Co / Bi4TaO8Cl Fenton-like catalyst as well as preparation method and application thereof

Abstract

The invention discloses a Co / Bi4TaO8Cl Fenton-like catalyst as well as a preparation method and application of the Co / Bi4TaO8Cl Fenton-like catalyst. The preparation method of the catalyst comprises the following steps: dispersing a Bi4TaO8Cl material into water to obtain a first solution, and carrying out ultrasonic treatment on the first solution to obtain a Bi4TaO8Cl dispersion liquid; dropwise adding a cobalt chloride solution into the Bi4TaO8Cl dispersion liquid to obtain a second solution, stirring the second solution for a period of time, centrifugally collecting precipitates, washing and drying to obtain powder; and calcining the obtained powder under the protection of an inert gas atmosphere to obtain the Co / Bi4TaO8Cl material. The Co / Bi4TaO8Cl Fenton-like catalyst prepared by the method has the advantages of high efficiency, rapidness, greenness and economy, the ARB inactivation efficiency can reach 100% within 10 minutes, the ARG degradation rate can reach 2.3 min <-1 >, and the Co / Bi4TaO8Cl Fenton-like catalyst has good environmental factor interference resistance and cycle stability.

Description

Technical Field

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

[0002] The global spread of antibiotic resistance (AMR) poses a serious threat to public health. Its transmission vectors - antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) spread through water bodies, forming "super bacteria", which seriously threaten ecological security and human health. Traditional water treatment technologies (such as ozone oxidation, ultraviolet disinfection, etc.) are difficult to synergistically remove ARB and ARGs. Therefore, innovative solutions with both high efficiency and environmental friendliness are urgently needed.

[0003] Advanced oxidation technologies (AOPs) based on peroxymonosulfate (PMS) achieve the degradation of pollutants by generating free radicals (SO4 •- •, •OH) and non-free radicals ( 1 O2). The former has strong oxidation ability to inactivate ARB, but is easily interfered by the complex components in water bodies; the latter can specifically damage the DNA structure of ARGs, but its oxidation ability is limited. To achieve the synergistic enhancement of the two, it is necessary to develop new catalysts to break through the bottleneck of traditional technologies. Existing Fenton-like catalysts have significant defects: for example, relying on a single metal active site leads to low electron transfer efficiency, and metal ion leaching causes secondary pollution; for another example, the catalytic system is limited to operating within a narrow pH range and requires additional chemical regulation; furthermore, the material cycle stability is poor, making it difficult to meet the requirements of green circular economy for resource reuse. Therefore, developing green catalysts with multi-active site synergy and stable structures is the key to breaking through the technical bottleneck of synchronous removal of ARB / ARGs. Summary of the Invention

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

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

[0006] A Co / Bi4TaO8Cl Fenton-like catalyst has Co loaded on the surface of the Bi4TaO8Cl material, and the loading amount of Co is less than 2.0% of the mass of the Bi4TaO8Cl material. Preferably, the loading amount of Co is 0.5 - 2 wt% of the mass of the Bi4TaO8Cl material.

[0007] In the second aspect, the present invention provides a preparation method of a Co / Bi4TaO8Cl Fenton-like catalyst, which is achieved by the following technical solutions.

[0008] A preparation method of the above Co / Bi4TaO8Cl Fenton-like catalyst comprises the following steps: S1. Disperse the Bi4TaO8Cl material in water to obtain a first solution, and subject the first solution to ultrasonic treatment to obtain a Bi4TaO8Cl dispersion; wherein, the concentration of Bi4TaO8Cl in the first solution is 8-12 g / L; S2. Drop the cobalt chloride solution into the Bi4TaO8Cl dispersion to obtain a second solution. After stirring the second solution for a period of time, centrifuge to collect the precipitate, wash and dry it to obtain a powder; wherein, the mass ratio of cobalt in the cobalt chloride solution to Bi4TaO8Cl in the Bi4TaO8Cl dispersion is (0.005~0.02):1; S3. Calcinate the powder obtained in step S2 under the protection of an inert gas atmosphere to obtain the Co / Bi4TaO8Cl material.

[0009] Further, in step S1, the preparation method of the Bi4TaO8Cl material is: fully grind and mix Bi2O3, BiOCl, Ta2O5, NaCl and KCl, then calcinate the mixture, naturally cool it to room temperature, wash away the impurities, and dry it to obtain Bi4TaO8Cl, wherein the molar ratio of Bi2O3, BiOCl, Ta2O5, NaCl, KCl is (2.9~3.1):(1.9~2.1):(0.9~1.1):30:30.

