A method for preparing Co3O4 / CuCo2O4 composite material based on Co-MOF material and its application

Abstract

The present invention provides a method and application for preparing a Co3O4 / CuCo2O4 composite material based on Co-MOF materials, belonging to the technical field of material synthesis and analytical detection. The method comprises the following steps: S1, preparing a Co-MOF material; S2, preparing a Co3O4 / CuCo2O4 material precursor; S3, preparing a Co3O4 / CuCo2O4 composite material; the composite material is obtained by combining a novel Co-MOF material having a two-dimensional wavy layered structure with a copper salt and then calcining it to obtain a novel Co3O4 / CuCo2O4 composite material; the Co3O4 / CuCo2O4 composite material prepared by the present invention has bimetallic properties, can degrade tetracycline antibiotics and some dyes, has stable chemical properties, excellent performance in catalytic degradation of chlortetracycline, and has anti-interference ability.

Description

Technical Field

[0001] This invention belongs to the field of materials synthesis and analysis technology, specifically a method and application for preparing Co3O4 / CuCo2O4 composite materials based on Co-MOF materials. Background Art

[0002] Tetracycline antibiotics (TCs) are being detected in an increasing number of environmental water bodies, such as groundwater, surface water, and drinking water. The widespread presence of antibiotics in the environment may lead to bacterial resistance, posing a potential threat, especially to aquatic life and human health.

[0003] Chlortetracycline (CTC) is a tetracycline antibiotic with strong antibacterial and broad-spectrum activity. It can treat livestock diseases and improve livestock survival rates, and is widely used in animal husbandry. However, due to its high biotoxicity and ability to induce biological mutations, incompletely digested chlortetracycline and its metabolites, if discharged directly into the environment without adequate treatment, can cause serious harm to ecosystems and aquatic environments. Therefore, these organic compounds must be removed before wastewater is discharged into the aquatic environment. Because of the high chemical stability of chlortetracycline, it is difficult to completely remove it using biological or conventional physical methods. Currently, there is an urgent need for efficient and energy-saving treatment methods to address the problem of chlortetracycline-containing wastewater.

[0004] Advanced oxidation processes (SR-AOPs) of sulfate radicals possess advantages such as speed and efficiency, making them a promising technology for the removal of total toxic substances (TCs). Developing catalysts with high catalytic activity is one of the key factors in solving the aforementioned problems. Among numerous metal or metal oxide catalyst materials, developing cobalt-containing bimetallic materials is highly beneficial for activating permonosulfate (PMS) to enhance the catalytic activity of the material. Therefore, there is an urgent need to develop a cobalt-containing bimetallic material for the removal of tetracycline antibiotics from the aquatic environment. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a method for preparing Co3O4 / CuCo2O4 composite materials based on Co-MOF materials and their applications.

[0006] The technical solution of this invention is: a method for preparing Co3O4 / CuCo2O4 composite materials based on Co-MOF materials, comprising the following steps:

[0007] Preparation of S1 and Co-MOF materials

[0008] Under conditions of 80–130 °C, tris(4-(1H-1,2,4-triazole)phenyl)amine, cobalt acetate, 1,3,5-benzotriic acid, water, and organic solvent were mixed in a mass ratio of 2:1–2.5:1–1.5:200–300:100–200 to obtain mixed solution A. Then, mixed solution A was sealed in a stainless steel reactor for reaction for 72–96 h. Finally, the mixture was cooled to room temperature using a constant cooling method to obtain the Co-MOF material.

[0009] Preparation of S2, Co3O4 / CuCo2O4 material precursors

[0010] The above Co-MOF material was ground uniformly to the micron size, and 7.5g was dispersed in 20mL of ethanol. The mixture was ultrasonically treated for 30-60min at a power of 100W and a frequency of 40kHz to obtain mixture B. Copper acetate was added to mixture B at a mass ratio of 1:2-5 and stirred for 1-2h. Then, the mixture was transferred to a stainless steel reactor and heated to 90-120℃ and maintained for 1-3h. After natural cooling, a suspension was obtained. The suspension was then centrifuged at 10000rpm to obtain the product. Finally, the product was washed with water and ethanol respectively, and vacuum dried at 60℃ for 2-3h to obtain the Co3O4 / CuCo2O4 material precursor.

[0011] Preparation of S3, Co3O4 / CuCo2O4 composite materials

[0012] 80 mg of the Co3O4 / CuCo2O4 material precursor was loaded into a ceramic boat, heated to 350 °C at a heating rate of 1 °C / min in air atmosphere, and calcined for 2 h to obtain the Co3O4 / CuCo2O4 material.

