CN106517445A - Preparation method for electroporation electrode structure and application - Google Patents

Preparation method for electroporation electrode structure and application Download PDF

Info

Publication number
CN106517445A
CN106517445A CN201611114099.3A CN201611114099A CN106517445A CN 106517445 A CN106517445 A CN 106517445A CN 201611114099 A CN201611114099 A CN 201611114099A CN 106517445 A CN106517445 A CN 106517445A
Authority
CN
China
Prior art keywords
preparation
sputtering
electrode structure
electroporation
heat treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201611114099.3A
Other languages
Chinese (zh)
Other versions
CN106517445B (en
Inventor
刘朝红
杜宝亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Haier Smart Technology R&D Co Ltd
Haier Smart Home Co Ltd
Original Assignee
Qingdao Haier Smart Technology R&D Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao Haier Smart Technology R&D Co Ltd filed Critical Qingdao Haier Smart Technology R&D Co Ltd
Priority to CN201611114099.3A priority Critical patent/CN106517445B/en
Publication of CN106517445A publication Critical patent/CN106517445A/en
Application granted granted Critical
Publication of CN106517445B publication Critical patent/CN106517445B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F2001/46133Electrodes characterised by the material
    • C02F2001/46138Electrodes comprising a substrate and a coating
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/04Disinfection

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention discloses a preparation method for an electroporation electrode structure. The method comprises the steps that (1) a metallic material is soaked in an oxidizing solution for oxidation etching at the room temperature; (2) the metallic material subjected to oxidation etching is placed in a calorstat for heat treatment after being washed; (3) the metallic material subjected to heat treatment is subjected to nano-silver sputtering; and (4) the electrode structure subjected to sputtering is washed then placed in the calorstat to be dried, and the electroporation electrode structure is obtained. The technical problems that an electroporation technology needs high voltage and high cost are solved, and the preparation method capable of achieving the electroporation effect under low voltage for the electrode structure is provided.