[0010] Furthermore, the grinding time is 30~60 minutes, preferably 40 minutes; the calcination temperature of the mixture is 600~900 °C, preferably 800 °C, and the calcination time is 2~4 hours, preferably 3.5 hours; the washing is carried out with ultrapure water at a temperature above 90 °C; the drying is vacuum drying.

[0011] Further, in step S1, the Bi4TaO8Cl material is dispersed in ultrapure water.

[0012] Further, in step S1, the ultrasonic treatment time is 20~40 minutes, preferably 30 minutes, and the ultrasonic treatment is carried out at 0~25 °C, preferably 0 °C.

[0013] Further, 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.

[0014] Further, in step S2, the stirring time of the second solution is 2~4 hours, preferably 3 hours, and the stirring temperature is 40~70 °C, preferably 60 °C.

[0015] Further, in step S2, the washing is carried out with absolute ethanol and ultrapure water.

[0016] Further, in step S2, the drying is vacuum drying.

[0017] Further, 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.

[0018] Further, 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.

[0019] In a third aspect, the present invention provides a use of a Co / Bi4TaO8Cl - like Fenton catalyst, which is achieved by the following technical solution.

[0020] An application of the above - mentioned Co / Bi4TaO8Cl - like Fenton catalyst in removing drug - resistant bacteria and drug - resistant genes in wastewater.

[0021] Further, the drug - resistant bacteria is Escherichia coli HB101.

[0022] Further, the drug - resistant gene is the tetracycline - resistant gene (tetA), which contains 191 base pairs in total.

[0023] Further, the dosage of the Co / Bi4TaO8Cl - like Fenton catalyst is 50 - 200 mg / L, and the temperature of the wastewater is 20 - 30 °C, preferably 25 °C.

[0024] 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 the following technical solution.

[0025] A method for removing drug - resistant bacteria and drug - resistant genes in wastewater, comprising the following steps: adding the above - mentioned Co / Bi4TaO8Cl - like Fenton catalyst to the wastewater, and then adding peroxymonosulfate, and shaking to carry out an advanced oxidation reaction.

[0026] Further, the concentration of peroxymonosulfate in the wastewater is 50 - 150 mg / L, preferably 100 mg / L.

[0027] Further, the dosage of the Co / Bi4TaO8Cl - like Fenton catalyst is 50 - 200 mg / L, and the temperature of the wastewater is 20 - 30 °C, preferably 25 °C.

[0028] This application has the following beneficial effects.

[0029] The Co / Bi4TaO8Cl Fenton-like catalyst obtained by the preparation method of the present invention has the advantages of high efficiency, rapidity, green economy, and its inactivation efficiency for ARB can reach 100% within 10 minutes, and the degradation rate for ARG can reach 2.3 min -1 , and has good resistance to environmental factor interference and cycle stability. The introduction of Co atoms induces charge reconstruction, thereby activating the oxidation activity of Bi sites towards PMS. Meanwhile, PMS is efficiently reduced at Co sites, realizing the efficient generation of free radicals (SO4 •- and •OH) and non-free radicals ( 1 O2). The Co / Bi4TaO8Cl Fenton-like catalyst obtained by the preparation method of the present invention can still maintain high-efficiency removal of ARB and ARG in actual wastewater and different pH ranges. The leaching amount of metal ions in the Co / Bi4TaO8Cl material is lower than the requirements of water quality standards, without secondary pollution, fully reflecting the characteristics of green and environmentally friendly. Description of the Drawings

