NH2-MIL-101 (Fe, Mn) piezoelectric catalyst, preparation method and application thereof, and method for removing basic groups, antibiotics and antibiotic resistance genes in water body

Abstract

The invention relates to the field of catalysts and environmental pollution treatment, in particular to an NH2-MIL-101 (Fe, Mn) piezoelectric catalyst, a preparation method and application thereof and a method for removing basic groups, antibiotics and antibiotic resistance genes in water. The preparation method comprises the following steps: mixing ferric salt, manganese salt and 2-aminoterephthalic acid, and reacting to obtain the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst. The NH2-MIL-101 (Fe, Mn) piezoelectric catalyst provided by the invention has excellent piezoelectric catalysis performance and good stability, and can obviously improve the reaction efficiency of piezoelectric catalysis PDS with electrons and holes, thereby improving the removal efficiency of basic groups, antibiotics and antibiotic resistance genes in water.

Description

Technical Field

[0001] The present invention relates to the fields of catalysts and environmental pollution treatment, and particularly to an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst, a preparation method and an application thereof, and a method for removing bases, antibiotics, and antibiotic resistance genes in water bodies. Background Art

[0002] The persulfate (PDS)-based Fenton advanced oxidation technology (PDS-AOP) has the advantages of high free radical yield, good selectivity, and wide pH application range, and has been widely used in the removal of pollutants. The catalytic degradation effect of PDS-AOP depends to a large extent on the activation method. However, the existing PDS activation mainly relies on energy and traditional catalysts to achieve, facing practical problems such as high energy consumption, poor stability, and secondary pollution. Therefore, it is very necessary to develop a low-energy consumption, green and efficient PDS activation method. In recent years, the use of piezotronic electrons generated by piezoelectric materials to activate PDS has gradually come into the view of researchers. Only a weak mechanical force (such as tides, winds, and laboratory ultrasounds) is required to induce the generation of piezotronic electrons and achieve the activation of PDS. However, the limited specific surface area of traditional piezoelectric catalysts and the long transport distance of charge carriers greatly limit the practical application of the piezocatalytic technology.

[0003] Metal-organic framework materials (MOFs), also known as porous coordination polymers, are self-assembled from metal ions or metal clusters and bidentate or multidentate ligands, and usually have a super-large surface area, adjustable pore size, adjustable chemical composition and surface function, and well-defined metal nodes. Due to their unique properties, MOFs have become a research hotspot in the catalytic field in recent years. Although many progresses have been made in thermal catalysis of MOFs, single-metal MOFs still have some challenging problems as catalysts, such as unsatisfactory catalytic activity and selectivity, poor stability, and difficulty in achieving multifunctional catalysis. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems in the related technologies to some extent. For this purpose, the present invention provides an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst, a preparation method and an application thereof, and a method for removing bases, antibiotics, and antibiotic resistance genes in water bodies. The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst provided by the present invention has excellent piezocatalytic performance and good stability, can significantly improve the reaction efficiency of piezocatalytic PDS with electrons and holes, thereby improving the removal efficiency of bases, antibiotics, and antibiotic resistance genes in water bodies; in addition, the piezoelectric catalyst can be recycled and easily recovered after the reaction, and will not cause pollution to the water environment.

[0005] For this reason, in the first aspect of the present invention, a preparation method of an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is provided, and the preparation method includes:

[0006] Mix an iron salt, a manganese salt, and 2-aminoterephthalic acid, and carry out a reaction to obtain an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst.

[0007] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst can be prepared by using the preparation method provided by the present invention, and the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst can catalyze and improve the efficiency of removing bases, antibiotics, and antibiotic resistance genes in water by PDS.

[0008] According to an embodiment of the present invention, the molar ratio of the iron salt, the manganese salt, and 2-aminoterephthalic acid is 1:(0.6 - 0.7):(0.6 - 0.7).

[0009] According to an embodiment of the present invention, the iron salt includes at least one of ferric chloride hexahydrate, ferric chloride, ferric nitrate, and iron oxalate.

[0010] According to an embodiment of the present invention, the manganese salt includes at least one of manganese nitrate tetrahydrate, manganese chloride, manganese sulfate, manganese acetate, and manganese oxalate.

[0011] According to an embodiment of the present invention, the temperature of the reaction is 100°C - 120°C.

[0012] According to an embodiment of the present invention, the time of the reaction is 10 h - 14 h.

[0013] According to an embodiment of the present invention, the preparation method further includes: adding the iron salt, the manganese salt, and 2-aminoterephthalic acid into a solvent, mixing, carrying out a reaction, and drying to obtain an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst.

[0014] According to an embodiment of the present invention, the solvent includes at least one of N,N-dimethylformamide, N,N-diethylformamide, ethanol, and methanol.

[0015] According to an embodiment of the present invention, the temperature of the drying is 40°C - 80°C.

[0016] According to an embodiment of the present invention, the time of the drying is 6 h - 18 h.

[0017] In the second aspect of the present invention, an NH obtained by the preparation method according to the first aspect is provided2 -MIL-101(Fe,Mn) piezoelectric catalyst.