Description

A kind of preparation method and application of electroporation electrodes structure
Technical field
The invention belongs to electrode structure technical field, and in particular to a kind of electrode structure preparation side for electroporation device Method.
Background technology
Electroporation technology is the electric field action by high intensity, instantaneously improves membrane passage, by nucleic acid, albumen and Other molecules import the high efficiency technical of various kinds of cell, are widely used to the fields such as biologic medical and genetic engineering.Electroporation sets The standby high field for producing is realized by applying thousands of to tens thousand of volts of high voltages at electrode two ends.In order to ensure that electricity is worn Hole equipment steady operation, proposes high requirement to the performance of electrode structure, causes the electrode structure of existing electroporation device With high costs, power control system is complicated, high energy consumption, limits the application of electroporation device.
In water treatment field, chlorination is wide variety of disinfection technology, but during chlorination, easily produces cause The by-product of cancer, affects human health.High field is produced using electroporation technology can be carried out quickly to microorganism in water Electroporation is sterilized, and improves disinfection efficiency.But current electroporation technology is relatively costly, is not suitable for water treatment field.
The content of the invention
The present invention needs high voltage for electroporation technology, causes the technical problem of high cost, there is provided one kind can be low The preparation method of the electrode structure of electroporation effect is realized under voltage.
To achieve these goals, the present invention is achieved using following technical proposals:
A kind of preparation method of electroporation electrodes structure, step is 1)At room temperature, metal material is immersed in oxidizing solution Carry out oxide etch;2)After metal material after oxide etch is rinsed, in being put in calorstat, heat treatment is carried out;3)By heat treatment Metal material afterwards carries out nanometer silver sputtering;4)Electrode structure after sputtering is cleaned, is then placed in calorstat and is dried It is dry, obtain electroporation electrodes structure.
In order to metal material framework surface oxidation generate needle-like array structure, the oxidizing solution be sodium hydroxide, The mixture of Ammonium persulfate. and deionized water.
In order to ensure that needle-like array structure keeps the mole dense of regular geometry, the sodium hydroxide and Ammonium persulfate. Degree ratio is 20-30:1;The concentration of the sodium hydroxide is 2-3mol/L.Further, the time that decorations are carved in the oxidation is 10- 30min。
In order to ensure that needle-like array structure is changed from hydroxide to oxide, and prevent needle-like array structure from caving in, institute The temperature for stating heat treatment is 150-200 DEG C, and heat treatment time is 3-6h.
In order to the silverskin of nano thickness is sputtered in needle-like array structure outer layer, the sputtering voltage is 1000-3000V, electric Current density is 0.5-2mA/cm2, operating air pressure 0-10Pa, sputtering time are 3-30min.
In order to ensure drying effect, the drying temperature is 50-70 DEG C, and the time is 10-30min.
The electrode structure obtained by above-mentioned preparation method in the present invention can apply to water process sterilization.
Compared with prior art, advantages of the present invention and good effect are:The preparation method of the present invention is first by metal material Material carries out oxide etch, forms metal hydroxidess needle-like array structure, then carry out heat in the frame structure of metal material Process, metal hydroxidess are converted into metal-oxide, form a length of tens microns, metal of a diameter of tens to hundreds of nanometer Oxide needle-like array structure;Then sputtering silver is carried out, and one layer of nanometer is obtained in metal-oxide needle-like array structure outer surface Silverskin, for protecting interior metal, prevents electrode to be corroded, and gives whole electrode structure good electric conductivity.Present invention system In the standby electrode structure for obtaining, needle-like micro nano structure can form high pressure in its tip aggregation electric charge, in holding electrode spacing phase Meanwhile, can greatly strengthen the electric field intensity between positive and negative electrode.Therefore, under relatively low running voltage, can between positive and negative electrode The strong electric field needed for electroporation effect is realized in generation, effectively reduces work difficulty.
Description of the drawings
Fig. 1. electroporation electrodes structure preparation flow figure in the present embodiment;
Fig. 2. in embodiment, foam copper product is before oxide etch heat treatment(A, b), after(C, d)Microscopic appearance;
Fig. 3. the stereoscan photograph of Bacillus coli cells perforation is carried out using electroporation electrodes structure manufactured in the present embodiment.
Specific embodiment
Technical scheme is described in further detail with reference to specific embodiment.
Present embodiments provide a kind of preparation method of electroporation electrodes structure, including oxide etch, heat treatment, sputtering and Four key steps of cleaning, as shown in figure 1, being specially:
1)At room temperature, metal material is immersed in oxidizing solution carries out oxide etch so that give birth on metal material framework surface Into needle-like array structure.
The metal material can be using common metals such as copper, nickel, aluminum, titaniums.
The oxidizing solution refers to sodium hydroxide NaOH, Ammonium persulfate. (NH4)2S2O8With the mixture of deionized water, institute The molar concentration rate for stating sodium hydroxide and Ammonium persulfate. is 20-30:1, the wherein concentration of sodium hydroxide is 2-3mol/L, aoxidizes and carves The time of decorations is 10-30min.
In the oxidizing solution, sodium hydroxide is oxidation promoter, and Ammonium persulfate. is oxidant.The Ammonium persulfate. it is dense Degree is bigger or the decorations time at quarter is longer, and the needle-like array structure that metal material framework surface can generate is longer, but Ammonium persulfate. Concentration is excessive or quarter decorations overlong time needle-like array structure will be difficult to keep its regular geometry.
2)Metal material deionized water after oxide etch is rinsed 3-5 time, sodium hydroxide is washed away and Ammonium persulfate. is residual Stay, then placing 3-6h in 150-200 DEG C of calorstat carries out heat treatment, and metal hydroxidess are converted into metal-oxide.
In the present embodiment, by taking foam copper as an example, microscopic appearance of the foam copper product before and after oxide etch, heat treatment is such as Shown in Fig. 2, the foam copper of wherein Fig. 2 a, Fig. 2 b for before processing, Fig. 2 c, Fig. 2 d are the foam copper after processing.Can from figure Go out, after oxidized etching, heat treatment, define in the frame structure of foam copper product a length of tens microns, a diameter of tens to Hundreds of nanometer of copper oxide needle-like array structure.Its related chemistry reaction equation is:
Oxide etch:2NaOH+(NH4)2S2O8+Cu→Cu(OH)2+Na2SO4+(NH4)2SO4
Heat treatment:Cu(OH)2→CuO+H2O
Heat treatment temperature is too low or process time is too short, and prepared array structure cannot complete hydroxide turning to oxide Become, heating-up temperature is too high, and needle-like array structure can be caused to cave in.