[0030] Figure 1 is the SEM electron micrograph of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention; Figure 2 is the TEM and HAADF-STEM images of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention, Figure 2 in which (a) is the TEM image of the Co / Bi4TaO8Cl material, Figure 2 in which (b) is the HAADF-STEM image of the Co / Bi4TaO8Cl material; Figure 3 is the XRD pattern of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention and the Bi4TaO8Cl material prepared in Comparative Example 1, Figure 3 in which 2θ on the abscissa is the diffraction angle directly measured in the experiment, and the unit is degree (°); Figure 4 is the EXAFS fitting spectrum of the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention, Figure 4 in which R+α on the abscissa represents the actual atomic spacing after correction, and the unit is angstrom (Å), and the ordinate FT[k 2 χ(k)] represents the amplitude after Fourier transform of k²-weighted χ(k); Figure 5 is the concentration result diagram of SO4 •- , •OH and 1 O2 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; Figure 6 Results of the inactivation efficiency of HB101 using the Co / Bi4TaO8Cl materials prepared in Examples 1-4 of the present invention and the Bi4TaO8Cl material prepared in Comparative Example 1 as catalysts, respectively; Figure 7 Results of the degradation rate (left axis) and degradation efficiency (right axis) of ampicillin-resistant gene (ampC) using the Co / Bi4TaO8Cl materials prepared in Examples 1-4 of the present invention and the Bi4TaO8Cl material obtained in Comparative Example 1 as catalysts, respectively; Figure 8 Results of the inactivation efficiency of HB101 and the degradation efficiency of ampC using the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention at different catalyst dosages; Figure 9 Results of the inactivation efficiency of HB101 and the degradation efficiency of ampC using the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention under different pH conditions; Figure 10 Results of the inactivation efficiency of HB101 and the degradation efficiency of ampC using the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention in different water bodies; Figure 11 Results of the concentration of metal ions leaked during the activation of PMS using the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention; Figure 12 Results of the cyclic test of the inactivation efficiency of HB101 and the degradation efficiency of ampC using the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention; Detailed implementation manners

[0031] In the present invention, Bi4TaO8Cl is an ideal carrier for single-metal active sites in PMS activation due to its narrow bandgap, high stability, and multi-active site synergistic effect. Anchoring Co on Bi4TaO8Cl to construct asymmetric Co-O-Bi dual reaction sites is expected to achieve simultaneous efficient redox of PMS, generating free radicals (SO4 •- and •OH) and non-free radicals ( 1 O2), thereby effectively solving the problem of low synergistic removal efficiency of ARBs and ARGs.

[0032] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0033] The sources of the drugs involved in the following examples 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), absolute ethanol (99%, Jiangtian Chemical Industry).

[0034] The drug-resistant bacteria is Escherichia coli HB101.

[0035] The drug-resistant gene is the ampicillin-resistant gene (ampC), which contains 191 base pairs in total. The acquisition method can be referred to DOI: 10.1016 / j.cej.2016.10.107.

[0036] The models of the instruments involved in the following examples are as follows: magnetic stirrer (HJ-3 type), digital display constant temperature water bath (HH.S21-8), vacuum drying oven (DZF-6020 type), ultrasonic cleaner (SB-3200DT), high-speed centrifuge (TG16-WS), box-type muffle furnace (KLSF-1200X), tube furnace (OTF-1200X).

[0037] Examples 1 to 4 A preparation method of Co / Bi4TaO8Cl-like Fenton catalyst, comprising the following steps: Step 1, grind Bi2O3, BiOCl, Ta2O5, NaCl and KCl with a mortar for 40 minutes. Then, place the mixture in an alumina crucible and calcine it in a muffle furnace at 800 °C for 3.5 hours. After natural cooling to room temperature, wash it with ultrapure water at 100 °C to remove impurities and dry it in vacuum to obtain Bi4TaO8Cl, where the molar ratio of Bi2O3, BiOCl, Ta2O5, NaCl, KCl is 3:2:1:30:30; Step 2, disperse Bi4TaO8Cl into ultrapure water to obtain a first solution, and ultrasonicate the first solution at 0 °C for 30 minutes to obtain a Bi4TaO8Cl dispersion, where the concentration of Bi4TaO8Cl in the first solution is 10 g / L; Step 3, drop the cobalt chloride aqueous solution into the Bi4TaO8Cl dispersion to obtain a second solution, stir the second solution at 60 °C for 3 hours, centrifuge to collect the precipitate, wash it with absolute ethanol and ultrapure water, and dry it in vacuum to obtain a yellow powder, where 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.

[0038] Table 1

[0039] Step 4: calcining the powder obtained in step 3 at 120° C. for 1.5 hours under a nitrogen atmosphere to obtain Co / Bi4TaO8Cl material, wherein the flow rate of nitrogen is 60 mL / min.

[0040] 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.

[0041] Comparative Example 1 A preparation method of 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. Then, the mixture is placed in an alumina crucible and calcined at 800°C in a muffle furnace for 3.5 hours. After naturally cooling to room temperature, the mixture is washed with ultrapure water at 100°C to remove impurities, and vacuum dried to obtain the Bi4TaO8Cl material.

