A Co / Bi4TaO8Cl-type Fenton catalyst and its preparation method and application

Abstract

The present invention discloses a Co / Bi4TaO8Cl type Fenton catalyst, a preparation method and an application. The steps of the catalyst preparation method are as follows: dispersing Bi4TaO8Cl material in water to obtain a first solution, ultrasonically treating the first solution to obtain a Bi4TaO8Cl dispersion; dripping a cobalt chloride solution into the Bi4TaO8Cl dispersion to obtain a second solution, stirring the second solution for a period of time, collecting the precipitate by centrifugation, washing, and drying to obtain a powder; calcining the obtained powder under the protection of an inert gas atmosphere to obtain a Co / Bi4TaO8Cl material. The Co / Bi4TaO8Cl type Fenton catalyst prepared by the present invention has the advantages of high efficiency, rapidity, and green economy. The inactivation efficiency of ARB can reach 100% within 10 minutes, and the degradation rate of ARG can reach 2.3min. ‑1 , with good resistance to environmental interference and cycle stability.

Description

Technical Field

[0001] The present invention relates to the technical field of water purification, and in particular to a green and recyclable Co / Bi4TaO8Cl-type Fenton catalyst, a preparation method and an application thereof. Background Art

[0002] The global spread of antibiotic resistance (AMR) poses a serious threat to public health. Its vectors—antibiotic-resistant bacteria (ARBs) and antibiotic-resistant genes (ARGs)—spread through water, forming "superbugs" that pose a serious threat to ecological security and human health. Traditional water treatment technologies (such as ozone oxidation and ultraviolet disinfection) are ineffective in synergistically removing ARBs and ARGs, necessitating the urgent need for innovative solutions that are both highly effective and environmentally friendly.

[0003] Advanced oxidation processes (AOPs) based on peroxymonosulfate (PMS) generate free radicals (SO4 •- , •OH) and non-free radicals ( 1 O2) to achieve the degradation of pollutants. The former has strong oxidizing ability to inactivate ARBs, but is easily interfered by the complex components of the water body; the latter can specifically destroy the DNA structure of ARGs, but its oxidizing ability is limited. In order to achieve synergistic efficiency between the two, it is necessary to develop new catalysts to break through the bottleneck of traditional technology. Existing Fenton-like catalysts have significant defects: for example, reliance on a single metal active site leads to low electron transfer efficiency, and metal ion leaching causes secondary pollution; the catalytic system is limited to a narrow pH range and requires additional chemical adjustment; and the material has poor cyclic stability, which makes it difficult to meet the requirements of the green circular economy for resource reuse. Therefore, the development of green catalysts with multi-active site synergy and stable structure is the key to breaking through the technical bottleneck of simultaneous removal of ARBs / ARGs. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a Co / Bi4TaO8Cl-type Fenton catalyst, a preparation method and an application thereof.

[0005] In a first aspect, the present invention provides a Co / Bi4TaO8Cl-type Fenton catalyst, which is achieved by adopting the following technical solution.

[0006] A Co / Bi4TaO8Cl-type Fenton catalyst is provided, wherein Co is loaded on the surface of a Bi4TaO8Cl material, wherein the loaded amount of Co is less than 2.0% by weight of the Bi4TaO8Cl material, and preferably, the loaded amount of Co is 0.5-2 wt% by weight of the Bi4TaO8Cl material.

[0007] In a second aspect, the present invention provides a method for preparing a Co / Bi4TaO8Cl-type Fenton catalyst, which is achieved by adopting the following technical solution.

[0008] A method for preparing the above-mentioned Co / Bi4TaO8Cl-type Fenton catalyst comprises the following steps:

[0009] S1. Dispersing Bi4TaO8Cl material in water to obtain a first solution, and ultrasonically treating the first solution to obtain a Bi4TaO8Cl dispersion; wherein the concentration of Bi4TaO8Cl in the first solution is 8-12 g / L;

[0010] S2. Add the cobalt chloride solution dropwise to the Bi4TaO8Cl dispersion to obtain a second solution. Stir the second solution for a period of time, collect the precipitate by centrifugation, wash, and dry to obtain a powder. The mass ratio of cobalt in the cobalt chloride solution to Bi4TaO8Cl in the Bi4TaO8Cl dispersion is (0.005-0.02):1.

