CN106139933A - A kind of preparation method of reactive electrochemical cathode film - Google Patents

A kind of preparation method of reactive electrochemical cathode film Download PDF

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Publication number
CN106139933A
CN106139933A CN201610485479.1A CN201610485479A CN106139933A CN 106139933 A CN106139933 A CN 106139933A CN 201610485479 A CN201610485479 A CN 201610485479A CN 106139933 A CN106139933 A CN 106139933A
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film
high molecular
molecular polymer
organic high
preparation
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CN106139933B (en
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李晓惠
吴丽红
田亚赛
杨芳
兴虹
许艳广
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Liaoning Institute of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/005—Combined electrochemical biological processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/263—Chemical reaction
    • B01D2311/2634—Oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/16—Membrane materials having positively charged functional groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention discloses the preparation method of a kind of reactive electrochemical cathode film, relate to electro-catalytic composite membrane field.The method includes: with polyacrylonitrile-based carbon fibre cloth as substrate, and macromolecule organic polymer is membrane matrix, and graphene oxide is for being blended filler, by blended immersion precipitation phase inversion process masking, by wet dip load iron ion in film after film forming.In film, the iron ion of load is as the Fe of film electricity Fenton integration coupled system2+Source also realizes Fe by the nagative potential on film negative electrode2+Original position electroreduction regeneration, utilize polyacrylonitrile-based carbon fibre cloth in Modified Membrane two electronics oxygen reduction cathode electric catalyticing characteristics be film electricity Fenton integration coupled system provide H2O2Source, thus realize inert organic high molecular polymer the being electrochemically reacted property of film that insulate modified, become conventional homogeneous electricity Fenton into the out-phase electricity Fenton occurred in film.The inventive method is simple, and solving the tradition electricity former water of Fenton needs a large amount of acid addings, adds Fe2+Technological deficiency.

Description

A kind of preparation method of reactive electrochemical cathode film
Technical field
The present invention relates to electro-catalytic composite membrane material field, more particularly relate to the system of a kind of reactive electrochemical cathode film Preparation Method.
Background technology
Embrane method is described as 21 century the most promising water technology, but embrane method has two aspects in the treatment of waste water at present Application limitation: one is membrane pollution problem, for decelerating membrane pollution, it is necessary to carry out film intermittent the most clear Wash, accelerate the loss of film, add operation and operating cost；Two is poisonous and hazardous in process municipal wastewater or industrial wastewater The organic efficiency of difficult degradation thing is low.
Reactive electrochemical cathode film can be by electric field to electronegative pollutant electrophoresis repulsive interaction and negative electrode electricity Catalysis produces two kinds of mechanism of action such as oxidation and antibacterial action of hydrogen peroxide and realizes the control to fouling membrane.Meanwhile, electro-catalysis Cathodic coating can have Fe2+In the presence of form film-electricity Fenton system, build membrance separation-Advanced oxidation technologies and couple skill Art, thus improve the removal effect of hazardous contaminant in water.But, current existing reactive electrochemical cathode film is Ensure electricity Fenton degraded water pollutant, need lasting in former water to add appropriate Fe2+, and former water ph value need to be adjusted to acid Property is to ensure Fe2+Stability in water, so its water outlet to add alkali further and neutralizes and remove Fe3+, this process can produce ferrum Mud also causes certain Environmental Residues.
Summary of the invention
The present invention provides the preparation method of a kind of reactive electrochemical cathode film, prepared reactive electrochemical cathode film Can be at neutral pH, former water without additionally adding Fe2+Under conditions of occur electricity Fenton effect.
