A ZnO-ZnMnO3 / CuS composite catalytic material, its preparation method and application

Abstract

The present invention discloses a ZnO-ZnMnO3 / CuS composite catalytic material, its preparation method and application. The preparation method is as follows: Dissolve zinc salt and manganese salt in deionized water, then add sodium hydroxide solution, and then add excessive hydrogen peroxide to form a suspension. The precursor obtained by hydrothermal reaction of the suspension is dried, calcined and ground to obtain ZnO-ZnMnO3 material; Take an appropriate amount of ZnO-ZnMnO3 and dissolve it in deionized water. After ultrasonic treatment, copper nitrate trihydrate solution and sodium sulfide nonahydrate solution are successively dropped in, stirred, aged at room temperature, washed, dried and ground to obtain ZnO-ZnMnO3 / CuS composite material. The preparation method of the present invention is simple, the conditions are easy to control, and the cost is low. A good synergistic effect is generated between Zn and Mn in the obtained composite catalytic material. The introduction of CuS further improves the electron transfer rate of ZnO-ZnMnO3, and at the same time enhances the catalytic activity of ZnMnO3 in the activation of PMS, generates more active free radicals, improves the catalytic efficiency of the composite material, has a significant degradation effect on antibiotics in wastewater, has a high reuse rate, and has good application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of wastewater treatment, and particularly relates to a ZnO-ZnMnO3 / CuS composite catalytic material, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, advanced oxidation processes (AOPs) have received increasing attention in the field of wastewater treatment. It mainly degrades organic pollutants by generating reactive oxygen species (ROS) such as ·OH and SO4·- in the system. Compared with other wastewater treatment methods, sulfate radical-based advanced oxidation processes (SR-AOPs) have various advantages such as strong oxidation ability and wide application range. Peroxymonosulfate (PMS) is an oxidant used to generate SO4·-, which has an asymmetric structure and is relatively easy to be activated by catalysts. The reaction system for activating PMS by transition metal catalysts and carbon material catalysts has the characteristics of excellent catalytic performance and low energy requirements, and is an important free radical activation technology. However, single transition metal materials often have problems such as low catalytic efficiency or large leaching. To improve their catalytic degradation efficiency, scholars have reported a variety of composite catalyst materials, and such catalysts exhibit better catalytic degradation performance and stability than single transition metal element catalysts.

[0003] Therefore, the development of transition metal-based composite catalysts is beneficial to make up for the defects of single-phase catalyst materials and provides a reliable option for removing antibiotic drugs in water. The combination of zinc and manganese has significant performance in activating PMS and shows excellent degradation efficiency of CIP. Moreover, transition metal dichalcogenides (TMDCs), especially copper sulfide (CuS), are widely used as electrocatalysts, which is one of the methods to regulate electron transfer and improve catalytic performance. Previous studies by the research group of the present invention have shown that the presence of S species can accelerate the Cu ion cycle and the system has extremely high degradation stability, which confirms the great potential of transition metal sulfides in activating persulfate to degrade organic pollutants. Based on this, the present invention provides a composite catalytic material containing transition metal sulfides with significant catalytic performance. Summary of the Invention

[0004] The present invention provides a ZnO-ZnMnO3 / CuS composite catalytic material, a preparation method thereof, and an application thereof. By using a simple preparation method, zinc manganese oxide is combined with CuS to effectively improve the catalytic activity of zinc manganese oxide in PMS activation and achieve efficient treatment of antibiotic wastewater.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] A preparation method of a ZnO-ZnMnO3 / CuS composite catalytic material, comprising the following steps:

[0007] (1) Dissolve zinc salt and manganese salt in deionized water, then add sodium hydroxide solution under stirring conditions, and then add excessive hydrogen peroxide to form a suspension. After subjecting the suspension to hydrothermal reaction, a precursor is obtained;

[0008] (2) After the precursor is dried, it is calcined and ground to obtain ZnO-ZnMnO3 material;

[0009] (3) Dissolve an appropriate amount of ZnO-ZnMnO3 material in deionized water and sonicate it. Then, sequentially drop in copper nitrate trihydrate solution and sodium sulfide nonahydrate solution, stir for 2 h, age at room temperature for 2 h, and then wash, dry, and grind to obtain ZnO-ZnMnO3 / CuS composite catalytic material.