[0011] S3. The powder obtained in step S2 is calcined under an inert gas atmosphere to obtain Co / Bi4TaO8Cl material.

[0012] Furthermore, in step S1, the preparation method of the Bi4TaO8Cl material is: after Bi2O3, BiOCl, Ta2O5, NaCl and KCl are fully ground and mixed, the mixture is calcined, naturally cooled to room temperature, washed to remove impurities, and dried to obtain Bi4TaO8Cl, wherein the molar ratio of Bi2O3, BiOCl, Ta2O5, NaCl and KCl is (2.9~3.1):(1.9~2.1):(0.9~1.1):30:30.

[0013] Furthermore, the grinding time is 30 to 60 minutes, preferably 40 minutes; the mixture is calcined at a temperature of 600 to 900°C, preferably 800°C, and the calcination time is 2 to 4 hours, preferably 3.5 hours; washing is performed with ultrapure water at a temperature above 90°C; and the drying is performed by vacuum drying.

[0014] Furthermore, in step S1, the Bi4TaO8Cl material is dispersed in ultrapure water.

[0015] Furthermore, in step S1, the ultrasonic treatment time is 20-40 minutes, preferably 30 minutes, and the ultrasonic treatment is performed at 0-25°C, preferably 0°C.

[0016] Furthermore, in step S2, the cobalt chloride solution is a mixture of cobalt chloride and ultrapure water, and the concentration of cobalt chloride in the cobalt chloride solution is 5-15 g / L, preferably 10 g / L.

[0017] Furthermore, in step S2, the second solution is stirred for 2 to 4 hours, preferably 3 hours, and the stirring temperature is 40 to 70°C, preferably 60°C.

[0018] Furthermore, in step S2, anhydrous ethanol and ultrapure water are used for washing.

[0019] Furthermore, in step S2, the drying is vacuum drying.

[0020] Furthermore, in step S3, the calcination temperature is 100-150° C., preferably 120° C., and the calcination time is 1-2 hours, preferably 1.5 hours.

[0021] Furthermore, in step S3, the inert gas used for calcination is nitrogen, and the flow rate of nitrogen is 50-100 mL / min, preferably 60 mL / min.

[0022] In a third aspect, the present invention provides a use of a Co / Bi4TaO8Cl-type Fenton catalyst, which is achieved by adopting the following technical solution.

[0023] An application of the above-mentioned Co / Bi4TaO8Cl-type Fenton catalyst in removing drug-resistant bacteria and drug-resistant genes in wastewater.

[0024] Furthermore, the resistant bacteria was Escherichia coli HB101.

[0025] Furthermore, the drug-resistant gene is the tetracycline resistance gene (tetA), which contains a total of 191 base pairs.

[0026] Furthermore, the dosage of the Co / Bi4TaO8Cl-type Fenton catalyst is 50-200 mg / L, and the temperature of the wastewater is 20-30°C, preferably 25°C.

[0027] In a fourth aspect, the present invention provides a method for removing drug-resistant bacteria and drug-resistant genes in wastewater, which is achieved by adopting the following technical solutions.

[0028] A method for removing drug-resistant bacteria and drug-resistant genes in wastewater comprises the following steps: adding the above-mentioned Co / Bi4TaO8Cl-type Fenton catalyst to the wastewater, then adding peroxymonosulfate, and shaking to carry out an advanced oxidation reaction.

[0029] Furthermore, the concentration of peroxymonosulfate in the wastewater is 50-150 mg / L, preferably 100 mg / L.

[0030] Furthermore, the dosage of the Co / Bi4TaO8Cl-type Fenton catalyst is 50-200 mg / L, and the temperature of the wastewater is 20-30°C, preferably 25°C.

[0031] This application has the following beneficial effects.

