A plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst, its preparation method, and its application.

Abstract

The application discloses a kind of plasma enhanced Z type Ag2MoO4 / Ag / In2S3 photocatalyst and its preparation method and application, its preparation method includes Ag2MoO4 nanoparticle is dispersed into AgNO3 solution, under light condition, magnetic stirring is carried out, centrifugal, take sediment, after washing, drying, fully ground, obtain Ag2MoO4 / Ag nanoparticle;Ag2MoO4 / Ag nanoparticle and In2S3 nanoparticle are mixed and dissolved in anhydrous ethanol, after stirring, centrifugal, take sediment, after washing, drying, fully ground, obtain Ag2MoO4 / Ag / In2S3 photocatalyst.1g / L Ag2MoO4 / Ag / In2S3 photocatalyst is irradiated by sunlight for 2h, and the degradation rate of tetracycline in seawater is as high as 98.14%.

Description

Technical Field

[0001] This invention relates to the field of photocatalyst technology, and more specifically, to a plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst, its preparation method, and its application. Background Technology

[0002] Tetracycline (TC) consists of four benzene rings and one tetrahydropyrimidine ring, and is soluble in both water and organic solvents. TC plays an important role in clinical disease treatment and livestock production. However, the widespread use of TC has also brought serious environmental problems. During production, use, and disposal, large amounts of TC enter the environment through medical wastewater, aquaculture wastewater, and solid waste leachate, leading to a continuous increase in its residual concentration in various environmental media, especially seawater.

[0003] Photocatalysis technology boasts advantages such as high efficiency, wide application, no secondary pollution, and strong controllability, making it a highly promising environmentally friendly water treatment technology. In recent years, the degradation of organic pollutants using semiconductor photocatalysts has become a research hotspot. However, most current photocatalysis research focuses on pollutant degradation in neutral or acidic water. Research on the removal of organic pollutants from alkaline water bodies such as seawater is relatively limited. Therefore, it is necessary to synthesize novel, highly active photocatalysts to remove organic pollutants, such as TC, from seawater.

[0004] Z-type nanocomposite photocatalysts, composed of two or more single photocatalysts, are a special type of photocatalytic material. They typically consist of a layered structure of nanomaterials arranged in specific layers or nanowires to form a unique nanostructure. Z-type photocatalysts with this structure possess a large specific surface area, which is beneficial for the adsorption and contact of organic pollutants. Furthermore, Z-type nanocomposite photocatalysts can be modified through surface modification, structural adjustment, and the deposition of noble metal particles. Specifically, noble metal nanoparticles such as Ag, Au, and Pt deposited on the surface of the photocatalyst particles can absorb visible light, thereby inducing a surface plasmon resonance (SPR) effect. The generated SPR effect helps improve the separation efficiency of photogenerated carriers, thus increasing the efficiency of the photocatalytic reaction. Therefore, plasma-enhanced Z-type photocatalysts exhibit significantly enhanced photocatalytic activity and can be used for the efficient degradation of organic pollutants in water and wastewater. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst, its preparation method, and its applications.

[0006] To achieve the above objectives, the present invention is implemented according to the following technical solution:

[0007] One objective of this invention is to provide a method for preparing a plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst, characterized by comprising the following steps:

[0008] S1. Obtain Ag2MoO4 nanoparticles;

[0009] S2. Disperse Ag2MoO4 nanoparticles into AgNO3 solution and stir magnetically under light irradiation to obtain mixed solution B; centrifuge mixed solution B, collect the precipitate, wash and dry it, and grind it thoroughly to obtain Ag2MoO4 / Ag nanoparticles.

[0010] S3, Obtaining In2S3 nanoparticles;

[0011] S4. Mix and dissolve Ag2MoO4 / Ag nanoparticles and In2S3 nanoparticles in anhydrous ethanol, stir, and obtain mixed solution D; centrifuge mixed solution D, take the precipitate, wash, dry, and grind thoroughly to obtain Ag2MoO4 / Ag / In2S3 photocatalyst.