[0010] The present invention successively adopts hydrothermal method, calcination method, and precipitation method to prepare ZnO-ZnMnO3 / CuS composite catalytic material.

[0011] Preferably, the molar ratio of the zinc salt, manganese salt, and sodium hydroxide is (2-5):1:(6-12).

[0012] Preferably, the molar ratio of the zinc salt, manganese salt, and sodium hydroxide is 4:1:10.

[0013] Preferably, the zinc salt is zinc nitrate hexahydrate and the manganese salt is manganese chloride tetrahydrate.

[0014] Preferably, the conditions of the hydrothermal reaction are hydrothermal temperature of 120-180 °C and heat preservation for 8-20 h.

[0015] Preferably, the conditions of the calcination are calcination temperature of 400-700 °C, heating rate of 5 °C / min, and calcination time of 1-4 h.

[0016] Preferably, in step (3), the mass ratio of the ZnO-ZnMnO3 material to copper nitrate trihydrate is (0.5-2):1.

[0017] Compared with the disadvantages and deficiencies of the prior art, the present invention has the following beneficial effects:

[0018] (1) The ZnO-ZnMnO3 / CuS composite catalytic material prepared by the present invention has remarkable catalytic performance. It can effectively degrade antibiotics in wastewater by activating PMS. The synergistic effect of ZnO-ZnMnO3 and CuS can significantly improve the activity of ZnMnO3 during the activation of PMS, generating more reactive free radicals through the activation of PMS to effectively degrade antibiotic pollutants such as ciprofloxacin, enrofloxacin, and tetracycline. The ZnO-ZnMnO3 / CuS composite catalytic material can degrade antibiotic wastewater within a wide pH range, and the pH value range of the antibiotic wastewater can reach 3 - 11. Compared with single ZnO, ZnMnO3, CuS, etc., the ZnO-ZnMnO3 / CuS composite catalytic material has better ability to activate PMS to degrade antibiotics. The ZnO-ZnMnO3 / CuS composite catalytic material has good removal effect, high reuse rate, and is clean and pollution-free in degrading antibiotics in wastewater, and it is a catalytic material that can be widely used and can efficiently remove antibiotics in water bodies;

[0019] (2) The preparation method of the present invention is simple, easy to operate, the conditions are easy to control, and the cost is low. In the ZnO-ZnMnO3 / CuS composite catalytic material, the combination of ZnO-ZnMnO3 and CuS is used to optimize the electron transfer ability and the ability of PMS attachment of the catalyst, thereby improving the catalytic efficiency of the composite material. Description of the Drawings

[0020] Figure 1 are the XRD diffraction patterns of ZnO-ZnMnO3, CuS, and ZnO-ZnMnO3 / CuS provided in Examples 1 - 2.

[0021] Figure 2 is a comparison chart of the degradation efficiency of different catalytic materials provided in Examples 1 - 2 for ciprofloxacin (CIP).

[0022] Figure 3 is the degradation chart of ZnO-ZnMnO3 / CuS nanocomposites with different molar ratios of ZnO and ZnMnO3 provided in Examples 2 - 5 for ciprofloxacin (CIP).

[0023] Figure 4 is the degradation chart of ZnO-ZnMnO3 / CuS nanocomposites with different masses of CuS provided in Examples 2 and 6 - 7 for ciprofloxacin (CIP).

[0024] Figure 5 is the degradation chart of ZnO-ZnMnO3 / CuS nanocomposite with different dosages and different dosages of potassium hydrogen persulfate for ciprofloxacin (CIP) provided in Example 2.

[0025] Figure 6It is the degradation diagram of ZnO-ZnMnO3 / CuS nanocomposite provided in Example 2 for ciprofloxacin (CIP) under the influence of different anions and humic acid.

