CN114477384A - Bimetal microelectrode antibacterial material, preparation method thereof, bimetal microelectrode-carbon-based material composite antibacterial material and water treatment device - Google Patents

Bimetal microelectrode antibacterial material, preparation method thereof, bimetal microelectrode-carbon-based material composite antibacterial material and water treatment device Download PDF

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CN114477384A
CN114477384A CN202210099405.XA CN202210099405A CN114477384A CN 114477384 A CN114477384 A CN 114477384A CN 202210099405 A CN202210099405 A CN 202210099405A CN 114477384 A CN114477384 A CN 114477384A
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microelectrode
bimetal
containing layer
carbon
silver
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CN114477384B (en
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葛岩
戚震辉
姚纪政
刘静仪
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Northwestern Polytechnical 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • 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
    • C02F2303/04—Disinfection

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Abstract

The application provides a bimetal microelectrode antibacterial material, a preparation method thereof, a bimetal microelectrode-carbon-based material composite antibacterial material and a water treatment device. The bimetal microelectrode antibacterial material comprises a substrate, a silver-containing layer and a ruthenium-containing layer; the silver-containing layer is arranged on the surface of the substrate, and the ruthenium-containing layer is arranged on the surface of the silver-containing layer. The preparation method of the bimetal microelectrode antibacterial material comprises the following steps: and electrochemically depositing the silver-containing layer and the ruthenium-containing layer on the surface of the substrate in sequence. The bimetal microelectrode-carbon-based material composite antibacterial material comprises a bimetal microelectrode antibacterial material and a carbon-based material. The water treatment device comprises a bimetal microelectrode-carbon-based material composite bacteriostatic material. The bimetal microelectrode-carbon-based material composite antibacterial material can actively and continuously release active oxygen sterilization substances, and achieves high-efficiency and lasting antibacterial effect and adsorption effect. The method is applied to various water treatment environments, and does not produce pollution to water bodies and the environment.

Description

Bimetal microelectrode antibacterial material, preparation method thereof, bimetal microelectrode-carbon-based material composite antibacterial material and water treatment device
Technical Field
The application relates to the field of water treatment, in particular to a bimetallic microelectrode antibacterial material, a preparation method thereof, a bimetallic microelectrode-carbon-based material composite antibacterial material and a water treatment device.
Background
Water is an indispensable substance for life maintenance and also a strategic resource for social sustainable development. However, the world health organization reports that about 25 million people do not have access to safe and sanitary water. For underdeveloped areas, water resource shortage and pathogenic microorganisms cause water quality deterioration, and water ecosystem and healthy survival problems of related areas are threatened. The main cause of most water-borne disease outbreaks is infection associated with microbial contamination. To date, over 1400 contaminants (including bacteria, viruses, parasitic protozoa and some fungal/helminth species) have been identified as being associated with many harmful diseases. These pathogenic microorganisms can infect human beings through ways of diet, respiration, skin contact and the like, and cause intestinal tract and respiratory tract diseases, even infectious diseases. The pathogenic bacteria in the water body cause the most common disease spreading events, and the common pathogenic bacteria comprise escherichia coli, helicobacter pylori, clostridium difficile, klebsiella, legionella, salmonella, vibrio, shigella and the like, and can cause the occurrence of typhoid fever, diarrhea, spasm, gastrointestinal diseases, respiratory diseases and the like. Pathogenic viruses in water include DNA viruses (such as adenovirus) and RNA viruses (such as enterovirus, norovirus, hepatitis virus, echovirus, coxsackievirus and the like), and can cause diseases such as human fever, myocarditis, hepatitis, meningitis, respiratory tract infection and the like. Common pathogenic protozoa in water include amoeba, cryptosporidium, giardia, etc., which can cause diarrhea, amoeba encephalitis, keratitis, pulmonary infection, giardiasis, etc. Pathogenic fungi such as P.fumigatus var, Candida albicans, Candida parapsilosis and Exophiala dermatitidis etc. often cause skin and mucosal infection problems.