[0013] Furthermore, the structural characteristics of the Co-MOF material lie in its unit cell parameters, specifically the following values: α=γ=90°, β=106.9929, It belongs to the orthorhombic crystal system, space group Pbca.

[0014] Note: The size and shape of the lattice parameters determine the physical and chemical properties of Co-MOF crystals, and are therefore of great significance for studying the structure and properties of Co-MOF materials.

[0015] Furthermore, in steps S1 and S2, the lining material of the stainless steel reactor is polytetrafluoroethylene.

[0016] Note: As a high-temperature, high-pressure, corrosion-resistant, and high-purity reaction vessel, the polytetrafluoroethylene (PTFE) reactor has good sealing performance, high digestion efficiency, and strong capacity. It can digest many samples that are difficult to digest using traditional methods, has a wide range of applications, and low elemental blank values ​​in the inner cup, thereby improving the accuracy and precision of analysis and reducing workload and environmental pollution.

[0017] Furthermore, in step S1, when cooling to room temperature using a constant cooling method, the constant cooling rate is 10℃ / h, and the organic solvent is N,N'-dimethylformamide.

[0018] Note: Using constant cooling can avoid segregation caused by sudden temperature drops, thus improving the material's performance. N,N'-dimethylformamide, as an organic solvent, can dissolve most organic substances and many inorganic substances, making it widely applicable.

[0019] Furthermore, when the Co3O4 / CuCo2O4 composite material is applied to the degradation of antibiotic pollutants, the removal rate can reach 97%.

[0020] Note: The Co3O4 / CuCo2O4 composite material has bimetallic properties and can degrade tetracycline antibiotics and some dyes. The material is chemically stable and has excellent performance in catalytic degradation of chlortetracycline. It has anti-interference ability. When degrading chlortetracycline pollutants in water, sulfate radicals, hydroxyl radicals, singlet oxygen and superoxide radicals play the main roles.

[0021] Furthermore, the Co3O4 / CuCo2O4 composite material is used in conjunction with persulfate as a catalyst for the degradation of antibiotic pollutants in water.

[0022] Note: Advanced oxidation processes for sulfate radicals (SR-AOPs) have advantages such as speed and efficiency, and are a promising TCs removal technology. The cobalt-containing bimetallic material of this invention is beneficial for activating permonosulfate (PMS) to improve the catalytic activity of the material.

[0023] Furthermore, the persulfate is sodium persulfate, and the mass ratio of the Co3O4 / CuCo2O4 composite material to sodium persulfate is 600-700:1.

[0024] Note: The catalytic effect of the material can be improved by controlling the mass ratio of Co3O4 / CuCo2O4 composite material to sodium persulfate.

[0025] Furthermore, the antibiotic pollutant in the water is chlortetracycline, and the degradation conditions are: temperature range of 25-45℃, degradation time of 20-50min, and pH range of 3-9.

[0026] Note: By limiting the degradation conditions of the Co3O4 / CuCo2O4 composite material, the degradation effect on chlortetracycline can be improved.

[0027] Compared with the prior art, the beneficial effects of the present invention are:

[0028] The Co3O4 / CuCo2O4 composite material of this invention is obtained by calcining a novel Co-MOF material with a two-dimensional wavy layered structure with copper salt. The preparation process is simple and controllable, exhibiting high efficiency and short time in degrading antibiotics. Furthermore, this composite material possesses bimetallic properties, enabling the degradation of tetracycline antibiotics and some dyes. It is chemically stable, demonstrates excellent performance in catalytic degradation of chlortetracycline, and exhibits anti-interference capabilities. The inorganic ion is H2PO4. - NO3 - Cl - HCO3 - SO4 2- It can maintain good degradation performance even in the presence of humic acid (HA). Attached Figure Description

[0029] Figure 1 This is a coordination environment diagram of the Co-MOF material when H atoms are omitted in this invention;

[0030] Figure 2 Here is a scanning electron microscope image of the morphology of the Co3O4 / CuCo2O4 composite material prepared in Example 3 of this invention;

[0031] Figure 3 This is a transmission electron microscope image of the morphology of the Co3O4 / CuCo2O4 composite material prepared in Example 3 of this invention;

[0032] Figure 4 This is a high-resolution transmission electron microscope (TEM) lattice fringe pattern of the Co3O4 / CuCo2O4 composite material prepared in Example 3 of this invention.