[0032] The Co / Bi4TaO8Cl Fenton-type catalyst prepared by the preparation method of the present invention has the advantages of high efficiency, rapidity, green economy, and its inactivation efficiency of ARB can reach 100% within 10 minutes, and the degradation rate of ARG can reach 2.3 min -1 , and has good resistance to environmental interference and cycle stability. The introduction of Co atoms induces charge reconstruction, thereby activating the oxidation activity of Bi sites to PMS. At the same time, PMS is efficiently reduced at the Co site, achieving free radical (SO4 •- and •OH) and non-radicals ( 1 The Co / Bi4TaO8Cl Fenton-like catalyst prepared by the present invention can still effectively remove ARB and ARG in actual wastewater and across different pH ranges. The metal ion leaching rate of the Co / Bi4TaO8Cl material is lower than the water quality standard requirement, and there is no secondary pollution, fully demonstrating its green and environmentally friendly characteristics. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a SEM electron microscope photograph of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention;

[0034] Figure 2 TEM and HAADF-STEM images of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention are shown. Figure 2 (a) is the TEM image of Co / Bi4TaO8Cl material. Figure 2 (b) is the HAADF-STEM image of Co / Bi4TaO8Cl material;

[0035] Figure 3 : are the XRD patterns of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention and the Bi4TaO8Cl material prepared in Comparative Example 1. Figure 3 The 2θ on the horizontal axis is the diffraction angle directly measured experimentally, in degrees (°);

[0036] Figure 4 This is the EXAFS fitting spectrum of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention. Figure 4 The horizontal axis R+α represents the actual atomic distance after correction, and the unit is angstrom (Å). The vertical axis FT[k 2 χ(k)] represents the amplitude after Fourier transform of k²-weighted χ(k);

[0037] Figure 5The SO4 generated during the PMS activation process of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention and the Bi4TaO8Cl material prepared in Comparative Example 1 is •- , •OH and 1 O2 concentration result graph;

[0038] Figure 6 Graph showing the deactivation efficiency of HB101 using the Co / Bi4TaO8Cl materials prepared in Examples 1 to 4 of the present invention and the Bi4TaO8Cl material prepared in Comparative Example 1 as catalysts, respectively;

[0039] Figure 7 Graph showing the degradation rate (left axis) and degradation efficiency (right axis) of the Co / Bi4TaO8Cl materials prepared in Examples 1 to 4 of the present invention and the Bi4TaO8Cl material obtained in Comparative Example 1 as catalysts for the anti-ampicillin resistance gene (ampC);

[0040] Figure 8 1 is a graph showing the inactivation efficiency of HB101 and the degradation efficiency of ampC by the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention at different catalyst dosages;

[0041] Figure 9 1 is a graph showing the inactivation efficiency of HB101 and the degradation efficiency of ampC by the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention under different pH conditions;

[0042] Figure 10 1 is a graph showing the inactivation efficiency of HB101 and the degradation efficiency of ampC by the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention in different water bodies;

[0043] Figure 11 This is a graph showing the metal ion concentration leaked from the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention during the PMS activation process;

[0044] Figure 12 This is a graph showing the cycle test results of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention for the inactivation efficiency of HB101 and the degradation efficiency of ampC. DETAILED DESCRIPTION

[0045] The Bi4TaO8Cl in the present invention is an ideal carrier of single metal active sites in PMS activation due to its narrow band gap, high stability and synergistic effect of multiple active sites. Anchoring Co on Bi4TaO8Cl to construct an asymmetric Co-O-Bi dual reaction site is expected to achieve efficient simultaneous redox of PMS and generate free radicals (SO4 •-and •OH) and non-radicals ( 1 O2), thereby effectively solving the problem of low efficiency of synergistic removal of ARBs and ARGs.

[0046] The present invention will be further described below with reference to the accompanying drawings and examples.

[0047] The sources of the drugs involved in the following embodiments are as follows: bismuth oxide (99%, Aladdin), bismuth oxychloride (99%, Aladdin), tantalum pentoxide (99%, Aladdin), sodium chloride (99%, Aladdin), potassium chloride (99%, Aladdin), cobalt chloride (99%, Aladdin), and anhydrous ethanol (99%, Jiangtian Chemical).

[0048] The resistant bacteria is Escherichia coli HB101.

[0049] The drug-resistant gene is the ampicillin resistance gene (ampC), which contains a total of 191 base pairs. The method for obtaining it can be found in DOI:10.1016 / j.cej.2016.10.107.