[0012] In the preferred embodiment, in step S2, the concentration of AgNO3 solution is 0.05 mol / L, the molar volume ratio (mol / mL) of Ag2MoO4 nanoparticles and AgNO3 solution is X:Y, the illumination is performed by a 300W xenon lamp, the magnetic stirring time is 0.5 h, and the drying conditions are drying at 65℃ for 2.0 h.

[0013] In the preferred embodiment, in step S4, the molar ratio of Ag2MoO4 / Ag nanoparticles to In2S3 nanoparticles is 1:1, the stirring conditions are stirring at room temperature for 1.0 h, and the drying conditions are drying at 65°C for 4.0 h.

[0014] In the preferred embodiment, in step S1, AgNO3 and Na2MoO4 are mixed and dissolved in deionized water, stirred, and mixed solution A is obtained; mixed solution A is centrifuged, the precipitate is collected, washed, dried, and then thoroughly ground to obtain Ag2MoO4 nanoparticles.

[0015] In the preferred embodiment, in step S1, the molar ratio of AgNO3 to Na2MoO4 is 2:1, the molar volume ratio (mol / mL) of Na2MoO4 to deionized water is 1:100, the stirring conditions are stirring at room temperature for 1.0 h, and the drying conditions are drying at 65°C for 2.0 h.

[0016] In the preferred embodiment, in step S3, InCl3 and Na2S·9H2O are mixed and dissolved in deionized water, stirred, and mixed solution C is obtained; mixed solution C is centrifuged, the precipitate is collected, washed, dried, and then thoroughly ground to obtain In2S3 nanoparticles.

[0017] In the preferred embodiment, in step S3, the molar ratio of InCl3 to Na2S·9H2O is 2:3, the molar volume ratio of InCl3 to deionized water is 1:50, the stirring conditions are stirring at room temperature for 1.0 h, and the drying conditions are drying at 65°C for 4.0 h.

[0018] A preferred embodiment of the preparation method of a plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst includes the following steps:

[0019] S1. AgNO3 and Na2MoO4 in a molar ratio of 2:1 were mixed and dissolved in 100 mL of deionized water and stirred at room temperature for 1.0 h to obtain mixed solution A. Mixed solution A was centrifuged to obtain a precipitate. The precipitate was washed multiple times and dried at 65℃ for 2.0 h, and then ground thoroughly to obtain Ag2MoO4 nanoparticles. The stirring conditions were: stirring at 4500 rpm for 1.0 h at room temperature; and centrifugation conditions were: stirring at 3000 rpm for 0.5 h.

[0020] S2. The prepared Ag2MoO4 nanoparticles were dispersed in a 0.05 mol / L AgNO3 solution, and the mixture was irradiated with a 300 W xenon lamp for 0.5 h under magnetic stirring to obtain mixture B. Then, the suspension sample was separated from the mixture solution B by multiple centrifugations. The suspension sample was washed multiple times and dried at 65℃ for 2.0 h, and then thoroughly ground to obtain Ag2MoO4 / Ag nanoparticles. The magnetic stirring conditions were 4500 rpm for 1.0 h at room temperature, and the centrifugation conditions were 3000 rpm for 0.5 h.

[0021] S3. Mix InCl3 and Na2S·9H2O in a molar ratio of 2:3 and dissolve them in 100 mL of deionized water. Stir at room temperature for 1.0 h to obtain mixed solution C. Centrifuge mixed solution C to obtain a precipitate. Wash the precipitate multiple times and dry it at 65℃ for 4.0 h. Then grind it thoroughly to obtain In2S3 nanoparticles. The stirring conditions are: stirring at 4500 rpm for 1.0 h at room temperature; centrifugation conditions are: stirring at 3000 rpm for 0.5 h.