[0033] Figure 5 This is a line graph showing the removal rate of chlortetracycline catalytically degraded by the Co3O4 / CuCo2O4 composite material prepared in Example 3 of this invention;

[0034] Figure 6 This is a line graph showing the interference resistance test of the Co3O4 / CuCo2O4 composite material prepared in Example 3 of this invention during the degradation of chlortetracycline;

[0035] Figure 7 This is a line graph showing the removal rate of chlortetracycline by the Co3O4 / CuCo2O4 composite material prepared in Example 3 of this invention at different pH ranges;

[0036] Figure 8 This is a line graph showing the removal effect of the Co3O4 / CuCo2O4 composite material prepared in Example 3 of this invention on tetracycline hydrochloride, oxytetracycline, and dyes. DETAILED DESCRIPTION

[0037] To further understand the content of the present invention, the present invention will be described in detail below through embodiments.

[0038] Example 1

[0039] like Figure 1 , 2 As shown in Figures 3 and 4, a method for preparing Co3O4 / CuCo2O4 composite materials based on Co-MOF materials includes the following steps:

[0040] Preparation of S1 and Co-MOF materials

[0041] At a temperature of 80℃, tris(4-(1H-1,2,4-triazole)phenyl)amine, cobalt acetate, 1,3,5-benzolic acid, water, and N,N'-dimethylformamide were mixed in a mass ratio of 2:1:1:200:100 to obtain mixed solution A. Then, mixed solution A was sealed in a stainless steel reactor with a polytetrafluoroethylene lining for reaction for 72 hours. Finally, the mixture was cooled to room temperature at a constant cooling rate of 10℃ / h to obtain the Co-MOF material.

[0042] Preparation of S2, Co3O4 / CuCo2O4 material precursors

[0043] The above Co-MOF material was ground uniformly to the micron size, and 7.5g was dispersed in 20mL of ethanol. The mixture was ultrasonically treated for 30min at a power of 100W and a frequency of 40kHz to obtain mixture B. Copper acetate was added to mixture B at a mass ratio of 1:2 and stirred for 1h. Then, the mixture was transferred to a stainless steel reactor and heated to 90℃ and held for 1h. After natural cooling, a suspension was obtained. The suspension was then centrifuged at 10000rpm to obtain the product. Finally, the product was washed with water and ethanol respectively, and vacuum dried at 60℃ for 2h to obtain the Co3O4 / CuCo2O4 material precursor.

[0044] Preparation of S3, Co3O4 / CuCo2O4 composite materials

[0045] 80 mg of Co3O4 / CuCo2O4 material precursor was loaded into a ceramic boat, heated to 350 °C at a heating rate of 1 °C / min in air atmosphere, and calcined for 2 h to obtain the material Co3O4 / CuCo2O4.

[0046] When the Co3O4 / CuCo2O4 composite material is applied to the degradation of antibiotic pollutants, the removal rate can reach 97%.

[0047] The Co3O4 / CuCo2O4 composite material is used in conjunction with persulfate as a catalyst for degrading antibiotic pollutants in water. The persulfate is sodium persulfate, the mass ratio of the Co3O4 / CuCo2O4 composite material to sodium persulfate is 600:1, the antibiotic pollutant in the water is chlortetracycline, and the degradation conditions are: temperature range of 25℃, degradation time of 20min, and pH range of 3.

[0048] Example 2

[0049] like Figure 1 , 2 As shown in Figures 3 and 4, a method for preparing Co3O4 / CuCo2O4 composite materials based on Co-MOF materials includes the following steps:

[0050] Preparation of S1 and Co-MOF materials

[0051] At a temperature of 100℃, tris(4-(1H-1,2,4-triazole)phenyl)amine, cobalt acetate, 1,3,5-benzolic acid, water, and N,N'-dimethylformamide were mixed in a mass ratio of 2:2:1.3:250:150 to obtain mixed solution A. Then, mixed solution A was sealed in a stainless steel reactor with a polytetrafluoroethylene lining for reaction for 85 hours. Finally, the mixture was cooled to room temperature at a constant cooling rate of 10℃ / h to obtain Co-MOF material.