[0050] The models of the instruments involved in the following examples are as follows: magnetic stirrer (HJ-3 model), digital constant temperature water bath (HH.S21-8), vacuum drying oven (DZF-6020 model), ultrasonic cleaner (SB-3200DT), high-speed centrifuge (TG16-WS), box-type muffle furnace (KLSF-1200X), and tube furnace (OTF-1200X).

[0051] Examples 1 to 4

[0052] A method for preparing a Co / Bi4TaO8Cl-type Fenton catalyst comprises the following steps:

[0053] Step 1: Grind Bi2O3, BiOCl, Ta2O5, NaCl, and KCl in a mortar for 40 minutes. The mixture is then placed in an alumina crucible and calcined at 800°C in a muffle furnace for 3.5 hours. After cooling naturally to room temperature, it is washed with 100°C ultrapure water to remove impurities and vacuum-dried to obtain Bi4TaO8Cl, where the molar ratio of Bi2O3, BiOCl, Ta2O5, NaCl, and KCl is 3:2:1:30:30.

[0054] Step 2: Dispersing Bi4TaO8Cl in ultrapure water to obtain a first solution, and ultrasonicating the first solution at 0°C for 30 minutes to obtain a Bi4TaO8Cl dispersion, wherein the concentration of Bi4TaO8Cl in the first solution is 10 g / L;

[0055] Step 3: Add a cobalt chloride aqueous solution dropwise to the Bi4TaO8Cl dispersion to obtain a second solution. The second solution is stirred at 60° C. for 3 hours, and the precipitate is collected by centrifugation, washed with anhydrous ethanol and ultrapure water, and dried under vacuum to obtain a yellow powder. The mass ratio of cobalt in the cobalt chloride solution to Bi4TaO8Cl in the Bi4TaO8Cl dispersion is X, and the concentration of cobalt chloride in the cobalt chloride solution is 10 g / L. X is shown in Table 1.

[0056] Table 1

[0057]

[0058] Step 4: calcining the powder obtained in step 3 at 120° C. for 1.5 hours under nitrogen atmosphere to obtain Co / Bi4TaO8Cl material, wherein the flow rate of nitrogen is 60 mL / min.

[0059] The cobalt loadings of the Co / Bi4TaO8Cl materials prepared in Examples 1 to 4 were measured by inductively coupled plasma mass spectrometry and were 0.89 wt%, 0.43 wt%, 1.38 wt% and 1.79 wt%, respectively.

[0060] Comparative Example 1

[0061] A method for preparing a Bi4TaO8Cl material comprises grinding Bi2O3, BiOCl, Ta2O5, NaCl, and KCl (molar ratio of 3:2:1:30:30) in a mortar for 40 minutes. The mixture is then placed in an alumina crucible and calcined at 800°C in a muffle furnace for 3.5 hours. After cooling naturally to room temperature, the mixture is washed with 100°C ultrapure water to remove impurities and vacuum dried to obtain the Bi4TaO8Cl material.

[0062] like Figure 1 The SEM electron microscope image shown shows that the thickness of the Co / Bi4TaO8Cl material is 130nm.

[0063] Figure 2 TEM [see Figure 2 (a)] and HAADF-STEM [see Figure 2 Middle (b)] The electron microscope photograph shows the two-dimensional nanoplate structure of the Co / Bi4TaO8Cl material, and cobalt atoms are doped into the Bi4TaO8Cl lattice by replacing Bi atoms, without cobalt particles.

[0064] Figure 3The XRD pattern of the Co / Bi4TaO8Cl material shows that the crystal structure of the material is similar to that of Bi4TaO8Cl, and the characteristic peaks of single-element Co are absent, further indicating the absence of Co nanoparticles in Co / Bi4TaO8Cl. Furthermore, compared with Bi4TaO8Cl, the diffraction peak of Co / Bi4TaO8Cl at 2θ = 37.55° shifts slightly toward higher angles. This is likely due to the fact that after Co doping, the larger atomic radius of Bi atoms (0.170 nm) in Bi4TaO8Cl is replaced by smaller atomic radius of Co atoms (0.125 nm), resulting in lattice contraction and an increase in the 2θ angle.

