Ag3PO4 / CoMoO4 composite material, preparation method thereof and application of Ag3PO4 / CoMoO4 composite material in ultrasonic catalytic degradation of organic pollutants in wastewater

Abstract

The invention discloses an Ag3PO4 / CoMoO4 composite material, a preparation method thereof and application of the Ag3PO4 / CoMoO4 composite material in ultrasonic catalytic degradation of organic pollutants in wastewater. The mass of the Ag3PO4 accounts for 50%-80% of the mass of the added CoMoO4. The preparation method comprises the following steps: pouring a stirred AgNO3 solution into a stirred CoMoO4 solution, then pouring a Na3PO4 solution into a mixed solution, mixing, stirring, carrying out suction filtration, washing, and drying to obtain the Ag3PO4 / CoMoO4 composite material. The prepared Ag3PO4 / CoMoO4 composite material is combined with ultrasonic to degrade NGB in water, the ultrasonic power is 500 W, the ultrasonic time is 120 min, and the degradation rate of NGB in water can reach 95.42 (+ / -1.24)%.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid ultrasonic catalysis, and specifically relates to an Ag3PO4 / CoMoO4 composite material and a preparation method thereof, and application thereof in ultrasonic catalytic degradation of organic pollutants in wastewater. Background Art

[0002] Effective purification of wastewater containing various synthetic organic dyes plays an important role in improving human health and quality of life, as well as protecting aquatic ecosystems. Naphthol green B (NGB) is a well-known colorant used in the textile industry. While several adsorbent materials can be used to remove dyes, their negative effects and toxicity have been addressed in numerous studies. Sonocatalytic degradation has been shown to be a more effective, safe, efficient, and universally applicable method for removing various organic pollutants from wastewater. Summary of the Invention

[0003] The purpose of the present invention is to provide an Ag3PO4 / CoMoO4 composite material with high degradation efficiency, which serves as an efficient acoustic catalyst for effectively solving water pollution. It has broad application potential and universality and has high acoustic catalytic degradation performance for different dyes.

[0004] The technical solution adopted by the present invention is: an Ag3PO4 / CoMoO4 composite material, the mass of Ag3PO4 accounts for 50%-80% of the mass of the added CoMoO4.

[0005] In the above-mentioned Ag 3 PO 4 / CoMoO 4 composite material, the mass of Ag 3 PO 4 accounts for 70% of the mass of the added CoMoO 4.

[0006] The above-mentioned Ag3PO4 / CoMoO4 composite material has a preparation method comprising the following steps: pouring the stirred AgNO3 solution into the stirred CoMoO4 solution, then pouring the Na3PO4 solution into the mixed solution, mixing and stirring, filtering, washing and drying to obtain the Ag3PO4 / CoMoO4 composite material.

[0007] The above-mentioned Ag3PO4 / CoMoO4 composite material, the preparation method of CoMoO4 includes the following steps: pouring Co(NO3)2·6H2O solution into Na2MoO4·2H2O solution, mixing and stirring, placing in a polytetrafluoroethylene reactor, carrying out a hydrothermal reaction, cooling to room temperature, centrifuging and collecting the precipitate, washing, drying, and then grinding to obtain a purple powder, and then calcining the obtained purple powder to a purple-green powder.

[0008] The hydrothermal reaction conditions of the above-mentioned Ag3PO4 / CoMoO4 composite material are 160°C for 15 hours.

[0009] The above-mentioned Ag3PO4 / CoMoO4 composite material is calcined at 500°C for 5 hours.

[0010] The application of the above-mentioned Ag3PO4 / CoMoO4 composite material in the ultrasonic catalytic degradation of organic pollutants in wastewater.

[0011] The above application method is as follows: adding Ag3PO4 / CoMoO4 composite material to wastewater containing organic pollutants and ultrasonically treating it.

[0012] In the above application, the organic pollutant is one or more of methyl orange, rose bengal B, gentian violet, methylene blue, and naphthol green B.

[0013] In the above application, the amount of Ag3PO4 / CoMoO4 composite material added to the organic pollutants was 0-2 g / L, and the initial concentration of the organic pollutants was 50 mg / L. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 1 is the XRD spectrum of the Ag3PO4 / CoMoO4 composite materials with different composite ratios obtained in Example 1.

[0015] Figure 2 SEM images of CoMoO4 (A), Ag3PO4 (B) and composite AC-70 (C).