[0022] S4. Ag2MoO4 / Ag nanoparticles and In2S3 nanoparticles with a molar ratio of 1:1 were mixed and dissolved in 100 mL of anhydrous ethanol and stirred at room temperature for 1.0 h to obtain mixed solution D. Mixed solution D was centrifuged to obtain a precipitate, which was washed multiple times and dried at 65℃ for 4.0 h and then thoroughly ground to obtain a plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst. The stirring conditions were: stirring at 4500 rpm for 1.0 h at room temperature; and centrifugation conditions were: stirring at 3000 rpm for 0.5 h.

[0023] The second objective of this invention is to provide a plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 composite material prepared by any of the above methods.

[0024] The third objective of this invention is to provide an application of the above-mentioned plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 composite material in the photocatalytic degradation of tetracycline.

[0025] In a preferred embodiment, the aforementioned plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 composite material is used for photocatalytic degradation of tetracycline under alkaline conditions.

[0026] Beneficial effects of the present invention

[0027] Compared with existing technologies, this invention prepares a plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst through precipitation, photoreduction, and wet mixing methods. The preparation method is simple and the catalyst yield is high. Furthermore, due to the generation of the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst, highly efficient photocatalytic redox reactions can be achieved, generating a variety of highly active free radicals to degrade organic pollutants in seawater. Compared with traditional Z-type photocatalysts, this plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst has more electron flow directions. In the process of photocatalytic degradation of organic pollutants in seawater, it ensures sufficient separation of electrons and holes and increases photocatalytic activity. At the same time, it reduces the recombination rate of photogenerated electrons and holes, improves photocatalytic activity, and has excellent recycling efficiency, improving the recovery and reuse rate of the photocatalyst. Attached Figure Description

[0028] Figure 1 This is the X-ray diffraction pattern of the plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst.

[0029] Figure 2 This is a scanning electron microscope image of a plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention.

[0031] Unless otherwise specified, all raw materials and reagents used in the following examples were commercially available.

[0032] Example 1

[0033] A method for preparing plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalysts includes the following steps:

[0034] 1) Mix 3.3974 g of AgNO3 and 2.0592 g of Na2MoO4 and dissolve them in 100 mL of deionized water. Stir at room temperature for 1.0 h to obtain mixed solution A. Centrifuge mixed solution A to obtain precipitate. Wash the precipitate several times and dry it at 65℃ for 2.0 h. Then grind it thoroughly to obtain Ag2MoO4 nanoparticles.

[0035] 2) The prepared Ag2MoO4 nanoparticles were dispersed in a 0.05 mol / L AgNO3 solution, and the mixture was irradiated with a 300 W xenon lamp for 0.5 h under magnetic stirring to obtain a mixed solution B. Then, the suspension sample was separated from the mixed solution B by multiple centrifugations. The suspension sample was washed multiple times and dried at 65 °C for 2.0 h before being thoroughly ground to obtain Ag2MoO4 / Ag nanoparticles.

[0036] 3) Mix 4.4236 g of InCl3 and 7.2054 g of Na2S·9H2O and dissolve them in 100 mL of deionized water. Stir at room temperature for 1.0 h to obtain mixed solution C. Centrifuge mixed solution C to obtain precipitate. Wash the precipitate several times and dry it at 65℃ for 2.0 h. Then grind it thoroughly to obtain In2S3 nanoparticles.

[0037] 4) Mix 3.7569 g of Ag2MoO4 / Ag and 3.2583 g of In2S3 and dissolve them in 100 mL of anhydrous ethanol. Stir at room temperature for 1.0 h to obtain mixed solution D. Centrifuge mixed solution D to obtain the composite. Wash the composite multiple times and dry it at 65 °C for 4.0 h. Then grind it thoroughly to obtain the plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst.

[0038] Figure 1 This is the X-ray diffraction pattern of the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst, from... Figure 1Characteristic peaks of Ag2MoO4, Ag, and In2S3 can be clearly observed, and the positions of these characteristic peaks do not shift significantly, indicating that the plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst has been successfully prepared. Figure 2 This is a scanning electron microscope image of a plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst. From... Figure 2 The presence of Ag₂MoO₄, Ag, and In₂S₃ nanoparticles can be clearly observed. The test results indicate that a plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst was successfully prepared.

