A CuS / Cu3(MoO4)2(OH)2 composite material, a preparation method and application thereof

Abstract

The application discloses a CuS / Cu3(MoO4)2(OH)2 composite and a preparation method and application thereof. The CuS / Cu3(MoO4)2(OH)2 composite material is prepared by using CuCl2, Na2MoO4 and Na2S as raw materials and adopting a hydrothermal method. The CuS / Cu3(MoO4)2(OH)2 composite acoustic catalyst provided by the application can be used for ultrasonic catalytic degradation of organic pollutants in cooperation with H2O2. When the ultrasonic power is 500 W and the ultrasonic time is 30 min, the degradation rates of acid orange 7, tetracycline, rhodamine B, congo red, methylene blue and basic red 2 in water can reach 89.6(±5.78)%, 92.91(±0.36)%, 96.93(±0.16)%, 97.73(±0.61)%, 98.53(±0.37)% and 99.87(±0.18)%, respectively.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of solid ultrasonic catalysis, and particularly relates to a CuS / Cu3(MoO4)2(OH)2 composite material, a preparation method thereof and application of the composite material in ultrasonic catalytic degradation of pollutants in water in cooperation with H2O2. BACKGROUND

[0002] In recent decades, the influence of synthetic pollutants on the environment has attracted people's attention. Textile, leather, papermaking, pharmaceutical and food industries produce a large amount of pollutant contaminated wastewater in the world. It is estimated that 10-15% of the total production of pollutants in the world is lost in the dyeing process and released into textile wastewater. The release of pollutants not only increases the colority of water bodies but also increases the COD, seriously polluting the environment. Ultrasonic treatment is a very effective method. Due to its unique cavitation effect, ultrasonic waves have the characteristics of mild degradation conditions, wide application range, simple facilities and environmental friendliness, and have attracted the attention of domestic and foreign scholars in the degradation of pollutants. Cu3(MoO4)2(OH)2 has high catalytic activity, good chemical stability, high reusability and environmental friendliness in ultrasonic catalytic degradation of organic pollutants. However, single semiconductor catalytic materials have the problems of fast e--h+ recombination rate, which limits their catalytic performance. In order to improve the catalytic activity, coupling a semiconductor with a narrow Eg (sensitizer) with an ultrasonic catalyst to form a heterojunction structure is an effective means to expand the utilization efficiency of ultrasonic-induced luminescence of the ultrasonic catalyst and inhibit the recombination of e--h+. SUMMARY

[0003] The purpose of the present application is to provide a CuS / Cu3(MoO4)2(OH)2 composite material with high degradation efficiency, green safety and reusability, and to provide a method for ultrasonic catalytic degradation of organic pollutants by CuS / Cu3(MoO4)2(OH)2 composite acoustic catalyst in cooperation with hydrogen peroxide.

[0004] The technical scheme adopted by the present application is to prepare a CuS / Cu3(MoO4)2(OH)2 composite material, which contains 35%, 40%, 45% and 50% of CuS respectively according to the molar ratio.

[0005] A preparation method of a CuS / Cu3(MoO4)2(OH)2 composite material, the preparation method comprising the following steps:

[0006] 1) Dissolve CuCl2 powder in distilled water and stir magnetically at room temperature until dissolved;

[0007] 2) According to the molar ratio of CuS:Cu3(MoO4)2(OH)2, dissolve Na2MoO4 and Na2S powder in distilled water at room temperature and continue to stir until dissolved;

[0008] 3) Add the dissolved CuCl2 solution to the mixed solution, continue stirring at room temperature until dissolution;

[0009] 4) Pour the mixed solution into a reaction kettle with a polytetrafluoroethylene liner and perform hydrothermal reaction; the obtained reaction product is suction filtered, washed, and vacuum dried to obtain a CuS / Cu3(MoO4)2(OH)2 composite with different molar ratios.

[0010] Preferably, in the above CuS / Cu3(MoO4)2(OH)2 composite material, in step 4), the hydrothermal reaction conditions are a temperature of 433.15 K for 12 h.

[0011] Preferably, in the above CuS / Cu3(MoO4)2(OH)2 composite material, in step 4), the drying conditions are a temperature of 333.15 K for 6 h under vacuum.

[0012] Preferably, in the above CuS / Cu3(MoO4)2(OH)2 composite material, the optimal composite ratio is 40% CuS.

[0013] The above CuS / Cu3(MoO4)2(OH)2 composite material is used as a sonocatalyst in combination with ultrasound for degrading organic pollutants.

[0014] In the above application, the CuS / Cu3(MoO4)2(OH)2 catalyst and H2O2 are added to wastewater containing one or more of acid orange 7 AO7, tetracycline TC, rhodamine B RhB, congo red CR, methylene blue MB, and basic red 2 BR2, and the ultrasonic time is 30 min and the ultrasonic power is 500 W.

[0015] In the above application, the amount of CuS / Cu3(MoO4)2(OH)2 composite material added is 2.0 g / L, and the concentration of H2O2 is 0.9 mol / L.