The present invention provides the preparation method of a kind of reactive electrochemical cathode film, comprises the following steps:
(1) immersion precipitation phase inversion process masking:
Graphene oxide and organic high molecular polymer are dissolved in organic solvent successively formation casting solution is blended, described The quality of graphene oxide is the 0.5%-10% of organic high molecular polymer quality, the quality of described organic high molecular polymer For organic high molecular polymer and the 9%-17% of organic solvent quality sum, with polyacrylonitrile-based carbon fibre cloth as substrate, One layer of blended casting solution is uniformly scraped on polyacrylonitrile-based carbon fibre cloth surface, after placing 15-30s, is placed in inversion of phases in coagulating bath and becomes Film, obtains the organic high molecular polymer composite membrane that Graphene is modified；
(2) load iron ion Fe3+:
The organic high molecular polymer composite membrane that the Graphene prepared is modified is immersed in strong alkali solution, during immersion Between be 3-12h, it be neutral for cleaning organic high molecular polymer composite membrane to pH value afterwards, and the organic polymer after cleaning is polymerized Thing composite membrane is immersed in Fe3+In solution, soak time is 4-24h, utilizes Graphene to Fe3+Chelating properties realize to Fe3+'s Load in film, cleans and has loaded Fe3+Organic high molecular polymer composite membrane to achromaticity and clarification；
(3) reduction Fe3+For Fe2+:
To have loaded Fe3+Organic high molecular polymer composite membrane be negative electrode, apply applied voltage, control cathode potential For-0.5--1.0V, the persistent period is 10-20min, forms load Fe2+Electrochemical cathode film.
Preferably, being blended in casting solution and be also added with perforating agent, the quality of perforating agent is organic high molecular polymer quality 1-5%.
Preferably, perforating agent is polyvinylpyrrolidone, LiCl, NH4One in Cl and Polyethylene Glycol.
Preferably, the one during organic high molecular polymer is Kynoar, polysulfones, polyether sulfone, polyacrylonitrile.
Preferably, organic solvent is N-Methyl pyrrolidone or DMF.
Preferably, in immersion precipitation phase inversion process masking step, use blade applicator equal on pan based fibers cloth surface Even scraping one layer of blended casting solution, the thickness that casting solution is blended is 150-300 μm.
Preferably, OH in strong alkali solution—Concentration is 0.01-2mol/L.
Preferably, Fe3+Solution concentration is 0.01-2mol/L.
In the present invention, the inert organic high molecular polymer membrane modifying that insulate for having membrance separation and out-phase electricity Fenton one concurrently The reactive electrochemistry filter membrane of body coupling, method is simple, technical feasibility, economical rationality.It has an advantage that collection membrane technology Being integrated with electricity Fenton technology, film also serves as two electricity of out-phase electricity Fenton effect while playing ultrafiltration or microfiltration separation function Son aoxidizes former negative electrode and Fe2+Source, former water is without additionally adding acid and iron ion, and solving the tradition electricity former water of Fenton needs to add in a large number Acid, add Fe2+Technological deficiency；The water mode of crossing of membrane filtration makes film negative electrode run with the form of porous flow guiding electrode, this operation side Formula can be strengthened effectively the contacting of dissolved oxygen and membrane electrode, improve the dissolved oxygen mass-transfer efficiency at electrode surface, improves electricity Fenton Hydrogen peroxide formation efficiency；The electrophoresis of film negative electrode and electrostatic repulsion and electricity Fenton effect can significant decelerating membrane pollutions And improve contaminant removal efficiency.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to Other accompanying drawing is obtained according to these accompanying drawings.
The reactive electrochemical cathode film fundamental diagram that Fig. 1 provides for the embodiment of the present invention 1；
The reactive electrochemical cathode film of the unsupported iron ion that Fig. 2 provides for the embodiment of the present invention 1 powers up outside difference Pressure catalysis generates hydrogen peroxide situation map；
The Inlet and outlet water ultraviolet of the reactive electrochemical cathode membrane degradation rhodamine B that Fig. 3 provides for the embodiment of the present invention 1-can See spectrogram；
Inlet and outlet water COD pair of the reactive electrochemical cathode membrane degradation rhodamine B of figure that Fig. 4 provides for the embodiment of the present invention 1 Than figure；
Applying that Fig. 5 provides for the embodiment of the present invention 1 and reactivity electrochemical cathode film application when not applying applied voltage Variations of flux trendgram in MBR (membrane bioreactor)；
Applying that Fig. 6 provides for the embodiment of the present invention 1 and reactivity electrochemical cathode film application when not applying applied voltage Figure is changed in the Inlet and outlet water COD of MBR (membrane bioreactor).
