CN103413948A - Microbial electrolysis cell (MEC) modified biological cathode preparation method and application thereof - Google Patents
Microbial electrolysis cell (MEC) modified biological cathode preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 15
- 230000000813 microbial effect Effects 0.000 title abstract description 7
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 53
- 229940070527 tourmaline Drugs 0.000 claims abstract description 53
- 239000011032 tourmaline Substances 0.000 claims abstract description 53
- 229920000767 polyaniline Polymers 0.000 claims abstract description 44
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000007796 conventional method Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 238000012986 modification Methods 0.000 claims description 23
- 230000004048 modification Effects 0.000 claims description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 17
- 239000002041 carbon nanotube Substances 0.000 claims description 17
- 244000005700 microbiome Species 0.000 claims description 15
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- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
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- 239000000126 substance Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- IDIJOAIHTRIPRC-UHFFFAOYSA-J hexaaluminum;sodium;2,2,4,4,6,6,8,8,10,10,12,12-dodecaoxido-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane;iron(2+);triborate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Fe+2].[Fe+2].[Fe+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-][Si]1([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O1 IDIJOAIHTRIPRC-UHFFFAOYSA-J 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910000246 schorl Inorganic materials 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229920000557 Nafion® Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 229910000245 dravite Inorganic materials 0.000 claims description 2
- 229940059939 kayexalate Drugs 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
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- 230000002708 enhancing effect Effects 0.000 abstract 1
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- 238000004065 wastewater treatment Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002906 microbiologic effect Effects 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000002210 biocatalytic effect Effects 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
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- 239000010970 precious metal Substances 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- 229910017116 Fe—Mo Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
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- 235000010755 mineral Nutrition 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000011105 stabilization Methods 0.000 description 1
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Classifications
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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
Abstract
The invention discloses a microbial electrolysis cell (MEC) modified biological cathode preparation method and application thereof. The invention uses an MWNT (multi-walled nanotube)/tourmaline/PANI (polyaniline) composite electrode as a substrate to prepare the MEC modified biological cathode. The preparation method comprises the following steps: mixing MWNT and tourmaline powder by ball milling, adding a solvent, aniline and ammonium persulfate, stirring to react under ice bath conditions, washing, and drying to obtain an MWNT/tourmaline/PANI composite; mixing the composite with a binding agent and acetone to obtain an MWNT/tourmaline/PANI composite electrode, naturally drying in air to obtain an MFC anode, carrying out biofilm domestication by a conventional method, transferring to an MEC cathode, and finally constructing the MWNT/tourmaline/PANI modified biological cathode. The modified biological cathode prepared by the method disclosed by the invention has the functions of stimulating biological catalytic activity and chemically enhancing the biological catalytic hydrogen production, has the advantages of high conductivity and low cost, and provides technical support for implementing large-scale application of MEC synchronous wastewater treatment and hydrogen production.
Description
Technical field
The invention belongs to new forms of energy and new material applied technical field, be specifically related to carbon nano-tube/tourmaline/polyaniline-modified biological-cathode application in microorganism electrolysis cell and preparation method thereof.
Background technology
Along with social progress and economic development, energy crisis and problem of environmental pollution in global range highlight day by day, and the energy demand that does not rely on fossil fuel to meet the mankind in continuable, eco-friendly mode becomes the trend in epoch.
MEC is the new technology of a kind of biological hydrogen production of growing up in recent years, as a kind of biology and electrochemistry synergy biodegradable organic, chemical energy can be changed into to the new bio process technology of Hydrogen Energy simultaneously, and MEC has caused increasing concern.Its basic functional principle is under the effect of additional low-tension supply, and in the electrochemically active microbial degradation aqueous solution adhered to by anode surface, organic substance generates CO
2, H
+And electronics, the electronics of generation is delivered to negative electrode through external circuit; H
+By proton membrane, spread or directly arrive negative electrode, being reduced into hydrogen at the cathode surface electron gain.