Currently, disinfection and filtration are mainly used for purifying water. The disinfection method is to kill microorganisms in water directly by a physical or chemical method, the physical method needs to be additionally provided with equipment for disinfection, such as ultraviolet lamps, ultrasonic sterilizers and the like, the cost is high, and once disinfection is stopped, the water is polluted; chemical methods require addition of chemicals such as chlorine, ozone and the like, introduce new pollution sources, and solve the problem of residual disinfection byproducts. The filtration method is to adsorb and retain microorganisms and pollutants in water through a filter medium, sand, gravel, charcoal, diatomite and the like are usually used as the filter medium, but the filter medium does not have sterilization performance, the microorganisms adsorbed by the filter medium are usually fixed on the surface of a material and cannot be removed, and after a period of use, the accumulation of the microorganisms can cause the failure of the filtration effect, and even the water body is polluted reversely.
Therefore, the development of a novel active, continuous and efficient bacteriostatic water filtering system has great practical significance for preventing and treating the microbial pollution of the water body.
Disclosure of Invention
The application aims to provide a bimetal microelectrode antibacterial material, a preparation method thereof, a bimetal microelectrode-carbon-based material composite antibacterial material and a water treatment device, so as to solve the problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a bimetal microelectrode antibacterial material comprises a substrate, a silver-containing layer and a ruthenium-containing layer;
the silver-containing layer is arranged on the surface of the substrate, and the ruthenium-containing layer is arranged on the surface of the silver-containing layer.
Preferably, the substrate comprises stainless steel.
The application also provides a preparation method of the bimetal microelectrode antibacterial material, which comprises the following steps:
and electrochemically depositing the silver-containing layer and the ruthenium-containing layer on the surface of the substrate in sequence.
Preferably, the conditions for electrochemically depositing the silver-containing layer comprise:
the stirring rate is 10rmp-200rmp, the pH of the system is 8-10, and the current density is 0.2mA/cm2-1.5mA/cm2The temperature is 20-40 ℃;
preferably, after the silver-containing layer is obtained, the processing object is dried and then the ruthenium-containing layer is electrochemically deposited.
Preferably, the conditions for electrochemically depositing the ruthenium-containing layer include:
stirring speed is 10rmp-200rmp, system pH is 3-6, current density is 5mA/cm2-20mA/cm2The temperature is 45-60 ℃.
The application also provides a bimetal microelectrode-carbon-based material composite antibacterial material, which comprises the bimetal microelectrode antibacterial material and the carbon-based material.
Preferably, the bimetallic microelectrode antibacterial material is in a net shape.
Preferably, the carbon-based material comprises biochar and/or activated carbon;
preferably, the particle size of the carbon-based material is 1mm to 5 mm.
The application also provides a water treatment device, which comprises the bimetal microelectrode-carbon-based material composite antibacterial material.
Compared with the prior art, the beneficial effect of this application includes:
the application provides a bimetal microelectrode antibacterial material, through setting up the silver-containing layer on the substrate surface, set up ruthenium-containing layer on silver-containing layer surface, need not external energy input, utilize the potential difference of the potential difference redox that exists between the metal, make metal silver, silver ion and metal ruthenium, ruthenium ion form bimetal microbattery system, continuously release active oxygen material through two electron redox reactions and similar fenton's reaction, make water filtration system have the high-efficient antibacterial effect of initiative.
According to the preparation method of the bimetal microelectrode antibacterial material, the silver-containing layer and the ruthenium-containing layer are obtained on the surface of the base material through an electrochemical deposition method, the structure is stable, the preparation method is simple, and the service life is long.
The application provides a bimetal microelectrode-carbon-based material composite antibacterial material lasts high-efficient antibacterial under bimetal microelectrode antibacterial material's effect, guarantees that carbon-based material can avoid the influence of pollutant, maintains composite antibacterial material's "automatically cleaning" function for carbon-based material realizes the continuous high-efficient absorption to aquatic pollutant, can be applied to all kinds of water treatment environment, can prolong filter media life, and the antibiotic material that produces does not all produce the pollution to water and environment.