Detailed description of the invention
Embodiment 1
The embodiment of the present invention 1 provides the preparation method of a kind of reactive electrochemical cathode film, comprises the following steps:
(1) immersion precipitation phase inversion process masking:
Graphene oxide (GO), polyvinylpyrrolidone (PVP) and Kynoar (PVDF) are dissolved in N-first successively Being formed in base ketopyrrolidine (NMP) and casting solution is blended, wherein, the quality of graphene oxide (GO) is Kynoar (PVDF) matter The 5% of amount, the quality of Kynoar (PVDF) is Kynoar (PVDF) and N-Methyl pyrrolidone (NMP) quality sum 11%, the quality of polyvinylpyrrolidone (PVP) is the 4% of Kynoar (PVDF) quality；Fine with polyacrylonitrile-based carbon Wei Bu is substrate, uniformly scrapes the blended casting solution of one layer of 200 μ m-thick on polyacrylonitrile-based carbon fibre cloth surface with film applicator, places After 20s, with water for coagulating bath phase under room temperature, convert 1h film forming, film is immersed in 24h in water and, to remove residual solvent, obtains stone The organic high molecular polymer composite membrane that ink alkene is modified.
(2) load iron ion Fe3+:
The organic high molecular polymer composite membrane that the Graphene prepared is modified is immersed in 1mol/L NaOH solution, Soak time is 6h, and it is neutral for cleaning organic high molecular polymer composite membrane to pH value afterwards, the organic polymer after cleaning Composite membrane of polymer is immersed in 1mol/L Fe3+In solution, soak time is 8h, utilizes Graphene to Fe3+Chelating properties real Now to Fe3+Film in load, clean loaded Fe3+Organic high molecular polymer composite membrane to achromaticity and clarification.
(3) reduction Fe3+For Fe2+:
To have loaded Fe3+Organic high molecular polymer composite membrane be negative electrode, apply applied voltage, control cathode potential For-0.5--1.0V, the persistent period is 10-20min, forms load Fe2+Reactive electrochemical cathode film.
The reactive electrochemical cathode film prepared is soaked in 0.5% formaldehyde and preserves.
Wherein, load iron ion Fe3+Step in, use low concentration strong base solution, the longest soak time, adopt Use high concentration strong base solution, then can use less soak time；Equally, the Fe of low concentration is used3+Solution, the longest leaching The bubble time, use high concentration Fe3+Solution, then can use less soak time.
By unsupported Fe3+Modified composite membrane clear water rinse after be mounted to membrane module with sheet frame form, composite membrane be the moon Pole, polyacrylonitrile-based carbon fibre cloth is anode, and electrode spacing 1cm, with the Na of 0.05mol/L2SO4Solution is former water, and aeration rate is 150L/h, is run in membrane filtration mode by pump negative pressure-pumping, and membrane flux is 100L/m2H, in the range of voltage 1.5-3.0V, Water outlet concentration of hydrogen peroxide is the most in rising trend with voltage increase, as shown in Figure 2.
