method according to claim 1, characterized in that, The amount of tourmaline powder used is 25% to 35% of the total mass of the molybdenum source, sulfur source and tourmaline powder; the molar ratio of the molybdenum source and sulfur source is 1:
2.
3. The method according to claim 2, characterized in that, The molybdenum source is at least one of ammonium molybdate, magnesium molybdate, and sodium molybdate; the sulfur source is thiourea and / or thioacetamide.
4. The method according to claim 3, characterized in that, The preparation method of the tourmaline-molybdenum disulfide piezoelectric composite material includes the following steps: S1. Mix the molybdenum source, sulfur source, and water, and stir to obtain a mixed solution; S2. Mix the tourmaline powder with the mixed solution obtained in step S1, stir, and sonicate to obtain a precursor solution; S3. Perform a hydrothermal reaction on the precursor solution obtained in step S2 to obtain a tourmaline-molybdenum disulfide piezoelectric composite material.
5. The method according to claim 4, characterized in that, In step S1, the stirring time is 30 minutes; In step S2, the stirring time is 30 minutes; the ultrasonication time is 30 minutes. In step S3, the hydrothermal reaction is carried out at a temperature of 200°C; the hydrothermal reaction takes 12 hours. After the hydrothermal reaction is completed, the process further includes: filtration, washing, and drying to obtain a tourmaline-molybdenum disulfide piezoelectric composite material; the drying is carried out under vacuum conditions; the drying temperature is 60°C; and the drying time is 12 hours.
6. The method according to claim 5, characterized in that, In step S3, the tourmaline-molybdenum disulfide piezoelectric composite material includes molybdenum disulfide and tourmaline, with the molybdenum disulfide growing on the surface of the tourmaline.
7. The method according to any one of claims 1 to 6, characterized in that, The degradation treatment of organic pollutant wastewater using tourmaline-molybdenum disulfide piezoelectric composite material as a catalyst for activating peracetic acid includes the following steps: Tourmaline-molybdenum disulfide piezoelectric composite material and organic pollutant wastewater are mixed, peracetic acid is added, and a piezoelectric catalytic degradation reaction is carried out under ultrasonic conditions to complete the degradation treatment of organic pollutant wastewater.
8. The method according to claim 7, characterized in that, The amount of the tourmaline-molybdenum disulfide piezoelectric composite material added is 0.1 g to 0.5 g per liter of the organic pollutant wastewater; the initial concentration of peracetic acid in the piezoelectric catalytic degradation reaction system is ≤2 mmol / L.
9. The method according to claim 8, characterized in that, The organic pollutants in the wastewater are at least one of bisphenol A, tetracycline, rhodamine B, and carbamazepine; the initial concentration of the organic pollutants in the wastewater is ≤20 mg / L.
10. The method according to claim 7, characterized in that, The piezoelectric catalytic degradation reaction takes 30 minutes.