[0039] To highlight the photocatalytic degradation performance of the prepared plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst in seawater, Ag2MoO4 nanoparticles, In2S3 nanoparticles, and Ag2MoO4 / In2S3 nanocomposite particles were prepared separately as photocatalysts for the photocatalytic degradation of organic pollutants in seawater.

[0040] Comparative Example 1

[0041] The preparation method of Ag2MoO4 nanoparticles includes the following steps:

[0042] 3.3974 g of AgNO3 and 2.0592 g of Na2MoO4 were mixed and dissolved in 100 mL of deionized water. The mixture was stirred at room temperature for 1.0 h to obtain a mixed solution. The mixed solution was centrifuged to obtain a precipitate. The precipitate was washed several times and dried at 65 °C for 2.0 h before being thoroughly ground to obtain Ag2MoO4 nanoparticles.

[0043] Comparative Example 2

[0044] The preparation method of In2S3 nanoparticles includes the following steps:

[0045] 4.4236 g of InCl3 and 7.2054 g of Na2S·9H2O were mixed and dissolved in 100 mL of deionized water. The mixture was stirred at room temperature for 1.0 h to obtain mixed solution C. Mixed solution C was centrifuged to obtain a precipitate. The precipitate was washed several times and dried at 65 °C for 2.0 h before being thoroughly ground to obtain In2S3 nanoparticles.

[0046] Comparative Example 3

[0047] The preparation method of Ag2MoO4 / In2S3 nanocomposite particles includes the following steps:

[0048] 1) Mix 3.3974 g of AgNO3 and 2.0592 g of Na2MoO4 and dissolve them in 100 mL of deionized water. Stir at room temperature for 1.0 h to obtain a mixed solution. Centrifuge the mixed solution to obtain a precipitate. Wash the precipitate several times and dry it at 65℃ for 2.0 h. Then grind it thoroughly to obtain Ag2MoO4 nanoparticles.

[0049] 2) Mix 4.4236 g of InCl3 and 7.2054 g of Na2S·9H2O and dissolve them in 100 mL of deionized water. Stir at room temperature for 1.0 h to obtain mixed solution C. Centrifuge mixed solution C to obtain precipitate. Wash the precipitate several times and dry it at 65℃ for 2.0 h. Then grind it thoroughly to obtain In2S3 nanoparticles.

[0050] 3) Mix 3.7569 g of Ag2MoO4 and 3.2583 g of In2S3 and dissolve them in 100 mL of anhydrous ethanol to obtain a mixed solution. Stir at room temperature for 1.0 h, centrifuge the mixed solution to obtain the composite, wash the composite multiple times, dry it at 65℃ for 4.0 h, and then grind it thoroughly to obtain plasma-enhanced Z-type Ag2MoO4 / In2S3 nanocomposite particles.

[0051] Experimental Example 1: Application of Plasma-Enhanced Z-Type Ag₂MoO₄ / Ag / In₂S₃ Photocatalyst in Photocatalytic Degradation of Organic Pollutants in Seawater

[0052] The following experiments verify the photocatalytic degradation performance of organic pollutants in seawater by plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst, Ag2MoO4 nanoparticles, In2S3 nanoparticles, and Ag2MoO4 / In2S3 nanocomposite particles.

[0053] (1) Effect of different catalysts on the degradation rate of tetracycline

[0054] Experimental Methods: First, simulated seawater (pH 8.0) was prepared by dissolving 2.5% NaCl, 1.1% MgCl2, 0.04% Na2SO4, and 0.16% CaCl2 in distilled water (unless otherwise specified, all seawater solutions below are prepared using this method). An appropriate amount of tetracycline was first dissolved in an appropriate amount of simulated seawater, stirred thoroughly, and then transferred to a volumetric flask to prepare a 10 mg / L tetracycline seawater solution. 100 mL of the 10 mg / L tetracycline seawater solution was placed in four specially designed quartz tubes, and 0.1 g of plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst, Ag2MoO4 nanoparticles, In2S3 nanoparticles, and Ag2MoO4 / In2S3 nanocomposite particles were added to each tube, respectively. The tubes were irradiated under simulated sunlight for 2.0 h, with 5 mL taken out and centrifuged every half hour. The supernatant was then measured at 200-800 nm using ultraviolet light. The degradation rate of tetracycline was calculated using the absorbance at 267.0 nm, and the results are shown in Table 1.

