CN114477384B - 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 PDFInfo
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- CN114477384B CN114477384B CN202210099405.XA CN202210099405A CN114477384B CN 114477384 B CN114477384 B CN 114477384B CN 202210099405 A CN202210099405 A CN 202210099405A CN 114477384 B CN114477384 B CN 114477384B
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Classifications
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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
Abstract
The application provides a bimetal microelectrode antibacterial material and 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 base material, a silver-containing layer and a ruthenium-containing layer; the silver-containing layer is arranged on the surface of the base material, 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 sequentially and electrochemically depositing the silver-containing layer and the ruthenium-containing layer on the surface of the substrate. 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 antibacterial material. The bimetal microelectrode-carbon-based material composite antibacterial material provided by the application can actively and continuously release active oxygen sterilizing substances, and achieves high-efficiency and durable antibacterial effect and adsorption effect. The method is applied to various water treatment environments, and does not pollute the water body and the environment.
Description
Technical Field
The application relates to the field of water treatment, in particular to a bimetal microelectrode antibacterial material and a preparation method thereof, a bimetal microelectrode-carbon-based material composite antibacterial material and a water treatment device.
Background
Water is an indispensable substance for life maintenance and is also a strategic resource for sustainable development of society. However, the world health organization reports that about 25 hundred million people cannot obtain safe and sanitary water. For less developed areas, the lack of water resources and pathogenic microorganisms cause deterioration of water quality threatening the water ecosystem and health survival problems of the relevant areas. The main cause of most outbreaks of water-borne diseases is infections associated with microbial contamination. Up to now, more than 1400 contaminants (including bacteria, viruses, parasitic protozoa and some fungal/helminth species) have been identified as being associated with a number of deleterious diseases. These pathogenic microorganisms can infect humans through dietary, respiratory, skin contact, etc. pathways, leading to intestinal, respiratory diseases and even infectious diseases. The occurrence of disease transmission caused by pathogenic bacteria in water is most common, and common pathogenic bacteria include colibacillus, helicobacter pylori, clostridium difficile, klebsiella, legionella, salmonella, vibrio, shigella and the like, and can cause typhoid fever, diarrhea, spasm, gastrointestinal diseases, respiratory diseases and the like. Pathogenic viruses in water bodies include DNA viruses (such as adenovirus) and RNA viruses (such as enterovirus, norovirus, hepatitis virus, epstein-Barr virus, coxsackie virus 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 bodies comprise amoeba, cryptosporidium, giardia and the like, and can cause diarrhea, amoeba encephalitis, keratitis, pulmonary infection, giardiasis and other diseases. Pathogenic fungi such as Aspergillus fumigatus variant, candida albicans, candida parapsilosis and Exophiala dermatitis often cause skin and mucous membrane infection problems.
The main methods for purifying water are disinfection and filtration. The disinfection method is to directly kill microorganisms in water by a physical or chemical method, and the physical method needs to be additionally provided with equipment for disinfection, such as ultraviolet lamps, ultrasonic disinfectors and the like, has high cost and can be at risk of pollution once disinfection is stopped; the chemical method needs to add chemical substances such as chlorine, ozone and the like, can introduce new pollution sources, and meanwhile, the problem of residual disinfection byproducts cannot be solved. The filtering method is to adsorb and retain microorganisms and pollutants in water through a filtering medium, sand, gravel, charcoal, diatomite and the like are often used as the filtering medium, but the filtering medium is not bactericidal, the microorganisms adsorbed by the filtering medium are usually fixed on the surface of a material and cannot be removed, and after a period of use, the filtering effect is invalid due to the accumulation of the microorganisms, and even water is polluted in turn.
Therefore, the development of a novel active continuous efficient antibacterial water filtering system has great practical significance for preventing and treating the microbial pollution of the water body.
Disclosure of Invention
The aim of the application is to provide a bimetal microelectrode antibacterial material and 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 above purpose, the present application adopts the following technical scheme:
a bimetallic microelectrode antibacterial material comprises a base material, a silver-containing layer and a ruthenium-containing layer;
the silver-containing layer is arranged on the surface of the base material, 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 sequentially and electrochemically depositing the silver-containing layer and the ruthenium-containing layer on the surface of the substrate.