The application provides a water treatment facilities can be applied to and last high-efficient antibacterial in all kinds of water treatment environment, has huge realistic meaning to prevention and cure water body microbial contamination.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a photograph showing the results of the antibacterial tests of example 1 and comparative examples 1 to 3;
FIG. 2 is an antibacterial curve of examples 1 to 4 and comparative examples 1 to 3;
FIG. 3 shows the action process H of the antibacterial material with the bimetal microelectrode2O2The detection curve of (1);
FIG. 4 is a detection curve of active oxygen substance OH in the action process of the antibacterial material with the bimetallic microelectrode;
FIG. 5 shows the active oxygen substance O in the action process of the antibacterial material of the bimetallic microelectrode2·-The detection curve of (1);
FIG. 6 is a schematic diagram of a bimetal microelectrode bacteriostatic material-carbon-based material composite bacteriostatic filtering system;
FIG. 7 is a photograph showing the evaluation of the adsorption performance of coconut shell activated carbon;
FIG. 8 is a schematic representation of a water treatment device provided herein;
FIG. 9 is a graph showing the change of E.coli concentration in a water sample treated by the water treatment apparatus provided herein;
FIG. 10 is a schematic diagram of the adsorption performance test of activated carbon, stainless steel mesh and the mixture of the two.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If the parts by mass of the component A are a parts and the parts by mass of the component B are B parts, the mass ratio of the component A to the component B is expressed as a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A bimetal microelectrode antibacterial material comprises a substrate, a silver-containing layer and a ruthenium-containing layer;
the silver-containing layer is arranged on the surface of the substrate, and the ruthenium-containing layer is arranged on the surface of the silver-containing layer.
Oxygen is reduced on the surface of the antibacterial material of the bimetallic microelectrode by electrons generated by galvanic couple reaction between the metal microelectrodes, so that a two-electron redox reaction is generated to generate hydrogen peroxide; the hydrogen peroxide and the metal react to generate a Fenton-like reaction (M is the metal) to generate a Reactive Oxygen Species (ROS). The active oxygen species, especially hydroxyl radical (. OH), has a very strong electron-gaining ability, i.e., oxidation, and at the same time, has a very strong sterilization ability.
In an alternative embodiment, the substrate comprises stainless steel.
The selection of the base material is not limited to stainless steel, and other materials may be selected as needed.
The application also provides a preparation method of the bimetal microelectrode antibacterial material, which comprises the following steps:
and electrochemically depositing the silver-containing layer and the ruthenium-containing layer on the surface of the substrate in sequence.
The silver-containing layer obtained by electrochemical deposition includes a simple substance of silver and silver ions, and the ruthenium-containing layer includes a simple substance of ruthenium, ruthenium ions (ruthenium chloride), ruthenium oxide (ruthenium dioxide), and the like.
In an alternative embodiment, the conditions for electrochemically depositing the silver-containing layer comprise:
stirring speed of 10-200 rmp, system pH of 8-10, and current density of 0.2mA/cm2-1.5mA/cm2The temperature is 20-40 ℃;
alternatively, in the condition for electrochemically depositing the silver-containing layer, the stirring rate may be any one of 10rpm, 20rpm, 30rpm, 40rpm, 50rpm, 60rpm, 70rpm, 80rpm, 90rpm, 100rpm, 110rpm, 120rpm, 130rpm, 140rpm, 150rpm, 160rpm, 170rpm, 180rpm, 190rpm, 200rpm, or between 10rpm and 200 rpm; the pH of the system can be 8, 9, 10 or 8-10Any value of (d); the current density may be 0.2mA/cm2、0.3mA/cm2、0.4mA/cm2、0.5mA/cm2、0.6mA/cm2、0.7mA/cm2、0.8mA/cm2、0.9mA/cm2、1.0mA/cm2、1.1mA/cm2、1.2mA/cm2、1.3mA/cm2、1.4mA/cm2、1.5mA/cm2Or 0.2mA/cm2-1.5mA/cm2Any value in between; the temperature can be any value between 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ or 20 ℃ to 40 ℃;
in an alternative embodiment, after the silver-containing layer is obtained, the ruthenium-containing layer is electrochemically deposited after the treatment object is dried.
In an alternative embodiment, the conditions for electrochemically depositing the ruthenium containing layer include:
stirring speed is 10rmp-200rmp, system pH is 3-6, current density is 5mA/cm2-20mA/cm2The temperature is 45-60 ℃.
