CN105428663A - Microbial fuel cell electrode having photocatalytic synergistic effect as well as preparation method and application of electrode - Google Patents
Microbial fuel cell electrode having photocatalytic synergistic effect as well as preparation method and application of electrode Download PDFInfo
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- CN105428663A CN105428663A CN201510924408.2A CN201510924408A CN105428663A CN 105428663 A CN105428663 A CN 105428663A CN 201510924408 A CN201510924408 A CN 201510924408A CN 105428663 A CN105428663 A CN 105428663A
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- carbon cloth
- electrode
- tourmaline
- tool
- fuel cell
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 61
- 239000000446 fuel Substances 0.000 title claims abstract description 25
- 230000000813 microbial effect Effects 0.000 title claims abstract description 21
- 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 40
- 229940070527 tourmaline Drugs 0.000 claims abstract description 33
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 33
- 239000011032 tourmaline Substances 0.000 claims abstract description 33
- 238000007146 photocatalysis Methods 0.000 claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 23
- 239000011812 mixed powder Substances 0.000 claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 11
- 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 24
- 238000004544 sputter deposition Methods 0.000 claims description 23
- 238000003760 magnetic stirring Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 230000002079 cooperative effect Effects 0.000 claims description 16
- 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 16
- 238000000034 method Methods 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 229910002114 biscuit porcelain Inorganic materials 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 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
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000007590 electrostatic spraying Methods 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 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
- 239000010802 sludge Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000003756 stirring Methods 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
- 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
- 229910052755 nonmetal Inorganic materials 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
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005421 electrostatic potential Methods 0.000 claims description 2
- 238000004134 energy conservation 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
- 239000007921 spray 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
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 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
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 244000005700 microbiome Species 0.000 description 8
- 230000002906 microbiologic effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003054 catalyst Substances 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 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
- 239000000523 sample 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
- 230000000593 degrading effect Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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, fuel cells
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a microbial fuel cell electrode having a photocatalytic synergistic effect as well as a preparation method and an application of the electrode. The electrode comprises a carbon cloth supporting body, a tourmaline and reducing substance mixed powder layer and a modified photocatalytic material, wherein the tourmaline and reducing substance mixed powder layer are attached to the outer surface of the carbon cloth supporting body, and the modified photocatalytic material is attached to the surface of the tourmaline and reducing substance mixed powder layer. Microbes and a photocatalyst in the electrode have a coupling effect during degradation of wastewater; the modified photocatalyst has the visible-light response, and limitations on usage conditions of the photocatalyst are greatly reduced; tourmaline has pyroelectricity and piezoelectricity and can produce permanent weak current, the service life of hole-electron pairs produced on the surface of the photocatalytic material is prolonged under the effect of the current, and the photocatalytic efficiency is improved. Besides, tourmaline and reducing substance mixed powder can effectively ease transfer of holes-electrons or oxidized ions produced by photocatalysis to a biological membrane, and the activity of the microbes is guaranteed.
Description
Technical field
The present invention relates to microbiological fuel cell technology and photocatalysis technology field, be specifically related to a kind of tool photocatalysis cooperative effect electrode of microbial fuel cell and its preparation method and application.
Background technology
Current environmental problem and energy problem have a strong impact on life and the economic development of people, and environmental problem is day by day serious, and energy shortage also becomes problem demanding prompt solution.Microbiological fuel cell (MFC) simultaneously again can the technology of electrogenesis as a kind of waste water treatment, is subject to the favor of numerous researcher.MFC reaction condition is gentle, and without the need to providing other energy in course of reaction, and contamination-free generates, and is a kind of water technology with Significance of Sustainable Development.
Microbiological fuel cell is under the condition of anoxic, utilizes microbe by organic electron transmission to anode, then realizes generating by transferring to negative electrode.But microbe has selectivity to organic degraded, have good degradation efficiency to organic molecule, it is low or be difficult to the problems such as degraded then to there is degradation efficiency in organic substance large molecules difficult biochemical to some.Therefore, microbe is limited in scope to utilization organic in waste water.