[0016] Figure 3 This is the image of the change in the removal rate of NGB by the AC sonocatalytic system under different Ag3PO4 composite percentages.

[0017] Figure 4 The effect of AC-70 dosage on NGB removal rate.

[0018] Figure 5 This is the degradation effect of K2S2O8+AC-70 system on different dyes.

[0019] Specific example method

[0020] The present invention is described in detail below with reference to the embodiments.

[0021] Example 1

[0022] (1) Preparation of Ag3PO4 / CoMoO4 composite materials with different composite ratios

[0023] 1) Preparation of CoMoO4: 1.2098 g of Na2MoO4·2H2O and 1.4552 g of Co(NO3)2·6H2O were weighed and dissolved in 40 mL of deionized water. The beaker was placed on a magnetic stirrer and stirred for 30 minutes. The Co(NO3)2·6H2O solution was then poured into the Na2MoO4·2H2O solution, and mixing and stirring were continued for 30 minutes. After stirring, the mixed solution was placed in a 100 mL polytetrafluoroethylene reactor and reacted at 160°C in a digital air drying oven for 15 hours. After the reaction was complete, it was cooled to room temperature, the precipitate was collected by centrifugation, washed repeatedly with distilled water and anhydrous ethanol, dried at 80°C, and then ground into a powder to obtain a purple powder. The purple powder was then poured into a crucible and calcined at 500°C in a TDW temperature controller for 5 hours to obtain a purple-green powder.

[0024] 2) Preparation of Ag3PO4 composite material: 2.5481 g of AgNO3 and 1.9006 g of Na3PO4·12H2O were weighed and dissolved in 40 mL of deionized water with stirring. The stirred Na3PO4 solution was poured into the AgNO3 solution, and the mixture was mixed and stirred for 30 min. After ultrasonication for 30 min, the solution was transferred to a polytetrafluoroethylene reactor and reacted at 180°C in a digital air drying oven for 24 h. After the reaction was complete, it was cooled to room temperature and the precipitate was collected by centrifugation. The precipitate was washed repeatedly with distilled water and anhydrous ethanol, dried at 60°C, and then ground into a powder to obtain a yellow powder.

[0025] 3) Preparation of Ag3PO4 / CoMoO4 composite material: Weigh different masses of CoMoO4, AgNO3, and Na3PO4·12H2O, dissolve each in 20 mL of deionized water and stir. Pour the stirred AgNO3 solution into the stirred CoMoO4 solution, then pour the Na3PO4 solution into the mixed solution, and stir for 1 hour. Wash the resulting precipitate three times with deionized water and dry it in an oven at 60°C for 15 hours. After the sample is dry, remove it and grind it thoroughly to obtain an Ag3PO4 / CoMoO4 composite material. Composite materials with composite ratios of 50%, 60%, 70%, and 80% are prepared. The resulting dried Ag3PO4 / CoMoO4 product is ground and labeled for later use.

[0026] The composites were named AC-50, AC-60, AC-70, and AC-80 according to the theoretical yield of Ag3PO4 and the ratio of CoMoO4.

[0027] (2) Characterization of Ag3PO4 / CoMoO4 composites

[0028] X-ray diffraction analysis was performed on Ag3PO4 / CoMoO4 composite materials with different mass ratios. The test results are as follows: Figure 1 As shown in the figure, all samples show sharp and obvious diffraction peaks. The peaks in Ag3PO4 / CoMoO4 are consistent with the peaks of pure phase Ag3PO4 and CoMoO4, and no other impurity phases are produced, which indicates that high-purity Ag3PO4 / CoMoO4 composite materials have been successfully prepared.

[0029] Figure 1 The X-ray diffraction analysis of Ag3PO4 / CoMoO4 composite materials with different mass ratios is as follows: Figure 1 As shown in the figure, all samples exhibit sharp and distinct diffraction peaks. It can be seen that the peaks of CoMoO4 in the composites with different mass ratios are well consistent with the peaks of pure CoMoO4. It can be seen that as the composite ratio increases, the peak becomes weaker and weaker. This is because the proportion of CoMoO4 is getting smaller and smaller. The peak of Ag3PO4 in the composite is completely consistent with the pure phase Ag3PO4 and becomes higher and higher as the composite ratio increases. There is no other impurity phase, which indicates that high-purity Ag3PO4 / CoMoO4 composite materials have been successfully prepared.