[0026] Figure 7 It is the degradation diagram of ZnO-ZnMnO3 / CuS nanocomposite provided in Example 2 for ciprofloxacin (CIP) at different pH values. Detailed implementation manners

[0027] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0028] 1. Preparation of catalytic material

[0029] The preparation method of ZnO-ZnMnO3 / CuS composite catalytic material is as follows:

[0030] (1) Dissolve zinc nitrate hexahydrate, manganese chloride tetrahydrate and sodium hydroxide in deionized water, then quickly add sodium hydroxide solution under stirring conditions, and then add excessive hydrogen peroxide to form a suspension. After hydrothermal reaction of the suspension, a precursor is obtained;

[0031] (2) After the precursor is dried, it is subjected to high-temperature calcination and grinding to obtain ZnO-ZnMnO3 material;

[0032] (3) Dissolve an appropriate amount of ZnO-ZnMnO3 material in deionized water and ultrasonicate it. Then, copper nitrate trihydrate solution and sodium sulfide nonahydrate solution are successively dropped in, stirred for 2 h, aged at room temperature for 2 h, then washed, dried and ground to obtain ZnO-ZnMnO3 / CuS composite material. Example 1

[0033] Prepare ZnO-ZnMnO3 / CuS composite catalytic material, and at the same time prepare ZnO, ZnMnO3, CuS, ZnO-ZnMnO3, ZnMnO3 / CuS, ZnO / CuS catalytic materials according to the corresponding methods. The specific methods are as follows:

[0034] (1) Preparation of ZnO catalytic material: Dissolve 1.3 mmol of Zn(NO3)2·6H2O and 2.6 mmol of sodium hydroxide in deionized water respectively. Then, quickly pour the sodium hydroxide solution into the zinc nitrate solution under stirring conditions, and add 1 mL of hydrogen peroxide to form a suspension. The suspension is taken out after being kept warm in an oven at 160 °C for 16 h, and the product is washed several times with deionized water and ethanol and then dried in an oven. Subsequently, the powder is heated and sintered in air at 600 °C at a rate of 5 °C / min for 2 h, and the ZnO catalytic material is obtained after grinding.

[0035] (2) Preparation of ZnMnO3 catalytic material: Dissolve 1.3 mmol of Zn(NO3)2·6H2O and 1.3 mmol of MnCl2·4H2O in deionized water to form solution A; dissolve 5.2 mmol of sodium hydroxide in deionized water to form solution B; quickly pour solution B into solution A under stirring conditions, and add 1 mL of hydrogen peroxide to form a suspension. The suspension is taken out after being kept warm in an oven at 160 °C for 16 h, and the product is washed several times with deionized water and ethanol and then dried in an oven. The dried powder is heated and sintered in air at 600 °C at a rate of 5 °C / min for 2 h, and the ZnMnO3 catalytic material is obtained after grinding.

[0036] (3) Preparation of CuS catalytic material: Dissolve copper nitrate trihydrate and sodium sulfide nonahydrate in deionized water and stir them according to a molar ratio of 1:1. After a period of time, drop the sodium sulfide nonahydrate solution into the copper nitrate trihydrate solution, continue stirring for 2 h, and age at room temperature for 2 h, then wash, dry and grind to obtain the CuS catalytic material.

[0037] (4) Preparation of ZnO-ZnMnO3 catalytic material: Dissolve 2.6 mmol of Zn(NO3)2·6H2O and 1.3 mmol of MnCl2·4H2O in deionized water to form solution A; dissolve 7.8 mmol of sodium hydroxide in deionized water to form solution B; quickly pour solution B into solution A under stirring conditions, and add 1 mL of hydrogen peroxide to form a suspension. The suspension is taken out after being kept warm in an oven at 160 °C for 16 h, and the product is washed several times with deionized water and ethanol and then dried in an oven. The dried powder is heated and sintered in air at 600 °C at a rate of 5 °C / min for 2 h, and the ZnO-ZnMnO3 catalytic material is obtained after grinding.