3)Metal material after heat treatment is placed in the sample base of sputtering equipment, nanometer silver sputtering is carried out with silver-colored target, Nano-silver layer is formed in metal oxide surface.Sputtering voltage is 1000-3000V, and electric current density is 0.5-2mA/cm2, work Air pressure 0-10Pa, sputtering time are 3-30min.It is isoparametric by sputtering voltage, electric current density, operating air pressure, sputtering time The thickness of the controllable nano-silver layer of regulation and control.
4)Electrode structure after sputtering is cleaned, cleanout fluid adopts dehydrated alcohol, rinsed 3-5 time, then in 50-70 10-30min drying is placed in DEG C calorstat, electroporation electrodes structure is obtained final product.
Electrode structure obtained in the present embodiment can reach higher sterilization rate using DC source or alternating current power supply.It is preferred that Using alternating current power supply, advantage is can be with rapid cleaning electrode surface, effective service life for extending electrode structure.By the electricity Pole structure is connected with the alternating source of electroporation device, to containing micro- under the conditions of 1-15 V voltages, flow rate of water flow 0.5-3L/min Biological water body is processed, it is possible to achieve the perforation of the microbial cell such as escherichia coli is dead(Fig. 3), sterilization rate is up to 99%.
Electrode structure obtained in the present embodiment realizes that the mechanism of action of electroporation effectiveness is at lower voltages:Oxidized etching Metal material surface afterwards generates needle-like array structure, and after Jing sputtering silvers, the silverskin protection interior metal on top layer simultaneously gives The good electric conductivity of whole electrode structure.As needle-like array structure is the geometry with regular micro/nano level, outside In the case that boundary's voltage is certain, needle-like micro nano structure can form high pressure in its tip aggregation electric charge, in holding electrode spacing When identical, can greatly strengthen the electric field intensity between positive and negative electrode.The microorganisms such as escherichia coli with current enter both positive and negative polarity it Between electric field region when, electric energy produce mechanical compress act on cause bacterial cell membrane phospholipid bilayer and protein lose Surely, cell membrane expands rupture, and cytoplasmic compartment or all outflow cause antibacterial finally dead.
The application of electrode scope of the present invention is wider, be able to can use in the case of 1-15V external voltages.When increase is containing micro- During the flow velocity of biological water body, can accordingly increase running voltage, carry out efficient inactivation treatment.
Electroporation electrodes structure preparation method in the present invention is simple, and preparation cost is cheap, is adapted to large-scale industry metaplasia Produce.Electrode structure can be in low-voltage(≤20 V)Under realize electroporation effectiveness, the requirement to power-supply system can be substantially reduced, if It is standby to safeguard simpler.The electrode structure prepared by the electroporation electrodes structure preparation method in the present invention can be used for small electrical and wear Hole equipment, and expand range of application of the equipment in fields such as water body purifications.
Embodiment 1
A kind of preparation method of electroporation electrodes structure, step is, 1)By sodium hydroxide and Ammonium persulfate. be successively added to from Oxidizing solution is prepared in sub- water, the wherein concentration of sodium hydrate aqueous solution is 2mol/L, the sodium hydroxide and Ammonium persulfate. Molar concentration rate be 20:1, it is cooled to room temperature stand-by;Will be initial metallic foam copper dehydrated alcohol or acetone etc. organic Solvent and deionized water cleaning, remove surface and oil contaminant and other impurities;Cleaned foam copper is completely immersed in into above-mentioned oxidisability In solution, oxidation processes 30min.2)The copper product after above-mentioned oxidation processes is taken out, deionized water is rinsed 3-5 time, Ran Houfang Heat treatment 3h is carried out in entering 200 DEG C of calorstat.3)Foam copper product after oxidized etching, heat treatment is placed in into sputtering equipment Sample base on, nanometer silver sputtering is carried out with silver-colored target, sputtering voltage is 1000V, and electric current density is 2mA/cm2, operating air pressure 10Pa, sputtering time are 20min.4)Foam copper product after sputtering is rinsed 3-5 time with dehydrated alcohol, then in 50 DEG C of calorstats 30 min of middle placement, obtain final product electroporation electrodes structure.
Embodiment 2
A kind of preparation method of electroporation electrodes structure, step is, 1)By sodium hydroxide and Ammonium persulfate. be successively added to from Oxidizing solution is prepared in sub- water, the wherein concentration of sodium hydrate aqueous solution is 2.5mol/L, the sodium hydroxide and persulfuric acid The molar concentration rate of ammonium is 30:1, it is cooled to room temperature stand-by;Will be initial metallic aluminum dehydrated alcohol or acetone etc. organic molten Agent and deionized water cleaning, remove surface and oil contaminant and other impurities;Cleaned aluminum is completely immersed in above-mentioned oxidizing solution, Oxidation processes 20min.2)The aluminum after above-mentioned oxidation processes is taken out, deionized water is rinsed 3-5 time, is then placed in 180 DEG C Calorstat in carry out heat treatment 5h.3)Foamed aluminium material after oxidized etching, heat treatment is placed in into the sample of sputtering equipment On base, nanometer silver sputtering is carried out with silver-colored target, sputtering voltage is 1500 V, and electric current density is 1 mA/cm2, 1 Pa of operating air pressure, Sputtering time is 10 min. 4)Aluminum after sputtering dehydrated alcohol is rinsed 3-5 time, is then placed in 60 DEG C of calorstats 20 min, obtain final product electroporation electrodes structure.
Embodiment 3
A kind of preparation method of electroporation electrodes structure, step is, 1)By sodium hydroxide and Ammonium persulfate. be successively added to from Oxidizing solution is prepared in sub- water, the wherein concentration of sodium hydrate aqueous solution is 3mol/L, the sodium hydroxide and Ammonium persulfate. Molar concentration rate be 25:1, it is cooled to room temperature stand-by;Will be initial metallic foam copper dehydrated alcohol or acetone etc. organic Solvent and deionized water cleaning, remove surface and oil contaminant and other impurities;Cleaned foam copper is completely immersed in into above-mentioned oxidisability In solution, oxidation processes 10min.2)The copper product after above-mentioned oxidation processes is taken out, deionized water is rinsed 3-5 time, Ran Houfang Heat treatment 6h is carried out in entering 150 DEG C of calorstat.3)Foam copper product after oxidized etching, heat treatment is placed in into sputtering equipment Sample base on, nanometer silver sputtering is carried out with silver-colored target, sputtering voltage is 3000V, and electric current density is 0.5mA/cm2, work gas Pressure 5Pa, sputtering time is 3min.4)Foam copper product after sputtering is rinsed 3-5 time with dehydrated alcohol, then in 70 DEG C of constant temperature 10min is placed in case, electroporation electrodes structure is obtained final product.
Above example is only several in several preferred implementation of the invention, it is noted that be the invention is not restricted to Above-described embodiment;For the person of ordinary skill of the art, still can be to the technical scheme described in previous embodiment Modify, or equivalent is carried out to which part technical characteristic;And these modifications or replacement, do not make relevant art side The essence of case departs from the spirit and scope of claimed technical solution of the invention.