Alternatively, in the condition for electrochemically depositing the ruthenium-containing layer, the stirring rate may be any one of 10rpm, 20rpm, 30rpm, 40rpm, 50rpm, 60rpm, 70rpm, 80rpm, 90rpm, 100rpm, 110rpm, 120rpm, 130rpm, 140rpm, 150rpm, 160rpm, 170rpm, 180rpm, 190rpm, 200rpm, or 10rpm to 200 rpm; the pH of the system can be 3, 4, 5, 6 or any value between 3 and 6; the current density may be 5.0mA/cm2、6.0mA/cm2、7.0mA/cm2、8.0mA/cm2、9.0mA/cm2、10.0mA/cm2、11.0mA/cm2、12.0mA/cm2、13.0mA/cm2、14.0mA/cm2、15.0mA/cm2、16.0mA/cm2、17.0mA/cm2、18.0mA/cm2、19.0mA/cm2、20.0mA/cm2Or 5.0mA/cm2-20.0mA/cm2Any value in between; the temperature may be 45 ℃, 50 ℃, 55 ℃, 60 ℃ or any value between 45 ℃ and 60 ℃.
The application also provides a bimetal microelectrode-carbon-based material composite antibacterial material, which comprises the bimetal microelectrode antibacterial material and the carbon-based material.
In an alternative embodiment, the bimetallic microelectrode bacteriostatic material is in a net shape.
It should be noted that the bimetallic microelectrode antibacterial material can also take other shapes, and is not limited to a net structure. When the antibacterial material is matched with a carbon-based material for use, the antibacterial material of the bimetal microelectrode can be folded, rotated, wound and the like, so that the carbon-based material can be better compounded with the antibacterial material of the bimetal microelectrode.
The carbon-based material intercepts and adsorbs pollutants in water, so that the aim of high-efficiency filtration is fulfilled. However, since the carbon-based material itself does not adsorb and filter harmful substances such as germs, the harmful substances adhere to the surface of the carbon-based material, and the adsorption ability of the carbon-based material is greatly reduced. In the antibacterial material compounded by the application, the carbon-based material adsorbs conventional pollutants, and active oxygen substances spontaneously generated by the bimetal microelectrode antibacterial material through a two-electron oxygen reduction reaction and a Fenton-like reaction can better play a role in antibacterial sterilization, so that the carbon-based material obtains a self-cleaning function, the negative influence of harmful substances such as germs on the adsorption capacity of the carbon-based material is weakened or eliminated, and a better treatment effect is obtained in an application level.
In an alternative embodiment, the carbon-based material comprises biochar and/or activated carbon;
it will be appreciated that the selection of the particular type of biochar and activated carbon is varied, for example, the activated carbon may be any one or a mixture of coal-based activated carbon, wood-based activated carbon, nutshell-based activated carbon, or synthetic material activated carbon.
In an alternative embodiment, the particle size of the carbon-based material is 1mm to 5 mm.
Alternatively, the particle size of the carbon-based material may be 1mm, 2mm, 3mm, 4mm, 5mm, or any value between 1mm and 5 mm.
The application also provides a water treatment device, which comprises the bimetal microelectrode-carbon-based material composite antibacterial material.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a bimetal microelectrode antibacterial material which comprises a base material 304L stainless steel, and a silver-containing layer and a ruthenium-containing layer which are arranged on the surface of the base material. The preparation method comprises the following steps:
placing a 40-mesh 304L stainless steel net in a silver plating working solution, depositing silver on the surface of a stainless steel piece by an electrochemical deposition method, continuously and uniformly stirring at a rotating speed of 50rpm in the electrodeposition process, wherein the pH is 10.0, and the current density range is 1mA/cm2The temperature is 25 ℃, and the deposition time is 1 min;
fully washing and drying the stainless steel mesh on which the metallic silver is deposited, continuously performing electrochemical deposition, depositing metallic ruthenium on the surface of the silver deposition layer, wherein the ruthenium deposition solution is a mixed solution of ruthenium chloride, sulfamic acid and ammonium chloride, the pH value is 3.0, and the current density range is 15mA/cm2And the temperature is 55 ℃, the deposition time is 1min, and 304L stainless steel net with a silver ruthenium deposition surface, namely the bi-metal microelectrode antibacterial material is obtained.
The obtained antibacterial material of the bimetal microelectrode is cut into 0.5mm multiplied by 0.5mm for antibacterial detection. The antibacterial detection method comprises the following steps: and placing the detection sample on an agar culture medium uniformly coated with the bacterial liquid for culture, and then observing the size of the inhibition zone.