The MEC cathod catalyst is one of technical problem of most critical, and Pt is used widely at MEC because having good catalytic performance, but it is expensive, has restricted the industrial application of MEC.For this reason, efficient cheap cathod catalyst screening is the emphasis of research with preparation.Some alloy electrodes, as Ni-W-P alloy electrode, Ni-Mo alloy copper sheet, Ni-Fe-Mo alloy, Co-Ni alloy etc., has stronger redox catalysis activity, be expected to substitute Pt catalyst (document Water Science and Technology, 2011,63 (3): 440-448; International Journal of Hydrogen Energy, 2011,36:10482-10489), but due to its manufacture method, the limiting factors such as raw material proportioning, be subject to certain restrictions its application in MEC.Metal oxide and sulfide are more potential cathod catalyst (document International Journal of Hydrogen Energy, 2010,35:3227-3233; International Journal ofHydrogen Energy, 2011,36:9439-9445), but this type of poor catalyst stability, its catalytic activity is along with extending running time and reducing gradually.With above-mentioned chemical catalyst, compare, take living things catalysis as the required applied voltage of the biological-cathode of core is low, can realize reducing costs lasting bio-hydrogen (document Environ Sci Technol, 2008,42 (2): 629-634; Bioelectrochemistry, 2010,78:39-43).Deficiency causes the product hydrogen level of biological-cathode lower because poorly conductive, microorganism catalysis performance be low etc. but also exist.Therefore, above-mentioned precious metals pt negative electrode and base metal negative electrode exist catalytic stability to differ from and there is the problem that hydrogen generation efficiency is low in biological-cathode, therefore it is significant to attempt exploitation MEC modification biological negative electrode.
In recent years, carbon nano-tube and mixing nano composite material thereof have obtained larger concern owing to having unique structure, electronics and mechanical performance etc.Tourmaline is that a kind of boracic is the crystal mineral of feature, and it can affect activity and the structure generation of water, thereby strengthen biological metabolism by self there being the far infrared of electric field and emission.Polyaniline obtains a wide range of applications with its unique characteristic electron, outstanding environmental stability and the controllable electric conductance in protonated and charge transfer process etc.The present invention utilizes the cathod catalyst of MWNT/ tourmaline/PANI modification biological negative electrode as MEC, can utilize the modification of MWNT, tourmaline and PANI increase electrode specific surface area and then be beneficial to microorganism colonization.Utilize tourmaline to improve microbial activity to the spread effect of microbe, the performance biocatalytic Activity.And utilize the high conduction performance of carbon nano-tube and polyaniline and strong redox property etc. synchronously to realize the chemical catalysis function and accelerate electronics transmission etc.In addition, the MWNT/ tourmaline/PANI modification biological negative electrode is higher than the Pt cathode stabilization, price has reduced several times.Therefore, the MWNT/ tourmaline/MEC is synchronously processed to waste water to PANI modification biological negative electrode and production capacity is significant.
Summary of the invention
The present invention is directed to the deficiency that existing Pt metal catalyst substitute exists, a kind of MWNT/ tourmaline/PANI modification biological negative electrode application in MEC and preparation method thereof is provided.
For reaching above purpose, the present invention by the following technical solutions:
A kind of microorganism electrolysis cell modification biological cathode preparation method, take MWNT, tourmaline and PANI combination electrode and prepare MEC modification biological negative electrode as base material; At first MWNT and tourmaline powder ball milling are mixed, add solvent, aniline and ammonium persulfate, stirring reaction under condition of ice bath, washing and drying obtains MWNT/ tourmaline/PANI compound; Compound and binding agent and acetone are mixed with and obtain MWNT/ tourmaline/PANI combination electrode, after natural air drying, according to conventional method, tame biofilm as the MFC anode, then move to the MEC negative electrode, finally construct MWNT/ tourmaline/PANI modification biological negative electrode.
Described preparation method, it specifically comprises the following steps:
(1) purifying of carbon nano-tube;
(2) by carbon nano-tube after purifying and tourmaline powder ball milling mixing in proportion;
(3) in mixture, add in proportion surfactant, HCl and H
2O, stir under ice bath;
(4), under the ice bath stirring condition, in said mixture, add in proportion aniline, the ammonium persulfate that is dissolved in HCl after decompression distillation, and continue ice bath stirring reaction a few hours;
(5) said mixture washing, centrifugal, suction filtration are obtained to MWNT/ tourmaline/PANI composite material;
(6) to above-mentioned composite material add in proportion binding agent and solvent even, and ultrasonic dispersion;
(7) ultrasonic mixture is coated in to conductive substrates equably, natural air drying obtains MWNT/ tourmaline/PANI combination electrode;
(8) above-mentioned combination electrode is tamed to biofilm as for the MFC anode;
(9), after taming successfully, move to the MEC negative electrode.
Described preparation method, the purification process of described carbon nano-tube is: under 50-80 ℃ of condition, ultrasonic 12-24 hour in sulfuric acid/nitric acid mixed liquor (3: 1).
Described preparation method, described tourmaline powder is 325-8000 purpose schorl powder or dravite powder; Described surfactant is DBSA or kayexalate.