[0018] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst provided by the present invention can catalyze and improve the efficiency of removing bases, antibiotics, and antibiotic resistance genes in water by PDS; in addition, the piezoelectric catalyst can be recycled and easily recovered after the reaction, and will not cause pollution to the water environment.

[0019] The third aspect of the present invention provides the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst obtained by the preparation method described in the first aspect or the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst described in the second aspect for use in removing at least one of bases, antibiotics, and antibiotic resistance genes in water.

[0020] The fourth aspect of the present invention provides a method for removing bases in water, the method using the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst to catalyze persulfate to remove bases in water;

[0021] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst obtained by the preparation method described in the first aspect or the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst described in the second aspect.

[0022] According to an embodiment of the present invention, the method includes the following steps:

[0023] Mix the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst with water containing bases to obtain a first mixture;

[0024] Add persulfate to the first mixture to obtain a second mixture, and perform ultrasonic treatment to achieve the removal of bases.

[0025] According to an embodiment of the present invention, the content of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst in the first mixture is 0.05 g / L to 0.4 g / L.

[0026] According to an embodiment of the present invention, the content of bases in the first mixture is 5 μmol / L to 15 μmol / L.

[0027] According to an embodiment of the present invention, the base includes at least one of A, T, C, and G.

[0028] According to an embodiment of the present invention, the content of persulfate in the second mixed solution is 0.2 g / L to 1.2 g / L.

[0029] According to an embodiment of the present invention, the power of the ultrasonic treatment is 20 W to 100 W, preferably 60 W to 100 W.

[0030] The fifth aspect of the present invention provides a method for removing antibiotics from water, which uses NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst to catalyze persulfate to remove antibiotics from water;

[0031] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst obtained by the preparation method described in the first aspect or the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst described in the second aspect.

[0032] According to an embodiment of the present invention, the method includes the following steps:

[0033] Mix the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst and the water containing antibiotics to obtain a third mixed solution;

[0034] Add persulfate to the third mixed solution to obtain a fourth mixed solution, and perform ultrasonic treatment to achieve the removal of antibiotics.

[0035] According to an embodiment of the present invention, the content of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst in the third mixed solution is 0.05 g / L to 0.4 g / L.

[0036] According to an embodiment of the present invention, the content of antibiotics in the third mixed solution is 3 mg / L - 8 mg / L.

[0037] According to an embodiment of the present invention, the antibiotics include at least one of sulfamethoxazole, ciprofloxacin, carbamazepine, and sulfadiazine.

[0038] According to an embodiment of the present invention, the content of persulfate in the fourth mixed solution is 0.2 g / L to 1.2 g / L.

[0039] According to an embodiment of the present invention, the power of the ultrasonic treatment is 20 W to 100 W, preferably 60 W to 100 W.

[0040] The sixth aspect of the present invention provides a method for removing antibiotic resistance genes in water, which uses NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst to catalyze persulfate to remove antibiotic resistance genes in water;

[0041] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst obtained according to the preparation method described in the first aspect or the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst described in the second aspect.

[0042] According to an embodiment of the present invention, the method includes the following steps:

[0043] Mix the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst with the water containing antibiotic resistance genes to obtain a fifth mixture;

[0044] Add persulfate to the fifth mixture to obtain a sixth mixture, and perform ultrasonic treatment to achieve the removal of antibiotic resistance genes.

[0045] According to an embodiment of the present invention, the content of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst in the fifth mixture is 0.05 g / L to 0.4 g / L.

[0046] According to an embodiment of the present invention, the content of antibiotic resistance genes in the fifth mixture is 3 mg / L - 8 mg / L.

[0047] According to an embodiment of the present invention, the antibiotic resistance genes include at least one of tetA and ampC.

[0048] According to an embodiment of the present invention, the content of persulfate in the sixth mixture is 0.2 g / L to 1.2 g / L.

[0049] According to an embodiment of the present invention, the power of the ultrasonic treatment is 20 W to 100 W, preferably 60 W to 100 W.

[0050] The additional aspects and advantages of the present invention will be partly given in the following description, partly will become obvious from the following description, or be understood through the practice of the present invention. Description of the Drawings

[0051] The above and / or additional aspects and advantages of the present invention will become apparent and be readily understood from the following description of embodiments in conjunction with the accompanying drawings, in which:

[0052] Figure 1 The SEM and XRD diagrams of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in Example 1 of the present invention are shown, where Figure A is the SEM diagram of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in Example 1; Figure B is the XRD diagram of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in Example 1;

[0053] Figure 2 The effect diagram of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in Example 2 of the present invention for catalyzing the removal of base T at different concentrations is shown;

[0054] Figure 3 The effect diagram of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in Example 3 of the present invention for catalyzing the removal of base T from different concentrations of PDS is shown;

[0055] Figure 4 The effect diagram of the removal of base T under different reaction conditions in Example 4 of the present invention is shown;

[0056] Figure 5 The effect diagram of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in Example 5 of the present invention for catalyzing the removal of base T at different ultrasonic powers is shown;

[0057] Figure 6 The effect diagram of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in Example 6 of the present invention for the cyclic performance test of catalyzing the removal of base T from PDS is shown;

[0058] Figure 7 The effect diagram of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in Example 7 of the present invention for catalyzing the removal of antibiotics is shown;

[0059] Figure 8 The effect diagram of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in Example 8 of the present invention for catalyzing the removal of antibiotic resistance genes is shown.