[0016] In the above application, the initial concentrations of acid orange 7, tetracycline, rhodamine B, congo red, methylene blue, and basic red 2 are all 8 mg / L.

[0017] The beneficial effects of the present application are: compared with Cu3(MoO4)2(OH)2, the sono-catalytic performance of CuS is lower, after compounding Cu3(MoO4)2(OH)2 and CuS, when the compounding ratio is 40%, the CuS / Cu3(MoO4)2(OH)2 composite material prepared will not cause secondary environmental pollution while degrading organic pollutants with ultrasonic and hydrogen peroxide, and belongs to the environment-friendly catalyst. The present application has the characteristics of high removal efficiency, high safety performance, short reaction time, low energy consumption, small environmental pollution and suitable for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 The XRD graph of the CuS / Cu3(MoO4)2(OH)2 composite material prepared for different CuS molar ratios.

[0019] Figure 2 The scanning electron microscope (SEM) spectrum of pure phase Cu3(MoO4)2(OH)2, pure phase CuS and CuS / Cu3(MoO4)2(OH)2 composite material.

[0020] (A)(B): Cu3(MoO4)2(OH)2; (C)(D): CuS; (E)(F): CuS / Cu3(MoO4)2(OH) 2。

[0021] Figure 3 The effect comparison chart of CuS / Cu3(MoO4)2(OH)2 composite sono-catalyst and different amounts of H2O2 synergistically sono-catalytic degradation of BR2.

[0022] Figure 4 The effect chart of CuS / Cu3(MoO4)2(OH)2 composite sono-catalyst and hydrogen peroxide synergistically sono-catalytic degradation of acid orange 7, tetracycline, rhodamine B, congo red, methylene blue and basic red 2. DETAILED DESCRIPTION

[0023] The present application will be described in detail below in combination with examples.

[0024] Comparative Example 1 Cu3(MoO4)2(OH)2 composite material

[0025] Preparation of Cu3(MoO4)2(OH)2: 0.8475g of CuCl2 was dissolved in 30mL of distilled water, 1.21g of Na2MoO4 was dissolved in 30mL of distilled water, and magnetic stirring was carried out at room temperature until dissolution. After dissolution, the Na2MoO4 solution was poured into the above CuCl2 solution, and magnetic stirring was carried out at room temperature until dissolution. Hydrothermal synthesis method was adopted, and the reaction was carried out at a temperature of 333.15K for 6h, and then grinding was carried out to obtain Cu3(MoO4)2(OH)2 nanomaterial.

[0026] Example 1 CuS / Cu3(MoO4)2(OH)2 composite material

[0027] Preparation of CuS / Cu3(MoO4)2(OH)2 composite material: 1.7048 g of CuCl2 was dissolved in 30 ml of distilled water, a certain mass of Na2MoO4 (1.9356 g) was weighed and dissolved in distilled water together with Na2S (0.4204 g, 0.4804 g, 0.5405 g, 0.60105 g), and stirred magnetically at room temperature until dissolved. 30 ml of the above CuCl2 solution was added to the system, and stirring was continued until dissolution. The suspension was poured into a reaction kettle with a polytetrafluoroethylene liner, and then placed in an oven for reaction at 433.15 K for 12 h. The obtained suspension was filtered under suction to obtain a dark green precipitate, which was washed with distilled water and anhydrous ethanol, and dried under vacuum at 333.15 K for 6 h. The CuS / Cu3(MoO4)2(OH)2 composite material with a CuS molar composite ratio of 35%, 40%, 45%, and 50% was obtained by grinding, and was marked as "CC-35", "CC-40", "CC-45", and "CC-50", respectively.

[0028] Example 2 Characterization and analysis of pure phase Cu3(MoO4)2(OH)2, pure phase CuS and CuS / Cu3(MoO4)2(OH)2 composite material

[0029] The CuS / Cu3(MoO4)2(OH)2 composite material with different molar ratios of Example 1 was subjected to X-ray diffraction analysis, and the detection results are shown in Figure 1 When the molar composite ratio of CuS / Cu3(MoO4)2(OH)2 is 35%-50%, all the samples exhibit sharp and obvious diffraction peaks, which can be well matched with the diffraction peaks of standard Cu3(MoO4)2(OH)2 and CuS, and no other impurities are produced, which indicates that the high-purity CuS / Cu3(MoO4)2(OH)2 composite material is successfully prepared.

[0030] The standard CuS and the prepared Cu3(MoO4)2(OH)2 and CuS / Cu3(MoO4)2(OH)2 composite material were analyzed by scanning electron microscopy, and the results are shown in Figure 2 Cu3(MoO4)2(OH)2 has a nanorod-like three-dimensional structure with a smooth surface, CuS has a nanoparticle structure, and a small amount of particle structure is attached to the surface of the main structure of CuS / Cu3(MoO4)2(OH)2 composite material.