[0042] like Figure 1 The SEM electron microscope photograph shown shows that the thickness of the Co / Bi4TaO8Cl material is 130nm.

[0043] 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 the appearance of cobalt particles.

[0044] Figure 3 The XRD graph shows that the crystal structure of Co / Bi4TaO8Cl material is similar to that of Bi4TaO8Cl material, and no characteristic peaks of Co single substance are observed, which further indicates that there are no Co nanoparticles in Co / Bi4TaO8Cl. In addition, compared with Bi4TaO8Cl, the diffraction peak of Co / Bi4TaO8Cl at 2θ = 37.55° is slightly shifted to a higher angle, which may be due to the fact that after doping with Co, the Bi atoms with larger atomic radius (0.170 nm) in Bi4TaO8Cl are replaced by Co atoms with smaller atomic radius (0.125 nm), resulting in lattice contraction and larger 2θ angle.

[0045] Figure 4 The EXAFS fitting spectrum shows that Co and O elements form coordination bonds in Co / Bi4TaO8Cl material.

[0046] Quantitatively detect the concentration of reactive oxygen species generated during the activation of PMS by the Co / Bi4TaO8Cl material prepared in Example 1 of the present invention and the Bi4TaO8Cl material prepared in Comparative Example 1 using molecular probe experiments. Specifically, add the material to an aqueous solution of terephthalic acid (TPA), add PMS (100 mg / L), shake the system, and carry out the catalytic reaction. Taking the time point when the material is added as 0 min, sample every 2 minutes, and use a FluoroMax-P spectrophotometer to measure the intensity of the fluorescence peak at 426 nm under excitation at 312 nm to obtain the concentration of •OH generated during the activation of PMS; use p-hydroxybenzoic acid (HBA) as a chemical probe to detect the concentration of SO4 •- in the catalytic system. 1 mol of HBA reacts with 1 mol of SO4 •- to form hydroquinone, and the excess PMS immediately converts it into a stable by-product 1,4-benzoquinone (BQ). Finally, detect the content of BQ in the system by liquid chromatography to obtain the concentration of SO4 •- ; use 9,10-diphenylanthracene (DPA) as a chemical probe to detect the concentration of 1 O2 in the system. DPA reacts with 1 O2 to form an indicative endoperoxide (DPAO2). The experimental process is the same as the quantification of •OH, except that DPA is used instead of TPA. The test results are as Figure 5 shown. Within 10 minutes, as the reaction time progresses, the concentrations of SO4 •- , •OH, and 1 O2 in the Co / Bi4TaO8Cl / PMS system gradually increase and finally reach 0.092 mmol·L -1 , 0.070 mmol·L -1 , and 0.087 mmol·L -1 , respectively. Therefore, the main reactive species in the Co / Bi4TaO8Cl / PMS system are SO4 •- , •OH, and 1 O2. In the Bi4TaO8Cl / PMS system, the concentrations of SO4 •- , •OH, and 1 O2 are 0.022 mmol·L -1 , 0.023 mmol·L -1 , and 0 mmol·L -1 , respectively, which are much lower than those in the Co / Bi4TaO8Cl / PMS system.

[0047] Test the synergistic removal of HB101 and ampC by the Co / Bi4TaO8Cl catalyst: Add HB101 and ampC to ultrapure water to configure the initial concentration of HB101 to be 107 cfu / mL (copy number is 7-log) and the initial concentration of ampC is 10 10 copies / mL (copy number is 10-log) of the composite aqueous solution (the pH value is 6.9 at this time after testing). Add the material into the composite aqueous solution at 25 °C, add PMS, stir the system, and carry out the advanced oxidation reaction. Take samples every 1 minute, calculate the bacterial density by the standard plate counting method, and quantitatively analyze ampC in the reaction solution with a real-time quantitative PCR (qPCR) instrument to obtain the cycle threshold. According to the standard curve, convert to obtain the gene copy number. The difference between the gene copy number at time t and the gene copy number at the initial time (10-log) is the degradation effect of the material on ampC. Perform a first-order kinetic fitting on the degradation curve according to the degradation effect to obtain the apparent rate constant (k), which represents the degradation rate of the catalyst on tetA. Among them, the catalyst dosage is 100 mg / L, the catalysts are the Co / Bi4TaO8Cl materials prepared in Examples 1 to 4 and the Co / Bi4TaO8Cl material prepared in Comparative Example 1, and the PMS dosage is 100 mg / L.