[0065] Figure 4 The EXAFS fitting spectrum shows that Co and O elements form coordination bonds in Co / Bi4TaO8Cl material.

[0066] The concentration of active oxygen species generated during the PMS activation process of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention and the Bi4TaO8Cl material prepared in Comparative Example 1 was quantitatively detected using a molecular probe experiment. Specifically, the material was added to an aqueous solution of terephthalic acid (TPA), PMS (100 mg / L) was added, the system was shaken, and a catalytic reaction was performed. The time point of adding the material was set as 0 min, and samples were taken every 2 minutes. The intensity of the fluorescence peak appearing at 426 nm under 312 nm excitation was measured using a FluoroMax-P spectrophotometer to obtain the concentration of •OH generated during the PMS activation process; p-hydroxybenzoic acid (HBA) was used as a chemical probe to detect SO4 in the catalytic system. •- 1 mol of HBA and 1 mol of SO4 •- The reaction generates hydroquinone, and the excess PMS immediately converts it into a stable byproduct 1,4-benzoquinone (BQ). Finally, the content of BQ in the system is detected by liquid chromatography to obtain SO4 •- The concentration of 9,10-diphenylanthracene (DPA) was used as a chemical probe to detect 1 O2 concentration. DPA and 1 O2 reacts to generate indicative endoperoxide (DPAO2). The experimental process is consistent with the quantitative determination of •OH, except that DPA is used instead of TPA. Figure 5 As shown in Figure 2, within 10 minutes, as the reaction time progresses, SO4 •- , •OH and 1 The concentration of O2 gradually increased and finally reached 0.092 mmol·L -1 , 0.070mmol·L -1 and 0.087 mmol·L-1 Therefore, the main active species in the Co / Bi4TaO8Cl / PMS system is SO4 •- , •OH and 1 O2. In the Bi4TaO8Cl / PMS system, SO4 •- , •OH and 1 The concentration of O2 was 0.022 mmol·L -1 , 0.023mmol·L -1 and 0 mmol·L -1 , much lower than the Co / Bi4TaO8Cl / PMS system.

[0067] Test the synergistic removal of HB101 and ampC by Co / Bi4TaO8Cl catalyst: HB101 and ampC were added to ultrapure water, and the initial concentration of HB101 was 10 7 cfu / mL (copy number is 7-log) and the initial concentration of ampC is 10 10 The material was added to a 25°C composite aqueous solution containing 10 copies / mL (10-log copies) (pH 6.9, as tested). PMS was then added and the system stirred to conduct an advanced oxidation reaction. Samples were taken every minute, and bacterial density was calculated using a standard plate count method. ampC in the reaction solution was quantified using a real-time quantitative PCR (qPCR) instrument to obtain the cycle threshold. The gene copy number was converted using a standard curve. The difference between the gene copy number at time t and the initial gene copy number (10-log) was the material's degradation effect on ampC. Based on the degradation effect, the degradation curve was fitted with a first-order kinetic fit to obtain the apparent rate constant (k), representing the catalyst's degradation rate for tetA. The catalyst dosage was 100 mg / L. The catalysts were the Co / Bi4TaO8Cl materials prepared in Examples 1-4 and the Co / Bi4TaO8Cl material prepared in Comparative Example 1, respectively. The PMS dosage was 100 mg / L.

[0068] like Figure 6 As shown in the figure, the inactivation efficiency of the catalyst for ARB is affected by the cobalt content. When the cobalt content is lower than 1 wt% (Comparative Example 1 and Example 2), the sterilization efficiency increases with the increase of the cobalt content. When the cobalt content exceeds 1 wt% (Example 3 and Example 4), the sterilization efficiency no longer increases. Therefore, the Co / Bi4TaO8Cl material with a cobalt content of 1 wt% has the best sterilization effect, and can completely inactivate ARB within 10 minutes.

[0069] like Figure 7As shown, Example 1 also has the best degradation effect on ampC, with a degradation efficiency of 4.6-log within 10 minutes and an apparent rate constant (k) of 2.3 min -1 Therefore, the Co / Bi4TaO8Cl material with a cobalt content of 1wt% is the optimal catalyst.