The obtained antibacterial material of the bimetal microelectrode is cut into cut pieces with the diameter of 0.5mm multiplied by 2mm for antibacterial curve detection. The detection method of the antibacterial curve comprises the following steps: adding different samples into a certain amount of bacteria culture solution, culturing for different time, and calculating the number of viable bacteria.
The obtained antibacterial material of the bimetallic microelectrode is cut into pieces with the diameter of 0.5mm multiplied by 2mm for detecting active oxygen substances. Active oxygen species H2O2OH and O2 -The detection method comprises the following steps: make H2O2Reaction with Catalase, characterization H by an increase in fluorescence intensity measured by a fluorescence spectrophotometer2O2Generation of (1); reacting OH with coumarin-3-carboxylic acid, and representing OH generation through the increase of fluorescence intensity measured by a fluorescence spectrophotometer; make O2 -Reaction with nitroblue tetrazolium chloride, characterization of decrease in absorption intensity measured by UV spectrophotometer, O2 -Is generated.
Example 2
The embodiment provides a bimetal microelectrode antibacterial material which comprises a base material 304L stainless steel, and a silver-containing layer and a ruthenium-containing layer which are arranged on the surface of the base material. The preparation method comprises the following steps:
placing a 40-mesh 304L stainless steel net in a silver plating working solution, depositing silver on the surface of a stainless steel piece by an electrochemical deposition method, continuously and uniformly stirring at a rotating speed of 50rpm in the electrodeposition process, wherein the pH is 10.0, and the current density range is 1mA/cm2The temperature is 25 ℃, and the deposition time is 1 min;
fully washing and drying the stainless steel mesh on which the metallic silver is deposited, continuously performing electrochemical deposition, depositing metallic ruthenium on the surface of the silver deposition layer, wherein the ruthenium deposition solution is a mixed solution of ruthenium chloride, sulfamic acid and ammonium chloride, the pH value is 3.0, and the current density range is 15mA/cm2And the temperature is 55 ℃, the deposition time is 5min, and 304L stainless steel net with a silver ruthenium deposition surface, namely the bi-metal microelectrode antibacterial material is obtained.
The obtained antibacterial material of the bimetal microelectrode is cut into 0.5mm multiplied by 0.5mm for antibacterial detection.
The obtained antibacterial material of the bimetal microelectrode is cut into cut pieces with the diameter of 0.5mm multiplied by 2mm for antibacterial curve detection.
Example 3
The embodiment provides a bimetal microelectrode antibacterial material which comprises a base material 304L stainless steel, and a silver-containing layer and a ruthenium-containing layer which are arranged on the surface of the base material. The preparation method comprises the following steps:
placing a 40-mesh 304L stainless steel net in silver plating working solution, and utilizing electricityThe chemical deposition method comprises depositing silver on the surface of stainless steel piece, and continuously and uniformly stirring at 50rpm during electrodeposition with pH of 10.0 and current density of 1mA/cm2The temperature is 25 ℃, and the deposition time is 5 min;
fully washing and drying the stainless steel mesh on which the metallic silver is deposited, continuously performing electrochemical deposition, depositing metallic ruthenium on the surface of the silver deposition layer, wherein the ruthenium deposition solution is a mixed solution of ruthenium chloride, sulfamic acid and ammonium chloride, the pH value is 3.0, and the current density range is 15mA/cm2And the temperature is 55 ℃, the deposition time is 1min, and 304L stainless steel net with a silver ruthenium deposition surface, namely the bi-metal microelectrode antibacterial material is obtained.
The obtained antibacterial material of the bimetal microelectrode is cut into 0.5mm multiplied by 0.5mm for antibacterial detection.
The obtained antibacterial material of the bimetal microelectrode is cut into cut pieces with the diameter of 0.5mm multiplied by 2mm for antibacterial curve detection.
