CN113651375B - Cu 3 B 2 O 6 Application in piezoelectric catalytic degradation or pollutant inhibition - Google Patents

Cu 3 B 2 O 6 Application in piezoelectric catalytic degradation or pollutant inhibition Download PDF

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CN113651375B
CN113651375B CN202110794116.7A CN202110794116A CN113651375B CN 113651375 B CN113651375 B CN 113651375B CN 202110794116 A CN202110794116 A CN 202110794116A CN 113651375 B CN113651375 B CN 113651375B
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rhodamine
ball milling
microorganisms
stirring
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CN113651375A (en
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范晓芸
廖肖敏
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Jinan University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/20—Prevention of biofouling
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/26—Reducing the size of particles, liquid droplets or bubbles, e.g. by crushing, grinding, spraying, creation of microbubbles or nanobubbles

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Abstract

The inventionDisclosed is a Cu 3 B 2 O 6 The application in the aspect of piezoelectric catalytic degradation or pollutant inhibition belongs to the field of pollution treatment. The contaminants include rhodamine contaminants and microorganisms. The study shows that Cu 3 B 2 O 6 The degradation rate of rhodamine B and the inhibition rate of Escherichia coli can approach 100%. And using Cu 3 B 2 O 6 The method for degrading pollutants by piezoelectric catalysis is simple to operate, and the Cu is prepared 3 B 2 O 6 The cost of the material is low, and the energy consumption is low. Cu 3 B 2 O 6 The method has good stability in a reaction system, can efficiently degrade the dye under the action of external mechanical force stirring, can achieve an ideal sterilization effect, provides a new scheme for efficiently degrading pollutants in the environmental water body, can be used for effectively treating the pollutants in the environmental water body, and has wide application prospects in the fields of environmental pollution and treatment.

Description

Cu 3 B 2 O 6 Application in piezoelectric catalytic degradation or pollutant inhibition
Technical Field
The invention belongs to the field of pollution control, and particularly relates to Cu 3 B 2 O 6 The application in piezoelectric catalytic degradation or pollutant inhibition.
Background
With the rapid development of social industrialization, china pursues the rapid development of economy and also increasingly diversifies the environmental pollution problem, and great challenges are brought to the environmental management. The discharge of industrial waste water makes the water body pollution phenomenon increasingly serious, such as: in the manufacturing process of the textile printing and dyeing industry, a large amount of dye waste water with high chroma and complex components is generated. In addition to organic pollutants, microorganisms in water such as Escherichia coli (Escherichia coli), salmonella (Salmonella), staphylococcus aureus (Staphylococcus aureus), etc. can also cause ecological pollution and even threaten human health. The traditional wastewater treatment methods such as physical adsorption, filtration, advanced oxidation and the like have the disadvantages of high reaction cost, complex process, undesirable treatment effect and possibility of secondary pollution, and the factors limit the practical application of the traditional treatment process. Therefore, with the phenomenon of water pollution becoming more serious, it is very important to develop a method capable of simultaneously degrading organic pollutants in water and inhibiting microorganisms.
The piezoelectric catalyst may mediate the conversion between mechanical energy and chemical energy, which may be assisted byLess energy in nature, such as wind, water flow, etc., produces a piezoelectric potential. The piezoelectric catalysis has the advantages of low pollution, low energy consumption, low cost, high stability and the like, and provides a new solution for degrading pollutants and inhibiting harmful microorganisms. In recent years, piezoelectric catalytic materials (e.g., baTiO) have been used 3 ，ZnO，SnS 2 ) A great deal of research and practical application is put into, for example, the patent CN112811900A provides a p-n-BaTiO 3 A preparation method of a/NiO heterojunction piezoelectric ceramic piezoelectric catalyst has the defects of complex synthesis process, low stability under the action of mechanical force, high required energy consumption and the like, influences the performance of piezoelectric catalysis, and hinders the development of industrial application of piezoelectric catalysis. Therefore, there is a great need to develop a piezoelectric catalytic material and a method capable of efficiently catalyzing degradation or inhibiting pollutants.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide Cu 3 B 2 O 6 The application in the aspect of piezoelectric catalytic degradation or pollutant inhibition. The pollutants comprise rhodamine pollutants and microorganisms, and the research of the invention shows that Cu is contained 3 B 2 O 6 The degradation rate of rhodamine B and the inhibition rate of Escherichia coli can approach 100%. And using Cu 3 B 2 O 6 The method for degrading pollutants by piezoelectric catalysis is simple to operate and prepares Cu 3 B 2 O 6 Low material cost, low energy consumption, and Cu 3 B 2 O 6 Has good stability in a reaction system (namely, after completing a round of dye or bacterial degradation experiment, recovering Cu 3 B 2 O 6 Performing the next degradation experiment, wherein the degradation efficiency of rhodamine B or the inhibition efficiency of escherichia coli can still be maintained above 99%; repeated experiments are performed for five times in total), the dye can be efficiently degraded under the action of external mechanical force stirring, an ideal sterilization effect can be achieved, a new scheme is provided for efficiently degrading pollutants in the environmental water body, the method can be used for effectively treating the pollutants in the environmental water body, and the method can solve the problem of environmental pollution and protect the ecological environmentHas ideal development prospect.
It is still another object of the present invention to provide a method for producing a copper alloy using Cu 3 B 2 O 6 A method for degrading rhodamine pollutants by piezoelectric catalysis.
It is still another object of the present invention to provide a method for using Cu 3 B 2 O 6 A method for piezoelectric catalysis of microbial inhibition.
The purpose of the invention is realized by the following technical scheme:
the invention firstly provides a Cu 3 B 2 O 6 The application in the aspect of piezoelectric catalytic degradation or pollutant inhibition.
Further, cu 3 B 2 O 6 The application in the aspect of piezoelectric catalytic degradation or inhibition of water body pollutants.
Preferably, the contaminants include at least one of rhodamine contaminants and microorganisms.
Further preferably, the rhodamine contaminant is rhodamine B.
Further preferably, the microorganism is escherichia coli.
The present invention shows that Cu 3 B 2 O 6 The degradation rate of rhodamine B and the inhibition rate of Escherichia coli can approach 100%.
In addition, the invention also provides a method for utilizing Cu 3 B 2 O 6 The method for degrading rhodamine pollutants by piezoelectric catalysis comprises the following steps:
s1, dissolving and diluting rhodamine pollutants, and performing ultrasonic treatment to obtain a solution A;
s2, under the condition of keeping out of the sun, adding Cu 3 B 2 O 6 Adding the solution A in the step S1 and stirring;
s3, ball-milling the solution obtained in the step S2 to degrade the rhodamine pollutants;
preferably, the rhodamine contaminant is rhodamine B.
Preferably, the concentration of the rhodamine pollutant in the solution A in the step S1 is 10-800 mg/L.
Further preferably, the concentration of the rhodamine pollutant in the solution A in the step S1 is 10-100 mg/L, and further 10mg/L.
Preferably, the ultrasonic time of the ultrasonic wave in the step S1 is 10-20 min, and the ultrasonic frequency is 40kHz; further 10min, the ultrasonic frequency is 40kHz.
Preferably, cu is said in step S2 3 B 2 O 6 The mass-to-volume ratio of the addition amount of (A) to the solution A is 0.5-80 mg/mL.
Further preferably, cu is used in step S2 3 B 2 O 6 The ratio of the amount of (1) to the mass volume of the solution A was 0.7mg/mL.
Preferably, the stirring time of the stirring in the step S2 is 10 to 30min.
Further preferably, the stirring time of the stirring in the step S2 is 30min.
Preferably, the stirring speed of the stirring in the step S2 is 50-200 rpm; further 50rpm.
Preferably, in step S3, the solution obtained in step S2 is added into a ball milling pot filled with agate balls, and the ball milling pot is sealed and then fixed on a ball mill for ball milling.
Preferably, the diameter of the agate ball is 3-10 mm.
Preferably, the rotation speed of the ball milling in the step S3 is 200-600 rpm; further 400 to 600rpm.
When the ball milling is carried out in the step S3, the faster the rotation speed of the ball milling is, the higher the mechanical force provided is, so that the rhodamine pollutant can be degraded by itself and can be subjected to Cu 3 B 2 O 6 Exert synergistic effect and effectively improve Cu 3 B 2 O 6 Degradation/inhibition of contaminants.
Further preferably, the rotation speed of the ball mill is set to 600rpm.
When the rotating speed of the ball mill is set to 600rpm, the degradation rate of the scheme to rhodamine pollutants is close to 100%, so that the influence of the ball milling speed on the degradation rate is not great, the energy waste is also caused, and the degradation cost is increased.
Preferably, the ball milling time in step S3 is 10min to 30min, and further 30min.
As a preferable mode, the above uses Cu 3 B 2 O 6 The method for degrading rhodamine pollutants by piezoelectric catalysis comprises the following steps:
s1, dissolving and diluting rhodamine pollutants to a concentration of 10mg/L, and carrying out ultrasonic treatment for 10min at the frequency of 40kHz to obtain a solution A;
s2, under the condition of keeping out of the sun, cu with the mass-to-volume ratio of 700mg/L to the solution A 3 B 2 O 6 Adding the solution A in the step S1;
and S3, the solution obtained in the step S2 is subjected to ball milling (rotating speed of 600 rpm) for 30min, and then the rhodamine pollutants can be degraded.
The invention also requests to protect a copper-based alloy utilizing Cu 3 B 2 O 6 A method of piezoelectric catalysis for the inhibition of microorganisms comprising the steps of:
s1, unfreezing glycerol frozen stock solution of microorganisms, culturing, centrifuging, and diluting the microorganisms to prepare solution B;
s2, under the condition of keeping out of the sun, adding Cu 3 B 2 O 6 Adding the mixture into the solution B in the step S1;
s3, ball-milling the solution obtained in the step S2 to degrade the microorganisms;
preferably, the microorganism is escherichia coli.
Preferably, the culturing condition in step S1 is culturing for 18-24 hours in a shaker at 36-37 ℃; further culturing in a shaker at 37 deg.C for 24 hr;
preferably, the concentration of the microorganisms in the solution B in the step S1 is 10-10 9 CFU/mL; further 10 8 CFU/mL。
Preferably, cu is said in step S2 3 B 2 O 6 The mass-to-volume ratio of the amount of (2) to the solution B is 0 to 500. Mu.g/mL but not 0, and further 100 to 500. Mu.g/mL.
Further preferably, the Cu 3 B 2 O 6 The mass-to-volume ratio of the amount of (1) to solution B was 500. Mu.g/mL.
When Cu 3 B 2 O 6 When the amount of (2) is 500. Mu.g/mL, the inhibition rate of the present invention on microorganisms is close to 100%, and therefore, cu is further added 3 B 2 O 6 The influence on the inhibition rate is small, the waste of materials is caused, and the inhibition cost is increased.
Preferably, in step S3, the solution obtained in step S2 is added into a ball milling jar filled with agate balls, and the ball milling jar is sealed and then fixed on a ball mill for ball milling.
Preferably, the diameter of the agate ball is 3-10 mm, and further 3mm.
Further preferably, the rotation speed of the ball mill is set to 400 to 600rpm, further 600rpm.
When the rotation speed of the ball mill is set to 600rpm, the inhibition rate of the scheme to microorganisms is close to 100%, so that the influence of the ball milling speed on the degradation rate is not great, the energy waste is also caused, and the degradation cost is increased.
Preferably, the ball milling in the step S3 is performed for 10min to 60min, and further for 30min to 60min; further 60min.
As a preferable mode, the above-mentioned method uses Cu 3 B 2 O 6 A method for degrading microorganisms by piezoelectric catalysis comprises the following steps:
s1, unfreezing glycerol frozen stock solution of microorganisms, culturing for 24 hours in a shaking table at 37 ℃, centrifuging, and dissolving and diluting the microorganisms to a concentration of 10 8 Preparing a solution B from CFU/mL;
s2, under the condition of keeping out of the sun, adding Cu with the mass-to-volume ratio of 500 mu g/mL to the solution B 3 B 2 O 6 Adding the solution B in the step S1;
and S3, ball-milling the solution obtained in the step S2 at the rotating speed of 600rpm for 60min to degrade the microorganisms.
Compared with the prior art, the invention has the following advantages and effects:
the invention provides Cu 3 B 2 O 6 The application in the aspect of piezoelectric catalytic degradation or pollutant inhibition is that rhodamine dyes and microorganism are used as the degraded pollutant. By Cu 3 B 2 O 6 The piezoelectric catalysis effect on the rhodamine B and the Escherichia coli can reach a degradation rate close to 100%. And using Cu 3 B 2 O 6 The method for degrading pollutants by piezoelectric catalysis is simple to operate and low in energy consumption, provides a new scheme for efficiently degrading pollutants in an environmental water body, can be used for effectively treating the pollutants in the environmental water body, and has wide application prospects in the fields of environmental pollution and treatment.
Drawings
FIG. 1 is Cu 3 B 2 O 6 The XRD pattern of the X-ray diffraction peak of (A) is compared with that of a standard card.
FIG. 2 is copper borate (Cu) 3 B 2 O 6 ) And (3) degrading the rhodamine B efficiency map of the powder under different ball milling rotating speed conditions.
FIG. 3 is copper borate (Cu) 3 B 2 O 6 ) The efficiency graph of the rhodamine B is reduced by the powder under the condition of agate balls with different particle sizes.
FIG. 4 shows copper borate (Cu) 3 B 2 O 6 ) And (3) an efficiency graph of powder degradation of rhodamine B with different concentrations.
FIG. 5 shows copper borate (Cu) in various amounts 3 B 2 O 6 ) Graph of the efficiency of the powder in inhibiting E.coli.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Cu 3 B 2 O 6 The samples were prepared by a simple high temperature solid phase method. The sample consists of CuO and B 2 O 3 Synthesis of CuO and B 2 O 3 Is close to 1, B 2 O 3 Is 3% more than CuO. The mixture is fully ground and put into a crucible and heated at 940 ℃ in air for 12h. During heating, the solid reactant isAnd grinding four times. After the sample is naturally cooled, the sample is washed by deionized water and dried at 60 ℃. Raw materials CuO and B 2 O 3 Are purchased from mclin.
Cu 3 B 2 O 6 The XRD pattern of the X-ray diffraction peak of (A) is shown in figure 1 in comparison with a standard card.
The E.coli used in the examples was E.coli (Escherichia coli) K-12, purchased from the institute for microorganisms in the Guangdong province.
Example 1A method of Using Cu 3 B 2 O 6 Method for degrading rhodamine B through piezoelectric catalysis
1. Experimental methods
S1, dissolving and diluting 1mg of rhodamine B to a concentration of 10ppm (10 mg/L), placing the rhodamine B into a ball milling tank with a volume of 100mL, and then placing the ball milling tank into an ultrasonic cleaning machine to perform ultrasonic treatment for 10min at a frequency of 40kHz to obtain a uniform and stable solution A;
s2, under the condition of keeping out of the sun, 35mg of Cu 3 B 2 O 6 (the mass-to-volume ratio of the solution A is 0.7 mg/mL) is added into the solution A in the step S1 and is magnetically stirred for 30min at the speed of 50 rpm;
s3, putting the solution A obtained in the step S2 into a ball milling tank filled with agate balls (the diameter is 3mm, and the total mass is 10 g), sealing the ball milling tank, fixing the ball milling tank on a ball mill, and carrying out ball milling for 30min at the rotating speed of 600rpm, wherein the interval sampling time is 5min, and the organic pollutant rhodamine B can be degraded.
After ball milling for 30min, centrifuging a sample, and performing ultraviolet-visible absorption spectrum test on the supernatant to obtain the degradation rate of the pollutants.
2. Results of the experiment
As shown in figure 2, the method can achieve a degradation rate close to 100% after degrading rhodamine B for 30min under the catalysis of piezoelectricity.
Example 2A method of Using Cu 3 B 2 O 6 Method for degrading rhodamine B through piezoelectric catalysis
1. Experimental methods
The same procedure as in example 1 was followed except that the rotation speed of the ball mill was 400rpm.
2. Results of the experiment
The result is shown in figure 2, and the degradation rate of 70% can be achieved after 30min of the rhodamine B is degraded by the piezoelectric catalysis according to the method disclosed by the invention.
Example 3A method of Using Cu 3 B 2 O 6 Method for degrading rhodamine B through piezoelectric catalysis
1. Experimental methods
The protocol of example 1 is the same, except that the ball mill is operated at 200rpm.
2. Results of the experiment
The result is shown in figure 2, and the degradation rate of 20% can be achieved after 30min of the rhodamine B is degraded by the piezoelectric catalysis according to the method disclosed by the invention.
Example 4A method of using Cu 3 B 2 O 6 Method for degrading rhodamine B through piezoelectric catalysis
1. Experimental method
The same protocol as in example 1, except that the agate balls have a diameter of 10mm.
2. Results of the experiment
The result is shown in figure 3, and the degradation rate of 60% can be achieved after 30min of the rhodamine B is degraded by the piezoelectric catalysis according to the method disclosed by the invention.
Example 5A method of using Cu 3 B 2 O 6 Method for degrading rhodamine B through piezoelectric catalysis
1. Experimental methods
The same protocol as in example 1, except that the agate balls had a diameter of 6mm.
2. Results of the experiment
The result is shown in figure 3, and the degradation rate of 80% can be achieved after the rhodamine B is degraded in a piezo-catalysis mode for 30min according to the method disclosed by the invention.
Example 6A method of using Cu 3 B 2 O 6 Method for degrading rhodamine B through piezoelectric catalysis
1. Experimental methods
The same protocol as in example 1 was used, except that the concentration of rhodamine B in solution A was 50ppm (50 mg/L).
2. Results of the experiment
The result is shown in figure 4, and the degradation rate of 60% can be achieved after 30min of the rhodamine B is degraded by the piezoelectric catalysis according to the method disclosed by the invention.
Example 7A method of using Cu 3 B 2 O 6 Method for degrading rhodamine B through piezoelectric catalysis
1. Experimental methods
The same protocol as in example 1, except that the concentration of rhodamine B in the solution A is 100ppm (100 mg/L).
2. Results of the experiment
The result is shown in figure 4, and the degradation rate of 15% can be achieved after 30min of the rhodamine B is degraded by the piezoelectric catalysis according to the method disclosed by the invention.
Example 8A method of using Cu 3 B 2 O 6 Method for inhibiting escherichia coli through piezoelectric catalysis
1. Experimental methods
S1, unfreezing the escherichia coli in the glycerol cryopreservation tube, and then inoculating the escherichia coli into a liquid LB culture medium in a thousandth ratio. Activating and culturing in shaker at 37 deg.C for 24 hr, centrifuging, resuspending with 0.9% (w/v) sodium chloride, centrifuging again, diluting with 0.9% sodium chloride to 10% concentration 8 CFU/mL, preparing solution B;
s2, under the dark condition, adding 25mg of Cu 3 B 2 O 6 (the mass-to-volume ratio of the solution B is 0.5 mg/mL) is added into the solution B in the step S1;
s3, putting the solution obtained in the step S2 into a ball milling tank filled with agate balls (the diameter is 3mm, and the total mass is 10 g), sealing the ball milling tank, and then fixing the ball milling tank on a ball mill to perform ball milling for 60min at the rotating speed of 600rpm, so that the escherichia coli can be inhibited.
After ball milling for 60min, taking 1mL of sample, diluting by 100000 times, inoculating the bacterial liquid into an LB solid culture medium, putting the LB solid culture medium into a constant-temperature incubator at 37 ℃ for culturing for 24h, and obtaining the inhibition rate of escherichia coli by a plate counting method.
2. Results of the experiment
As shown in FIG. 5, the above method of the present invention can achieve 100% degradation rate after 60min of piezoelectric catalysis inhibition of Escherichia coli.
Example 9A method of using Cu 3 B 2 O 6 Method for inhibiting escherichia coli through piezoelectric catalysis
1. Experimental methods
The same as that of example 8 except that Cu is used 3 B 2 O 6 The amount of (2) was 5mg (mass-to-volume ratio to the solution B was 0.1 mg/mL).
2. Results of the experiment
As shown in FIG. 5, the above method of the present invention can achieve a degradation rate of 30% after 60min of piezoelectric catalysis for inhibiting Escherichia coli.
Example 10A method of using Cu 3 B 2 O 6 Method for inhibiting escherichia coli through piezoelectric catalysis
1. Experimental method
The same as that of example 8 except that Cu is used 3 B 2 O 6 The amount of (2) was 15mg (mass-to-volume ratio to the solution B was 0.3 mg/mL).
2. Results of the experiment
The result graph is shown in FIG. 5, and the degradation rate of 70% can be achieved after the piezoelectric catalysis inhibits the Escherichia coli for 60min according to the method of the invention.
Comparative example 1
1. Experimental method
The same as the scheme of example 1, except that Cu is described in step S2 3 B 2 O 6 The amount of (2) added is 0mg.
2. Results of the experiment
According to the method, the degradation rate is only 20% after the rhodamine B is degraded in a piezoelectric catalysis mode for 30min.
Comparative example 2
1. Experimental methods
The protocol of example 1 is different in that no ball milling is used in step S3.
2. Results of the experiment
According to the method, the degradation rate is only 20% after 30min of catalytic degradation of rhodamine B.