Claims (8)

1. a kind of preparation method of electroporation electrodes structure, it is characterised in that step is
1)At room temperature, metal material is immersed in oxidizing solution carries out oxide etch;
2)After metal material after oxide etch is rinsed, in being put in calorstat, heat treatment is carried out;
3)Metal material after heat treatment is carried out into nanometer silver sputtering;
4)Electrode structure after sputtering is cleaned, and then drying is placed in calorstat, is obtained electroporation electrodes structure.
2. preparation method according to claim 1, it is characterised in that the oxidizing solution is sodium hydroxide, persulfuric acid The mixture of ammonium and deionized water.
3. preparation method according to claim 1, it is characterised in that the molar concentration of the sodium hydroxide and Ammonium persulfate. Than being 20-30:1;The concentration of the sodium hydroxide is 2-3mol/L.
4. preparation method according to claim 1, it is characterised in that it is 10-30min that the time of decorations is carved in the oxidation.
5. preparation method according to claim 1, it is characterised in that the temperature of the heat treatment is 150-200 DEG C, at heat The reason time is 3-6h.
6. preparation method according to claim 1, it is characterised in that the sputtering voltage is 1000-3000V, electric current is close Spend for 0.5-2mA/cm2, operating air pressure 0-10Pa, sputtering time are 3-30min.
7. preparation method according to claim 1, it is characterised in that the drying temperature is 50-70 DEG C, and the time is 10- 30min。
8. the electrode structure that the preparation method according to any one of claim 1-7 is obtained is applied to water process sterilization.
CN201611114099.3A 2016-12-07 2016-12-07 Preparation method and application of electroporation electrode structure Active CN106517445B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611114099.3A CN106517445B (en) 2016-12-07 2016-12-07 Preparation method and application of electroporation electrode structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611114099.3A CN106517445B (en) 2016-12-07 2016-12-07 Preparation method and application of electroporation electrode structure

Publications (2)

Publication Number Publication Date
CN106517445A true CN106517445A (en) 2017-03-22
CN106517445B CN106517445B (en) 2021-05-25

Family

ID=58342463

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611114099.3A Active CN106517445B (en) 2016-12-07 2016-12-07 Preparation method and application of electroporation electrode structure

Country Status (1)