Example 4
The embodiment provides a bimetal microelectrode antibacterial material which comprises a base material 304L stainless steel, and a silver-containing layer and a ruthenium-containing layer which are arranged on the surface of the base material. The preparation method comprises the following steps:
placing a 40-mesh 304L stainless steel net in a silver plating working solution, depositing silver on the surface of a stainless steel piece by an electrochemical deposition method, continuously and uniformly stirring at a rotating speed of 50rpm in the electrodeposition process, wherein the pH is 10.0, and the current density range is 1mA/cm2The temperature is 25 ℃, and the deposition time is 5 min;
fully washing and drying the stainless steel mesh on which the metallic silver is deposited, continuously performing electrochemical deposition, and depositing metallic ruthenium on the surface of the silver deposition layer, wherein the ruthenium deposition solution is a mixed solution of ruthenium chloride, sulfamic acid and ammonium chloride, the pH value is 3.0, and the current density range is 15mA/cm2And the temperature is 55 ℃, the deposition time is 5min, and 304L stainless steel net with a silver ruthenium deposition surface, namely the bi-metal microelectrode antibacterial material is obtained.
The obtained antibacterial material of the bimetal microelectrode is cut into 0.5mm multiplied by 0.5mm for antibacterial detection.
The obtained antibacterial material of the bimetal microelectrode is cut into cut pieces with the diameter of 0.5mm multiplied by 2mm for antibacterial curve detection.
Comparative example 1
The antimicrobial test was conducted by cutting a 40 mesh 304L stainless steel net used in examples 1 to 4 into pieces of 0.5mm by 0.5 mm.
The antimicrobial curve test was performed by cutting a 40 mesh 304L stainless steel net used in examples 1 to 4 into 0.5mm by 2mm pieces.
Comparative example 2
The stainless steel net with a single silver deposit prepared in example 1 was cut into pieces of 0.5mm x 0.5mm for antimicrobial examination.
The stainless steel net with a single silver deposit prepared in example 1 was cut into 0.5mm × 2mm pieces for antimicrobial curve test.
Comparative example 3
Placing a 40-mesh 304L stainless steel net in a ruthenium plating working solution for electrochemical deposition, and depositing metal ruthenium on the surface of the stainless steel net, wherein the pH value is 3.0, and the current density range is 15mA/cm2The temperature was 55 ℃ and the deposition time was 1min, and a 304L stainless steel mesh having a mono-ruthenium deposition layer surface was obtained.
Cutting the stainless steel net with the ruthenium deposition layer into cut pieces of 0.5mm multiplied by 0.5mm for antibacterial detection.
And cutting the stainless steel net with the ruthenium deposition layer into cut pieces with the diameter of 0.5mm multiplied by 2mm for carrying out the antibacterial curve detection.
The results of the antibiotic tests of example 1 and comparative example 1, comparative example 2 and comparative example 3 are shown in fig. 1.
As can be seen from FIG. 1, the results of comparative examples 1 to 3 are not found in the inhibition zone, while the results of the bimetallic microelectrode antibacterial material provided by the present application (example 1) show that the inhibition zone is obvious, which indicates that the bimetallic microelectrode antibacterial material has good bactericidal performance.
The antibacterial curve test of examples 1, 2, 3 and 4 and comparative examples 1, 2 and 3 is shown in fig. 2.
As can be seen from FIG. 2, the antibacterial materials of the bimetallic microelectrode provided in examples 1 to 4 have good antibacterial effect.
In the course of the reaction H2O2And active oxygen species OH, O2·-The presence and amount of (c) changes are shown in fig. 3, fig. 4 and fig. 5, respectively.
In FIG. 3, the abscissa is the wavelength and the ordinate is the fluorescence intensity, and from FIG. 3, the reactant H can be determined2O2The presence of (a) confirms the presence of a two-electron oxygen reduction reaction. FIG. 4 shows the wavelength on the abscissa and the fluorescence intensity on the ordinate, from which FIG. 4 the presence of the reactive oxygen species OH can be determined; FIG. 5 shows the wavelength on the abscissa and the absorbance on the ordinate, and from FIG. 5, the active oxygen species O can be determined2·-Presence of (a); fig. 4 and 5 can demonstrate the presence of a fenton-like reaction.
Example 5
The bimetal microelectrode antibacterial material obtained in the embodiment 1 is coiled into a spiral shape and placed into a container, coconut shell activated carbon is filled in gaps until the bimetal microelectrode antibacterial material is completely covered, and a bimetal microelectrode antibacterial material-carbon-based material composite antibacterial filtering system is formed by combination.
The principle of the bimetal microelectrode bacteriostatic material-carbon-based material composite bacteriostatic filtering system is shown in fig. 6.