[0031] Example 3 Effect comparison of CuS / Cu3(MoO4)2(OH)2 composite sonocatalyst and different amounts of H2O2 on the synergistic sonocatalytic degradation of BR2

[0032] As shown in Figure 3 , when the ultrasonic time is 30 min and the initial concentration of H2O2 increases from 0.25 mol / L to 0.90 mol / L, the removal rate of BR2 gradually increases, which is 87.28(±0.66)%, 90.58(±1.68)%, 94.6(±1.36)% and 99.87(±0.18)% respectively. When the initial concentration of H2O2 increases from 0.90 mol / L to 1.00 mol / L, the removal rate of BR2 decreases, which is 95.42(±2.78)%. The possible reason for this decrease is that the free radicals are quenched by excess H2O2. Therefore, the optimal concentration of H2O2 is 0.90 mol / L.

[0033] Example 4 Synergistic sonocatalytic degradation of acid orange 7, tetracycline, rhodamine B, congo red, methylene blue and BR2 by CuS / Cu3(MoO4)2(OH)2 composite sonocatalyst and hydrogen peroxide

[0034] 1) The concentration of the pollutant solution is 8 mg / L, 2 g / L of CuS / Cu3(MoO4)2(OH)2(CC-40) composite material with a molar ratio of 40% and 0.9 mol / L of H2O2 are added respectively to configure a suspension.

[0035] 2) The suspension in step 1) is placed in a 500 W ultrasonic cleaner for ultrasonic treatment for 30 min. After treatment, the suspension is centrifuged and the supernatant is taken to measure the absorbance and calculate the efficiency of H2O2 synergistic CuS / Cu3(MoO4)2(OH)2 composite sonocatalyst ultrasonic degradation of each pollutant. It can be seen from Figure 4 that the removal rates of H2O2 / CC-40 / US system for AO7, TC, RhB, CR, MB and BR2 organic pollutants are 89.6(±5.78)%, 92.91(±0.36)%, 96.93(±0.16)%, 97.73(±0.61)%, 98.53(±0.37)% and 99.87(±0.18)% respectively. The results show that the synergistic effect of H2O2 / CC-40 / US system can efficiently remove different organic pollutants, which has potential application value and provides some research basis for the practical application of treating organic wastewater.

Claims

1. A CuS / Cu3(MoO4)2(OH)2 composite material, characterized in that, The CuS / Cu3(MoO4)2(OH)2 composite material contains 35%-50% CuS by molar percentage. The preparation method of the CuS / Cu3(MoO4)2(OH)2 composite material includes the following steps: preparing CuCl2 solution, and simultaneously dissolving Na2MoO4 and Na2S together in distilled water according to the molar ratio of Cu3(MoO4)2(OH)2:CuS, stirring until dissolved; adding the dissolved CuCl2 solution to the mixed solution, and stirring continuously at room temperature until dissolved; pouring the mixed solution into a reaction vessel with a polytetrafluoroethylene liner for hydrothermal reaction; filtering, washing, and vacuum drying the obtained reactants to obtain CuS / Cu3(MoO4)2(OH)2 composites with different molar ratios.

2. The CuS / Cu3(MoO4)2(OH)2 composite material according to claim 1, characterized in that, The CuS / Cu3(MoO4)2(OH)2 composite material contains 40% CuS by molar percentage.

3. The method for preparing a CuS / Cu3(MoO4)2(OH)2 composite material according to claim 1 or 2, characterized in that, The process includes the following steps: preparing a CuCl2 solution; simultaneously, according to the molar ratio of Cu3(MoO4)2(OH)2:CuS, dissolving Na2MoO4 and Na2S together in distilled water and stirring until dissolved; adding the dissolved CuCl2 solution to the mixed solution and stirring continuously at room temperature until dissolved; pouring the mixed solution into a reaction vessel lined with polytetrafluoroethylene for hydrothermal reaction; filtering, washing, and vacuum drying the resulting reactants to obtain CuS / Cu3(MoO4)2(OH)2 composites with different molar ratios.

4. The preparation method according to claim 3, characterized in that, The hydrothermal reaction conditions were 433.15 K for 12 h.

5. The preparation method according to claim 4, characterized in that, The vacuum drying process involved vacuum drying at 333.15 K for 6 hours.

6. The application of the CuS / Cu3(MoO4)2(OH)2 composite material as described in claim 1 or 2 in the ultrasonic catalytic degradation of organic pollutants.

7. The application according to claim 6, characterized in that, The method is as follows: CuS / Cu3(MoO4)2(OH)2 composite material and H2O2 are added to the wastewater containing organic pollutants, and ultrasonication is performed for 30 minutes at an ultrasonic power of 500W.

8. The application according to claim 7, characterized in that, The initial concentration of organic pollutants was adjusted to 8 mg / L; the amount of CuS / Cu3(MoO4)2(OH)2 composite material added was 2.0 g / L, and the H2O2 concentration was 0.9 mol / L.

9. The application of the CuS / Cu3(MoO4)2(OH)2 composite material according to claim 6 in the ultrasonic catalytic degradation of organic pollutants, characterized in that, The organic pollutant is one or more of Acid Orange 7, tetracycline, Rhodamine B, Congo Red, Methylene Blue, and Basic Red 2.

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