Preferably, 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/cm 2 -1.5mA/cm 2 The temperature is 20-40 ℃;
preferably, after the silver-containing layer is obtained, the ruthenium-containing layer is electrochemically deposited after drying the treatment object.
Preferably, the conditions for electrochemically depositing the ruthenium-containing layer include:
the stirring rate is 10rmp-200rmp, the pH of the system is 3-6, and the current density is 5mA/cm 2 -20mA/cm 2 The 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 bimetal microelectrode antibacterial material is net-shaped.
Preferably, the carbon-based material comprises biochar and/or activated carbon;
preferably, the particle size of the carbon-based material is 1mm to 5mm.
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 effects of this application include:
according to the bimetal microelectrode antibacterial material, the silver-containing layer is arranged on the surface of the base material, the ruthenium-containing layer is arranged on the surface of the silver-containing layer, external energy input is not needed, the potential difference of potential difference oxidation reduction existing between metals is utilized, so that metal silver, silver ions, metal ruthenium and ruthenium ions form a bimetal microbattery system, active oxygen substances are continuously released through a two-electron oxidation reduction reaction and Fenton-like reaction, and the water filtering system has an active efficient antibacterial effect.
According to the preparation method of the bimetallic microelectrode antibacterial material, the silver-containing layer and the ruthenium-containing layer are obtained on the surface of the substrate through an electrochemical deposition method, so that the structure is stable, the preparation method is simple, and the service life is long.
The bimetal microelectrode-carbon-based material composite antibacterial material provided by the application can continuously and efficiently inhibit bacteria under the action of the bimetal microelectrode antibacterial material, ensure that the carbon-based material can be prevented from being influenced by pollutants, maintain the self-cleaning function of the composite antibacterial material, enable the carbon-based material to realize continuous and efficient adsorption of pollutants in water, be applied to various water treatment environments, prolong the service life of the filter material, and ensure that the generated antibacterial substances do not pollute water and the environment.
The water treatment device can be applied to continuous high-efficiency bacteriostasis in various water treatment environments, and has great practical significance for preventing and treating microbial contamination of water bodies.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain 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 antibacterial test conducted in example 1 and comparative examples 1 to 3;
FIG. 2 is an antibacterial curve of examples 1-4 and comparative examples 1-3;
FIG. 3 shows H in the course of action of the bimetallic microelectrode bacteriostatic material 2 O 2 Is a detection curve of (2);
FIG. 4 is a graph showing the detection of active oxygen species OH during the action of the bi-metallic microelectrode bacteriostatic material;
FIG. 5 shows the active oxygen species O during the action of the bimetallic microelectrode bacteriostatic material 2 · - Is a detection curve of (2);
FIG. 6 is a schematic diagram of a bi-metallic microelectrode bacteriostatic material-carbon based material composite bacteriostatic filtration system;
FIG. 7 is a photograph showing evaluation of adsorption performance of coconut shell activated carbon;
FIG. 8 is a schematic view of a water treatment device according to the present application;
FIG. 9 is a graph showing the concentration change of E.coli in a water sample treated using the water treatment apparatus provided herein;
FIG. 10 is a schematic diagram of adsorption performance test of activated carbon, stainless steel mesh and mixture of the two.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, 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, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list 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 ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: 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 not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
A bimetallic microelectrode antibacterial material comprises a base material, a silver-containing layer and a ruthenium-containing layer;
the silver-containing layer is arranged on the surface of the base material, and the ruthenium-containing layer is arranged on the surface of the silver-containing layer.
Oxygen is reduced by electrons generated by galvanic reaction between metal microelectrodes on the surface of the bimetallic microelectrode antibacterial material, and a two-electron redox reaction occurs to generate hydrogen peroxide; the hydrogen peroxide and the metal can react to generate Fenton-like reaction (M is metal) to generate Reactive Oxygen Species (ROS). The active oxygen substance, especially hydroxyl radical (OH), has extremely strong electron-obtaining capability, namely oxidizing property, and has extremely strong sterilization capability.