Fe will be loaded3+Composite membrane component be placed in containing 0.05mol/L Na2SO4And in the former water of 40mg/L rhodamine B, Ibid, control cathode potential under not water yielding condition is-1.0V to film assembling mode, and persistent period 10min, by Fe3+Prereduction is Fe2+.Controlling water outlet membrane flux is 20L/m2H, aeration rate is 150L/h, and controlling applied voltage respectively is 2.0V and 3.0V.As Shown in Fig. 1, oxygen in water is transported to polyacrylonitrile-based carbon fibre cloth (Fig. 1 upper strata) surface with water outlet and diffusion, Polyacrylonitrile carbon fiber cloth surface occurs two electronics oxidation original work to generate H2O2, H2O2With PVDF/GO composite membrane (Fig. 1 lower floor) The Fe of interior load2+Fenton effect occurs, and the OH that Fenton effect produces changes with the rhodamine B (Fig. 1 " P ") in former water Learn advanced oxidation reaction (Fig. 1 " AOP "), by rhodamine B mineralising or be decomposed into middle little molecular product (Fig. 1 " Pm"), Fenton The Fe that reaction generates3+It is Fe that tunicle negative electrode synchronizes electroreduction2+Realize in-situ regeneration.Rhodamine B is at 2.0V and 3.0V applied voltage Under percent of decolourization can reach 58.3% and 74.5%, as shown in Figure 3；COD clearance (mineralization rate) respectively reaches 19.6% He 14.7%, as shown in Figure 4.
By two groups of load Fe3+Composite membrane component parallel be placed in MBR (membrane bioreactor), one group at 2V applied voltage Under power up operation, one group of not powered operation (matched group), the operation result of 20d shows, powers up the film of operation relative to not powered Matched group there is more preferable antifouling property, as it is shown in figure 5, two groups of membrane module water outlet COD comparing results show to go out at Yuan Shui Power up operation film during existing impact load and can guarantee that the stability of effluent quality, as shown in Figure 6.
Embodiment 2
The embodiment of the present invention 2 provides the preparation method of a kind of reactive electrochemical cathode film, comprises the following steps:
(1) immersion precipitation phase inversion process masking:
It is dissolved in graphene oxide (GO) and polysulfones successively in N,N-dimethylformamide (DMF) to be formed and casting film is blended Liquid, wherein, quality is polysulfones quality the 0.5% of graphene oxide (GO), the quality of polysulfones is polysulfones and N, N-dimethyl methyl The 17% of amide (DMF) quality sum；With polyacrylonitrile-based carbon fibre cloth as substrate, with film applicator at polyacrylonitrile-based carbon fibre The blended casting solution of one layer of 150 μ m-thick is uniformly scraped on cloth surface, after placing 15s, with water for coagulating bath phase under room temperature, converts 1h and becomes Film, is immersed in film 24h in water and, to remove residual solvent, obtains the organic high molecular polymer composite membrane that Graphene is modified.
(2) load iron ion Fe3+:
The organic high molecular polymer composite membrane that the Graphene prepared is modified is immersed in 0.01mol/L KOH solution In, soak time is 12h, and it is neutral for cleaning organic high molecular polymer composite membrane to pH value, the organic polymer after cleaning Composite membrane of polymer is immersed in 0.01mol/L Fe3+In solution, soak time is 24h, utilizes Graphene to Fe3+Chelating special Property realize to Fe3+Film in load, clean loaded Fe3+Organic high molecular polymer composite membrane to achromaticity and clarification.
(3) reduction Fe3+For Fe2+:
To have loaded Fe3+Organic high molecular polymer composite membrane be negative electrode, apply applied voltage, control cathode potential For-0.5--1.0V, the persistent period is 10-20min, forms load Fe2+Reactive electrochemical cathode film.
The reactive electrochemical cathode film prepared is soaked in 0.5% formaldehyde and preserves.
Embodiment 3
The embodiment of the present invention 3 provides the preparation method of a kind of reactive electrochemical cathode film, comprises the following steps:
(1) immersion precipitation phase inversion process masking:
It is dissolved in graphene oxide (GO), LiCl and polyether sulfone successively in N-Methyl pyrrolidone (NMP) to be formed and is blended Casting solution, wherein, quality is polyether sulfone quality the 10% of graphene oxide (GO), the quality of polyether sulfone is polyether sulfone and N-first The 9% of base ketopyrrolidine (NMP) quality sum, the quality of LiCl is the 1% of polyether sulfone quality；With polyacrylonitrile-based carbon fibre cloth For substrate, uniformly scrape the blended casting solution of one layer of 300 μ m-thick on polyacrylonitrile-based carbon fibre cloth surface with film applicator, place 30s After, with water for coagulating bath phase under room temperature, convert 1h film forming, film is immersed in 24h in water and, to remove residual solvent, obtains Graphene Modified organic high molecular polymer composite membrane.
(2) load iron ion Fe3+:
The organic high molecular polymer composite membrane that the Graphene prepared is modified is immersed in 2mol/L NaOH solution, Soak time is 3h, and it is neutral for cleaning organic high molecular polymer composite membrane to pH value, the organic polymer polymerization after cleaning Thing composite membrane is immersed in 2mol/L Fe3+In solution, soak time is 4h, utilizes Graphene to Fe3+Chelating properties realize right Fe3+Film in load, clean loaded Fe3+Organic high molecular polymer composite membrane to achromaticity and clarification.
(3) reduction Fe3+For Fe2+:
To have loaded Fe3+Organic high molecular polymer composite membrane be negative electrode, apply applied voltage, control cathode potential For-0.5--1.0V, the persistent period is 10-20min, forms load Fe2+Reactive electrochemical cathode film.
The reactive electrochemical cathode film prepared is soaked in 0.5% formaldehyde and preserves.
Although preferred embodiments of the present invention have been described, but those skilled in the art once know basic creation Property concept, then can make other change and amendment to these embodiments.So, claims are intended to be construed to include excellent Select embodiment and fall into all changes and the amendment of the scope of the invention.
Obviously, those skilled in the art can carry out various change and the modification essence without deviating from the present invention to the present invention God and scope.So, if these amendments of the present invention and modification belong to the scope of the claims in the present invention and equivalent technologies thereof Within, then the present invention is also intended to comprise these change and modification.

Claims (8)

1. the preparation method of a reactive electrochemical cathode film, it is characterised in that comprise the following steps:
(1) immersion precipitation phase inversion process masking:
Graphene oxide and organic high molecular polymer are dissolved in organic solvent successively formation casting solution, described oxidation are blended The quality of Graphene is the 0.5%-10% of organic high molecular polymer quality, and the quality of described organic high molecular polymer is for having Machine high molecular polymer and the 9%-17% of organic solvent quality sum, with polyacrylonitrile-based carbon fibre cloth as substrate, poly-third One layer of blended casting solution is uniformly scraped on alkene itrile group carbon cloth surface, after placing 15-30s, is placed in inversion of phases film forming in coagulating bath, To the organic high molecular polymer composite membrane that Graphene is modified；
(2) load iron ion Fe3+:
Being immersed in strong alkali solution by the organic high molecular polymer composite membrane that the Graphene prepared is modified, soak time is 3-12h, it is neutral for cleaning organic high molecular polymer composite membrane to pH value afterwards, and the organic high molecular polymer after cleaning is multiple Close film and be immersed in Fe3+In solution, soak time is 4-24h, utilizes Graphene to Fe3+Chelating properties realize to Fe3+Film in Load, cleans and has loaded Fe3+Organic high molecular polymer composite membrane to achromaticity and clarification；
(3) reduction Fe3+For Fe2+:
To have loaded Fe3+Organic high molecular polymer composite membrane be negative electrode, apply applied voltage, control cathode potential be- 0.5--1.0V, the persistent period is 10-20min, forms load Fe2+Electrochemical cathode film.
The preparation method of a kind of reactive electrochemical cathode film the most according to claim 1, it is characterised in that described blended Being also added with perforating agent in casting solution, the quality of described perforating agent is the 1-5% of described organic high molecular polymer quality.
The preparation method of a kind of reactive electrochemical cathode film the most according to claim 2, it is characterised in that described drilling Agent is polyvinylpyrrolidone, LiCl, NH4One in Cl and Polyethylene Glycol.
The preparation method of a kind of reactive electrochemical cathode film the most according to claim 1, it is characterised in that described organic High molecular polymer is the one in Kynoar, polysulfones, polyether sulfone, polyacrylonitrile.