[0038] (5) Preparation of ZnO / CuS composite material: Dissolve the ZnO material obtained in (1) in an appropriate amount of deionized water and ultrasonicate for 30 min to form a suspension. At the same time, dissolve copper nitrate trihydrate and sodium sulfide nonahydrate in deionized water and stir them respectively according to a molar ratio of 1:1. After a period of time, drop the copper nitrate trihydrate solution into the suspension. After 20 min, add the sodium sulfide nonahydrate solution and continue stirring for 2 h. Then age at room temperature for 2 h, wash, dry, and grind to obtain the ZnO / CuS composite material.

[0039] (6) Preparation of ZnMnO3 / CuS composite material: Dissolve the ZnMnO3 material obtained in (2) in an appropriate amount of deionized water and ultrasonicate for 30 min to form a suspension. At the same time, dissolve copper nitrate trihydrate and sodium sulfide nonahydrate in deionized water and stir them respectively according to a molar ratio of 1:1. After a period of time, drop the copper nitrate trihydrate solution into the suspension. After 20 min, add the sodium sulfide nonahydrate solution and continue stirring for 2 h. Then age at room temperature for 2 h, wash, dry, and grind to obtain the ZnMnO3 / CuS composite material. Example 2

[0040] Dissolve 5.2 mmol of Zn(NO3)2·6H2O and 1.3 mmol of MnCl2·4H2O in deionized water to form solution A; dissolve 13 mmol of sodium hydroxide in deionized water to form solution B; quickly pour solution B into solution A under stirring conditions, and then add 1 mL of hydrogen peroxide to form a suspension. The suspension is taken out after being kept warm in an oven at 160 °C for 16 h, and the product is washed several times with deionized water and ethanol and then dried in an oven. The dried powder is heated and sintered in air at 600 °C at a rate of 5 °C / min for 2 h, and then ground to obtain the monomer. Weigh 0.3 g of the monomer and dissolve it in an appropriate amount of deionized water and ultrasonicate for 30 min. At the same time, dissolve 1 mmol of copper nitrate trihydrate and 1 mmol of sodium sulfide nonahydrate (i.e., a molar ratio of 1:1) in deionized water and stir them respectively. After a period of time, drop the copper nitrate trihydrate solution into the suspension. After 20 min, add the sodium sulfide nonahydrate solution and continue stirring for 2 h. Then age at room temperature for 2 h, wash, dry, and grind to obtain a ZnO-ZnMnO3 / CuS composite catalytic material with a molar ratio of ZnO to ZnMnO3 of 3:1, denoted as ZnO-ZnMnO3(3:1) / CuS(0.3g). The mass ratio of the ZnO-ZnMnO3 material to copper nitrate trihydrate in this composite material is approximately 1.24:1. Example 3

[0041] The preparation method was the same as that of Example 2, except that: Zn(NO3)2·6H2O was 2.6 mmol, MnCl2·4H2O was 1.3 mmol, and sodium hydroxide was 7.8 mmol, to obtain a ZnO-ZnMnO3 / CuS composite catalyst material with a molar ratio of ZnO to ZnMnO3 of 1:1, denoted as ZnO-ZnMnO3(1:1) / CuS(0.3g). Example 4

[0042] The preparation method was the same as that of Example 2, except that: Zn(NO3)2·6H2O was 3.9 mmol, MnCl2·4H2O was 1.3 mmol; sodium hydroxide was 10.4 mmol, to obtain a ZnO-ZnMnO3 / CuS composite catalyst material with a molar ratio of ZnO to ZnMnO3 of 2:1, denoted as ZnO-ZnMnO3(2:1) / CuS(0.3g). Example 5

[0043] The preparation method was the same as that of Example 2, except that: Zn(NO3)2·6H2O was 6.5 mmol, MnCl2·4H2O was 1.3 mmol; sodium hydroxide was 15.6 mmol, to obtain a ZnO-ZnMnO3 / CuS composite catalyst material with a molar ratio of ZnO to ZnMnO3 of 4:1, denoted as ZnO-ZnMnO3(4:1) / CuS(0.3g). Example 6