Summary of the invention
the technical problem solved:for solving existing microbiological fuel cell to problems such as utilization organic in waste water are limited in scope, the invention provides a kind of tool photocatalysis cooperative effect electrode of microbial fuel cell and its preparation method and application.
technical scheme:a kind of tool photocatalysis cooperative effect electrode of microbial fuel cell, comprise carbon cloth supporter, tourmaline and tool reducing substances mixing bisque and modified photocatalytic material, described tourmaline and tool reducing substances mixing bisque are attached to the outer surface of carbon cloth supporter, and modified photocatalytic material is attached to tourmaline and tool reducing substances mixing bisque surface; Described modified photocatalytic material has visible light-responded.
Above-mentioned tool reducing substances is at least one in iron powder, aluminium powder, and the mass ratio of tourmaline and tool reducing substances remains between 0.4-1.2, and ratio is too low, and tourmaline promotes that light-catalysed effect reduces, and ratio is too high, is unfavorable for ensureing microbial activity.
Above-mentioned tourmaline 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 is 0.8wt.%-16wt.%, and powder layer thickness is at 0.5 μm-10 μm.Load capacity within the scope of this to TiO
2photocatalysis facilitation effect is best.
Above-mentioned modified photocatalytic material is doping type TiO
2catalysis material, or semiconductors coupling catalysis material.
The concrete grammar that modified photocatalytic material is attached to tourmaline and tool reducing substances mixing bisque surface is: the titanium colloidal sol preparing element doping with sol-gal process, titanium colloidal sol is dropped in the outer surface containing the carbon cloth supporter of tourmaline and tool reducing substances mixing bisque rotated with 1r/s-5r/s speed, repeat above-mentioned steps after drying to drip, in protective atmosphere, then obtain the electrode of tool photocatalytic effect in 400-600 DEG C of roasting; Controlled the load capacity of modified photocatalytic material by the speed of rotation and titanium colloidal sol rate of addition controlling carbon cloth, the load capacity of modified photocatalytic material is 1wt.%-10wt.%.
The concrete preparation method of titanium colloidal sol is: the one of getting in 4-8mL isopropyl titanate, isopropyl titanate, butyl titanate, titanium tetrachloride is titanium source, under magnetic stirring apparatus effect, dropwise adds in 6-14mL absolute ethyl alcohol and obtains solution A; Get 6-14mL absolute ethyl alcohol, successively add the one in 0.8-2.0mL deionized water and 1.0-2.6mL glacial acetic acid, citric acid, formic acid, add the bismuth nitrate and the urea that are 0.008-0.012 with titanium source mol ratio again, under the effect of magnetic stirring apparatus, mix to obtain solution B; Under magnetic stirring apparatus effect, with 0.5-2 drip/speed of s is dropwise added drop-wise to solution B in solution A, dropwise rear continuation and stir 20-60min and obtain titanium colloidal sol.
Modified photocatalytic material is obtained by following methods: 1) carried with doped type TiO
2catalysis material: use the sputtering instrument that three targets spatter altogether, three sputtering targets are respectively pure TiO
2target, nonmetal doping TiO
2target, metal-doped TiO
2target, 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 change TiO by the sputtering frequency sputtering instrument
2the content of middle doped chemical, prepares modified photocatalytic material; 2) load semiconductors coupling catalysis material: use the sputtering instrument that two targets spatter altogether, two sputtering targets are respectively p-type semiconductor material and n-type semiconductor, 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, change dissimilar semiconductor ratio by the sputtering angle and sputtering frequency that control sputtering instrument, prepare modified photocatalytic material.