In an alternative embodiment, the substrate comprises stainless steel.
The choice 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 sequentially and electrochemically depositing the silver-containing layer and the ruthenium-containing layer on the surface of the substrate.
The silver-containing layer obtained by electrochemical deposition includes a silver simple substance and silver ions, and the ruthenium-containing layer includes a ruthenium simple substance, ruthenium ions (ruthenium chloride), ruthenium oxide (ruthenium dioxide), and the like.
In an alternative embodiment, 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/cm 2 -1.5mA/cm 2 The temperature is 20-40 ℃;
alternatively, in the conditions 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 10rpm-200 rpm; the system pH can be 8, 9, 10 or any value between 8 and 10; the current density can be 0.2mA/cm 2 、0.3mA/cm 2 、0.4mA/cm 2 、0.5mA/cm 2 、0.6mA/cm 2 、0.7mA/cm 2 、0.8mA/cm 2 、0.9mA/cm 2 、1.0mA/cm 2 、1.1mA/cm 2 、1.2mA/cm 2 、1.3mA/cm 2 、1.4mA/cm 2 、1.5mA/cm 2 Or 0.2mA/cm 2 -1.5mA/cm 2 Any value in between; the temperature may be 20 ℃, 25 ℃, 30 ℃, 35 ℃,40 ℃ or any value between 20 ℃ and 40 ℃;
in an alternative embodiment, after the silver-containing layer is obtained, the treatment object is dried and then the ruthenium-containing layer is electrochemically deposited.
In an alternative embodiment, the conditions for electrochemically depositing the ruthenium-containing layer include:
the stirring rate is 10rmp-200rmp, the pH of the system is 3-6, and the current density is 5mA/cm 2 -20mA/cm 2 The temperature is 45-60 ℃.
Alternatively, in the conditions for electrochemically depositing the ruthenium-containing layer, the stirring rate may be any value between 10rpm, 20rpm, 30rpm, 40rpm, 50rpm, 60rpm, 70rpm, 80rpm, 90rpm, 100rpm, 110rpm, 120rpm, 130rpm, 140rpm, 150rpm, 160rpm, 170rpm, 180rpm, 190rpm, 200rpm, or 10rpm-200 rpm; the system pH can be 3, 4, 5, 6 or any value between 3 and 6; the current density can be 5.0mA/cm 2 、6.0mA/cm 2 、7.0mA/cm 2 、8.0mA/cm 2 、9.0mA/cm 2 、10.0mA/cm 2 、11.0mA/cm 2 、12.0mA/cm 2 、13.0mA/cm 2 、14.0mA/cm 2 、15.0mA/cm 2 、16.0mA/cm 2 、17.0mA/cm 2 、18.0mA/cm 2 、19.0mA/cm 2 、20.0mA/cm 2 Or 5.0mA/cm 2 -20.0mA/cm 2 Any 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 bi-metallic microelectrode bacteriostatic material is in the form of a mesh.
It should be noted that the bi-metal microelectrode antibacterial material can also take other shapes, and is not limited to a net structure. When the antibacterial material is matched with the carbon-based material, 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 can intercept and adsorb pollutants in water, thus achieving the purpose of high-efficiency filtration. However, the carbon-based material itself does not adsorb and filter harmful substances such as germs, but rather, the harmful substances adhere to the surface of the carbon-based material, resulting in a significant decrease in the adsorption capacity of the carbon-based material. In the antibacterial material compounded by the application, the carbon-based material adsorbs conventional pollutants, and the active oxygen substances spontaneously generated by the bi-metal microelectrode antibacterial material through the di-electron oxygen reduction reaction and the Fenton-like reaction can better play a role in resisting bacteria and sterilizing, so that the carbon-based material has a self-cleaning function, and the negative influence of harmful substances such as bacteria on the adsorption capacity of the carbon-based material is weakened or eliminated, so that a better treatment effect is obtained on an application level.