[0030] Figure 2 The following are SEM images of CoMoO4, Ag3PO4 and composite AC-70. Figure 2 It can be seen that CoMoO4 synthesized by hydrothermal method presents irregular shape. Ag3PO4 presents polyhedral structure. Meanwhile, the composite AC synthesized by coprecipitation method. Figure 2 As shown, it can be seen that the polyhedral shape of Ag3PO4 is embedded in CoMoO4. This result shows that CoMoO4 and Ag3PO4 have been successfully composited.

[0031] Example 2: Ag3PO4 / CoMoO4 composite material synergistically used for ultrasonic catalytic degradation of NGB

[0032] (1) Method for removing NGB by stirring adsorption of Ag3PO4 / CoMoO4 composite materials with different composite ratios:

[0033] Use an analytical balance to weigh 0.04g CoMoO4, at which point the Ag3PO4 composite ratio is considered to be 0%, and add it to a 250mL conical flask. Add 40mL of a 50mg / L NGB solution to the flask. After magnetic stirring, take a sample and centrifuge it. Take the supernatant and detect its absorbance using a UV-visible spectrophotometer. Calculate the efficiency of the CoMoO4 composite material in removing NGB by adsorption. Measure the adsorption removal rate of NGB by AC-50, AC-60, AC-70, and AC-80 using the same method. Compare the reactions of adding Ag3PO4 / CoMoO4 composite materials with different composite ratios to the NGB solution. The results are shown in the figure below. Figure 3 “Adsorption” refers to the removal effect of NGB in the presence of only a catalyst but without ultrasound.

[0034] (II) Synergistic ultrasonic catalytic degradation of NGB using Ag3PO4 / CoMoO4 composite materials with different composite ratios:

[0035] Use an analytical balance to weigh 0.04g of CoMoO4, at which point the Ag3PO4 composite ratio is considered to be 0%, and add it to a 250mL conical flask, and add 40mL of a 50mg / L NGB solution to the flask. Use an iron stand to place the above-mentioned conical flask above the ultrasonic cleaner so that the water surface in the instrument is just in contact with the bottom of the conical flask. Use a black plastic bag to provide a dark environment for the reaction to remove interference from the light source. Ultrasonicate for 120 minutes at an ultrasonic power of 500W. The reacted solution is extracted with a syringe and filtered through a membrane to obtain the supernatant. The absorbance is measured by an ultraviolet spectrophotometer, and the efficiency of ultrasonic degradation of NGB by CoMoO4 composite material is calculated. The efficiency of synergistic ultrasonic catalytic degradation of NGB by AC-50, AC-60, AC-70, and AC-80 is measured in the same way, and the reaction of adding Ag3PO4 / CoMoO4 composite materials with different composite ratios to the NGB solution is compared. The results are as follows Figure 3 "Degradation" is the NGB removal effect under the synergistic action of ultrasound and catalyst. As can be seen from the figure, AC-70 has the best NGB removal effect, reaching 95.42 (±1.24)%. This is because the combination of CoMoO4 and Ag3PO4 forms a heterojunction, which increases the specific surface area, provides more active sites, and thus improves the removal efficiency. When the combination ratio exceeds 70%, the removal rate decreases. This may be because the excessive addition of Ag3PO4 reduces the contact area with the dye and covers the active sites of CoMoO4, resulting in a decrease in the amount of ROS generated, which in turn affects the sonocatalytic activity.

[0036] (III) Method for removing NGB by stirring and adsorption of Ag3PO4 / CoMoO4 composite materials with different addition amounts:

[0037] Use a balance to accurately weigh a certain amount of AC-70 and add it to a 250mL conical flask, add 50mg / LNGB solution to the conical flask, place the conical flask on a magnetic stirrer and stir, and carry out under dark conditions. After stirring, centrifuge the sample, collect the supernatant sample, and calculate the adsorption removal rate of AC-70 on NGB by measuring the absorbance. Change the input amount of AC-70 to 0g / L, 0.5g / L, 1.0g / L, 1.5g / L, and 2.0g / L and measure the adsorption removal rate under different addition amounts. The results are as follows Figure 4 “Adsorption” refers to the removal effect of NGB in the presence of only a catalyst but without ultrasound.