Preferably, a kind of preparation method of tool photocatalysis cooperative effect electrode of microbial fuel cell, (1) get the mixing of 0.25g8000 order tourmaline powder, 0.06g8000 order iron powder and 0.06g epoxy powder, adopt the method for electrostatic spraying to be sprayed to by mixed-powder on the circular carbon cloth that diameter is 5cm; (2) by spraying after carbon cloth as 1h in the resistance furnace of 200 DEG C, obtain the carbon cloth of mixed powder load; (3) be titanium source with isopropyl titanate, get 5mL isopropyl titanate, under magnetic stirring apparatus effect, dropwise to join in 10mL absolute ethyl alcohol to obtain solution A; (4) get 10mL absolute ethyl alcohol, successively add 1.5mL deionized water and 1.8mL glacial acetic acid, then add and isopropyl titanate mol ratio be 0.01 bismuth nitrate and urea, under the effect of magnetic stirring apparatus, mix to obtain solution B; (5) under the effect of magnetic stirring apparatus, by solution B by 0.5-2 drip/speed of s is added drop-wise in solution A, dropwises rear continuation and stirs 50min, then in temperature be to leave standstill 6h in the insulating box of 25 DEG C to obtain titanium colloidal sol; (6) with the speed of 1.5/s the titanium colloidal sol in step (5) is added drop-wise on the carbon cloth rotated with 2r/s speed in step (2), is evenly paved with until carbon cloth surfaces the baking oven 10min after one deck titanium colloidal sol, carbon cloth being put into 60 DEG C; (7) step (6) is repeated once, at N
2under protection, carbon cloth is put into tube furnace 490 DEG C of roasting 3h, both obtain the carbon cloth electrode of tool photocatalytic effect.
The application of described tool photocatalysis cooperative effect electrode of microbial fuel cell, the carbon cloth electrode of tool photocatalysis is fixed in reactor, get the anaerobic sludge of volume ratio 1:1 and sanitary wastewater to mix and add in reactor, in insulating box at 31 DEG C biofilm, both the composite anode after biofilm; By at least one in sunlight, daylight light, energy-conservation light, ultraviolet light, the distance of light source distance composite anode is within 50cm, and the concentration control COD of pollutant is at below 5000mg/L.
beneficial effect:(1) in microbe and electrode, photochemical catalyst has coupling in the process of degrading waste water, the catalysis material of electrode surface is decomposed into easy biochemical fluorescence probe biorefractory organic in waste water under the irradiation of visible ray or sunlight, and fluorescence probe is thoroughly degraded after arriving the antimicrobial surface of inner side growth through carbon cloth.Improve the efficiency of fuel cell generation of microbiological fuel cell, widen substrate utilization scope.
(2) modified photochemical catalyst has visible light-responded, greatly reduces the restriction of photochemical catalyst service condition.
(3) tourmaline has pyroelectricity and piezoelectricity, can produce permanent weak current, and under the effect of this electric current, the life-span that the hole-electron of catalysis material Surface Creation is right is extended, and improves photocatalysis efficiency.In addition, tourmaline and reducing substances mixed powder can effectively alleviate photocatalysis produce hole-electron and dithizone to biomembranous transfer, ensure that microbial activity.
Accompanying drawing explanation
Fig. 1 is the structural representation of microbiological fuel cell;
Fig. 2 is the structural representation of tool photocatalysis cooperative effect electrode of microbial fuel cell of the present invention, is from left to right followed successively by microbial layer, carbon cloth, tourmaline powder and reduced powder mixed layer, photocatalysis layer.
Embodiment
Be described in detail to the specific embodiment of the present invention below, should be understood that, embodiment described herein, only for instruction and explanation of the present invention, should not limit the scope of the invention with this.
embodiment 1
(1) get the mixing of 0.25g tourmaline powder (8000 order), 0.06g iron powder (8000 order) and 0.06g epoxy powder, adopt the method for electrostatic spraying to be sprayed to by mixed-powder on the circular carbon cloth that diameter is 5cm.
(2) by spraying after carbon cloth as 1h in the resistance furnace of 200 DEG C, obtain the carbon cloth of mixed powder load.
(3) be titanium source with isopropyl titanate, get 5mL isopropyl titanate, under magnetic stirring apparatus effect, dropwise to join in 8mL absolute ethyl alcohol to obtain solution A.
(4) get 8mL absolute ethyl alcohol, successively add 1.5mL deionized water and 1.8mL glacial acetic acid, then add and isopropyl titanate mol ratio be 0.01 bismuth nitrate and urea, under the effect of magnetic stirring apparatus, mix to obtain solution B.