In an alternative embodiment, the carbon-based material comprises biochar and/or activated carbon;
it will be appreciated that the particular type of biochar and activated carbon chosen will vary, for example, the activated carbon may be any one or a mixture of coal-based activated carbon, wood-based activated carbon, fruit shell-based activated carbon, synthetic material activated carbon.
In an alternative embodiment, the carbon-based material has a particle size of 1mm to 5mm.
Alternatively, the particle size of the carbon-based material may be any value between 1mm, 2mm, 3mm, 4mm, 5mm, or 1mm-5mm.
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 it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
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 304L stainless steel. The preparation method comprises the following steps:
placing a 40-mesh 304L stainless steel mesh in silver plating working solution, depositing silver on the surface of a stainless steel piece by using an electrochemical deposition method, and electrodepositingIn the process, the stirring is continuously and evenly carried out at 50rpm, the pH is 10.0, and the current density is 1mA/cm 2 The temperature is 25 ℃, and the deposition time is 1min;
fully washing and drying a stainless steel mesh deposited with metallic silver, continuously carrying out electrochemical deposition, and depositing metallic ruthenium on the surface of a 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/cm 2 The temperature is 55 ℃, the deposition time is 1min, and the 304L stainless steel mesh with the silver ruthenium deposition surface, namely the bimetallic microelectrode antibacterial material, is obtained.
Cutting the obtained bimetal microelectrode antibacterial material into 0.5mm multiplied by 0.5mm for antibacterial detection. The antibacterial detection method comprises the following steps: and (3) placing the detection sample on an agar culture medium uniformly coated with bacterial liquid for culture, and then observing the size of a bacteriostasis zone.
Cutting the obtained bimetal microelectrode antibacterial material into cut pieces with the thickness of 0.5mm multiplied by 2mm for antibacterial curve detection. The antibacterial curve detection method comprises the following steps: and (3) adding different samples into a certain amount of bacterial culture solution, culturing for different times, and calculating the number of living bacteria.
Cutting the obtained bimetal microelectrode antibacterial material into cut pieces with the thickness of 0.5mm multiplied by 2mm, and detecting active oxygen substances. Active oxygen substance H 2 O 2 (OH) and (O) 2 - The detection method of (1) comprises the following steps: make H 2 O 2 By reaction with catalase, the increase in fluorescence intensity measured by a fluorescence spectrophotometer characterizes H 2 O 2 Is generated; reacting OH with coumarin-3-carboxylic acid, and characterizing the generation of OH by increasing the fluorescence intensity as measured by a fluorescence spectrophotometer; make · O 2 - Reaction with nitrotetrazolium chloride, characterization of decrease in absorption intensity by UV Spectrophotometer, O 2 - 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 304L stainless steel. The preparation method comprises the following steps:
placing a 40-mesh 304L stainless steel mesh in silver plating working solution, depositing silver on the surface of a stainless steel piece by using an electrochemical deposition method, continuously and uniformly stirring at 50rpm in the electrodeposition process, wherein the pH is 10.0, and the current density is 1mA/cm 2 The temperature is 25 ℃, and the deposition time is 1min;
fully washing and drying a stainless steel mesh deposited with metallic silver, continuously carrying out electrochemical deposition, and depositing metallic ruthenium on the surface of a 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/cm 2 The temperature is 55 ℃, the deposition time is 5min, and the 304L stainless steel mesh with the silver ruthenium deposition surface, namely the bimetallic microelectrode antibacterial material, is obtained.
Cutting the obtained bimetal microelectrode antibacterial material into 0.5mm multiplied by 0.5mm for antibacterial detection.
Cutting the obtained bimetal microelectrode antibacterial material into cut pieces with the thickness 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 304L stainless steel. The preparation method comprises the following steps:
placing a 40-mesh 304L stainless steel mesh in silver plating working solution, depositing silver on the surface of a stainless steel piece by using an electrochemical deposition method, continuously and uniformly stirring at 50rpm in the electrodeposition process, wherein the pH is 10.0, and the current density is 1mA/cm 2 The temperature is 25 ℃, and the deposition time is 5min;
fully washing and drying a stainless steel mesh deposited with metallic silver, continuously carrying out electrochemical deposition, and depositing metallic ruthenium on the surface of a 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/cm 2 The temperature is 55 ℃, the deposition time is 1min, and the 304L stainless steel mesh with the silver ruthenium deposition surface, namely the bimetallic microelectrode antibacterial material, is obtained.