[0060] Figure 9Shows the NH prepared in Example 9 of the present invention 2 -MIL-101(Fe,Mn) piezoelectric catalyst for catalytic removal of base A, base G, and base C by PDS. Detailed implementation manners

[0061] The embodiments of the present invention will be described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as a limitation to the present invention.

[0062] It should be noted that the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of such features. Further, in the description of the present invention, unless otherwise specified, the meaning of "a plurality" is two or more.

[0063] In the ranges disclosed herein, the endpoints and any value are not limited to the exact range or value. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0064] To make it easier to understand the present invention, certain technical and scientific terms are specifically defined below. Unless otherwise clearly defined elsewhere in this document, all other technical and scientific terms used herein have the meanings commonly understood by those of ordinary skill in the art to which the present invention pertains.

[0065] In this document, the term "comprising" or "including" is an open expression, that is, it includes the content specified by the present invention, but does not exclude other aspects.

[0066] In this document, the terms "optionally", "optional" or "option" generally mean that the subsequent events or conditions may or may not occur, and this description includes the cases where such events or conditions occur, as well as the cases where such events or conditions do not occur.

[0067] According to an embodiment of the present invention, a first aspect of the present invention provides a method for preparing an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst, and the preparation method includes:

[0068] Mix ferric salt, manganese salt, and 2-aminoterephthalic acid, and carry out a reaction to obtain an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst.

[0069] The present invention utilizes Mn in the manganese salt to modify NH 2 -MIL-101(Fe) to obtain a bimetallic organic framework material NH 2 -MIL-101(Fe,Mn), which can activate PDS under ultrasonic conditions, effectively separate the generated electrons and holes to directly or indirectly reduce and remove bases, thereby improving the base removal efficiency; in addition, the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst can also catalyze the removal of antibiotics and antibiotic resistance genes by PDS.

[0070] According to specific embodiments of the present invention, the molar ratio of the iron salt, manganese salt, and 2-aminoterephthalic acid is 1:(0.6 - 0.7):(0.6 - 0.7). As some specific examples, the molar ratio of the iron salt, manganese salt, and 2-aminoterephthalic acid can be 1:0.6:0.6, 1:0.66:0.66, 1:0.7:0.7, etc.

[0071] According to specific embodiments of the present invention, the type of the iron salt is not particularly limited. As some specific examples, the iron salt includes at least one of ferric chloride hexahydrate, ferric chloride, ferric nitrate, and ferric oxalate.

[0072] According to specific embodiments of the present invention, the type of the manganese salt is not particularly limited. As some specific examples, the manganese salt includes at least one of manganese nitrate tetrahydrate, manganese chloride, manganese sulfate, manganese acetate, and manganese oxalate.

[0073] According to specific embodiments of the present invention, the temperature of the reaction is 100°C - 120°C. As some specific examples, the temperature of the reaction can be 100°C, 110°C, 120°C, etc.

[0074] According to specific embodiments of the present invention, the time of the reaction is 10h - 14h. As some specific examples, the time of the reaction can be 10h, 12h, 14h, etc.

[0075] According to specific embodiments of the present invention, the heating rate of the reaction is 5°C / min - 15°C / min. As some specific examples, the heating rate of the reaction can be 5°C / min, 10°C / min, 15°C / min, etc.

[0076] According to specific embodiments of the present invention, the preparation method further includes: adding the iron salt, manganese salt, and 2-aminoterephthalic acid to a solvent, mixing, reacting, and drying to obtain the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst.

[0077] According to specific embodiments of the present invention, the type of the solvent is not particularly limited. As some specific examples, the solvent includes at least one of N,N-dimethylformamide, N,N-diethylformamide, ethanol, and methanol.

[0078] According to specific embodiments of the present invention, the drying temperature is 40°C - 80°C. As some specific examples, the drying temperature can be 40°C, 60°C, 80°C, etc.

[0079] According to specific embodiments of the present invention, the drying time is 6h - 18h. As some specific examples, the drying time can be 6h, 12h, 18h, etc.

[0080] According to specific embodiments of the present invention, the preparation method further includes: mixing an iron salt, a manganese salt, and 2-aminoterephthalic acid, stirring, and reacting to obtain NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst.

[0081] According to specific embodiments of the present invention, the stirring time is 30min - 90min. As some specific examples, the stirring time can be 30min, 60min, 90min, etc.

[0082] According to an embodiment of the present invention, the second aspect of the present invention provides an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst obtained by the preparation method according to the first aspect.

[0083] According to an embodiment of the present invention, the third aspect of the present invention provides an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst obtained by the preparation method according to the first aspect or the application of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst according to the second aspect in removing at least one of bases, antibiotics, and antibiotic resistance genes in water bodies.

[0084] According to an embodiment of the present invention, the fourth aspect of the present invention provides a method for removing bases in water bodies. The method uses an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst to catalyze persulfate to remove bases in water bodies;

[0085] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst obtained by the preparation method according to the first aspect or the NH 2-MIL-101(Fe,Mn) piezoelectric catalyst.