[0044] The preparation method was the same as that of Example 2, except that: the monomer dosage was 0.2 g, to obtain a ZnO-ZnMnO3 / CuS composite catalyst material with a molar ratio of ZnO to ZnMnO3 of 3:1, denoted as ZnO-ZnMnO3(3:1) / CuS(0.2g), and the mass ratio of the ZnO-ZnMnO3 material to copper nitrate trihydrate in this composite material was approximately 0.83:1. Example 7

[0045] The preparation method was the same as that of Example 2, except that: the monomer dosage was 0.4 g, to obtain a ZnO-ZnMnO3 / CuS composite catalyst material with a molar ratio of ZnO to ZnMnO3 of 3:1, denoted as ZnO-ZnMnO3(3:1) / CuS(0.4g), and the mass ratio of the ZnO-ZnMnO3 material to copper nitrate trihydrate in this composite material was approximately 1.65:1.

[0046] 2. Sample Testing and Characterization

[0047] XRD tests were conducted on the ZnO-ZnMnO3, CuS, and ZnO-ZnMnO3(3:1) / CuS(0.3g) samples prepared in Examples 1-2, and the obtained XRD diffraction patterns are as follows Figure 1 shown. It can be seen from Figure 1 that the diffraction peaks corresponding to the ZnO-ZnMnO3(3:1) / CuS(0.3g) sample respectively correspond to the crystal planes of ZnO, ZnMnO3, and CuS. Thus, it can be known that ZnO-ZnMnO3 / CuS was successfully prepared.

[0048] 3. Degradation experiment

[0049] Ciprofloxacin (CIP) was selected as the target pollutant to carry out degradation experiment research. 0.01 g of CIP was dissolved in 1000 mL of water to prepare the water to be treated.

[0050] (1) Using the materials prepared in Examples 1-2 as catalysts, 10 groups of degradation experiments were set up correspondingly. First, the 10 groups of water to be treated were respectively placed in transparent reaction vessels. 30 mg of catalyst and 30 mg of PMS were added to each group of water to be treated. The transparent reaction vessels filled with water to be treated were placed on a magnetic stirrer. After degradation for a certain period of time, the water to be treated was filtered. The degradation results are as follows Figure 2 shown. It can be seen from Figure 2 that the natural degradation of CIP in the constant temperature shaker (CIP experimental group) can be ignored, and the degradation of CIP by PMS alone (PMS / CIP experimental group) can be ignored. The adsorption effect of ZnO-ZnMnO3(3:1) / CuS(0.3g) (ZnO-ZnMnO3(3:1) / CuS(0.3g) experimental group) on CIP is very limited. The materials prepared in Example 1 all have a certain degree of degradation of CIP. However, compared with other materials prepared in Example 1, the ZnO-ZnMnO3(3:1) / CuS(0.3g) prepared in Example 2 has the strongest ability to degrade ciprofloxacin, and the degradation rate reaches 68.1% in 60 min, indicating that ZnO-ZnMnO3(3:1) / CuS(0.3g) / PMS has excellent activation ability for PMS, thereby effectively degrading CIP.

[0051] (2) Using the ZnO-ZnMnO3(3:1) / CuS(0.3 g) prepared in Example 2 and the ZnO-ZnMnO3 / CuS materials with other molar ratios prepared in Examples 3-5 as catalysts, 4 groups of degradation experiments were set up. First, the 4 groups of water to be treated were respectively placed in transparent reaction vessels. 30 mg of catalyst was added to each group of water to be treated, and at the same time, 30 mg of PMS was added. The transparent reaction vessels containing the water to be treated were placed on a magnetic stirrer. After degradation for a certain time, the water to be treated was filtered. The degradation results are as Figure 3 shown. As can be seen from Figure 3 , the CAT / PMS system has a certain degree of degradation of CIP. Among them, the ZnO-ZnMnO3(3:1) / CuS(0.3 g) prepared in Example 2 has a stronger ability to activate PMS for the degradation of CIP than the catalysts in the other 3 groups of degradation experiments.