[0055] Table 1. Degradation rate of tetracycline in seawater by different photocatalysts

[0056]

[0057] The photocatalytic degradation of tetracycline in seawater under simulated sunlight was compared between the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst and three other photocatalysts (Ag₂MoO₄ / In₂S₃, Ag₂MoO₄, and In₂S₃). Table 1 shows the different effects of Ag₂MoO₄ / Ag / In₂S₃, Ag₂MoO₄ / In₂S₃, Ag₂MoO₄, and In₂S₃ photocatalysts on the photocatalytic degradation of tetracycline in seawater. As can be seen from Table 1, under the condition of irradiation time of 2.0 h, the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst prepared in this invention has the highest degradation rate, reaching 98.14%.

[0058] (2) Effect of substrate concentration on tetracycline degradation rate

[0059] Experimental Methods: 100 mL of tetracycline aqueous solutions with concentrations of 10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, and 30 mg / L were placed in five specially designed quartz tubes. 0.1 g of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst was added to each tube. The tubes were irradiated under simulated sunlight for 2.0 h, with 5 mL samples taken every half hour for centrifugation. The supernatant was then measured at 200-800 nm using ultraviolet light. The absorbance at 267.0 nm was used to calculate the tetracycline degradation rate. The results are shown in Table 2.

[0060] Table 2. Degradation rate of tetracycline in seawater by plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst at different substrate concentrations

[0061]

[0062] The effects of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalysts on the photocatalytic degradation of tetracycline in seawater under simulated sunlight irradiation were compared at different substrate concentrations. Table 2 shows the different effects of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalysts at five different concentrations (10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, and 30 mg / L) on the photocatalytic degradation of tetracycline in seawater. As can be seen from Table 2, when the tetracycline concentration is 10 mg / L and the simulated sunlight irradiation time is 2.0 h, the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst prepared in this invention exhibits the highest degradation rate, reaching 98.14%.

[0063] (3) Effect of catalyst dosage on tetracycline degradation rate

[0064] Experimental Methods: 100 mL of a 10 mg / L tetracycline solution was placed in four specially designed quartz tubes. Plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalysts of 0.5 g / L, 1.0 g / L, 1.5 g / L, and 2.0 g / L were added respectively. The tubes were irradiated under simulated sunlight for 2.0 h, with 5 mL samples taken every half hour for centrifugation. The supernatant was then measured at 200-800 nm using ultraviolet light. The absorbance at 267.0 nm was used to calculate the tetracycline degradation rate. The results are shown in Table 3.

[0065] Table 3. Degradation rate of tetracycline in seawater by plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst under different catalyst dosages

[0066]

[0067] The effects of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalysts on the photocatalytic degradation of tetracycline in seawater under simulated sunlight irradiation were compared under different catalyst dosages. Table 3 shows the different effects of four different catalyst dosages (0.5 g / L, 1.0 g / L, 1.5 g / L, and 2.0 g / L) on the photocatalytic degradation of tetracycline in seawater. As can be seen from Table 3, when the catalyst dosage is 2.0 g / L and the simulated sunlight irradiation time is 2.0 h, the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst prepared in this invention exhibits the highest degradation rate, reaching 100.00%.

[0068] (4) Effect of solution pH on tetracycline degradation rate

[0069] Experimental Methods: 100 mL of a 10 mg / L tetracycline solution was placed in three specially designed quartz tubes. The pH values ​​of each solution were adjusted to 4.0, 6.0, and 8.0, respectively. Then, 0.1 g of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst was added to each tube. The tubes were irradiated under simulated sunlight for 2.0 h, with 5 mL samples taken every half hour and centrifuged. The supernatant was then measured at 200-800 nm using ultraviolet light. The absorbance at 267.0 nm was used to calculate the tetracycline degradation rate. The results are shown in Table 4.