[0070] The deactivation effect of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 and ampC at different catalyst dosages was tested. The test method was basically the same as the method described above for "Testing the synergistic removal of HB101 and ampC by catalysts". The only difference was that only the Co / Bi4TaO8Cl material prepared in Example 1 was used as the catalyst and the catalyst dosage was 30 mg / L, 60 mg / L, 100 mg / L, 150 mg / L, and 200 mg / L. The test results are shown in Figure 2. Figure 8 As shown, the catalyst dosage affects its deactivation effect on HB101 and ampC. When the catalyst dosage is less than 100 mg / L, the deactivation effect of the Co / Bi4TaO8Cl material prepared in Example 1 on both HB101 and ampC increases with increasing catalyst dosage. When the catalyst dosage exceeds 100 mg / L, the deactivation effect of the Co / Bi4TaO8Cl material prepared in Example 1 on both HB101 and ampC no longer improves. Therefore, 100 mg / L is the optimal dosage for the Co / Bi4TaO8Cl material prepared in Example 1.

[0071] The inactivation effect of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 and ampC at different pH values was tested. The test method was essentially the same as the aforementioned "Testing the Synergistic Removal of HB101 and ampC by Catalysts," with the only difference being that the pH of the HB101 and ampC composite aqueous solution was adjusted to 5.2, 6.1, 6.9, 7.6, or 8.3 before the catalyst was added. The test results are shown in Table 1. Figure 9 As shown in the results, the inactivation effects of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 and ampC slowly decreased with decreasing pH value within the pH range of 5.2-8.3. However, the inactivation efficiency of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 was still higher than 6-log, and the degradation efficiency on ampC was higher than 3.5-log. Therefore, changes in the pH value of the water body would not significantly inhibit the inactivation effect of the Co / Bi4TaO8Cl material on HB101 and ampC.

[0072] Test Example 1 Preparation of Co / Ti3C2T xThe inactivation effect of the material on HB101 and ampC in three real water bodies, namely river water, lake water and hospital wastewater, is basically the same as the method of "testing the synergistic removal of HB101 and ampC by the catalyst" mentioned above. The only difference is that HB101 and ampC are added to the real water body and the initial bacterial concentration is configured to be 10 7 cfu / mL (copy number is 7-log) and the initial concentration of ampC is 10 10 The composite aqueous solution was prepared at 10 copies / mL (10-log copies / mL). The actual water body was ultrapure water, river water (Haihe River, Tianjin), lake water (Donghu Lake, Tianjin) or hospital wastewater (Peking Union Medical College Hospital, Beijing). The catalyst was the Co / Bi4TaO8Cl material prepared in Example 1. The test results are shown in Figure 2. Figure 10 As shown, the inactivation efficiency of the Co / Bi4TaO8Cl material prepared in Example 1 on bacteria and ampC in three actual water bodies, namely river water, lake water and hospital wastewater, is slightly reduced, but the inactivation efficiency on bacteria is still higher than 6-log, and the degradation efficiency on ampC is higher than 3.5-log. Therefore, the Co / Bi4TaO8Cl material still has excellent inactivation effect on bacteria and ampC in actual water bodies.

[0073] In order to test the amount of metal ion leakage of the catalyst during the PMS activation process, the present invention detected the leakage of tantalum, bismuth and cobalt ions in the Co / Bi4TaO8Cl material prepared in Example 1 during the 10-minute PMS activation process. Specifically, the Co / Bi4TaO8Cl material prepared in Example 1 was added to the composite aqueous solution of HB101 and ampC (the configuration method is the same as "Testing the synergistic removal of HB101 and ampC by the catalyst"), PMS was added, the system was shaken, and a catalytic reaction was carried out. The time point of adding the Co / Bi4TaO8Cl material prepared in Example 1 was 0 min, and samples were taken every 2 minutes to test the concentrations of tantalum, bismuth and cobalt ions using an inductively coupled plasma mass spectrometer. The dosage of the Co / Bi4TaO8Cl material prepared in Example 1 was 100 mg / L, the dosage of PMS was 100 mg / L, the temperature of the tetA aqueous solution was 25°C, and the pH value of the composite aqueous solution of HB101 and ampC before the catalyst was added was 6.9. The test results are as follows Figure 11 As shown, the maximum concentrations of tantalum, bismuth, and cobalt ions leaked from the Co / Bi4TaO8Cl material prepared in Example 1 during the PMS activation process are 0.01, 0.02, and 0.12 mg / L, respectively, which are far below the allowable limits specified in the Chinese national standard (GB 25467-2010). Therefore, the metal ions leaked from the Co / Bi4TaO8Cl material during the PMS activation process will not cause secondary pollution.

