CN105428663B - Microbial fuel cell electrode with photocatalysis synergistic effect and preparation method and application thereof - Google Patents
Microbial fuel cell electrode with photocatalysis synergistic effect and preparation method and application thereof Download PDFInfo
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- CN105428663B CN105428663B CN201510924408.2A CN201510924408A CN105428663B CN 105428663 B CN105428663 B CN 105428663B CN 201510924408 A CN201510924408 A CN 201510924408A CN 105428663 B CN105428663 B CN 105428663B
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- carbon cloth
- tourmaline
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- fuel cell
- sputtering
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 55
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 27
- 239000000446 fuel Substances 0.000 title claims abstract description 23
- 230000000813 microbial effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002195 synergetic effect Effects 0.000 title abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 72
- 239000004744 fabric Substances 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000011032 tourmaline Substances 0.000 claims abstract description 32
- 229940070527 tourmaline Drugs 0.000 claims abstract description 32
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 32
- 239000011812 mixed powder Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 30
- 229910052719 titanium Inorganic materials 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 24
- 238000004544 sputter deposition Methods 0.000 claims description 22
- 238000003760 magnetic stirring Methods 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 230000002079 cooperative effect Effects 0.000 claims description 13
- 239000004065 semiconductor Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
- 229910002114 biscuit porcelain Inorganic materials 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000007590 electrostatic spraying Methods 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005477 sputtering target Methods 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005421 electrostatic potential Methods 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000010802 sludge Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 1
- 244000005700 microbiome Species 0.000 abstract description 13
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000005616 pyroelectricity Effects 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 4
- 230000001808 coupling effect Effects 0.000 abstract 1
- 230000004298 light response Effects 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000002906 microbiologic effect Effects 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002163 immunogen Effects 0.000 description 1
- -1 isopropyl Ester Chemical class 0.000 description 1
- 229940098458 powder spray Drugs 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
-
- 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
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/009—Apparatus with independent power supply, e.g. solar cells, windpower or fuel cells
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- 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
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
A microbial fuel cell electrode with a photocatalytic synergistic effect and a preparation method and application thereof comprise a carbon cloth support body, a tourmaline and reducing substance mixed powder layer and a modified photocatalytic material, wherein the tourmaline and reducing substance mixed powder layer is attached to the outer surface of the carbon cloth support body, and the modified photocatalytic material is attached to the surface of the tourmaline and reducing substance mixed powder layer. The microorganism and the photocatalyst in the electrode have a coupling effect in the process of degrading wastewater; the modified photocatalyst has visible light response, so that the limitation of the use condition of the photocatalyst is greatly reduced; the tourmaline has pyroelectricity and piezoelectricity, can generate permanent weak current, and under the action of the current, the service life of a hole-electron pair generated on the surface of the photocatalytic material is prolonged, and the photocatalytic efficiency is improved. In addition, the mixed powder of the tourmaline and the reducing substance can effectively relieve the transfer of hole-electron or oxidizing ion generated by photocatalysis to a biological membrane so as to ensure the microbial activity.
Description
Technical field
The present invention relates to microbiological fuel cell technology and photocatalysis technology field, and in particular to one kind tool photocatalysis collaboration
Effect electrode of microbial fuel cell and its preparation method and application.
Background technology
Environmental problem and energy problem seriously affect the life and economic development of people at present, environmental problem getting worse,
Energy shortage also becomes urgent problem to be solved.Microbiological fuel cell（MFC）It can be produced electricity again at the same time as a kind of wastewater treatment
Technology, favored be subject to numerous researchers.MFC reaction conditions are gentle, other energy need not be provided in reaction process, and without dirt
Thing generation is contaminated, is a kind of water technology with Significance of Sustainable Development.
Microbiological fuel cell is under conditions of anoxic, using microorganism by the electron transmission of organic matter to anode, so
Afterwards power generation is realized by being transferred to cathode.But degraded of the microorganism to organic matter has selectivity, has to organic molecule
Preferable degradation efficiency, to some difficult biochemical organic matter macromoleculars, then there are degradation efficiency is low or the problems such as be difficult to degraded.
Therefore, microorganism is limited to the utilization scope for the Organic substance in water that gives up.
The content of the invention
The technical problem of solution：It is limited to the utilization scope for the Organic substance in water that gives up etc. for the existing microbiological fuel cell of solution
Problem, the present invention provides one kind tool photocatalysis cooperative effect electrode of microbial fuel cell and its preparation method and application.