[0070] Table 4. Degradation rate of tetracycline in seawater by plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst at different solution pH values

[0071]

[0072] The effects of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst on the photocatalytic degradation of tetracycline in seawater under simulated sunlight irradiation were compared under different pH conditions. Table 4 shows the different effects of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst on the photocatalytic degradation of tetracycline in seawater under three pH conditions (4.0, 6.0, and 8.0). As can be seen from Table 4, when the pH of the reaction solution is 8.0 (the original pH of the seawater) and the simulated sunlight irradiation time is 2.0 h, the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst prepared in this invention has the highest degradation rate, reaching 98.14%.

[0073] (5) Effect of reaction solution type on tetracycline degradation rate

[0074] Experimental Methods: 100 mL of a 10 mg / L tetracycline deionized water solution and a simulated seawater solution were placed in two specially designed quartz tubes, respectively. 0.1 g of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst was added to each tube. The tubes were irradiated under simulated sunlight for 2.0 h, with 5 mL samples taken every half hour for centrifugation. The supernatant was then measured at 200-800 nm using ultraviolet light. The absorbance at 267.0 nm was used to calculate the tetracycline degradation rate. The results are shown in Table 5.

[0075] Table 5. Degradation rate of tetracycline in seawater by plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst under different reaction solutions

[0076]

[0077] The photocatalytic degradation of tetracycline by the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst under simulated sunlight irradiation was compared under different reaction solutions. Table 5 shows the different effects of the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst on the photocatalytic degradation of tetracycline in two reaction solutions (deionized water and simulated seawater). As can be seen from Table 5, when the reaction solution is a deionized aqueous solution and the simulated sunlight irradiation time is 2.0 h, the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst prepared in this invention has the highest degradation rate, reaching 100.00%.

[0078] (6) Effects of plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst on photocatalytic degradation of different organic pollutants in seawater

[0079] Experimental Methods: 100 mL of 10 mg / L seawater solutions of methylene blue (MB), malachite green (MG), norfloxacin (NFX), naphthalene (NAP), and tetracycline (TC) were placed in four specially designed quartz tubes. 0.1 g of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst was added to each tube. The tubes were irradiated under simulated sunlight for 2.0 h. After the reaction, 5 mL of the solution was centrifuged, and the supernatant was measured at 200-800 nm using ultraviolet light. The absorbance at the corresponding wavelengths was used to calculate the degradation rate of different organic pollutants. The results are shown in Table 6.

[0080] Table 6. Degradation rates of different organic pollutants in seawater by plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst

[0081]

[0082] The photocatalytic degradation effects of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalysts on different organic pollutants in seawater under simulated sunlight irradiation were compared. Table 6 shows the different photocatalytic degradation effects of the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalysts on five organic pollutants (methylene blue, malachite green, norfloxacin, naphthalene, and tetracycline). As can be seen from Table 6, when the simulated sunlight irradiation time is 2.0 h, the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst prepared in this invention exhibits the highest degradation rate for tetracycline in seawater, reaching 98.14%.

[0083] In summary, the optimal conditions for the photocatalytic degradation of organic pollutants in seawater using the plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst were determined to be: seawater pH 8.0, plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst dosage of 2.0 g / L, and irradiation under light for 2.0 h. Under these conditions, the degradation rate of tetracycline in seawater was the highest.

[0084] (7) Effect of varying the number of times plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst is used on the degradation rate of tetracycline in seawater

[0085] Experimental Methods: 100 mL of a 10 mg / L tetracycline solution was placed in a specially made quartz tube, and 0.1 g of plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst was added. The tube was irradiated under simulated sunlight for 2.0 h, with 5 mL taken out and centrifuged every half hour. The supernatant was measured at 200-800 nm using ultraviolet light. The absorbance at 267.0 nm was used to calculate the degradation rate of tetracycline. Every 2.0 h, the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst was removed from the solution, washed, and dried. The obtained plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst was subjected to five photocatalytic degradation cycles. The results are shown in Table 7.