Described preparation method, the mass ratio of described MWNT/ tourmaline/PANI is 24: 3-12: 8-72.
Described preparation method, the HCl solution amount of substance concentration of described step (3) and (4) is 0.5-1mol/L, condition of ice bath is 0-5 ℃; In described step (4), the stirring reaction time is 12-24 hour.
Described preparation method, described binding agent is polytetrafluoroethylene or 5%Nafion solution; Described conductive substrates is carbon cloth, carbon felt or carbon paper.
Described preparation method, the natural air drying time in described step (7) is 24-48 hour.
In described preparation method, described step (9), tame successfully stable for Voltage-output in MFC.
The application of microorganism electrolysis cell modification biological negative electrode in microorganism electrolysis cell prepared by described method.
Beneficial effect of the present invention is:
(1) preparation method of the present invention is simple, easily operation, and cost is low, has greatly reduced the dependence to the precious metals pt catalyst, has the application prospect of wide model in fields such as microorganism electrolysis cell processing waste water;
(2) MWNT/ tourmaline/PANI modification biological negative electrode is as the cathod catalyst of MEC, not only can utilize the modification of MWNT, tourmaline and PANI increase electrode specific surface area and then be beneficial to microorganism colonization, and can utilize tourmaline to improve microbial activity to the spread effect of microbe, the performance biocatalytic Activity.Can also utilize the high conduction performance of carbon nano-tube and polyaniline and strong redox property etc. synchronously to realize the chemical catalysis function and accelerate electronics transmission etc.
(3) using MWNT/ tourmaline/PANI modification biological negative electrode and synchronously process waste water and produce hydrogen as the cathod catalyst of MEC, can steady in a long-term move, hydrogen yield is high, reaches 1.61m
3m
-3d
-1, the COD clearance reaches 92.3%, for the commercial applications of MEC is had laid a good foundation.
The accompanying drawing explanation
Fig. 1 MWNT/ tourmaline/PANI modification biological cathode flow path figure;
Fig. 2 microbiological fuel cell structural representation;
Fig. 3 microorganism electrolysis cell structural representation;
The linear sweep voltammetry curve chart of the different negative electrodes of Fig. 4
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
MFC (the microbiological fuel cell used in the present invention, Microbial fuel cell, MFC) structure as shown in Figure 2, comprises MFC anode 1, MFC negative electrode 2, MFC water inlet 3, MFC delivery port 4, MFC reference electrode mouth 5, MFC external resistance 6, MFC data acquisition unit 7 and MFC computer 8.The MFC matrix solution is comprised of following material: in every premium on currency, contain glucose 1.0g, ammonium chloride 0.31g, potassium chloride 0.13g, sodium hydrogen phosphate 11.88g, sodium dihydrogen phosphate 2.55g, magnesium sulfate 0.2g and micro-10mL, COD is 1000mg/L, and the pH value is 7.0.
Structure as shown in Figure 3 for MEC used in the present invention (microorganism electrolysis cell, Microbial electrolysis cell, MEC), comprise MEC anode 9, MEC negative electrode 10, MEC water inlet 11, MEC delivery port 12, MEC reference electrode mouth 13, gas collection mouth 14, gas sampling mouth 15, gasometric determination pipe 16, water seal equilibration flask 17, D.C. regulated power supply 18, MEC external resistance 19, MEC data acquisition unit 20, MEC computer 21.The MEC matrix solution is comprised of following material: in every premium on currency, contain sodium acetate 1.28g, ammonium chloride 0.31g, potassium chloride 0.13g, sodium hydrogen phosphate 11.88g, sodium dihydrogen phosphate 2.55g, magnesium sulfate 0.20g and micro-10mL, COD is 1000mg/L, and the pH value is 7.0.
The first step: MWNT/ tourmaline/PANI modified electrode preparation
The unpurified carbon nano-tube of 2g (MWNT) is joined to 100mL nitric acid/sulfuric acid mixture liquid (1: 3, v/v) in, 80 ℃ of lower stirring reactions 12 hours, the black liquor of suction filtration gained, deionized water is washed till neutrality, and after filtering, drying obtains purifying carbon nano-tube.