(5) under the effect of magnetic stirring apparatus, the speed of solution B by 0.5/s being dropwise added drop-wise in solution A, dropwising rear continuation and stir 50min, is then leave standstill 6h in the insulating box of 25 DEG C to obtain titanium colloidal sol in temperature.
(6) with the speed of 1/s the titanium colloidal sol in step (5) is added drop-wise on the carbon cloth rotated with 2r/s speed in step (2), is evenly paved with until carbon cloth surfaces the baking oven 10min after one deck titanium colloidal sol, carbon cloth being put into 60 DEG C.
(7) step (6) is repeated once, at N
2under protection, carbon cloth is put into tube furnace 450 DEG C of roasting 3h, both obtain the carbon cloth electrode of tool photocatalytic effect.
(8) carbon cloth electrode of the tool photocatalysis of above-mentioned preparation is fixed in reactor, gets 60mL anaerobic sludge and 60mL sanitary wastewater and mix and add in reactor, in insulating box at 31 DEG C biofilm.
Electrode TiO prepared by the method
2load capacity is 12%, and after loading microorganisms, in 12h, the degradation rate of Pyrogentisinic Acid reaches 92.8% on this electrode, and does not have the degradation rate of treated carbon cloth loading microorganisms Pyrogentisinic Acid under the same conditions to only have 76.3%.
embodiment 2
(1) get the mixing of 0.25g tourmaline powder (8000 order), 0.06g iron powder (8000 order) and 0.06g epoxy powder, adopt the method for electrostatic spraying to be sprayed to by mixed-powder on the circular carbon cloth that diameter is 5cm.
(2) by spraying after carbon cloth as 1h in the resistance furnace of 200 DEG C, obtain the carbon cloth of mixed powder load.
(3) be titanium source with isopropyl titanate, get 5mL isopropyl titanate, under magnetic stirring apparatus effect, dropwise to join in 10mL absolute ethyl alcohol to obtain solution A.
(4) get 10mL absolute ethyl alcohol, successively add 1.5mL deionized water and 1.8mL glacial acetic acid, then add and isopropyl titanate mol ratio be 0.01 bismuth nitrate and urea, under the effect of magnetic stirring apparatus, mix to obtain solution B.
(5) under the effect of magnetic stirring apparatus, the speed of solution B by 2/s being dropwise added drop-wise in solution A, dropwising rear continuation and stir 50min, is then leave standstill 6h in the insulating box of 25 DEG C to obtain titanium colloidal sol in temperature.
(6) with the speed of 1.5/s the titanium colloidal sol in step (5) is added drop-wise on the carbon cloth rotated with 2r/s speed in step (2), is evenly paved with until carbon cloth surfaces the baking oven 10min after one deck titanium colloidal sol, carbon cloth being put into 60 DEG C.
(7) step (6) is repeated once, at N
2under protection, carbon cloth is put into tube furnace 490 DEG C of roasting 3h, both obtain the carbon cloth electrode of tool photocatalytic effect.
(8) carbon cloth electrode of the tool photocatalysis of above-mentioned preparation is fixed in reactor, gets 60mL anaerobic sludge and 60mL sanitary wastewater and mix and add in reactor, in insulating box at 31 DEG C biofilm.
Electrode TiO prepared by the method
2load capacity is 14.3%, and after loading microorganisms, in 12h, the degradation rate of Pyrogentisinic Acid reaches 93.1% on this electrode, and does not have the degradation rate of treated carbon cloth loading microorganisms Pyrogentisinic Acid under the same conditions to only have 76.3%.
embodiment 3
(1) get the mixing of 0.25g tourmaline powder (8000 order), 0.06g iron powder (8000 order) and 0.06g epoxy powder, adopt the method for electrostatic spraying to be sprayed to by mixed-powder on the circular carbon cloth that diameter is 5cm.
(2) by spraying after carbon cloth as 1h in the resistance furnace of 200 DEG C, obtain the carbon cloth of mixed powder load.
(3) be placed in magnetron sputtering chamber by the carbon cloth containing mixed powder, the argon-mixed total gas pressure of adjustment oxygen is 1pa, wherein O
2point covering total gas pressure ratio is 8%.Fixing pure TiO
2the sputtering power of target is 98kw/m
2, fixing nonmetal doping TiO
2the sputtering power of target is 6.2kw/m
2, fixing metal doped Ti O
2the sputtering power of target is 7.3kw/m
2, at room temperature deposit 25min and obtain codope type TiO
2.