[0052] Preparation of S2, Co3O4 / CuCo2O4 material precursors

[0053] The above Co-MOF material was ground uniformly to the micron size, and 7.5g was dispersed in 20mL of ethanol. The mixture was ultrasonically treated for 45min at a power of 100W and a frequency of 40kHz to obtain mixture B. Copper acetate was added to mixture B at a mass ratio of 1:3 and stirred for 1.5h. Then, the mixture was transferred to a stainless steel reactor and heated to 100℃ and held for 2h. After natural cooling, a suspension was obtained. The suspension was then centrifuged at 10000rpm to obtain the product. Finally, the product was washed with water and ethanol respectively, and vacuum dried at 60℃ for 2.5h to obtain the Co3O4 / CuCo2O4 material precursor.

[0054] Preparation of S3, Co3O4 / CuCo2O4 composite materials

[0055] 80 mg of Co3O4 / CuCo2O4 material precursor was loaded into a ceramic boat, heated to 350 °C at a heating rate of 1 °C / min in air atmosphere, and calcined for 2 h to obtain the material Co3O4 / CuCo2O4.

[0056] When the Co3O4 / CuCo2O4 composite material is applied to the degradation of antibiotic pollutants, the removal rate can reach 97%.

[0057] The Co3O4 / CuCo2O4 composite material is used in conjunction with persulfate as a catalyst for degrading antibiotic pollutants in water. The persulfate is sodium persulfate, the mass ratio of the Co3O4 / CuCo2O4 composite material to sodium persulfate is 650:1, the antibiotic pollutant in the water is chlortetracycline, and the degradation conditions are: temperature range of 35℃, degradation time of 40 min, and pH range of 6.

[0058] Example 3

[0059] like Figure 1 , 2 As shown in Figures 3 and 4, a method for preparing Co3O4 / CuCo2O4 composite materials based on Co-MOF materials includes the following steps:

[0060] Preparation of S1 and Co-MOF materials

[0061] At a temperature of 130℃, tris(4-(1H-1,2,4-triazole)phenyl)amine, cobalt acetate, 1,3,5-benzolic acid, water, and N,N'-dimethylformamide were mixed in a mass ratio of 2:2.5:1.5:300:200 to obtain mixed solution A. Then, mixed solution A was encapsulated in a stainless steel reactor with a polytetrafluoroethylene lining for reaction for 96 hours. Finally, the mixture was cooled to room temperature at a constant cooling rate of 10℃ / h to obtain Co-MOF material.

[0062] Preparation of S2, Co3O4 / CuCo2O4 material precursors

[0063] The above Co-MOF material was ground uniformly to the micron size, and 7.5g was dispersed in 20mL of ethanol. The mixture was ultrasonically treated for 30-60min at a power of 100W and a frequency of 40kHz to obtain mixture B. Copper acetate was added to mixture B at a mass ratio of 1:5 and stirred for 2h. Then, the mixture was transferred to a stainless steel reactor and heated to 120℃ and maintained for 3h. After natural cooling, a suspension was obtained. The suspension was then centrifuged at 10000rpm to obtain the product. Finally, the product was washed with water and ethanol respectively, and vacuum dried at 60℃ for 3h to obtain the Co3O4 / CuCo2O4 material precursor.

[0064] Preparation of S3, Co3O4 / CuCo2O4 composite materials

[0065] 80 mg of Co3O4 / CuCo2O4 material precursor was loaded into a ceramic boat, heated to 350 °C at a heating rate of 1 °C / min in air atmosphere, and calcined for 2 h to obtain the material Co3O4 / CuCo2O4.

[0066] When the Co3O4 / CuCo2O4 composite material is applied to the degradation of antibiotic pollutants, the removal rate can reach 97%.

[0067] The Co3O4 / CuCo2O4 composite material is used in conjunction with persulfate as a catalyst for degrading antibiotic pollutants in water. The persulfate is sodium persulfate, the mass ratio of the Co3O4 / CuCo2O4 composite material to sodium persulfate is 700:1, the antibiotic pollutant in the water is chlortetracycline, and the degradation conditions are: temperature range of 45℃, degradation time of 50 min, and pH range of 9.

[0068] Test case

[0069] 1. Antibiotic degradation performance test of the Co3O4 / CuCo2O4 composite material prepared in Example 3: The Co3O4 / CuCo2O4 composite material prepared in Example 3 was used to synergistically activate persulfate (PMS) degradation of chlortetracycline (CTC). The specific operation process is as follows:

[0070] 5 mg of the Co3O4 / CuCo2O4 composite material was weighed and placed in a 100 mL glass bottle. 50 mL of LTC solution (initial concentration c0 was 20 mg / L) was added, and the PMS dosage was 1 mmol / L. The degradation experiment was conducted in a constant temperature water bath shaker at 180 rpm / min. Every so often, 2 mL of the reaction solution was taken, filtered through a 0.45 μm filter membrane, and the reaction solution was quenched with 20 mM Na2S2O3. The experiment lasted 30 min, and the concentration change was measured using a UV-Vis spectrophotometer. The formula calculates the degradation rate, where c0 and c are the mass concentrations of the solution before and after degradation, respectively, in mg / L. The conclusion is as follows: Figure 5 As shown, the prepared Co3O4 / CuCo2O4 composite material achieved a degradation rate of 97.3% after 30 minutes when used to degrade CTC.