Cutting the obtained bimetal microelectrode antibacterial material into 0.5mm multiplied by 0.5mm for antibacterial detection.
Cutting the obtained bimetal microelectrode antibacterial material into cut pieces with the thickness 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 304L stainless steel. The preparation method comprises the following steps:
placing a 40-mesh 304L stainless steel mesh in silver plating working solution, depositing silver on the surface of a stainless steel piece by using an electrochemical deposition method, continuously and uniformly stirring at 50rpm in the electrodeposition process, wherein the pH is 10.0, and the current density is 1mA/cm 2 The temperature is 25 ℃, and the deposition time is 5min;
fully washing and drying a stainless steel mesh deposited with metallic silver, continuously carrying out electrochemical deposition, and depositing metallic ruthenium on the surface of a 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/cm 2 The temperature is 55 ℃, the deposition time is 5min, and the 304L stainless steel mesh with the silver ruthenium deposition surface, namely the bimetallic microelectrode antibacterial material, is obtained.
Cutting the obtained bimetal microelectrode antibacterial material into 0.5mm multiplied by 0.5mm for antibacterial detection.
Cutting the obtained bimetal microelectrode antibacterial material into cut pieces with the thickness of 0.5mm multiplied by 2mm for antibacterial curve detection.
Comparative example 1
The 40 mesh 304L stainless steel mesh used in examples 1-4 was cut into 0.5mm by 0.5mm pieces for antibacterial test.
The 40 mesh 304L stainless steel mesh used in examples 1-4 was cut into 0.5mm 2mm pieces for antibacterial curve detection.
Comparative example 2
The stainless steel mesh with a single silver deposit layer prepared in example 1 was cut into pieces of 0.5mm×0.5mm for antibacterial detection.
The stainless steel mesh with a single silver deposit layer prepared in example 1 was cut into pieces of 0.5mm×2mm for antibacterial curve detection.
Comparative example 3
40 mesh 304Placing the L stainless steel mesh in ruthenium plating working solution, performing electrochemical deposition, and depositing metal ruthenium on the surface of the stainless steel mesh, wherein the pH value is 3.0, and the current density range is 15mA/cm 2 The temperature was 55℃and the deposition time was 1min, a 304L stainless steel mesh with a single ruthenium deposition layer surface was obtained.
The stainless steel mesh with the single ruthenium deposition layer is cut into pieces with the thickness of 0.5mm multiplied by 0.5mm for antibacterial detection.
Cutting the stainless steel mesh with the single ruthenium deposition layer into cut pieces with the thickness of 0.5mm multiplied by 2mm for antibacterial curve detection.
The results of the antibacterial 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 1-3 are not found with the inhibition zone, while the results of the bimetallic microelectrode inhibition material (example 1) provided by the application show that the inhibition zone is obvious, indicating that the bimetallic microelectrode inhibition material has good bactericidal performance.
The antibacterial curve detection of example 1, example 2, example 3 and example 4 and comparative examples 1, 2 and 3 is shown in fig. 2.
As can be seen from FIG. 2, the bimetallic microelectrode antibacterial material provided in examples 1-4 has good antibacterial effect.
H in the reaction process 2 O 2 And active oxygen species OH, O 2 · - The presence and amount changes of (a) are shown in figures 3, 4 and 5, respectively.
In FIG. 3, the abscissa indicates the wavelength, and the ordinate indicates the fluorescence intensity, from which the reactant H can be determined in FIG. 3 2 O 2 Confirming the presence of a two electron oxygen reduction reaction. FIG. 4 is a graph showing the wavelength on the abscissa and the fluorescence intensity on the ordinate, and the presence of the reactive oxygen species OH can be determined from FIG. 4; the wavelength is plotted on the abscissa in FIG. 5, the absorbance is plotted on the ordinate, and the active oxygen species O can be determined from FIG. 5 2 · - Is present; figures 4 and 5 can demonstrate the presence of Fenton-like reactions.