(4) carbon cloth in (3) to be annealed at nitrogen protection, annealing temperature 490 DEG C after 2h both the carbon cloth electrode of tool photocatalytic effect.
(5) carbon cloth electrode of the tool photocatalysis of above-mentioned preparation is fixed in reactor, gets 60mL anaerobic sludge and 60mL sanitary wastewater and mix and add in reactor, in insulating box at 31 DEG C biofilm.
Electrode TiO prepared by the method
2load capacity is 12%, and after loading microorganisms, in 12h, the degradation rate of Pyrogentisinic Acid reaches 91.6% on this electrode, and does not have the degradation rate of treated carbon cloth loading microorganisms Pyrogentisinic Acid under the same conditions to only have 76.3%.
embodiment 4
(1) get the mixing of 0.25g tourmaline powder (8000 order), 0.06g iron powder (8000 order) and 0.06g epoxy powder, adopt the method for electrostatic spraying to be sprayed to by mixed-powder on the circular carbon cloth that diameter is 5cm.
(2) by spraying after carbon cloth as 1h in the resistance furnace of 200 DEG C, obtain the carbon cloth of mixed powder load.
(3) be placed in magnetron sputtering chamber by the carbon cloth containing mixed powder, the argon-mixed total gas pressure of adjustment oxygen is 1pa, wherein O
2point covering total gas pressure ratio is 8%.The sputtering power of fixing p-type semiconductor material target is 65kw/m
2, the sputtering power of fixing n-type semiconductor target is 53kw/m
2, at room temperature deposit 35min and obtain semiconductor compound photocatalyst.
(4) carbon cloth in (3) to be annealed at nitrogen protection, annealing temperature 500 DEG C after 2h both the carbon cloth electrode of tool photocatalytic effect.
(8) carbon cloth electrode of the tool photocatalysis of above-mentioned preparation is fixed in reactor, gets 60mL anaerobic sludge and 60mL sanitary wastewater and mix and add in reactor, in insulating box at 31 DEG C biofilm.
Electrode TiO prepared by the method
2load capacity is 12%, and after loading microorganisms, in 12h, the degradation rate of Pyrogentisinic Acid reaches 89.7% on this electrode, and does not have the degradation rate of treated carbon cloth loading microorganisms Pyrogentisinic Acid under the same conditions to only have 76.3%.
Claims (9)
1. a tool photocatalysis cooperative effect electrode of microbial fuel cell, it is characterized in that comprising carbon cloth supporter, tourmaline and tool reducing substances mixing bisque and modified photocatalytic material, described tourmaline and tool reducing substances mixing bisque are attached to the outer surface of carbon cloth supporter, and modified photocatalytic material is attached to tourmaline and tool reducing substances mixing bisque surface; Described modified photocatalytic material has visible light-responded.
2. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 1, it is characterized in that described tool reducing substances is at least one in iron powder, aluminium powder, the mass ratio of tourmaline and tool reducing substances remains between 0.4-1.2.
3. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 1, it is characterized in that described tourmaline 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 is 0.8wt.%-16wt.%, and powder layer thickness is at 0.5 μm-10 μm.
4. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 1, it is characterized in that described modified photocatalytic material is doping type TiO
2catalysis material, or semiconductors coupling catalysis material.
5. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 1, it is characterized in that the concrete grammar that modified photocatalytic material is attached to tourmaline and tool reducing substances mixing bisque surface is: the titanium colloidal sol preparing element doping with sol-gal process, titanium colloidal sol is dropped in the outer surface containing the carbon cloth supporter of tourmaline and tool reducing substances mixing bisque rotated with 1r/s-5r/s speed, repeat above-mentioned steps after drying to drip, in protective atmosphere, then obtain the electrode of tool photocatalytic effect in 400-600 DEG C of roasting; Controlled the load capacity of modified photocatalytic material by the speed of rotation and titanium colloidal sol rate of addition controlling carbon cloth, the load capacity of modified photocatalytic material is 1wt.%-10wt.%.
6. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 5, it is characterized in that the concrete preparation method of titanium colloidal sol is: the one of getting in 4-8mL isopropyl titanate, isopropyl titanate, butyl titanate, titanium tetrachloride is titanium source, under magnetic stirring apparatus effect, dropwise add in 6-14mL absolute ethyl alcohol and obtain solution A; Get 6-14mL absolute ethyl alcohol, successively add the one in 0.8-2.0mL deionized water and 1.0-2.6mL glacial acetic acid, citric acid, formic acid, add the bismuth nitrate and the urea that are 0.008-0.012 with titanium source mol ratio again, under the effect of magnetic stirring apparatus, mix to obtain solution B; Under magnetic stirring apparatus effect, with 0.5-2 drip/speed of s is dropwise added drop-wise to solution B in solution A, dropwise rear continuation and stir 20-60min and obtain titanium colloidal sol.
7. have photocatalysis cooperative effect electrode of microbial fuel cell according to claim 4, it is characterized in that modified photocatalytic material is obtained by following methods:
1) carried with doped type TiO
2catalysis material: use the sputtering instrument that three targets spatter altogether, three sputtering targets are respectively pure TiO
2target, nonmetal doping TiO
2target, metal-doped TiO
2target, 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 change TiO by the sputtering frequency sputtering instrument
2the content of middle doped chemical, prepares modified photocatalytic material;
2) load semiconductors coupling catalysis material: use the sputtering instrument that two targets spatter altogether, two sputtering targets are respectively p-type semiconductor material and n-type semiconductor, 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, change dissimilar semiconductor ratio by the sputtering angle and sputtering frequency that control sputtering instrument, prepare modified photocatalytic material.
8. the preparation method of a tool photocatalysis cooperative effect electrode of microbial fuel cell, it is characterized in that step is that (1) gets the mixing of 0.25g8000 order tourmaline powder, 0.06g8000 order iron powder and 0.06g epoxy powder, adopt the method for electrostatic spraying to be sprayed to by mixed-powder on the circular carbon cloth that diameter is 5cm; (2) by spraying after carbon cloth as 1h in the resistance furnace of 200 DEG C, obtain the carbon cloth of mixed powder load; (3) be titanium source with isopropyl titanate, get 5mL isopropyl titanate, under magnetic stirring apparatus effect, dropwise to join in 10mL absolute ethyl alcohol to obtain solution A; (4) get 10mL absolute ethyl alcohol, successively add 1.5mL deionized water and 1.8mL glacial acetic acid, then add and isopropyl titanate mol ratio be 0.01 bismuth nitrate and urea, under the effect of magnetic stirring apparatus, mix to obtain solution B; (5) under the effect of magnetic stirring apparatus, by solution B by 0.5-2 drip/speed of s is added drop-wise in solution A, dropwises rear continuation and stirs 50min, then in temperature be to leave standstill 6h in the insulating box of 25 DEG C to obtain titanium colloidal sol; (6) with the speed of 1.5/s the titanium colloidal sol in step (5) is added drop-wise on the carbon cloth rotated with 2r/s speed in step (2), is evenly paved with until carbon cloth surfaces the baking oven 10min after one deck titanium colloidal sol, carbon cloth being put into 60 DEG C; (7) step (6) is repeated once, at N
2under protection, carbon cloth is put into tube furnace 490 DEG C of roasting 3h, both obtain the carbon cloth electrode of tool photocatalytic effect.
9. the application of the arbitrary described tool photocatalysis cooperative effect electrode of microbial fuel cell of claim 1 ~ 7, the carbon cloth electrode of tool photocatalysis is it is characterized in that to be fixed in reactor, get the anaerobic sludge of volume ratio 1:1 and sanitary wastewater to mix and add in reactor, in insulating box at 31 DEG C biofilm, both the composite anode after biofilm; By at least one of sunlight, daylight light, energy-conservation light, ultraviolet light, the distance of light source distance composite anode is within 50cm, and the concentration control COD of pollutant is at below 5000mg/L.
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