[0052] (3) Using the ZnO-ZnMnO3(3:1) / CuS(0.3 g) prepared in Example 2 and the ZnO-ZnMnO3 / CuS materials with different mass ratios of CuS prepared in Examples 6-7 as catalysts, 3 groups of degradation experiments were set up. First, the 3 groups of water to be treated were respectively placed in transparent reaction vessels. 30 mg of catalyst was added to each group of water to be treated, and at the same time, 30 mg of PMS was added. The transparent reaction vessels containing the water to be treated were placed on a magnetic stirrer. After degradation for a certain time, the water to be treated was filtered. The degradation results are as Figure 4 shown. As can be seen from Figure 4 , the CAT / PMS system has a certain degree of degradation of CIP. Among them, the ZnO-ZnMnO3(3:1) / CuS(0.3 g) prepared in Example 2 has a stronger ability to activate PMS for the degradation of CIP than the catalysts in the other 3 groups of degradation experiments.

[0053] 4. Effects of ZnO-ZnMnO3(3:1) / CuS(0.3 g) composite material and PMS dosage on the degradation of CIP

[0054] (1) Using the ZnO-ZnMnO3(3:1) / CuS(0.3 g) material prepared in Example 2 as a catalyst, 5 groups of degradation experiments with different catalyst dosages were set up. First, the 5 groups of water to be treated were respectively placed in transparent reaction vessels. 30 mg, 40 mg, 50 mg, 60 mg, and 70 mg of catalyst were added to the 5 groups of water to be treated respectively, and 30 mg of PMS was added to each group. The transparent reaction vessels containing the water to be treated were placed on a magnetic stirrer. After degradation for a certain time, the water to be treated was filtered. The degradation results are as Figure 5 shown in (a). As can be seen from Figure 5As can be seen from (a), when the dosage of PMS is 30 mg, the degradation rate of CIP in the system with a catalyst dosage of 60 mg is the highest. Therefore, a catalyst dosage of 60 mg was selected for further study.

[0055] (2) Using the ZnO-ZnMnO3(3:1) / CuS(0.3g) material prepared in Example 2 as the catalyst, five degradation experiments with different dosages of PMS were set up. First, the five groups of water to be treated were placed in transparent reaction vessels. 60 mg of the catalyst was added to each group of water to be treated, and at the same time, 30 mg, 50 mg, 70 mg, 80 mg, and 90 mg of PMS were added respectively. The transparent reaction vessels containing the water to be treated were placed on a magnetic stirrer. After degradation for a certain time, the water to be treated was filtered. The degradation results are as Figure 5 shown in (b). As can be seen from Figure 5 (b), when the catalyst dosage is 60 mg, the degradation rate of CIP in the system with a PMS dosage of 80 mg is the highest, and the degradation rate reaches 88.7%.

[0056] 5. Influence of coexisting anions and organic matter in the degraded wastewater on the ZnO-ZnMnO3(3:1) / CuS(0.3g) composite material

[0057] Using the ZnO-ZnMnO3(3:1) / CuS(0.3g) material prepared in Example 2 as the catalyst, four degradation experiments were set up. First, the four groups of water to be treated were placed in transparent reaction vessels. 60 mg of the degradation material was added to each group of water to be treated, and at the same time, 80 mg of PMS was added. In the four groups of experiments, Cl - , NO3 - , HCO3 - and humic acid (HA) were added. The addition amounts of the four substances were set as four groups of experiments with 1 mmol, 5 mmol, 10 mmol, and 15 mmol respectively. The transparent reaction vessels containing the water to be treated were placed on a magnetic stirrer. After degradation for a certain time, the water to be treated was filtered.

[0058] The degradation results are as Figure 6 shown. As can be seen from Figure 6 , it can be seen that Cl - , NO3 - have little effect on the degradation efficiency of the catalyst-activated PMS for degrading CIP, while HCO3 - and HA have a certain impact on the degradation ability of the system. This may be caused by the consumption of HCO3 - and HA or the attachment of a certain amount of active substances.