[0074] To test the reusability of the catalyst, the present invention used the Co / Bi4TaO8Cl material prepared in Example 1 and tested it five times according to the method of "Testing the Catalyst's Coordinated Removal of HB101 and ampC". After each test, the Co / Bi4TaO8Cl material was filtered and recovered and cleaned in an ultrasonic cleaner with anhydrous ethanol and ultrapure water. The test results are shown in Figure 2. Figure 12 As shown in the figure, after 5 cycles, the inactivation efficiency of HB101 and the degradation efficiency of ampC of the Co / Bi4TaO8Cl material decreased slightly, but the inactivation efficiency of HB101 was still above 6.4 log, and the degradation efficiency of ampC exceeded 3.6-log, indicating that the Co / Bi4TaO8Cl of the present invention has excellent stability and reusability.

[0075] The embodiments of this specific implementation method are all preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Therefore, any equivalent changes made based on the structure, shape, and principle of the present invention should be included in the scope of protection of the present invention.

Claims

1. Application of a Co / Bi4TaO8Cl-type Fenton catalyst in removing drug-resistant bacteria and drug-resistant genes from wastewater, characterized by: The preparation method of Co / Bi4TaO8Cl-type Fenton catalyst comprises the following steps: S1. Dispersing Bi4TaO8Cl material in water to obtain a first solution, and ultrasonically treating the first solution to obtain a Bi4TaO8Cl dispersion; wherein the concentration of Bi4TaO8Cl in the first solution is 8-12 g / L; S2. Add the cobalt chloride solution dropwise to the Bi4TaO8Cl dispersion to obtain a second solution. Stir the second solution for a period of time, collect the precipitate by centrifugation, wash, and dry to obtain a powder. The mass ratio of cobalt in the cobalt chloride solution to Bi4TaO8Cl in the Bi4TaO8Cl dispersion is (0.005-0.02):

1. S3. The powder obtained in step S2 was calcined under an inert gas atmosphere to obtain a Co / Bi4TaO8Cl material; In step S1, the preparation method of the Bi4TaO8Cl material is as follows: Bi2O3, BiOCl, Ta2O5, NaCl and KCl are fully ground and mixed, the mixture is calcined, naturally cooled to room temperature, washed to remove impurities, and dried to obtain Bi4TaO8Cl, wherein the molar ratio of Bi2O3, BiOCl, Ta2O5, NaCl and KCl is (2.9~3.1):(1.9~2.1):(0.9~1.1):30:

30.

2. The application according to claim 1, characterized in that: In the preparation method of the Bi4TaO8Cl material, the grinding time is 30 to 60 minutes; the mixture is calcined at a temperature of 600 to 900°C for 2 to 4 hours; and ultrapure water with a temperature of above 90°C is used for washing.

3. The application according to claim 1, characterized in that: In step S1, the ultrasonic treatment time is 20-40 minutes, and the ultrasonic treatment is performed at 0-25°C.

4. The application according to claim 1, characterized in that: In step S2, the concentration of cobalt chloride in the cobalt chloride solution is 5-15 g / L.

5. The application according to claim 1, characterized in that: In step S2, the second solution is stirred for 2 to 4 hours at a temperature of 40 to 70°C.

6. The application according to claim 1, characterized in that: In step S3, the calcination temperature is 100-150° C., and the calcination time is 1-2 hours.

7. The use according to claim 1, characterized in that: In step S3, the inert gas used for calcination is nitrogen, and the flow rate of nitrogen is 50-100 mL / min.

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