[0048] As Figure 6 shown, the inactivation efficiency of the catalyst on ARB is affected by the cobalt content. When the cobalt content is less 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% (Examples 3 and 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 it can completely inactivate ARB within 10 minutes.

[0049] As Figure 7 shown, Example 1 also has the best degradation effect on ampC. The degradation efficiency of ampC reaches 4.6-log within 10 minutes, and the apparent rate constant (k) reaches 2.3 min -1 , so the Co / Bi4TaO8Cl material with a cobalt content of 1 wt% is the optimal catalyst.

[0050] Test the inactivation effects of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 and ampC under different catalyst dosages. The test method 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: the catalyst only uses the Co / Bi4TaO8Cl material prepared in Example 1 and the catalyst dosages are 30 mg / L, 60 mg / L, 100 mg / L, 150 mg / L, and 200 mg / L. The test results are as Figure 8As shown, the dosage of the catalyst affects its inactivation effect on HB101 and ampC. When the dosage of the catalyst is lower than 100 mg / L, with the increase of the catalyst dosage, the inactivation effects of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 and ampC both increase. When the dosage of the catalyst exceeds 100 mg / L, the inactivation effects of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 and ampC no longer increase. Therefore, 100 mg / L is the optimal dosage of the Co / Bi4TaO8Cl material prepared in Example 1.

[0051] Test the inactivation effects of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 and ampC at different pH values. The test method is basically the same as the method of "testing the synergistic removal of HB101 and ampC by the catalyst" described above. The only difference is that: before adding the catalyst, the pH value of the composite aqueous solution of HB101 and ampC is adjusted to 5.2, 6.1, 6.9, 7.6 or 8.3. The test results are as Figure 9 shown, the inactivation effects of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 and ampC both decrease slowly with the decrease of the pH value in the range of pH 5.2 - 8.3. However, the inactivation efficiency of the Co / Bi4TaO8Cl material prepared in Example 1 on HB101 is still higher than 6-log, and the degradation efficiency on ampC is above 3.5-log. Therefore, the change of the water body pH value will not significantly inhibit the inactivation effects of the Co / Bi4TaO8Cl material on HB101 and ampC.

[0052] Test the inactivation effects of the Co / Ti3C2T prepared in Example 1 x material on HB101 and ampC in three actual water bodies: river water, lake water and hospital wastewater. The test method is basically the same as the method of "testing the synergistic removal of HB101 and ampC by the catalyst" described above. The only difference is that: HB101 and ampC are added to the actual water bodies to prepare a composite aqueous solution with an initial bacterial concentration of 10 7 cfu / mL (copy number is 7-log) and an initial ampC concentration of 10 10 copies / mL (copy number is 10-log). The actual water bodies are ultrapure water, river water (Haihe River, Tianjin), lake water (Donghu Lake, Tianjin) or hospital wastewater (Peking Union Medical College Hospital, Beijing), and the catalyst is the Co / Bi4TaO8Cl material prepared in Example 1. The test results are as Figure 10As shown, in Example 1, when preparing the Co / Bi4TaO8Cl material, the inactivation efficiency of bacteria and ampC in three actual water bodies, namely river water, lake water and hospital wastewater, decreased slightly, but the inactivation efficiency of bacteria was still higher than 6-log, and the degradation efficiency of ampC was above 3.5-log. Therefore, the Co / Bi4TaO8Cl material still has excellent inactivation effect on bacteria and ampC in actual water bodies.

[0053] In order to test the leakage amount of metal ions during the activation process of the catalyst by PMS, the present invention detected the leakage amounts of tantalum, bismuth and cobalt ions of 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 preparation method was the same as that of "testing the synergistic removal of HB101 and ampC by the catalyst"), PMS was added, the system was shaken, and the catalytic reaction was carried out. Taking the time point when the Co / Bi4TaO8Cl material prepared in Example 1 was added as 0 min, samples were taken every 2 minutes, and the concentrations of tantalum, bismuth and cobalt ions were measured by inductively coupled plasma mass spectrometry. 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 adding the catalyst was 6.9. The test results are as Figure 11 shown, during the activation of PMS by the Co / Bi4TaO8Cl material prepared in Example 1, the highest concentrations of leaked tantalum, bismuth and cobalt ions were 0.01, 0.02 and 0.12 mg / L respectively, which were far lower than the allowable limits specified in the Chinese national standard (GB 25467-2010). Therefore, the metal ions leaked during the activation of PMS by the Co / Bi4TaO8Cl material will not cause secondary pollution.