[0086] According to a specific embodiment of the present invention, the method includes the following steps:

[0087] Mix NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst with a water body containing a base to obtain a first mixture;

[0088] Add persulfate to the first mixture to obtain a second mixture, and perform ultrasonic treatment to achieve the removal of the base.

[0089] According to a specific embodiment of the present invention, the content of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst in the first mixture is 0.05 g / L to 0.4 g / L. As some specific examples, the content of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst in the first mixture can be 0.05 g / L, 0.1 g / L, 0.2 g / L, 0.4 g / L, etc.

[0090] According to a specific embodiment of the present invention, the content of the base in the first mixture is 5 μmol / L to 15 μmol / L. As some specific examples, the content of the base in the first mixture can be 5 μmol / L, 10 μmol / L, 15 μmol / L, etc.

[0091] According to a specific embodiment of the present invention, the type of the base is not particularly limited. As some specific examples, the base includes at least one of A, T, C, and G.

[0092] According to a specific embodiment of the present invention, the content of persulfate in the second mixture is 0.2 g / L to 1.2 g / L. As some specific examples, the content of persulfate in the second mixture can be 0.2 g / L, 0.4 g / L, 0.8 g / L, 1.2 g / L, etc.

[0093] According to a specific embodiment of the present invention, the power of the ultrasonic treatment is 20 W to 100 W. As some specific examples, the power of the ultrasonic treatment can be 20 W, 40 W, 60 W, 80 W, 100 W, etc., and preferably 60 W to 100 W.

[0094] According to an embodiment of the present invention, a fifth aspect of the present invention provides a method for removing antibiotics from a water body. The method uses NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst to catalyze persulfate to remove antibiotics from the water body;

[0095] The NH2 The -MIL-101(Fe,Mn) piezoelectric catalyst is NH obtained by the preparation method according to the first aspect 2 -MIL-101(Fe,Mn) piezoelectric catalyst or the NH described in the second aspect 2 -MIL-101(Fe,Mn) piezoelectric catalyst.

[0096] According to a specific embodiment of the present invention, the method comprises the following steps:

[0097] Mix the -MIL-101(Fe,Mn) piezoelectric catalyst and the water body containing antibiotics to obtain a third mixture; 2

[0098] Add persulfate to the third mixture to obtain a fourth mixture, and perform ultrasonic treatment to achieve the removal of antibiotics.

[0099] According to a specific embodiment of the present invention, the content of the -MIL-101(Fe,Mn) piezoelectric catalyst in the third mixture is 0.05 g / L to 0.4 g / L. As some specific examples, the content of the -MIL-101(Fe,Mn) piezoelectric catalyst in the third mixture can be 0.05 g / L, 0.1 g / L, 0.2 g / L, 0.4 g / L, etc. 2 2

[0100]

[0100] According to a specific embodiment of the present invention, the content of antibiotics in the third mixture is 3 mg / L - 8 mg / L. As some specific examples, the content of antibiotics in the third mixture can be 3 mg / L, 5 mg / L, 8 mg / L, etc.

[0101] According to a specific embodiment of the present invention, the type of antibiotics is not particularly limited. As some specific examples, the antibiotics include at least one of sulfamethoxazole, ciprofloxacin, carbamazepine, and sulfadiazine.

[0102] According to a specific embodiment of the present invention, the content of persulfate in the fourth mixture is 0.2 g / L to 1.2 g / L. As some specific examples, the content of persulfate in the fourth mixture can be 0.2 g / L, 0.4 g / L, 0.8 g / L, 1.2 g / L, etc.

[0103] According to a specific embodiment of the present invention, the power of the ultrasonic treatment is 20 W to 100 W. As some specific examples, the power of the ultrasonic treatment can be 20 W, 40 W, 60 W, 80 W, 100 W, etc., and preferably 60 W to 100 W.

[0104] According to an embodiment of the present invention, a sixth aspect of the present invention provides a method for removing antibiotic resistance genes from water bodies, which uses NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst to catalyze persulfate to remove antibiotic resistance genes from water bodies;

[0105] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst obtained by the preparation method described in the first aspect or the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst described in the second aspect.

[0106] According to a specific embodiment of the present invention, the method includes the following steps:

[0107] Mix the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst with the water body containing antibiotic resistance genes to obtain a fifth mixture;

[0108] Add persulfate to the fifth mixture to obtain a sixth mixture, and perform ultrasonic treatment to achieve the removal of antibiotic resistance genes.

[0109] According to a specific embodiment of the present invention, the content of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst in the fifth mixture is 0.05 g / L to 0.4 g / L. As some specific examples, the content of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst in the fifth mixture can be 0.05 g / L, 0.1 g / L, 0.2 g / L, 0.4 g / L, etc.

[0110] According to a specific embodiment of the present invention, the content of antibiotic resistance genes in the fifth mixture is 3 mg / L - 8 mg / L. As some specific examples, the content of antibiotic resistance genes in the fifth mixture can be 3 mg / L, 5 mg / L, 8 mg / L, etc.

[0111] According to a specific embodiment of the present invention, the type of the antibiotic resistance gene is not particularly limited. As some specific examples, the antibiotic resistance gene includes at least one of tetA and ampC.