Technical solution：One kind tool photocatalysis cooperative effect electrode of microbial fuel cell, including carbon cloth supporter, tourmaline
With tool reducing substances mixing bisque and modified photocatalytic material, the tourmaline and tool reducing substances mixing bisque attachment
In the outer surface of carbon cloth supporter, modified photocatalytic material is attached to tourmaline and tool reducing substances mixed powder layer surface；Institute
Modified photocatalytic material is stated with visible light-responded.
Above-mentioned tool reducing substances is the mass ratio of at least one of iron powder, aluminium powder, tourmaline and tool reducing substances
Example is maintained between 0.4-1.2, and the too low then tourmaline of ratio promotes light-catalysed effect to reduce, and ratio is excessive, is unfavorable for ensureing
Microbial activity.
Above-mentioned tourmaline and tool reducing substances mixing bisque are attached to the appearance of carbon cloth supporter by electrostatic spray
Face, control electrostatic potential 60-90kv ,-electrostatic induced current 10-20 μ A, load capacity is 0.8wt.%-16 wt.%, and powder layer thickness is 0.5
μm-10μm.Load capacity is within this range to TiO2Photocatalysis facilitation effect is optimal.
Above-mentioned modified photocatalytic material is doping type TiO2Catalysis material, or semiconductors coupling catalysis material.
Modified photocatalytic material is attached to tourmaline and the specific method of tool reducing substances mixed powder layer surface is：With molten
Sol-gel prepares the titanium colloidal sol of element doping, and titanium colloidal sol is dropped in and is gone back so that 1r/s-5r/s speed is rotating containing tourmaline and tool
The outer surface of the carbon cloth supporter of immunogenic substance mixing bisque, repeat the above steps dropwise addition after drying, then in protective atmosphere
The electrode of tool photocatalytic effect is obtained in 400-600 DEG C of roasting；By the speed of rotation and titanium colloidal sol rate of addition that control carbon cloth
To control the load capacity of modified photocatalytic material, the load capacity of modified photocatalytic material is 1wt.%-10 wt.%.
The specific preparation method of titanium colloidal sol is：Take 4-8mL isopropyl titanates, isopropyl titanate, butyl titanate, titanium tetrachloride
In one kind be titanium source, under magnetic stirring apparatus effect, solution A is added dropwise in 6-14mL absolute ethyl alcohols to obtain；Take 6-14mL without
Water-ethanol, gradually adds one kind in 0.8-2.0mL deionized waters and 1.0-2.6mL glacial acetic acid, citric acid, formic acid, then adds
It is the bismuth nitrate and urea of 0.008-0.012 with titanium source molar ratio, under the action of magnetic stirring apparatus, is uniformly mixed to obtain solution
B；Under magnetic stirring apparatus effect, solution B is added drop-wise in solution A dropwise with the speed of 0.5-2 drops/s, is continued after being added dropwise
Stirring 20-60min obtains titanium colloidal sol.
Modified photocatalytic material is made by following methods：1）Carried with doped type TiO2Catalysis material：Splashed altogether using three targets
Sputtering instrument, three sputtering targets are respectively pure TiO2Target, nonmetal doping TiO2Target, metal-doped TiO2Target, with containing tourmaline
Carbon cloth supporter with tool reducing substances mixed powder is base material, with the speed moving substrate of 1cm/s-5cm/s while sputtering,
TiO can be changed by the sputtering frequency for sputtering instrument2The content of middle doped chemical, prepares modified photocatalytic material；2）Load
Semiconductors coupling catalysis material：The sputtering instrument splashed altogether using two targets, two sputtering targets are respectively p-type semiconductor material and n
Type semi-conducting material, using the carbon cloth supporter containing tourmaline and tool reducing substances mixed powder as base material, while sputtering with
The speed moving substrate of 1cm/s-5cm/s, changes different type by controlling sputtering angle and the sputtering frequency of sputtering instrument
Semiconductor ratio, prepares modified photocatalytic material.