[0038] (IV) Synergistic ultrasonic catalytic degradation of NGB by Ag3PO4 / CoMoO4 composite materials with different addition amounts:

[0039] Use a balance to accurately weigh a certain amount of AC-70 and add it to a 250mL conical flask, add 50mg / LNGB solution to the conical flask, and place the conical flask accurately above the ultrasonic site. Cover with a black plastic bag to create a dark environment, and sonicate at 500W power for 120 minutes. Collect the supernatant sample, and calculate the ultrasonic degradation rate of NGB by AC-70 synergistically with ultrasound by measuring the absorbance. Similarly, the input amount of AC-70 was changed to 0g / L, 0.5g / L, 1.0g / L, 1.5g / L, and 2.0g / L, and the ultrasonic degradation rates under different addition amounts were measured respectively. The results are as follows Figure 4 "Degradation" refers to the removal effect of NGB under the synergistic effect of ultrasound and catalyst. Figure 4 As can be seen from the figure, when the AC-70 dosage is 1.0 g / L, the NGB removal efficiency reaches 95.42% (±1.24)%. This increase in degradation rate can be attributed to the increased active sites provided by the Ag3PO4 / CoMoO4 catalyst. As the dosage continues to increase, the removal efficiency decreases. This may be due to the excessive addition of the AC-70 composite catalyst causing catalyst agglomeration, which reduces the number of active sites on the catalyst surface and inhibits ultrasonic penetration, thus affecting the catalyst's sonocatalytic activity and leading to a decrease in NGB removal.

[0040] Example 2 Study on ultrasonic degradation of different dyes by K2S2O8+AC-70 system

[0041] Under the experimental conditions of 1.0 g / L AC-70 composite catalyst addition, 50 mg / L NGB dye concentration, 0.7 mmol / L K2S2O8 concentration, 6 dye pH value, 500 W ultrasonic power, and 10 min ultrasonic time, a 10 mg / L methyl orange (MO) solution, a 2 mg / L rose bengal B (RhB) solution, a 10 mg / L gentian violet (GV) solution, and a 10 mg / L methylene blue (MB) solution were prepared. The degradation effect of K2S2O8+AC-70 system on different dyes was evaluated. Under the experimental conditions, the degradation rates of NGB, MO, RhB, GV and MB were 98.47(±0.3)%, 99.27(±0.26)%, 97.13(±0.11)%, and 99.57(±0.13)% respectively. Figure 5 It can be seen that the AC-70 composite catalyst not only has a good degradation effect on azo dye NGB, but also has a good removal rate for other organic dyes, showing a certain universality.

Claims

1. An Ag3PO4 / CoMoO4 composite material, characterized in that The mass of Ag3PO4 accounts for 50%-80% of the mass of the added CoMoO4.

2. The Ag3PO4 / CoMoO4 composite material according to claim 1, characterized in that: The mass of Ag3PO4 accounts for 70% of the mass of the added CoMoO4.

3. The Ag3PO4 / CoMoO4 composite material according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: pouring the stirred AgNO3 solution into the stirred CoMoO4 solution, then pouring the Na3PO4 solution into the mixed solution, mixing and stirring, filtering, washing and drying to obtain the Ag3PO4 / CoMoO4 composite material.

4. An Ag3PO4 / CoMoO4 composite material according to claim 1 or 2, characterized in that The preparation method of CoMoO4 includes the following steps: pouring Co(NO3)2·6H2O solution into Na2MoO4·2H2O solution, mixing and stirring, placing in a polytetrafluoroethylene reactor, carrying out a hydrothermal reaction, cooling to room temperature, collecting the precipitate by centrifugation, washing, drying, and then grinding to obtain a purple powder, and then calcining the obtained purple powder into a purple-green powder.

5. The Ag3PO4 / CoMoO4 composite material according to claim 4, characterized in that: The hydrothermal reaction was carried out at 160°C for 15 h.

6. The Ag3PO4 / CoMoO4 composite material according to claim 4, characterized in that: The calcination was carried out at 500° C. for 5 h.

7. Use of the Ag3PO4 / CoMoO4 composite material according to claim 1 or 2 in ultrasonic catalytic degradation of organic pollutants in wastewater.

8. The use according to claim 7, characterized in that The method is as follows: Ag3PO4 / CoMoO4 composite material is added to wastewater containing organic pollutants and ultrasonically treated.

9. The use according to claim 7, characterized in that The organic pollutants are one or more of methyl orange, rose bengal B, gentian violet, methylene blue, and naphthol green B.

10. The use according to claim 7, characterized in that Among the organic pollutants, the addition amount of Ag3PO4 / CoMoO4 composite material was 0-2g / L, and the initial concentration of organic pollutants was 50mg / L.

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