[0112] According to a specific embodiment of the present invention, the content of persulfate in the sixth mixture is 0.2 g / L to 1.2 g / L. As some specific examples, the content of persulfate in the sixth mixture can be 0.2 g / L, 0.4 g / L, 0.8 g / L, 1.2 g / L, etc.

[0113] According to specific embodiments of the present invention, the power of the ultrasonic treatment is 20 W to 100 W. As some specific examples, the power of the ultrasonic treatment can be 20 W, 40 W, 60 W, 80 W, 100 W, etc., and preferably 60 W to 100 W.

[0114] According to specific embodiments of the present invention, the type of the ultrasonic treatment device is not particularly limited. As some specific examples, the ultrasonic treatment device includes but is not limited to an ultrasonic cleaner.

[0115] The solutions of the present invention will be explained below in conjunction with embodiments. Those skilled in the art will understand that the following embodiments are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those without specific techniques or conditions noted in the embodiments, the techniques or conditions described in the literature in the art or according to the product specifications are followed. For reagents or instruments without the manufacturer noted, they are all conventional products that can be obtained through commercial purchase.

[0116] Example 1

[0117] This example provides an NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst and its preparation method. The preparation method includes the following steps:

[0118] Weigh 1.087 g of ferric chloride hexahydrate, 0.994 g of manganese nitrate tetrahydrate, and 1.070 g of 2-aminoterephthalic acid and dissolve them in 60 mL of N,N-dimethylformamide. After stirring for 60 minutes, transfer the solution to a reaction kettle and react at 110 °C for 12 h. Then, wait for the reaction kettle to cool to room temperature, wash the reactants three times with N,N-dimethylformamide at 70 °C, and dry at 60 °C for 12 hours to obtain the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst.

[0119] The SEM and XRD diagrams of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in this example are as Figure 1 shown. It can be Figure 1 seen that the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst was successfully prepared using the above preparation method.

[0120] Example 2: This example explores the effect of NH 2 -MIL-101(Fe,Mn) piezoelectric catalysts with different concentrations on the catalytic removal of base T by PDS

[0121] In this example, the NH 2The preparation process of the -MIL-101(Fe,Mn) piezoelectric catalyst was the same as that in Example 1. In this example, base T was used as the pollutant in the water body.

[0122] Prepare 30 mL of a 10 μmol / L aqueous solution of base T in a beaker. Weigh 1.5 mg, 3 mg, 6 mg, and 12 mg of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst powder and add it to the base T solution. Stir to make the adsorption of the base T solution reach equilibrium. Weigh 30 mg of potassium persulfate and add it to the base T solution. Place the mixed solution in an ultrasonic cleaner and start the ultrasonic reaction with an ultrasonic power of 100 W.

[0123] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in this example for the catalytic removal of base T by PDS at different concentrations is as Figure 2 shown. It can be seen from the figure that as the concentration of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst increases continuously, the removal efficiency of base T also increases continuously. When the concentration of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is 0.05 g / L and 0.1 g / L, the removal efficiencies of base T are 47.77% and 65.74% respectively. When the concentration of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst reaches 0.2 g / L, the removal efficiency of base T is 91.39%. And when the concentration of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst reaches 0.4 g / L, the removal efficiency of base T is 89.40%. This may be because after the concentration of the catalyst reaches a certain level, the particles aggregate, and the surface reaction area of the catalyst decreases, resulting in a slight decrease in the degradation rate. This result indicates that the preferred concentration of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst for the catalytic removal of base T by PDS is 0.2 g / L.

[0124] Example 3: In this example, the effect of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst on the catalytic removal of base T by PDS at different concentrations was explored.

[0125] In this example, the preparation process of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst was the same as that in Example 1. In this example, base T was used as the pollutant in the water body.

[0126] Prepare 30 mL of a 10 μmol / L aqueous solution of base T in a beaker. Weigh 6 mg of NH 2The -MIL-101(Fe,Mn) piezoelectric catalyst powder was added to the base T solution, and the mixture was stirred until the adsorption of the base T solution reached equilibrium. 6 mg, 12 mg, 18 mg, 24 mg, 30 mg, and 36 mg of potassium persulfate were weighed and added to the base T solution respectively. The mixed solution was placed in an ultrasonic cleaner, and the ultrasonic reaction was started with an ultrasonic power of 100 W.

[0127] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in this example for removing base T with different concentrations of PDS is as Figure 3 shown. It can be seen from the figure that as the concentration of PDS increases, the removal efficiency of base T also increases. When the concentrations of PDS are 0.2 g / L, 0.4 g / L, 0.6 g / L, and 0.8 g / L, the removal efficiencies of base T are 35.45%, 44.35%, 55.78%, and 66.74% respectively. When the concentration of PDS reaches 1.0 g / L, the removal efficiency of base T is 91.39%. When the concentration of PDS reaches 1.2 g / L, the removal efficiency of base T is 91.23%. Considering the economic benefits, the preferred concentration of PDS is 1.0 g / L.

[0128] Example 4: In this example, the removal effect of base T under different reaction conditions was explored.

[0129] In this example, the preparation process of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst was the same as that in Example 1. In this example, base T was used as the pollutant in the water body.