Preferably, a kind of preparation method for having photocatalysis cooperative effect electrode of microbial fuel cell,（1）Take 0.25g
8000 mesh tourmaline powders, 8000 mesh iron powders of 0.06g and the mixing of 0.06g epoxy powders, will be mixed using the method for electrostatic spraying
Powder spray is closed to the circular carbon cloth of a diameter of 5cm；（2）By the carbon cloth after spraying as 1h in 200 DEG C of resistance furnace, to obtain the final product
The carbon cloth of mixed powder load；（3）Using isopropyl titanate as titanium source, 5mL isopropyl titanates are taken, under magnetic stirring apparatus effect, are added dropwise
Enter into 10mL absolute ethyl alcohols to obtain solution A；（4）10mL absolute ethyl alcohols are taken, gradually add 1.5mL deionized waters and 1.8mL ice vinegar
Acid, then add with isopropyl titanate molar ratio be 0.01 bismuth nitrate and urea, under the action of magnetic stirring apparatus, be uniformly mixed
Obtain solution B；（5）Under the action of magnetic stirring apparatus, solution B is added drop-wise in solution A by the speed of 0.5-2 drops/s, is dripped
Continue to stir 50min after finishing, then standing 6h in the insulating box that temperature is 25 DEG C obtains titanium colloidal sol；（6）With the speed of 1.5 drops/s
Step（5）In titanium colloidal sol be added drop-wise to step（2）In on the rotating carbon cloth of 2r/s speed, to treat that carbon cloth surfaces are uniformly paved with one
Carbon cloth is put into 10min in 60 DEG C of baking oven after layer titanium colloidal sol；（7）Repeat step（6）Once, in N2Under protection, carbon cloth is put
Enter 490 DEG C of roasting 3h in tube furnace, the carbon cloth electrode that must both have photocatalytic effect.
The application of the tool photocatalysis cooperative effect electrode of microbial fuel cell, will have the carbon cloth electrode of photocatalysis
It is fixed in reactor, takes volume ratio 1：1 anaerobic sludge and sanitary wastewater, which is uniformly mixed, to be added in reactor, in constant temperature
The interior biofilm at 31 DEG C of case, had both obtained the composite anode after biofilm；With in sunlight, daylight light, energy saving light, ultraviolet light
At least one, for the distance of light source distance composite anode within 50cm, the concentration of pollutant controls COD in below 5000mg/L.
Beneficial effect：（1）Microorganism has coupling, electrode with photochemical catalyst in electrode during degrading waste water
Biorefractory organic in waste water is decomposed into easy biochemistry by the catalysis material on surface under the irradiation of visible ray or sunlight to be had
Machine thing small molecule, fluorescence probe are thoroughly degraded after the antimicrobial surface of inner side growth is reached through carbon cloth.Improve micro- life
The efficiency of fuel cell generation of thing fuel cell, has widened substrate utilization scope.
（2）Modified photochemical catalyst have it is visible light-responded, greatly reduce the limitation of photochemical catalyst use condition.
（3）Tourmaline has pyroelectricity and piezoelectricity, can produce permanent weak current, under the action of the electric current,
The service life of the electron-hole pair of catalysis material Surface Creation is extended, and improves photocatalysis efficiency.In addition, tourmaline and
Reducing substances mixed powder can effectively alleviate the transfer of the hole-electron and dithizone of photocatalysis generation to biomembrane,
Ensure that microbial activity.
Brief description of the drawings
Fig. 1 is the structure diagram of microbiological fuel cell；
Fig. 2 be the present invention tool photocatalysis cooperative effect electrode of microbial fuel cell structure diagram, from left to right according to
Secondary is microbial layer, carbon cloth, tourmaline powder and reduced powder mixed layer, photocatalysis layer.
Embodiment
The embodiment of the present invention is described in detail below, it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and should not be limited the scope of the invention with this.
Embodiment 1
（1）Take 0.25g tourmaline powders（8000 mesh）, 0.06g iron powders（8000 mesh）Mixed with 0.06g epoxy powders,
Mixed-powder is sprayed on the circular carbon cloth of a diameter of 5cm using the method for electrostatic spraying.
（2）By the carbon cloth after spraying as 1h in 200 DEG C of resistance furnace, up to the carbon cloth of mixed powder load.
（3）Using isopropyl titanate as titanium source, 5mL isopropyl titanates are taken, under magnetic stirring apparatus effect, are added dropwise to
Solution A is obtained in 8mL absolute ethyl alcohols.
（4）8mL absolute ethyl alcohols are taken, gradually add 1.5mL deionized waters and 1.8mL glacial acetic acid, then add and metatitanic acid isopropyl
Ester molar ratio is 0.01 bismuth nitrate and urea, under the action of magnetic stirring apparatus, is uniformly mixed to obtain solution B.
（5）Under the action of magnetic stirring apparatus, solution B is added drop-wise in solution A dropwise by the speed of 0.5 drop/s, is added dropwise
After continue to stir 50min, then standing 6h in temperature is 25 DEG C of insulating box obtains titanium colloidal sol.