[0086] Table 7. Degradation rate of tetracycline in five-cycle degradation experiments using plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst

[0087]

[0088] As shown in Table 7, the plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst exhibits good stability. After five repeated experiments, the degradation rate remained essentially unchanged, indicating that the prepared plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst has excellent stability and high reusability.

[0089] The technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made in accordance with the technical solutions of the present invention fall within the protection scope of the present invention.

Claims

1. A method for preparing a plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst, characterized in that, Includes the following steps: S1. Obtain Ag2MoO4 nanoparticles; S2. Ag2MoO4 nanoparticles were dispersed in AgNO3 solution and magnetically stirred under light irradiation to obtain mixed solution B. Mixed solution B was centrifuged, the precipitate was collected, washed, dried, and then thoroughly ground to obtain Ag2MoO4 / Ag nanoparticles. The concentration of AgNO3 solution was 0.05 mol / L, and the molar volume ratio of Ag2MoO4 nanoparticles to AgNO3 solution was 1:2000 (mol / mL). S3, Obtaining In2S3 nanoparticles; S4. Mix and dissolve Ag2MoO4 / Ag nanoparticles and In2S3 nanoparticles in anhydrous ethanol, stir to obtain mixed solution D; centrifuge mixed solution D, take the precipitate, wash, dry and grind it thoroughly to obtain Ag2MoO4 / Ag / In2S3.

2. The preparation method of the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst according to claim 1, characterized in that, In step S2, the light is irradiated with a 300W xenon lamp, the magnetic stirring time is 0.5h, and the drying conditions are drying at 65℃ for 2.0h.

3. The method for preparing the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst according to claim 1, characterized in that, In step S4, the molar ratio of Ag2MoO4 / Ag nanoparticles to In2S3 nanoparticles is 1:1, the stirring conditions are 1.0 h at room temperature, and the drying conditions are 4.0 h at 65 °C.

4. The method for preparing the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst according to claim 1, characterized in that, In step S1, AgNO3 and Na2MoO4 are mixed and dissolved in deionized water and stirred to obtain mixed solution A; mixed solution A is centrifuged, the precipitate is collected, washed, dried and then thoroughly ground to obtain Ag2MoO4 nanoparticles.

5. The method for preparing the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst according to claim 4, characterized in that, In step S1, the molar ratio of AgNO3 to Na2MoO4 is 2:1, the molar volume ratio of Na2MoO4 to deionized water is 1:100 (mol / mL), the stirring conditions are 1.0 h at room temperature, and the drying conditions are 2.0 h at 65 °C.

6. The method for preparing the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst according to claim 1, characterized in that, In step S3, InCl3 and Na2S·9H2O are mixed and dissolved in deionized water and stirred to obtain mixed solution C; mixed solution C is centrifuged, the precipitate is collected, washed, dried and then thoroughly ground to obtain In2S3 nanoparticles.

7. The method for preparing the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst according to claim 6, characterized in that, In step S3, the molar ratio of InCl3 to Na2S·9H2O is 2:3, the molar volume ratio of InCl3 to deionized water is 1:50, the stirring conditions are 1.0 h at room temperature, and the drying conditions are 4.0 h at 65 °C.

8. A plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst prepared by the method according to any one of claims 1 to 7.

9. The application of the plasma-enhanced Z-type Ag2MoO4 / Ag / In2S3 photocatalyst as described in claim 8 in the photocatalytic degradation of tetracycline.

10. The application of the plasma-enhanced Z-type Ag₂MoO₄ / Ag / In₂S₃ photocatalyst according to claim 9 in the photocatalytic degradation of tetracycline, characterized in that, Used for photocatalytic degradation of tetracycline under alkaline conditions.

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