[0130] 30 mL of 10 μmol / L aqueous solution of base T was prepared in a beaker. The following reaction conditions were used to remove base T in this example: (1) directly perform ultrasonic treatment with an ultrasonic power of 100 W; (2) add potassium persulfate and stir without ultrasonic treatment; (3) add NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst and stir without ultrasonic treatment; (4) add NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst, stir and perform ultrasonic treatment with an ultrasonic power of 100 W; (5) add PDS, stir and perform ultrasonic treatment with an ultrasonic power of 100 W; (6) add PDS and NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst and stir without ultrasonic treatment; (7) add PDS and NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst, stir and perform ultrasonic treatment with an ultrasonic power of 100 W.

[0131] The removal effect of base T under different reaction conditions in this example is as Figure 4As shown, where US represents ultrasonic treatment. It can be seen from the figure that direct ultrasonic treatment, adding PDS and stirring without ultrasonic treatment, adding NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst and stirring without ultrasonic treatment, adding NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst and stirring with ultrasonic treatment, adding PDS and NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst and stirring without ultrasonic treatment have almost negligible effects on the removal of base T. However, under the condition of adding PDS and stirring with ultrasonic treatment, 21.15% of base T can be removed within 60 minutes. In contrast, under the reaction condition of adding PDS and NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst and ultrasonic treatment, the removal rate of base T reaches 91.39% within 60 minutes, thus indicating that NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst piezoelectric catalysis of PDS can significantly improve the removal efficiency of base T.

[0132] Example 5: This example explores the effect of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst on the catalytic removal of base T by PDS under different ultrasonic powers

[0133] In this example, the preparation process of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is the same as that in Example 1. In this example, base T is used as the pollutant in water.

[0134] Prepare 30 mL of 10 μmol / L aqueous solution of base T in a beaker, weigh 6 mg of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst powder and add it to the base T solution, and stir to make the adsorption of the base T solution reach equilibrium. Weigh 30 mg of potassium persulfate and add it to the base T solution, and place the mixed solution in an ultrasonic cleaner. The power of the ultrasonic cleaner is adjusted to 20 W, 40 W, 60 W, 80 W, and 100 W respectively to start the reaction. Among them, the concentration of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is 0.2 g / L, and the concentration of PDS is 1.0 g / L.

[0135] The effect of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in this example on the catalytic removal of base T by PDS under different ultrasonic powers is as Figure 5As shown. It can be seen from the figure that as the ultrasonic power continues to increase, the performance of removing base T also continuously improves. When the ultrasonic power increases to 100 W, the removal efficiency of base T is 91.39%.

[0136] Example 6: In this example, the cyclic stability of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst was investigated

[0137] In this example, the preparation process of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst was the same as that in Example 1. In this example, base T was used as the pollutant in the water body.

[0138] 30 mL of 10 μmol / L aqueous solution of base T was prepared in a beaker. 6 mg of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst powder was added to the base T solution, and stirred until the adsorption of the base T solution reached equilibrium. 30 mg of potassium persulfate was weighed and added to the base T solution. The mixed solution was placed in an ultrasonic cleaner, and ultrasonic reaction began at an ultrasonic power of 100 W. After the reaction ended, the catalyst was recovered from the remaining solution using a suction filtration device. Then, this catalyst was added to 30 mL of base T solution with a concentration of 10 μmol / L, and the above steps for removing base T were repeated for the experiment. This was repeated five times.

[0139] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in this example for the catalytic performance of PDS to remove base T is as Figure 6 shown. It can be seen from the figure that after the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst was recycled five times, the removal efficiency of base T within 60 minutes changed from 91.39% to 81.74%, and the performance only decreased by about 9.65%, indicating that the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst provided by the present invention has recyclability and property stability.

[0140] Example 7: In this example, the effect of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst catalyzing PDS to remove antibiotics was investigated

[0141] In this example, the preparation process of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst was the same as that in Example 1. In this example, antibiotics were used as the pollutants in the water body.

[0142] Prepare 30 mL of sulfamethoxazole (SMX), ciprofloxacin (CIP), carbamazepine (CBZ), and sulfadiazine (SDZ) solutions respectively, with a concentration of 5 mg / L. Weigh 6 mg of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst powder and add it to the antibiotic solution, stir to make the adsorption of the antibiotic solution reach equilibrium. Weigh 30 mg of potassium persulfate and add it to the solution, place the mixed solution in an ultrasonic cleaner, start ultrasonic reaction, and the ultrasonic power is 100 W.

[0143] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in this example for catalyzing PDS to remove antibiotics is as Figure 7 shown. It can be seen from the figure that within 60 minutes, the degradation rates of sulfamethoxazole (SMX), ciprofloxacin (CIP), carbamazepine (CBZ), and sulfadiazine (SDZ) are 96.45%, 90.28%, 98.96%, and 81.13% respectively, which indicates that the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst provided by the present invention also has good degradation effects on different antibiotics when catalyzing PDS, and has good universality.

[0144] Example 8: In this example, explore the effect of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst on catalyzing PDS to remove antibiotic resistance genes

[0145] In this example, the preparation process of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is the same as that in Example 1. In this example, the antibiotic resistance gene is used as the pollutant in the water body.