（6）With the speed of 1 drop/s step（5）In titanium colloidal sol be added drop-wise to step（2）In with the rotating carbon of 2r/s speed
On cloth, carbon cloth is put into 10min in 60 DEG C of baking oven after carbon cloth surfaces are uniformly paved with one layer of titanium colloidal sol.
（7）Repeat step（6）Once, in N2Under protection, carbon cloth is put into 450 DEG C of roasting 3h in tube furnace, must both have light
The carbon cloth electrode of catalytic effect.
（8）The carbon cloth electrode of the tool photocatalysis of above-mentioned preparation is fixed in reactor, take 60 mL anaerobic sludges and
60 mL sanitary wastewaters, which are uniformly mixed, to be added in reactor, in insulating box at 31 DEG C biofilm.
Electrode TiO prepared by this method2Load capacity is 12%, on this electrode after loading microorganisms in 12h Pyrogentisinic Acid drop
Up to 92.8%, the degradation rate without treated carbon cloth loading microorganisms Pyrogentisinic Acid under the same conditions only has solution rate
76.3%。
Embodiment 2
（1）Take 0.25g tourmaline powders（8000 mesh）, 0.06g iron powders（8000 mesh）Mixed with 0.06g epoxy powders,
Mixed-powder is sprayed on the circular carbon cloth of a diameter of 5cm using the method for electrostatic spraying.
（2）By the carbon cloth after spraying as 1h in 200 DEG C of resistance furnace, up to the carbon cloth of mixed powder load.
（3）Using isopropyl titanate as titanium source, take 5mL isopropyl titanates, magnetic stirring apparatus effect under, be added dropwise to 10mL without
Solution A is obtained in water-ethanol.
（4）10mL absolute ethyl alcohols are taken, gradually add 1.5mL deionized waters and 1.8mL glacial acetic acid, then are added and isopropyl titanate
Molar ratio is 0.01 bismuth nitrate and urea, under the action of magnetic stirring apparatus, is uniformly mixed to obtain solution B.
（5）Under the action of magnetic stirring apparatus, solution B is added drop-wise in solution A dropwise by the speed of 2 drops/s, is dripped
Continue to stir 50min after finishing, then standing 6h in the insulating box that temperature is 25 DEG C obtains titanium colloidal sol.
（6）With the speed of 1.5 drops/s step（5）In titanium colloidal sol be added drop-wise to step（2）In it is rotating with 2r/s speed
On carbon cloth, carbon cloth is put into 10min in 60 DEG C of baking oven after carbon cloth surfaces are uniformly paved with one layer of titanium colloidal sol.
（7）Repeat step（6）Once, in N2Under protection, carbon cloth is put into 490 DEG C of roasting 3h in tube furnace, must both have light
The carbon cloth electrode of catalytic effect.
（8）The carbon cloth electrode of the tool photocatalysis of above-mentioned preparation is fixed in reactor, take 60 mL anaerobic sludges and
60 mL sanitary wastewaters, which are uniformly mixed, to be added in reactor, in insulating box at 31 DEG C biofilm.
Electrode TiO prepared by this method2Load capacity is 14.3%, on this electrode Pyrogentisinic Acid in 12h after loading microorganisms
Up to 93.1%, the degradation rate without treated carbon cloth loading microorganisms Pyrogentisinic Acid under the same conditions only has degradation rate
76.3%。
Embodiment 3
（1）Take 0.25g tourmaline powders（8000 mesh）, 0.06g iron powders（8000 mesh）Mixed with 0.06g epoxy powders,
Mixed-powder is sprayed on the circular carbon cloth of a diameter of 5cm using the method for electrostatic spraying.
（2）By the carbon cloth after spraying as 1h in 200 DEG C of resistance furnace, up to the carbon cloth of mixed powder load.
（3）Carbon cloth containing mixed powder is placed in magnetron sputtering chamber, the adjustment argon-mixed total gas pressure of oxygen is 1pa, wherein
O2Partial pressure accounts for total gas pressure ratio as 8%.Fixed pure TiO2The sputtering power of target is 98kw/m2, fixed nonmetal doping TiO2Target splashes
It is 6.2kw/m to penetrate power2, fixed metal-doped TiO2The sputtering power of target is 7.3kw/m2, 25min is deposited at room temperature to be obtained
Codope type TiO2。
（4）Will（3）In carbon cloth must both have photocatalytic effect after nitrogen protection, the 2h that anneals at 490 DEG C of annealing temperature
Carbon cloth electrode.