Example 5
The bimetal microelectrode antibacterial material obtained in the example 1 is coiled into a spiral shape and is put into a container, coconut shell active carbon is filled in a gap until the bimetal microelectrode antibacterial material is completely covered, and the bimetal microelectrode antibacterial material-carbon based material composite antibacterial filtration system is formed.
The principle of the bimetal microelectrode antibacterial material-carbon based material composite antibacterial filtration system is shown in figure 6.
Firstly, evaluating the adsorption performance of the coconut shell activated carbon, wherein the specific method comprises the following steps:
the material to be measured is soaked into methylene blue solution with the concentration of 15mg/L, and the concentration change of the methylene blue solution before and after adsorption is used as an evaluation index of the adsorption capacity. During the adsorption process, samples of methylene blue solution were taken from each vessel at different adsorption times, and the adsorption capacity was characterized in terms of the decrease in ultraviolet absorption intensity. The color change is shown in fig. 7.
As shown in fig. 8, the above-mentioned bimetal microelectrode antibacterial material-carbon-based material composite antibacterial filtration system is filled into a container to form a water treatment device.
Three batches of water samples to be treated were treated using the water treatment apparatus, and the results are shown in fig. 9. As can be seen from FIG. 9, by using the water treatment device provided by the application, escherichia coli in a water body can be effectively removed, and the reusability of the bimetal microelectrode antibacterial material-carbon-based composite antibacterial water filtration system is shown.
Comparative example 4
The 40 mesh 304L stainless steel mesh used in examples 1-4 was cut into 10mm X10 mm pieces for adsorptivity detection.
Comparison of adsorption results of activated carbon, 40 mesh 304L stainless steel mesh, and a mixture of both (fig. 10 arranged sequentially from top to bottom): the material to be measured is soaked into methylene blue solution with the concentration of 15mg/L in groups, and the concentration change of the methylene blue solution before and after adsorption is used as an evaluation index of the adsorption capacity. During the adsorption process, samples of methylene blue solution were taken from each vessel at different adsorption times, and the adsorption capacity was characterized in terms of the decrease in ultraviolet absorption intensity.
As shown in fig. 10, the introduction of the 40 mesh 304L stainless steel mesh did not affect the adsorption performance of the carbon-based material.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution 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 scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, 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 already known to a person skilled in the art.
Claims (1)
1. The water treatment device is characterized by comprising a bimetal microelectrode-carbon-based material composite antibacterial material; the bimetal microelectrode-carbon-based material composite antibacterial material comprises a bimetal microelectrode antibacterial material and coconut shell activated carbon, wherein the bimetal microelectrode antibacterial material is coiled into a spiral shape and is put into a container, and the coconut shell activated carbon is filled in a gap until the bimetal microelectrode antibacterial material is completely covered; the bimetal microelectrode antibacterial material comprises a base material, a silver-containing layer and a ruthenium-containing layer;
the silver-containing layer is arranged on the surface of the base material, the ruthenium-containing layer is arranged on the surface of the silver-containing layer, and the base material comprises stainless steel; the bimetal microelectrode antibacterial material is net-shaped; the particle size of the coconut shell active carbon is 1mm-5mm;
the preparation method of the bimetal microelectrode antibacterial material comprises the following steps:
sequentially electrochemically depositing the silver-containing layer and the ruthenium-containing layer on the surface of the substrate;
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/cm 2 -1.5mA/cm 2 The temperature is 20-40 ℃;
after the silver-containing layer is obtained, drying a treatment object and then electrochemically depositing the ruthenium-containing layer;
the conditions for electrochemically depositing the ruthenium-containing layer include:
the stirring rate is 10rmp-200rmp, the pH of the system is 3-6, and the current density is 5mA/cm 2 -20mA/cm 2 The temperature is 45-60 ℃.
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