[0146] Prepare 10 mL of 5 mg / L tetA and ampC solutions in a beaker respectively. Weigh 2 mg of NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst powder and add it to the antibiotic resistance gene solution, stir to make the adsorption of the solution reach equilibrium. Weigh 10 mg of potassium persulfate and add it to the solution, place the mixed solution in an ultrasonic cleaner, start ultrasonic reaction, the ultrasonic power is 100 W, and take samples for agarose gel electrophoresis experiment after 60 min.

[0147] The NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst prepared in this example for catalyzing PDS to remove antibiotic resistance genes is as Figure 8 shown. It can be seen from the figure that as time increases, the content of antibiotic resistance genes decreases. At 60 min, almost no bands of resistance genes tetA and ampC can be observed, indicating that the NH2 The -MIL-101(Fe,Mn) piezoelectric catalyst can also achieve good degradation effect on different antibiotic resistance genes when catalyzing PDS.

[0148] Example 9: This example explores the effect of the -MIL-101(Fe,Mn) piezoelectric catalyst catalyzing PDS on removing various bases. 2 The effect of the -MIL-101(Fe,Mn) piezoelectric catalyst catalyzing PDS on removing various bases

[0149] In this example, the preparation process of the -MIL-101(Fe,Mn) piezoelectric catalyst is the same as that in Example 1. In this example, base A, base G, and base C are respectively used as pollutants in the water body. 2 -MIL-101(Fe,Mn) piezoelectric catalyst is the same as that in Example 1. In this example, base A, base G, and base C are respectively used as pollutants in the water body.

[0150] Prepare 30 mL solutions of base A, base G, and base C respectively, with a concentration of 10 μmol / L. Weigh 6 mg of -MIL-101(Fe,Mn) piezoelectric catalyst powder and add it to the base solution, and stir until the adsorption of the base solution reaches equilibrium. Weigh 30 mg of potassium persulfate and add it to the solution, and place the mixed solution in an ultrasonic cleaner. Start the ultrasonic reaction with an ultrasonic power of 100 W. 2 -MIL-101(Fe,Mn) piezoelectric catalyst powder and add it to the base solution, and stir until the adsorption of the base solution reaches equilibrium. Weigh 30 mg of potassium persulfate and add it to the solution, and place the mixed solution in an ultrasonic cleaner. Start the ultrasonic reaction with an ultrasonic power of 100 W.

[0151] The -MIL-101(Fe,Mn) piezoelectric catalyst prepared in this example catalyzes the removal of base A, base G, and base C by PDS as 2 shown. It can be seen from the figure that the degradation rates of base A, base G, and base C within 60 minutes are 94.40%, 84.94%, and 89.97% respectively, which indicates that the -MIL-101(Fe,Mn) piezoelectric catalyst provided by the present invention has good removal effect on different bases when catalyzing PDS. Figure 9 shown. It can be seen from the figure that the degradation rates of base A, base G, and base C within 60 minutes are 94.40%, 84.94%, and 89.97% respectively, which indicates that the -MIL-101(Fe,Mn) piezoelectric catalyst provided by the present invention has good removal effect on different bases when catalyzing PDS. 2 -MIL-101(Fe,Mn) piezoelectric catalyst has good removal effect on different bases when catalyzing PDS.

[0152] Comparative Example 1

[0153] This comparative example provides an -MIL-101(Fe) and its preparation method. The preparation method includes the following steps: 2 -MIL-101(Fe) and its preparation method, the preparation method includes the following steps:

[0154] Weigh 1.087 g of ferric chloride hexahydrate and 1.070 g of 2-aminoterephthalic acid and dissolve them in 60 mL of N,N-dimethylformamide. After stirring for 60 minutes, transfer the solution to a reaction kettle and react at 110 °C for 12 h. Then, wait for the reaction kettle to cool to room temperature, wash the reactant three times with N,N-dimethylformamide at 70 °C, and dry it at 60 °C for 12 hours to obtain the -MIL-101(Fe). 2 -MIL-101(Fe).

[0155] Prepare 30 mL of 10 μmol / L aqueous solution of base T in a beaker, and weigh 6 mg of NH 2 -MIL-101(Fe) powder and add it to the base T solution, and stir to make the adsorption of the base T solution reach equilibrium. Weigh 30 mg of potassium persulfate and add it to the base T solution, and place the mixed solution in an ultrasonic cleaner. Start the ultrasonic reaction with an ultrasonic power of 100 W.

[0156] In this comparative example, the removal efficiency of base T within 60 minutes is 74.56%. On the one hand, the bimetallic MOF provided in the embodiments of the present invention has more diverse catalytic active sites and adsorption sites than the monometallic MOF, making it exhibit excellent performance in selective catalysis and multifunctional catalysis; on the other hand, the organic ligand can covalently bond with the two metal sites in a single node, which is beneficial to improving its thermal stability and chemical stability. Therefore, the performance of the NH 2 -MIL-101(Fe,Mn) piezoelectric catalyst is significantly better than that of NH 2 -MIL-101(Fe).