Country Link
CN (1) CN106517445B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112897650A (en) * 2021-04-25 2021-06-04 清华大学 Wastewater treatment device, preparation method thereof and wastewater treatment method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103219503A (en) * 2013-03-12 2013-07-24 北京理工大学 Combined electrode material and preparation method thereof
CN105514406A (en) * 2016-02-23 2016-04-20 陕西科技大学 Method for producing copper oxide nanowire array under room temperature
CN105513831A (en) * 2015-11-23 2016-04-20 北京化工大学 Electrode material in hollow tubular structure, and preparation method for electrode material
CN105540771A (en) * 2016-01-21 2016-05-04 清华大学 Electroporation disinfecting device, method and application of nanowire modified three-dimensional electrodes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103219503A (en) * 2013-03-12 2013-07-24 北京理工大学 Combined electrode material and preparation method thereof
CN105513831A (en) * 2015-11-23 2016-04-20 北京化工大学 Electrode material in hollow tubular structure, and preparation method for electrode material
CN105540771A (en) * 2016-01-21 2016-05-04 清华大学 Electroporation disinfecting device, method and application of nanowire modified three-dimensional electrodes
CN105514406A (en) * 2016-02-23 2016-04-20 陕西科技大学 Method for producing copper oxide nanowire array under room temperature

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAILONG HU等: "Highly enhanced field emission from CuO nanowire arrays by coating of carbon nanotube network film", 《VACUUM》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112897650A (en) * 2021-04-25 2021-06-04 清华大学 Wastewater treatment device, preparation method thereof and wastewater treatment method
CN112897650B (en) * 2021-04-25 2022-09-06 清华大学 Wastewater treatment device, preparation method thereof and wastewater treatment method

Also Published As

Publication number Publication date
CN106517445B (en) 2021-05-25

Similar Documents

Publication Publication Date Title
CN101962792B (en) Method for preparing pore diameter controllable through hole anodized aluminum oxide film
WO2004079051A1 (en) High electric field electrolysis cell
CN105712428A (en) Antimony-doped tin oxide-carbon nanotube compounded adsorptive electrode and preparation method thereof
CN104087970B (en) A kind of rich surface cupric oxide doped iridium dioxide Ni-Ti anode containing iridium dioxide and preparation method thereof
CN102418118A (en) Method for electrochemically aided preparation of silver powder with special form
CN112239203B (en) Electrochemical preparation method of porous graphene dispersion liquid
CN105088312A (en) Method for preparing titania nanotube allay films
CN106498478A (en) A kind of preparation method of transparent independent titanium dioxide nano-pipe array thin film
CN110071302A (en) A kind of titanium-based Asia titanium oxide bipolar plates and preparation method thereof
CN106517445A (en) Preparation method for electroporation electrode structure and application
CN207267816U (en) A kind of household electrical appliance, alternate electrodes sterilizing unit and sterilizing element
CN110526237B (en) Device and method for preparing noble metal/graphene composite nano material
CN104016450A (en) Device for treating difficultly degradable waste water through electro-Fenton method on basis of hydrogen peroxide generated on cathode
CN110980889A (en) Electrode and preparation method thereof
CN105195161A (en) Ti/TiO2NT/Yb-Fe2O3-PbO2 electrode and method for degrading paraquat through electro-catalysis
CN106045003A (en) Method for treating organic dyestuff wastewater with heterogeneous electric Fenton system
CN108298645A (en) Coated electrode and preparation method thereof suitable for desulfurization wastewater processing
CN106311258A (en) Preparation method of ferric vanadate photocatalysts
CN105121014A (en) Photocatalyst and production method for same
CN105734641B (en) A kind of preparation method of composite construction Nano tube array of titanium dioxide
CN103690974B (en) The preparation method of a kind of sterilizing unit and porous composite sheet thereof
CN113438789A (en) Flexible large-area glow discharge plasma disinfection and sterilization device
CN107337262A (en) A kind of method of oxygen impressed current anode catalyzing oxidizing degrading Organic Pollutants In Water under low-voltage
CN113321234A (en) Nano composite material, preparation method and application thereof
CN104944531B (en) A kind of method that Ti nano-electrodes efficiently remove nitrate in groundwater

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20210428

Address after: 266101 No. 1 Haier Road, Laoshan District, Shandong, Qingdao

Applicant after: QINGDAO HAIER SMART TECHNOLOGY R&D Co.,Ltd.

Applicant after: Haier Smart Home Co., Ltd.

Address before: 266101 No. 1 Haier Road, Laoshan District, Shandong, Qingdao

Applicant before: QINGDAO HAIER SMART TECHNOLOGY R&D Co.,Ltd.

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant