LU501768B1 - Metal-organic Frame/iron-manganese Composite Catalytic Membrane Electrode and Manufacturing Method Thereof - Google Patents
Metal-organic Frame/iron-manganese Composite Catalytic Membrane Electrode and Manufacturing Method Thereof Download PDFInfo
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- LU501768B1 LU501768B1 LU501768A LU501768A LU501768B1 LU 501768 B1 LU501768 B1 LU 501768B1 LU 501768 A LU501768 A LU 501768A LU 501768 A LU501768 A LU 501768A LU 501768 B1 LU501768 B1 LU 501768B1
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- manganese composite
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- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 21
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002033 PVDF binder Substances 0.000 claims abstract description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000004020 conductor Substances 0.000 claims abstract description 6
- 239000010865 sewage Substances 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000000614 phase inversion technique Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 6
- 244000005700 microbiome Species 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910002551 Fe-Mn Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000012982 microporous membrane Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000012736 patent blue V Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
- C02F1/4678—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction of metals
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
- C02F2001/46142—Catalytic coating
-
- 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
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- General Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
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- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a metal-organic framework/iron-manganese composite catalytic membrane electrode and a manufacturing method thereof. The manufacturing method comprises the following steps: synthesizing polycrystalline catalyst by hybrid loading of metal-organic framework and iron-manganese composite nanoparticles through graphene oxide, using polyvinylidene fluoride as the electrode membrane support layer and filter layer, and making phase inversion preparation with conductive material as the substrate. Wherein, the graphene oxide, the metal-organic framework and the iron-manganese composite nanoparticles are all prepared by chemical in-situ. The polycrystalline hybrid metal catalytic electrode membrane obtained by the invention can be coupled with a bioelectrochemical system to form a new M-BES system for electroreduction removal of heavy metal ions in sewage; At the same time, it can promote the active growth of electricity-producing microorganisms, improve the removal efficiency of organic pollution and improve the anti-pollution ability of the membrane.
Description
DESCRIPTION LU501768 Metal-organic Frame/iron-manganese Composite Catalytic Membrane Electrode and Manufacturing Method Thereof
TECHNICAL FIELD The invention belongs to the technical field of sewage purification and wastewater resource utilization, and particularly relates to a metal-organic frame/iron-manganese composite catalytic membrane electrode and a manufacturing method thereof.
BACKGROUND Microporous membranes can remove molecular organic pollutants from water. Microporous membrane is widely used because of its high organic matter removal rate. Using microporous membrane to remove heavy metal ions from wastewater has been facing technical challenges. Because the ionic radius of metals in water is much smaller than the molecular radius, it is difficult to separate them by microporous membrane.
Bio-electrochemical system (BES) can convert organic matter in wastewater into bio-electric energy by using anode electricity-producing microorganisms, which is transmitted to the cathode electrode through an external circuit, so that a self-energy electric field can be formed near the cathode. Combining membrane technology with BES is a research hotspot in recent years. Some research results have proved that using conductive film as membrane cathode can achieve good membrane pollution migration effect. The organic matter in the wastewater is far away from the membrane surface due to the micro-electric field, which ensures the stable flux of the membrane and has the characteristics of anti-pollution.
SUMMARY Aiming at the shortcomings of the prior art, the invention provides a metal-organic framework/iron-manganese composite catalytic membrane electrode and a manufacturing method thereof. The obtained catalytic electrode membrane can be coupled with a bioelectrochemical system for electroreduction and removal of heavy metal ions.
The specific technical scheme is as follows: One of the aims of the present invention is to provide a metal-organic framework/iron-manganese composite catalytic membrane electrode and manufacturing method thereof. The manufacturing method includes: synthesizing polycrystalline catalyst by hybrid loading of metal-organic framework (MOF) and iron-manganese composite nanoparticles through graphene oxide, using polyvinylidene fluoride (PVDF) as electrode membrane SUPPYt501768 layer and filter layer, and using conductive material as substrate for phase inversion preparation.
Wherein, the graphene oxide, the metal-organic framework and the iron-manganese composite nanoparticles are all prepared by chemical in-situ.
The invention develops a novel polycrystalline hybrid metal catalytic electrode membrane. By in-situ chemical reaction, the natural specific surface area and high porosity of graphene oxide are utilized, and iron-manganese nano hybrid crystals are nested into the copper metal framework, and then the hybridized metal crystals are loaded into the surface of graphene oxide membrane, and graphene oxide sheets are naturally filled to form the polycrystalline hybrid metal catalyst. The catalyst utilizes the micro-electric field generated by BES to electro-reduce the heavy metal ions in wastewater on the surface of metal film, thus realizing electro-reduction and removal of heavy metal ions. The reduced metal can improve the electron migration rate of the electrode film, trigger the micro-electric field to continuously strengthen naturally, and make the electro-reduction rate of heavy metals on the surface of the electrode film keep high efficiency. When the reduced heavy metals change the surface morphology of the electrode membrane, the pore size of the microporous membrane surface is laterally reduced, and the removal efficiency of organic matter is improved cooperatively.
Further, the preparation method of the polycrystalline hybrid metal catalytic electrode film comprises the following steps: (1) Strong oxidation of diacid to prepare graphene oxide; (2) Metal-organic framework (MOF) synthesized by copper-based metal coordination; (3) In-situ acidification of two components of ferromanganese to synthesize ferromanganese composite nanoparticles; (4) Preparing electrode film casting solution: mixing graphene oxide, metal-organic framework and iron-manganese composite nanoparticles with dimethylformamide to synthesize polycrystalline catalyst, Adding polyvinylidene fluoride (PVDF) and pore-forming agent; (5) Film making: coating a film on the conductive material substrate, and then curing the film by in-situ phase inversion method.
Furthermore, in step (1), K2,MnO4 and graphite powder are added into the mixed solution of H»SO4 and H:PO4 to prepare graphene oxide.
Specifically, step (1) can be realized under the following conditions: K,MnO4 and graphite powder are added into the mixed solution of H,SO4 and H;PO4 in an appropriate proportion, and, 501768 the mixture reacts at a certain temperature for 12h; Naturally cooling to room temperature, and pouring 30% H,O, and ice water; Centrifuge and wash with deionized water, HCI and ethanol in turn. After washing for many times, the remaining materials were solidified with diethyl ether, and the obtained suspension was filtered on a microfiltration membrane with an aperture of 0.45; Finally, the solid obtained on the filter is collected and dried in vacuum at room temperature for 24 hours, so as to obtain diacid exfoliated graphene oxide (DAOGO).
Furthermore, in step (2), the organic ligand is benzoic acid.
Specifically, step (2) can be realized under the following conditions: adding copper nitrate and benzoic acid in an appropriate proportion into deionized water, then adding the mixed solution into a reaction kettle, hydrothermally heating for 24h, naturally cooling to room temperature, collecting the precipitate, and cleaning with ethanol for several times to obtain sky blue crystals, which are MOF.
Furthermore, in step (3), acetic acid is added to ferroferric oxide nanoparticles and potassium permanganate to prepare iron-manganese composite nanoparticles.
Specifically, the step (3) can be realized under the following conditions: adding Fe304 nanoparticles and potassium permanganate in a proper proportion into a reaction kettle, dropping acetic acid at a constant speed, keeping the temperature at a proper temperature for 12 hours, naturally cooling to room temperature, and collecting the precipitate with a magnet to obtain the red-brown nanoparticle synthetic powder, namely Fe;O4-Fes:O; flower-like composite nanoparticles.
Furthermore, in step (4), the pore-forming agent is polyvinylpyrrolidone (PVP).
Polyvinylpyrrolidone (PVP) can form a composite pore-forming agent with the nanocrystals prepared above.
Specifically, step (4) can be realized under the following conditions: adding graphene oxide into dimethylformamide, and continuously stirring and dissolving until the lightly shaken solution has no particles attached to the cup wall; At this time, the previously prepared copper-based MOF and Fe-Mn composite nano-materials are respectively added into the mixed solution, and the mixture is continuously stirred evenly, the MOF and Fe-Mn composite nano-materials are complexed by the adsorption of MOF, and nano Fe-Mn composite crystals are naturally filled into the metal skeleton to form a polycrystalline hybrid metal mixed structure;
Then adding PVDF and PVP into the mixed solution, ultrasonically stirring until the solute (550 1768 completely dispersed, and then vacuum defoaming in a vacuum drying oven; To prevent the catalyst from settling, shake the bottle with an oscillator.
In step (4), the mass ratio of graphene oxide to dimethylformamide is preferably 1: (15-20); The mass ratio of graphene oxide, metal-organic framework and iron-manganese composite nanoparticles is 1: (0.5-1): (1-3).
Furthermore, in step (5), before coating the film, the magnetic polycrystalline catalyst is pulled to the surface of polyvinylidene fluoride by a magnet.
Furthermore, in step (5), the conductive material substrate is a carbon fiber conductive substrate.
Specifically, step (5) can be realized under the following conditions: adding a magnet above the deaerated electrode film casting solution to make the metal crystals in the casting solution fully suspend under the action of the magnetic field; Continuously coating a film on the conductive fiber substrate to control the film thickness; After coating, the flat film stays in the magnetic field for 30s, and the phase inversion process is completed in deionized water. After 24 hours of transformation, the flat membrane was cleaned with deionized water and then preserved by wet method.
The second object of the present invention is to provide a polycrystalline hybrid metal catalytic electrode membrane, which is obtained by the above preparation method.
After testing, the catalytic electrode film ORR of the polycrystalline hybrid metal catalytic electrode film was tested by cyclic voltammetry, and the cyclic voltammetry curve had obvious redox peak, which indicated that the catalyst had good catalytic performance for heavy metal reduction.
The third object of the present invention is to provide an application of the polycrystalline hybrid metal catalytic electrode membrane in sewage treatment, which is coupled with a bioelectrochemical system to form a new M-BES system for electro-reduction removal of heavy metal ions.
The new M-BES system has the advantages of electro-reduction of heavy metals, acceleration of ORR oxygen reduction rate, and reduction and recovery of heavy metals.
In the process of electro-reduction treatment of heavy metal wastewater by the new M-BES system mentioned above, organic matter is removed synchronously and electrochemically, which can promote each other. LU501768 In the invention, the copper ion removal performance test of the M-BES system is carried out: the polycrystalline hybrid metal catalytic electrode film is used as BES cathode and aluminum foil is used as anode; Inoculating electricity-producing microorganisms in anode chamber, acclimating anaerobic sludge; Experiments prove that the invention can effectively reduce heavy metal ions.
The invention has the following beneficial effects: According to the invention, the polycrystalline hybrid metal catalytic electrode membrane is prepared, which is used as a reduction site of heavy metals in a bioelectrochemical system (BES) and can effectively reduce heavy metal ions; and can significantly improve the electrochemical performance of BES and promote the active growth of electricity-producing microorganisms; Meanwhile, the removal efficiency of organic pollution can be improved, and the effluent quality can be greatly improved; The enhanced micro-electric field generated by BES itself can adsorb with positively charged heavy metal ions and electrostatically repel with negatively charged pollutants in sewage, which can improve the anti-pollution ability of membrane.
BRIEF DESCRIPTION OF THE FIGURES Fig. 1 is a cyclic voltammogram of a polycrystalline hybrid metal catalytic electrode film in a specific embodiment; Fig. 2 is a diagram of Cu?" electroreduction removal performance of polycrystalline hybrid metal catalytic electrode film in specific embodiment.
In Fig. 1, the abscissa represents voltage, unit V, ordinate represents current, unit A, scanning rate 0.01V/s, scanning cyclic voltammograms in 0.1mol/L CuSO4, MO and M4 are electrode films without catalysis and electrode films with catalyst respectively; In Fig. 2, the abscissa represents time, unit D, and the ordinate represents effluent concentration and removal efficiency, unit mg/L and%, and the influent concentration of copper sulfate is 200mg/L.
DESCRIPTION OF THE INVENTION The principles and features of the present invention are described below with examples, which are only used to explain the present invention, not to limit its scope.
1. Preparation of polycrystalline hybrid metal catalytic electrode membrane, comprising the following steps:
(1) Preparation of DAOGO (graphene oxide stripped by diacid): add 12.0g of K,MnO4 and = 1768
2.0g of graphite powder to 200ml mixed solution of H>SOsand H3PO4 (the volume ratio of H»SO4 solution to H3PO4 solution is 9:1), the concentration of H,SO4 solution is 98.6wt%%, and that of H:PO4 solution is 85.5wt%; Stir vigorously at 50°C for 12 hours, and naturally cool to room temperature; Pour 300mL ice deionized water and 2ml 30% H>0O»; 150mL deionized water, 150mL 30% HCI and 150 ml ethanol were used for centrifugal washing in turn; After washing for many times, the remaining materials were solidified with 200mL ether, and the obtained suspension was filtered on PTFE membrane with aperture of 0.45um; Collecting the solid obtained on the filter membrane and vacuum drying at room temperature for 24h to obtain DAOGO (double acid stripping graphene oxide).
(2) Copper-based metal coordination synthesis of MOF (metal-organic framework): accurately weigh 0.53g of copper nitrate and 0.26g of benzoic acid, mix and add them into 20mL of deionized water, ultrasonically vibrate for 10min, add the mixed solution into a 100mL reaction kettle, heat it in a vacuum drying oven at 80°C for 24 hours, naturally cool it to room temperature, vacuum filter and collect the precipitate, clean it with ethanol several times, and naturally dry it to obtain sky blue crystals, which is MOF.
(3) In-situ acidification of ferromanganese to synthesize ferromanganese composite nanoparticles: accurately weigh 0.12g of ferroferric oxide nanoparticles and 0.20g of potassium permanganate into SOmL deionized water, ultrasonically vibrate for 20 minutes, then put the mixed solution into a 100mL stainless steel reaction kettle, drop ImL acetic acid at a constant speed, heat it in a vacuum drying oven at 120°C for 12 hours, naturally cool it to room temperature, and collect the precipitate with a magnet. Cleaning with deionized water and ethanol for several times, drying in a drying oven at 60°C for 5 hours, and obtaining red-brown nanoparticle synthetic powder, which is Fe;Os-manganese dioxide flower-shaped composite nanoparticle.
(4) Preparation of electrode film casting solution: put 16.95g of dimethylformamide (DMF) into a 100mL conical flask, and add 1.00g of DAOGO obtained in step (1); To prevent DMF from volatilization, the conical flask was sealed with sealing film, and the sealed conical flask was put into an ultrasonic vibration device to vibrate for 12 hours, and no particles attached to the cup wall in the gently shaking solution; At this time, 0.50g and 1.00g of MOF obtained in step (2) and Fe-Mn composite nanoparticles obtained in step (3) are respectively weighed into the casting solution, stirred for 6h by a mechanical stirrer, and the MOF and Fe-Mn composite, 1768 nanocrystals are complexed together by the adsorption of metal skeleton; Then weigh
2.40gPVDF and 0.40g PVP respectively, and put the conical flask containing the mixed solution into an ultrasonic vibration device to vibrate for 12 hours to completely disperse the solute; Putting the evenly dispersed casting solution into a vacuum drying oven for vacuum defoaming for 2h; In order to prevent catalyst precipitation in the casting solution, shake the bottle with the aid of an oscillator.
(5) Magnetic suspension film making: the magnetic poles are used to pull the metal crystals in the film casting solution, so that the catalytic crystals in the film casting solution are fully suspended under the action of the magnetic field. Wash and dry 130g/m 2 carbon fiber conductive substrate with acetone and ethanol, and flatten the pressing surface of the flat scraping plate; The film coating is completed with a film scraper and a film scraper, the film scraper is set with a film thickness of 300um, the film casting solution is poured into the film casting tank, and the film coating is started at a film coating speed of 0.5 m/min; After coating, the scraping plate stays in the air for 30s, and during the stay, the catalyst is pulled on the surface of the scraping plate by magnetic poles; Quickly putting the prepared flat film into deionized water to complete the phase inversion process; After 24 hours of transformation, the flat membrane was cleaned by deionized water and then preserved by wet method to obtain the polycrystalline hybrid metal catalytic electrode membrane.
2. Examine the electro-reduction performance of heavy metals of the polycrystalline hybrid metal catalytic electrode membrane: The ORR of catalytic electrode film was tested by cyclic voltammetry at a scanning speed of 0.01V/s, and the electrode film with and without catalyst was characterized by cyclic voltammetry in 0.1mol/L copper sulfate solution, respectively. The results are shown in Fig. 1. It can be seen from Fig. 1 that the cyclic voltammetry curve has obvious redox peak, which shows that the catalyst has good catalytic performance for heavy metal reduction.
3. Coupling the polycrystalline hybrid metal catalytic electrode membrane with a bioelectrochemical system, and testing the removal performance of copper ions: Polycrystalline hybrid metal catalytic electrode film is BES cathode and aluminum foil is anode. Inoculating electricity-producing microorganisms in anode chamber, acclimating anaerobic sludge; The 800mg/L COD wastewater prepared by BES enters the water from the anode, and the electricity generation starts to test smoothly. 200mg/L CuSO4 solution Wit 1501768 prepared as simulated copper-containing wastewater, which was directly connected from the cathode, and the water quality of heavy metal raw water and effluent from BES cathode was analyzed. The experimental results are shown in Fig. 2. As shown in Fig. 2, the polycrystalline hybrid metal catalytic electrode membrane can effectively reduce heavy metal ions.
What has been described above is only the preferred embodiment of the present invention, and it is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of protection of the present invention.
Claims (10)
1. A metal-organic framework/iron-manganese composite catalytic membrane electrode and manufacturing method thereof, which is characterized in that the preparation method includes: synthesizing polycrystalline catalyst by hybrid loading of metal-organic framework (MOF) and iron-manganese composite nanoparticles through graphene oxide, using polyvinylidene fluoride (PVDF) as electrode membrane support layer and filter layer, and using conductive material as substrate for phase inversion preparation.
2. The preparation method according to claim 1, which is characterized in that the graphene oxide, the metal-organic framework and the iron-manganese composite nanoparticles are all prepared by chemical in-situ.
3. The preparation method according to claim 1 or 2, which is characterized by comprising the following steps: (1) strong oxidation of diacid to prepare graphene oxide; (2) metal-organic framework (MOF) synthesized by copper-based metal coordination; (3) in-situ acidification of two components of ferromanganese to synthesize ferromanganese composite nanoparticles; (4) preparing electrode film casting solution: mixing graphene oxide, metal-organic framework and iron-manganese composite nanoparticles with dimethylformamide to synthesize polycrystalline catalyst; adding polyvinylidene fluoride (PVDF) and pore-forming agent; (5) film making: coating a film on the conductive material substrate, and then curing the film by in-situ phase inversion method.
4. The preparation method according to claim 3, which is characterized in that in step (1), K2MnO4 and graphite powder are added into the mixed solution of H:SO4 and H3PO4 to prepare graphene oxide.
5. The preparation method according to claim 3, which is characterized in that in step (2), the organic ligand is benzoic acid.
6. The preparation method according to claim 3, which is characterized in that in step (3), acetic acid is added to ferroferric oxide nanoparticles and potassium permanganate to prepare iron-manganese composite nanoparticles.
7. The preparation method according to claim 3, which is characterized in that in step (4), the pore-forming agent 1s polyvinylpyrrolidone (PVP).
8. The preparation method according to claim 3, which is characterized in that in step Fuso 1768 before coating the film, the magnetic polycrystalline catalyst is pulled to the surface of polyvinylidene fluoride by a magnet.
9. A polycrystalline hybrid metal catalytic electrode membrane, which is obtained by the preparation method according to any one of claims 1-8.
10. An application of the polycrystalline hybrid metal catalytic electrode membrane according to claim 9 in sewage treatment, which is characterized in that the polycrystalline hybrid metal catalytic electrode membrane is coupled with a bioelectrochemical system to form a new M-BES system for electro-reduction removal of heavy metal ions.
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