[0071] 2. The applicable pH range of the Co3O4 / CuCo2O4 composite material prepared in Example 3

[0072] like Figure 6 As shown, in step 1, when 5 mg of Co3O4 / CuCo2O4 material was added to a 50 mL CTC solution (initial concentration c0 was 20 mg / L), and the PMS dosage was 1 mmol / L, the removal rate of CTC could be maintained above 97% at pH 5–9, indicating that Co3O4 / CuCo2O4 has good acid and alkali tolerance over a wide pH range.

[0073] 3. Test on the anti-interference performance of the Co3O4 / CuCo2O4 composite material prepared in Example 3

[0074] like Figure 7 As shown, during the synergistic degradation of CTC by the Co3O4 / CuCo2O4 composite material and PMS in step 1, 10 mmol / L of interfering ions NO3 were added. - Cl - HCO3 - SO4 - Humic acid (HA), NO3 - Cl - SO4 - The effect on CTC degradation is negligible; HCO3 - The presence of the substance enhances the degradation performance of CTC, demonstrating that the Co3O4 / CuCo2O4 composite material has strong resistance to inorganic anion interference.

[0075] 4. The degradation performance of the Co3O4 / CuCo2O4 composite material prepared in Example 3 was tested for other pollutants, as follows: Figure 8 As shown, repeating the process in step 1 and replacing the pollutants in step 1 with pollutants such as tetracycline, oxytetracycline, rhodamine B, and methylene blue, the Co3O4 / CuCo2O4 materials all showed good catalytic degradation effects.

Claims

1. An application of a Co3O4 / CuCo2O4 composite material in synergistic use with persulfate for the degradation of antibiotic pollutants in water, characterized in that, The preparation method of this Co3O4 / CuCo2O4 composite material includes the following steps: Preparation of S1 and Co-MOF materials At a temperature of 80℃, tris(4-(1H-1,2,4-triazole)phenyl)amine, cobalt acetate, 1,3,5-benzotriic acid, water, and an organic solvent were mixed in a mass ratio of 2:1~2.5:1~1.5:200~300:100~200 to obtain mixed solution A. Then, mixed solution A was sealed in a stainless steel reactor for reaction for 72-96 hours. Finally, the mixture was cooled to room temperature using a constant cooling method to obtain the Co-MOF material. Preparation of S2, Co3O4 / CuCo2O4 material precursors The above Co-MOF material was ground uniformly to the micron size, and 7.5g was dispersed in 20 mL of ethanol. The mixture was ultrasonically treated for 30-60 min at a power of 100W and a frequency of 40 kHz to obtain mixture B. Copper acetate was added to mixture B at a mass ratio of 1:2~5 and stirred for 1-2 h. Then, the mixture was transferred to a stainless steel reactor and heated to 90-120℃ and maintained for 1-3 h. After natural cooling, a suspension was obtained. The suspension was then centrifuged at 10000 rpm to obtain the product. Finally, the product was washed with water and ethanol respectively, and vacuum dried at 60℃ for 2-3 h to obtain the Co3O4 / CuCo2O4 material precursor. Preparation of S3, Co3O4 / CuCo2O4 composite materials 80 mg of the Co3O4 / CuCo2O4 material precursor was loaded into a ceramic boat, heated to 350 °C at a heating rate of 1 °C / min in air atmosphere, and calcined for 2 h to obtain the Co3O4 / CuCo2O4 material.

2. The application according to claim 1, characterized in that, In steps S1 and S2, the lining material of the stainless steel reactor is polytetrafluoroethylene.

3. The application according to claim 1, characterized in that, In step S1, when cooling to room temperature using a constant cooling method, the constant cooling rate is 10℃ / h, and the organic solvent is N,N'-dimethylformamide.

4. The application according to claim 1, characterized in that, The antibiotic pollutant in the water is chlortetracycline, and the degradation conditions are: temperature range of 25-45℃, degradation time of 20-50min, and pH range of 3-9.

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