The preparation method of a kind of reactive electrochemical cathode film the most according to claim 1, it is characterised in that described organic Solvent is N-Methyl pyrrolidone or N,N-dimethylformamide.
The preparation method of a kind of reactive electrochemical cathode film the most according to claim 1, it is characterised in that described submergence In precipitated phase conversion method masking step, blade applicator is used uniformly to scrape one layer of blended casting solution on pan based fibers cloth surface, The thickness that casting solution is blended is 150-300 μm.
The preparation method of a kind of reactive electrochemical cathode film the most according to claim 1, it is characterised in that described highly basic OH in property solution—Concentration is 0.01-2mol/L.
The preparation method of a kind of reactive electrochemical cathode film the most according to claim 1, it is characterised in that described Fe3+ Solution concentration is 0.01-2mol/L.
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CN107008156A (en) * 2017-04-21 2017-08-04 中国科学院生态环境研究中心 Graphene filtering composite membrane and preparation method thereof
CN107473364A (en) * 2017-08-01 2017-12-15 大连海事大学 A kind of Fenton fluid bed catalytic type filler and preparation method thereof
CN108927228A (en) * 2018-08-07 2018-12-04 哈尔滨工业大学 A kind of preparation method of carbon cloth load type Fenton catalyst
CN109809531A (en) * 2019-03-01 2019-05-28 吉林师范大学 A kind of preparation and regeneration method of the iron solvay-type carbon film gas-diffusion electrode applied to Fenton system
CN110255672A (en) * 2018-06-28 2019-09-20 武汉纺织大学 electro-Fenton cathode membrane material with aeration function and preparation method and application thereof
CN112023714A (en) * 2020-07-21 2020-12-04 东华大学 Functional carbon fiber membrane capable of adsorbing and degrading micro-plastic and preparation method thereof

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CN104941464A (en) * 2015-06-29 2015-09-30 天津工业大学 Catalytic hollow fiber membrane and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106587277A (en) * 2016-12-05 2017-04-26 南京理工大学 Carbon black-nanometer iron oxide/polytetrafluoroethylene heterogeneous tubular membrane electrode
CN107008156A (en) * 2017-04-21 2017-08-04 中国科学院生态环境研究中心 Graphene filtering composite membrane and preparation method thereof
CN107008156B (en) * 2017-04-21 2019-12-03 中国科学院生态环境研究中心 Graphene filters composite membrane and preparation method thereof
CN107473364A (en) * 2017-08-01 2017-12-15 大连海事大学 A kind of Fenton fluid bed catalytic type filler and preparation method thereof
CN107473364B (en) * 2017-08-01 2021-05-28 大连海事大学 Catalytic filler for Fenton fluidized bed and preparation method thereof
CN110255672A (en) * 2018-06-28 2019-09-20 武汉纺织大学 electro-Fenton cathode membrane material with aeration function and preparation method and application thereof
CN110255672B (en) * 2018-06-28 2022-05-13 武汉纺织大学 electro-Fenton cathode membrane material with aeration function and preparation method and application thereof
CN108927228A (en) * 2018-08-07 2018-12-04 哈尔滨工业大学 A kind of preparation method of carbon cloth load type Fenton catalyst
CN109809531A (en) * 2019-03-01 2019-05-28 吉林师范大学 A kind of preparation and regeneration method of the iron solvay-type carbon film gas-diffusion electrode applied to Fenton system
CN109809531B (en) * 2019-03-01 2021-11-09 吉林师范大学 Preparation and regeneration method of iron-complexing type carbon film electro-Fenton cathode
CN112023714A (en) * 2020-07-21 2020-12-04 东华大学 Functional carbon fiber membrane capable of adsorbing and degrading micro-plastic and preparation method thereof
CN112023714B (en) * 2020-07-21 2021-06-18 东华大学 Functional carbon fiber membrane capable of adsorbing and degrading micro-plastic and preparation method thereof

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