Firstly, evaluating the adsorption performance of coconut shell activated carbon, and the specific method comprises the following steps:
soaking the material to be detected into a methylene blue solution with the concentration of 15mg/L, and taking the concentration change of the methylene blue solution before and after adsorption as an evaluation index of adsorption capacity. During the adsorption process, samples of the methylene blue solution were taken from each vessel at different adsorption times and the adsorption capacity was characterized by the decrease in the ultraviolet absorption intensity. The color change is shown in fig. 7.
As shown in fig. 8, the bimetal microelectrode antibacterial material-carbon-based material composite antibacterial filtering system is put into a container to form a water treatment device.
The water treatment apparatus was used to treat three batches of water samples to be treated, and the results are shown in fig. 9. As can be seen from fig. 9, the water treatment device provided by the present application can effectively remove escherichia coli in a water body, and simultaneously shows the reusability of the bimetallic microelectrode bacteriostatic material-carbon-based composite bacteriostatic water filtration system.
Comparative example 4
The 40 mesh 304L stainless steel net used in examples 1 to 4 was cut into pieces of 10mm by 10mm for adsorption test.
Comparison of adsorption results of activated carbon, 40 mesh 304L stainless steel mesh and the mixture thereof (fig. 10 arranged in order from top to bottom): and soaking the materials to be detected into methylene blue solution with the concentration of 15mg/L in groups, and taking the concentration change of the methylene blue solution before and after adsorption as an evaluation index of adsorption capacity. During the adsorption process, samples of the methylene blue solution were taken from each vessel at different adsorption times and the adsorption capacity was characterized by the decrease in the ultraviolet absorption intensity.
As shown in fig. 10, the introduction of the 40 mesh 304L stainless steel net did not affect the adsorption performance of the carbon-based material.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those of skill in the art will understand that although some embodiments herein include some features included in other embodiments, not others, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is already known to a person skilled in the art.

Claims (10)

1. A bimetal microelectrode antibacterial material is characterized by comprising a base material, a silver-containing layer and a ruthenium-containing layer;
the silver-containing layer is arranged on the surface of the substrate, and the ruthenium-containing layer is arranged on the surface of the silver-containing layer.
2. The bimetallic microelectrode bacteriostatic material of claim 1, wherein the substrate comprises stainless steel.
3. The preparation method of the bimetal microelectrode bacteriostatic material of claim 1 or 2, which comprises the following steps:
and electrochemically depositing the silver-containing layer and the ruthenium-containing layer on the surface of the substrate in sequence.
4. The preparation method of the bimetallic microelectrode antibacterial material as claimed in claim 3, wherein the conditions for electrochemically depositing the silver-containing layer include:
the stirring rate is 10rmp-200rmp, the pH of the system is 8-10, and the current density is 0.2mA/cm2-1.5mA/cm2The temperature is 20-40 ℃.
5. The preparation method of the bimetal microelectrode antibacterial material according to claim 4, wherein after the silver-containing layer is obtained, a treatment object is dried and then the ruthenium-containing layer is electrochemically deposited.
6. The preparation method of the bimetallic microelectrode bacteriostatic material according to any one of claims 3 to 5, wherein the conditions for electrochemically depositing the ruthenium-containing layer comprise the following steps:
stirring speed is 10rmp-200rmp, system pH is 3-6, current density is 5mA/cm2-20mA/cm2The temperature is 45-60 ℃.
7. A bimetal microelectrode-carbon-based material composite bacteriostatic material, which is characterized by comprising the bimetal microelectrode bacteriostatic material and the carbon-based material according to claim 1 or 2.
8. The bimetal microelectrode-carbon based material composite bacteriostatic material of claim 7, wherein the bimetal microelectrode-carbon based material is in a net shape.
9. The double-metal microelectrode-carbon-based material composite bacteriostatic material according to claim 7 or 8, wherein the carbon-based material comprises biochar and/or activated carbon;
preferably, the particle size of the carbon-based material is 1mm to 5 mm.
10. A water treatment device, characterized in that the device comprises the bimetallic microelectrode-carbon-based material composite bacteriostatic material of any one of claims 7 to 9.
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AU2018321190A1 (en) * 2018-02-05 2019-08-22 China University Of Mining And Technology System for controlling migration of heavy metal elements of filling body in goaf based on electrophoresis principle
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