[0157] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0158] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for preparing NH2-MIL-101 (Fe, Mn) piezoelectric catalyst, characterized in that: The preparation method comprises: Iron salt, manganese salt and 2-aminoterephthalic acid are mixed and reacted to obtain NH2-MIL-101 (Fe, Mn) piezoelectric catalyst.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the iron salt, the manganese salt and the 2-aminoterephthalic acid is 1:(0.6-0.7):(0.6-0.7); Optionally, the iron salt includes at least one of ferric chloride hexahydrate, ferric chloride, ferric nitrate, and ferric oxalate; Optionally, the manganese salt includes at least one of manganese nitrate tetrahydrate, manganese chloride, manganese sulfate, manganese acetate, and manganese oxalate; Optionally, the reaction temperature is 100°C-120°C; Optionally, the reaction time is 10 h-14 h.

3. The preparation method according to claim 1, characterized in that: The preparation method further comprises: adding iron salt, manganese salt and 2-aminoterephthalic acid into a solvent, mixing, reacting, and drying to obtain NH2-MIL-101 (Fe, Mn) piezoelectric catalyst; Optionally, the solvent includes at least one of N,N-dimethylformamide, N,N-diethylformamide, ethanol, and methanol; Optionally, the drying temperature is 40°C-80°C; Optionally, the drying time is 6h-18h.

4. An NH2-MIL-101 (Fe, Mn) piezoelectric catalyst obtained according to the preparation method according to any one of claims 1 to 3.

5. Use of the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst obtained by the preparation method according to any one of claims 1 to 3 or the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst according to claim 4 in removing at least one of bases, antibiotics, and antibiotic resistance genes from water.

6. A method for removing bases from water, characterized in that: The method uses NH2-MIL-101 (Fe, Mn) piezoelectric catalyst to catalyze persulfate to remove bases in water; The NH2-MIL-101 (Fe, Mn) piezoelectric catalyst is the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst obtained by the preparation method according to any one of claims 1 to 3 or the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst according to claim 4.

7. The method according to claim 6, characterized in that The method comprises the following steps: Mixing NH2-MIL-101 (Fe, Mn) piezoelectric catalyst and water containing a base to obtain a first mixed solution; Peroxydisulfate is added to the first mixed solution to obtain a second mixed solution, which is then subjected to ultrasonic treatment to achieve base removal.

8. The method according to claim 7, characterized in that The content of NH2-MIL-101 (Fe, Mn) piezoelectric catalyst in the first mixed solution is 0.05 g / L to 0.4 g / L; Optionally, the content of the base in the first mixed solution is 5 μmol / L to 15 μmol / L; Optionally, the base includes at least one of A, T, C, and G; Optionally, the content of peroxydisulfate in the second mixed solution is 0.2 g / L to 1.2 g / L; Optionally, the power of the ultrasonic treatment is 20W to 100W, preferably 60W to 100W.

9. A method for removing antibiotics from water, characterized in that: The method uses NH2-MIL-101 (Fe, Mn) piezoelectric catalyst to catalyze peroxydisulfate to remove antibiotics from water; The NH2-MIL-101 (Fe, Mn) piezoelectric catalyst is the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst obtained by the preparation method according to any one of claims 1 to 3 or the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst according to claim 4.

10. The method according to claim 9, characterized in that The method comprises the following steps: mixing the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst and water containing antibiotics to obtain a third mixed solution; Peroxydisulfate is added to the third mixed solution to obtain a fourth mixed solution, which is then subjected to ultrasonic treatment to achieve removal of the antibiotics.

11. The method according to claim 10, characterized in that The content of NH2-MIL-101 (Fe, Mn) piezoelectric catalyst in the third mixed solution is 0.05 g / L to 0.4 g / L; Optionally, the content of antibiotics in the third mixed solution is 3 mg / L-8 mg / L; Optionally, the antibiotic includes at least one of sulfamethoxazole, ciprofloxacin, carbamazepine, and sulfadiazine; Optionally, the content of peroxydisulfate in the fourth mixed solution is 0.2 g / L to 1.2 g / L; Optionally, the power of the ultrasonic treatment is 20W to 100W, preferably 60W to 100W.

12. A method for removing antibiotic resistance genes in water, characterized in that: The method uses NH2-MIL-101 (Fe, Mn) piezoelectric catalyst to catalyze persulfate to remove antibiotic resistance genes in water; The NH2-MIL-101 (Fe, Mn) piezoelectric catalyst is the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst obtained by the preparation method according to any one of claims 1 to 3 or the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst according to claim 4.

13. The method according to claim 12, characterized in that The method comprises the following steps: mixing the NH2-MIL-101 (Fe, Mn) piezoelectric catalyst and water containing the antibiotic resistance gene to obtain a fifth mixed solution; Peroxydisulfate is added to the fifth mixed solution to obtain a sixth mixed solution, which is then subjected to ultrasonic treatment to achieve removal of the antibiotic resistance gene.

14. The method according to claim 13, characterized in that The content of NH2-MIL-101 (Fe, Mn) piezoelectric catalyst in the fifth mixed liquid is 0.05 g / L to 0.4 g / L; Optionally, the content of the antibiotic resistance gene in the fifth mixed solution is 3 mg / L-8 mg / L; Optionally, the antibiotic resistance gene comprises at least one of tetA and ampC; Optionally, the content of peroxydisulfate in the sixth mixed solution is 0.2 g / L to 1.2 g / L; Optionally, the power of the ultrasonic treatment is 20W to 100W, preferably 60W to 100W.

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