（5）The carbon cloth electrode of the tool photocatalysis of above-mentioned preparation is fixed in reactor, take 60 mL anaerobic sludges and
60 mL sanitary wastewaters, which are uniformly mixed, to be added in reactor, in insulating box at 31 DEG C biofilm.
Electrode TiO prepared by this method2Load capacity is 12%, on this electrode after loading microorganisms in 12h Pyrogentisinic Acid drop
Up to 91.6%, the degradation rate without treated carbon cloth loading microorganisms Pyrogentisinic Acid under the same conditions only has solution rate
76.3%。
Embodiment 4
（1）Take 0.25g tourmaline powders（8000 mesh）, 0.06g iron powders（8000 mesh）Mixed with 0.06g epoxy powders,
Mixed-powder is sprayed on the circular carbon cloth of a diameter of 5cm using the method for electrostatic spraying.
（2）By the carbon cloth after spraying as 1h in 200 DEG C of resistance furnace, up to the carbon cloth of mixed powder load.
（3）Carbon cloth containing mixed powder is placed in magnetron sputtering chamber, the adjustment argon-mixed total gas pressure of oxygen is 1pa, wherein
O2Partial pressure accounts for total gas pressure ratio as 8%.The sputtering power of fixed p-type semiconductor material target is 65kw/m2, fixed n-type semiconductor
The sputtering power of target is 53kw/m2, 35min is deposited at room temperature obtains semiconductor compound photocatalyst.
（4）Will（3）In carbon cloth must both have photocatalytic effect after nitrogen protection, the 2h that anneals at 500 DEG C of annealing temperature
Carbon cloth electrode.
（8）The carbon cloth electrode of the tool photocatalysis of above-mentioned preparation is fixed in reactor, take 60 mL anaerobic sludges and
60 mL sanitary wastewaters, which are uniformly mixed, to be added in reactor, in insulating box at 31 DEG C biofilm.
Electrode TiO prepared by this method2Load capacity is 12%, on this electrode after loading microorganisms in 12h Pyrogentisinic Acid drop
Up to 89.7%, the degradation rate without treated carbon cloth loading microorganisms Pyrogentisinic Acid under the same conditions only has solution rate
76.3%。
Claims (7)
1. one kind tool photocatalysis cooperative effect electrode of microbial fuel cell, it is characterised in that including carbon cloth supporter, tourmaline
With tool reducing substances mixing bisque and modified photocatalytic material, the tourmaline and tool reducing substances mixing bisque attachment
In the outer surface of carbon cloth supporter, modified photocatalytic material is attached to tourmaline and tool reducing substances mixed powder layer surface；Institute
Modified photocatalytic material is stated with visible light-responded；It is described to have reducing substances at least one of iron powder, aluminium powder, tourmaline
And the mass ratio of tool reducing substances is maintained between 0.4-1.2；The modified photocatalytic material is doping type TiO2Light is urged
Change material, or semiconductors coupling catalysis material.
2. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 1, it is characterised in that it is described electrically
Stone and tool reducing substances mixing bisque are attached to the outer surface of carbon cloth supporter by electrostatic spray, control electrostatic potential
60-90kV, electrostatic induced current 10-20 μ A, load capacity are 0.8wt.%-16 wt.%, and powder layer thickness is at 0.5 μm -10 μm.
3. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 1, it is characterised in that modified light is urged
Change material is attached to tourmaline and the specific method of tool reducing substances mixed powder layer surface is：Element is prepared with sol-gal process
The titanium colloidal sol of doping, titanium colloidal sol is dropped in rotating containing tourmaline and tool reducing substances mixing bisque with 1r/s-5r/s speed
Carbon cloth supporter outer surface, repeat the above steps dropwise addition after drying, is then roasted in protective atmosphere in 400-600 DEG C
To the electrode of tool photocatalytic effect；Modified photocatalytic material is controlled by controlling the speed of rotation and the titanium colloidal sol rate of addition of carbon cloth
The load capacity of material, the load capacity of modified photocatalytic material is 1wt.%-10 wt.%.
4. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 3, it is characterised in that titanium colloidal sol
Specifically preparation method is：It is titanium source to take one kind in 4-8mL isopropyl titanates, isopropyl titanate, butyl titanate, titanium tetrachloride,
Under magnetic stirring apparatus effect, it is added dropwise in 6-14mL absolute ethyl alcohols and obtains solution A；6-14mL absolute ethyl alcohols are taken, are gradually added
One kind in 0.8-2.0mL deionized waters and 1.0-2.6mL glacial acetic acid, citric acid, formic acid, then add and be with titanium source molar ratio
The bismuth nitrate and urea of 0.008-0.012, under the action of magnetic stirring apparatus, is uniformly mixed to obtain solution B；Make in magnetic stirring apparatus
Under, solution B is added drop-wise in solution A dropwise with the speed of 0.5-2 drops/s, continues stirring 20-60min after being added dropwise and obtains titanium
Colloidal sol.
5. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 1, it is characterised in that modified light is urged
Change material to be made by following methods：
1）Carried with doped type TiO2Catalysis material：The sputtering instrument splashed altogether using three targets, three sputtering targets are respectively pure TiO2
Target, nonmetal doping TiO2Target, metal-doped TiO2Target, with the carbon cloth supporter containing tourmaline and tool reducing substances mixed powder
For base material, with the speed moving substrate of 1cm/s-5cm/s while sputtering, can be changed by the sputtering frequency for sputtering instrument
TiO2The content of middle doped chemical, prepares modified photocatalytic material；
2）Load semiconductors coupling catalysis material：The sputtering instrument splashed altogether using two targets, two sputtering targets are respectively that p-type is partly led
Body material and n-type semiconductor, using the carbon cloth supporter containing tourmaline and tool reducing substances mixed powder as base material, sputtering
At the same time with the speed moving substrate of 1cm/s-5cm/s, changed not by controlling sputtering angle and the sputtering frequency of sputtering instrument
Same type semiconductor ratio, prepares modified photocatalytic material.
6. a kind of preparation method for having photocatalysis cooperative effect electrode of microbial fuel cell, it is characterised in that step is（1）Take
8000 mesh tourmaline powders of 0.25g, 8000 mesh iron powders of 0.06g and the mixing of 0.06g epoxy powders, using the side of electrostatic spraying
Method sprays to mixed-powder on the circular carbon cloth of a diameter of 5cm；（2）Carbon cloth after spraying is placed in 200 DEG C of resistance furnace
1h, up to the carbon cloth of mixed powder load；（3）Using isopropyl titanate as titanium source, 5mL isopropyl titanates are taken, under magnetic stirring apparatus effect,
It is added dropwise in 10mL absolute ethyl alcohols and obtains solution A；（4）Take 10mL absolute ethyl alcohols, gradually add 1.5mL deionized waters and
1.8mL glacial acetic acid, then add with isopropyl titanate molar ratio be 0.01 bismuth nitrate and urea, in the effect of magnetic stirring apparatus
Under, it is uniformly mixed to obtain solution B；（5）Under the action of magnetic stirring apparatus, solution B is added drop-wise to solution by the speed of 0.5-2 drops/s
In A, continue to stir 50min after being added dropwise, then standing 6h in the insulating box that temperature is 25 DEG C obtains titanium colloidal sol；（6）With 1.5
The speed of drop/s is step（5）In titanium colloidal sol be added drop-wise to step（2）In on the rotating carbon cloth of 2r/s speed, to treat carbon cloth surfaces
Uniformly it is paved with after one layer of titanium colloidal sol and carbon cloth is put into 10min in 60 DEG C of baking oven；（7）Repeat step（6）Once, in N2Protection
Under, carbon cloth is put into 490 DEG C of roasting 3h in tube furnace, up to having the carbon cloth electrode of photocatalytic effect.
7. the application of any tool photocatalysis cooperative effect electrode of microbial fuel cell of claim 1 ~ 5, it is characterised in that
The carbon cloth electrode for having photocatalysis is fixed in reactor, takes volume ratio 1：1 anaerobic sludge and sanitary wastewater mixing is equal
It is even to add in reactor, in insulating box at 31 DEG C biofilm, up to the composite anode after biofilm；With sunlight, fluorescent lamp
Light, energy saving light, at least one of ultraviolet light, the distance of light source distance composite anode is within 50cm, the concentration of pollutant
COD is controlled in below 5000mg/L.
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| CN108793422B (en) * | 2018-05-22 | 2019-09-27 | 大连理工大学 | Photochemical catalyst electrode couples microbiological fuel cell and promotes coking waste water treatment method |
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| CN110165243A (en) * | 2019-05-30 | 2019-08-23 | 大连理工大学 | A kind of novel piezoelectric material building photocatalysis automatic bias pollution control system |
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