Comparative example 3
1. Experimental method
The same as example 8 except that Cu is used in step S2 3 B 2 O 6 The amount of (B) added was 0mg.
2. Results of the experiment
According to the method, the degradation rate is only 5% after the Escherichia coli is degraded by piezoelectric catalysis for 60min.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1.Cu 3 B 2 O 6 The application in the aspect of piezoelectric catalytic degradation or pollutant inhibition is characterized in that: the contaminants include at least one of rhodamine contaminants and microorganisms;
the microorganism is Escherichia coli.
2. Use according to claim 1, characterized in that:
the rhodamine contaminant is rhodamine B.
3. By using Cu 3 B 2 O 6 The method for degrading rhodamine pollutants by piezoelectric catalysis is characterized by comprising the following steps: the method comprises the following steps:
s1, dissolving and diluting rhodamine pollutants, and performing ultrasonic treatment to obtain a solution A;
s2, under the condition of keeping out of the sun, adding Cu 3 B 2 O 6 Adding the solution A in the step S1 and stirring;
and S3, ball-milling the solution obtained in the step S2 to degrade the rhodamine pollutants.
4. The method of claim 3, wherein:
the rhodamine contaminant is rhodamine B.
5. The method according to claim 3 or 4, characterized in that:
the concentration of rhodamine pollutant in the solution A in the step S1 is 10-800 mg/L;
the ultrasonic time of the ultrasonic wave in the step S1 is 10-20 min, and the ultrasonic frequency is 40kHz;
cu in step S2 3 B 2 O 6 The mass-volume ratio of the addition amount of the (B) to the solution A is 0.5-80 mg/mL;
the stirring time of the stirring in the step S2 is 10-30 min;
the stirring speed of the stirring in the step S2 is 50-200 rpm;
the diameter of the agate ball used for ball milling in the step S3 is 3-10 mm;
the rotation speed of the ball milling in the step S3 is 200-600 rpm;
the ball milling time in the step S3 is 10-30 min.
6. The method of claim 5, wherein:
the concentration of rhodamine pollutant in the solution A in the step S1 is 10-100 mg/L;
the ultrasonic time of the ultrasonic wave in the step S1 is 10min, and the ultrasonic frequency is 40kHz;
cu in step S2 3 B 2 O 6 The mass-to-volume ratio of the addition amount of (A) to the solution A is 0.7 mg/mL;
the stirring time of the stirring in the step S2 is 30min;
the stirring speed of the stirring in the step S2 is 50 rpm;
the rotation speed of the ball milling in the step S3 is 400-600 rpm;
and the ball milling time of the step S3 is 30min.
7. By using Cu 3 B 2 O 6 A method of piezoelectric catalysis for the inhibition of microorganisms, characterized by: the method comprises the following steps:
s1, unfreezing glycerol frozen stock solution of microorganisms, culturing, centrifuging, and diluting the microorganisms to prepare solution B;
s2, under the condition of keeping out of the sun, adding Cu 3 B 2 O 6 Adding the solution B into the solution B in the step S1;
s3, ball-milling the solution obtained in the step S2 to degrade the microorganisms;
the microorganism is Escherichia coli.
8. The method of claim 7, wherein:
the culture condition of the step S1 is that the culture is carried out for 18 to 24 hours in a shaking table at the temperature of 36 to 37 ℃;
the concentration of the microorganisms in the solution B in the step S1 is 10 to 10 9 CFU/mL；
Cu in step S2 3 B 2 O 6 The mass-volume ratio of the addition amount of (A) to the solution B is 0-500 [ mu ] g/mL but not 0;
the diameter of the agate ball used for ball milling in the step S3 is 3-10 mm;
the rotating speed of the ball mill in the step S3 is set to be 400-600 rpm;
and the ball milling time in the step S3 is 10-60 min.
9. The method of claim 8, wherein:
the culture condition of the step S1 is that the culture is carried out for 24 hours in a shaker at 37 ℃;
the concentration of the microorganisms in the solution B in the step S1 is 10 8 CFU/mL；
Cu in step S2 3 B 2 O 6 The mass volume ratio of the addition amount of the (B) to the solution B is 100 mu g/mL-500 mu g/mL;
the diameter of the agate ball used for ball milling in the step S3 is 3 mm;
the rotating speed of the ball mill in the step S3 is set to be 600rpm;
the ball milling time in the step S3 is 30-60 min.
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