[0059] 6. Influence of ZnO-ZnMnO3(3:1) / CuS(0.3g) composite material on pH value of aqueous solution

[0060] Taking the ZnO-ZnMnO3(3:1) / CuS(0.3g) material prepared in Example 2 as the catalyst, 5 groups of degradation experiments were set up to analyze the pH value range of the composite material for degrading antibiotic wastewater. First, the 5 groups of water to be treated were respectively placed in transparent reaction vessels. 60 mg of the degradation material was added to each group of water to be treated, and 80 mg of PMS was added at the same time. The pH values of the CIP solution were adjusted to 3, 5, 7, 9, and 11 with 1M sulfuric acid and sodium hydroxide solutions respectively. The transparent reaction vessels filled with the water to be treated were placed on a magnetic stirrer. After degradation for a certain time, the water to be treated was filtered.

[0061] The degradation results are as Figure 7 shown. It can be seen from Figure 7 that when the pH value is 11, the degradation rate of 0.01 g / L CIP by the ZnO-ZnMnO3(3:1) / CuS(0.3g)+PMS system at 60 min is 86.9%, and the degradation efficiency is the highest. Secondly, when the pH value is 7, the degradation rate of 0.01 g / L CIP by the ZnO-ZnMnO3(3:1) / CuS(0.3g)+PMS system at 60 min is 82.8%.

[0062] In this invention, ZnO-ZnMnO3 / CuS composite material was synthesized. A good synergistic effect was generated between Zn and Mn. The introduction of CuS enhanced the electron mobility and high electrical conductivity of ZnO-ZnMnO3, accelerated the catalysis of ZnO-ZnMnO3 in PMS activation, and made the ZnO-ZnMnO3 / CuS composite material have higher catalytic activity.

[0063] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a ZnO-ZnMnO3 / CuS composite catalytic material, characterized in that, It includes the following steps: (1) Dissolve zinc salt and manganese salt in deionized water, then quickly add sodium hydroxide solution under stirring conditions, and then add excessive hydrogen peroxide to form a suspension. After carrying out hydrothermal reaction on the suspension, a precursor is obtained; (2) Calcinate and grind the dried precursor to obtain ZnO-ZnMnO3 material; (3) Dissolve an appropriate amount of ZnO-ZnMnO3 in deionized water and sonicate it. Then, successively add copper nitrate trihydrate solution and sodium sulfide nonahydrate solution. The mass ratio of the ZnO-ZnMnO3 material to copper nitrate trihydrate is (0.5~2):

1. Stir for 2 h, age at room temperature for 2 h, then wash, dry and grind to obtain ZnO-ZnMnO3 / CuS composite material.

2. The preparation method of the ZnO-ZnMnO3 / CuS composite catalytic material according to claim 1, characterized in that, The molar ratio of the zinc salt, manganese salt and sodium hydroxide is (2~5):1:(6~12).

3. The preparation method of the ZnO-ZnMnO3 / CuS composite catalytic material according to claim 2, wherein, The molar ratio of the zinc salt, manganese salt and sodium hydroxide is 4:1:

10.

4. The preparation method of the ZnO-ZnMnO3 / CuS composite catalytic material according to any one of claims 1-3, characterized in that, The zinc salt is zinc nitrate hexahydrate and the manganese salt is manganese chloride tetrahydrate.

5. The preparation method of the ZnO-ZnMnO3 / CuS composite catalytic material according to claim 1, characterized in that, The conditions of the hydrothermal reaction are hydrothermal temperature of 120 - 180 °C and heat preservation for 8 - 20 h.

6. The preparation method of the ZnO-ZnMnO3 / CuS composite catalytic material according to claim 1, wherein, The conditions of the calcination are calcination temperature of 400 - 700 °C, heating rate of 5 °C / min, and calcination time of 1 - 4 h.

7. A ZnO-ZnMnO3 / CuS composite catalytic material prepared by the preparation method according to any one of claims 1 - 6.

8. An application of the ZnO-ZnMnO3 / CuS composite catalytic material according to claim 7 in activating PMS to degrade antibiotic-containing wastewater, wherein the pH value of the wastewater is 3 - 11.

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