[0054] In order to test the reusability of the catalyst, the present invention used the Co / Bi4TaO8Cl material prepared in Example 1 to conduct 5 tests according to the method of "testing the synergistic removal of HB101 and ampC by the catalyst". After each test, the Co / Bi4TaO8Cl material was filtered and recovered, and was cleaned in an ultrasonic cleaner with anhydrous ethanol and ultrapure water. The test results are as Figure 12 shown, after 5 cycles, the inactivation efficiency of the Co / Bi4TaO8Cl material for HB101 and the degradation efficiency of ampC both decreased slightly, but the inactivation efficiency for 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.

[0055] The embodiments of this specific implementation manner are all preferred embodiments of the present invention, and do not limit the protection scope of the present invention accordingly. Therefore, all equivalent changes made according to the structure, shape, and principle of the present invention should be covered within the protection scope of the present invention.

Claims

1. A Co / Bi4TaO8Cl-like Fenton catalyst, characterized in that: Co is loaded on the surface of the Bi4TaO8Cl material, and the loading amount of Co is less than 2.0% of the mass of the Bi4TaO8Cl material.

2. The preparation method of the Co / Bi4TaO8Cl Fenton-like catalyst according to claim 1, characterized in that: It includes the following steps: S1. Disperse the Bi4TaO8Cl material in water to obtain a first solution, and ultrasonically treat the first solution to obtain a Bi4TaO8Cl dispersion; wherein, the concentration of Bi4TaO8Cl in the first solution is 8-12 g / L; S2. Drop the cobalt chloride solution into the Bi4TaO8Cl dispersion to obtain a second solution. After stirring the second solution for a period of time, centrifuge to collect the precipitate, wash and dry it to obtain a powder; wherein, the mass ratio of cobalt in the cobalt chloride solution to Bi4TaO8Cl in the Bi4TaO8Cl dispersion is (0.005~0.02):1; S3. Calcinate the powder obtained in step S2 under the protection of an inert gas atmosphere to obtain the Co / Bi4TaO8Cl material.

3. The preparation method of a Co / Bi4TaO8Cl-like Fenton catalyst according to claim 2, characterized in that: In step S1, the preparation method of the Bi4TaO8Cl material is: fully grind and mix Bi2O3, BiOCl, Ta2O5, NaCl and KCl, then calcine the mixture, naturally cool it to room temperature, wash away the impurities, and dry it to obtain Bi4TaO8Cl, wherein the molar ratio of Bi2O3, BiOCl, Ta2O5, NaCl, KCl is (2.9~3.1):(1.9~2.1):(0.9~1.1):30:

30.

4. The preparation method of a Co / Bi4TaO8Cl-like Fenton catalyst according to claim 3, characterized in that: The grinding time is 30~60 minutes; the calcination temperature of the mixture is 600~900 °C, and the calcination time is 2~4 hours; the washing is carried out with ultrapure water at a temperature above 90 °C.

5. The preparation method of a Co / Bi4TaO8Cl-like Fenton catalyst according to claim 2, characterized in that: In step S1, the ultrasonic treatment time is 20~40 minutes, and the ultrasonic treatment is carried out at 0~25 °C.

6. The preparation method of a Co / Bi4TaO8Cl-like Fenton catalyst according to claim 2, characterized in that: In step S2, the concentration of cobalt chloride in the cobalt chloride solution is 5-15 g / L.

7. The preparation method of a Co / Bi4TaO8Cl-like Fenton catalyst according to claim 2, characterized in that: In step S2, the stirring time of the second solution is 2~4 hours, and the stirring temperature is 40~70 °C.

8. The preparation method of a Co / Bi4TaO8Cl-like Fenton catalyst according to claim 2, characterized in that: In step S3, the calcination temperature is 100~150 °C, and the calcination time is 1~2 hours.

9. The preparation method of a Co / Bi4TaO8Cl Fenton-like catalyst according to claim 2, characterized in that: In step S3, the inert gas used for calcination is nitrogen, and the flow rate of nitrogen is 50~100 mL / minute.

10. Application of the Co / Bi4TaO8Cl Fenton-like catalyst according to claim 1 in removing drug-resistant bacteria and drug-resistant genes in wastewater.

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