Carbon nano-tube after the 0.2g purifying and 0.05g8000 purpose schorl powder are mixed, ball milling 30min under the 400r/min condition, the mass ratio that obtains carbon nano-tube and tourmaline is the mixture of 2: 1.In mixture, add 1mL surfactant DBSA, the dense HCl of 30mL and 70mL H
2O, ultrasonic agitation 3 hours, go in 0-5 ℃ of ice bath, obtains mixed liquor A; By the aniline 0.6mL preserved under 0-5 ℃ of condition of ice bath after decompression distillation, be dissolved in the HCl solution of 10mL1mol/L, add in above-mentioned mixed liquor A, obtain mixed liquid B; Under stirring, with the speed of 20/min to the HCl solution (the 1.5g ammonium persulfate is dissolved in the HCl solution of 10mL1mol/L) that adds ammonium persulfate in mixed liquid B, under 0-5 ℃ of condition of ice bath, continued stirring reaction 12 hours, make aniline oxidation polymerization, form ammonium persulfate at MWNT and tourmaline surface; Washing, centrifugal, dry, the mass ratio that obtains MWNT, tourmaline and PANI is the composite material of 24: 6: 72.
To after above-mentioned composite material ball milling, get 0.2g, slowly add respectively again 0.5mL deionized water and 2.5mL isopropyl alcohol, with microsyringe, get the Nafion solution of 4mL5%, after being placed in ultrasonic washing instrument ultrasonic agitation 15min, the mixture of Nafion and catalyst is coated onto on the carbon cloth electrode as far as possible equably, and the mass ratio that air drying namely made MWNT, tourmaline, PANI in 24 hours is the catalysis electrode of 24: 6: 72.Preparation method according to above-mentioned catalysis electrode can make the Pt/C catalysis electrode by conventional Pt/C catalyst and binding agent mixing.
Second step: tame biofilm in MWNT/ tourmaline/PANI modified electrode MFC, as shown in Figure 2, by water inlet 3,60mL anaerobic sludge bacterial strain and 60mL matrix solution are mixed and add biofilm in the MFC reactor with 1: 1 ratio.The MWNT/ tourmaline of the above-mentioned preparation/PANI modified electrode of take is anode, and conventional Pt/C is negative electrode.Access 1000 Ohmic resistances, start to record electricity generation process in the system closed-loop path, when voltage is low, changes MFC mesostroma solution and anaerobic sludge bacterial strain mixed liquor; Continue to change until the resistance both end voltage is greater than 600mV, and keep stable, show that the success of domestication biofilm is (about cultivation, the domestication colonization method of anaerobic sludge bacterial strain, in this area, belong at present routine techniques, can list of references: the influencing factor of microbiological fuel cell electrogenesis, the process engineering journal, 2009,9:526-530).
The 3rd step: MWNT/ tourmaline/PANI modification biological negative electrode MEC performance test
As shown in Figure 3, by MEC water inlet 11, the 120mL matrix solution is added in the MEC reactor.The carbon cloth electrode of take is anode, take respectively the MWNT/ tourmaline of above-mentioned preparation/PANI modified biological negative electrode and Pt/C catalysis electrode to be the MEC negative electrode, at negative electrode with cover plate by MEC and air insulated, make whole microorganism electrolysis cell solution be in anaerobic state.Utilize DC power supply at the additional 0.3-1.0V voltage in electrolytic cell anode and cathode two ends, make the electrolytic cell operation produce hydrogen.Access 10 Ohmic resistances, start to record the voltage at resistance two ends in the system closed-loop path, when voltage is low, changes MEC mesostroma solution; Lasting replacing realizes that under different applied voltages, hydrogen is produced in the MEC operation.The performance of different catalysis electrodes in MEC is as shown in table 1.
The performance of the different catalysis electrodes of table 1 in MEC
The 4th step: MWNT/ tourmaline/PANI modified biological electrochemical cathode performance test
The mensuration of cathode performance is used linear sweep voltammetry (LSV), three electrode test systems are adopted in experiment, wherein above-mentioned MWNT/ tourmaline/PANI modified biological negative electrode is work electrode, reference electrode is the Ag/AgCl electrode, (2 * 2cm) conducts are to the utmost point, and electrolyte is the 50mM phosphate buffer solution, before carrying out electro-chemical test for pure platinum plate electrode, first in electrolyte, lead to high pure nitrogen 15min, to remove oxygen wherein.For fear of the damage of high potential to electrode, the potential scan scope-1.0～-0.3V, sweep speed is 2mV/s, carries out under room temperature condition, result as shown in Figure 4.As can be seen from Figure 4, the catalytic perfomance of MWNT/ tourmaline prepared by the present embodiment/PANI modified biological negative electrode is better than the Pt/C catalysis electrode, and corresponding overpotential is low, and the performance of pure biological-cathode is poor comparatively speaking.
Differently from embodiment 1 be in the first step to get respectively carbon nano-tube after the 0.2g purifying, 0.1g8000 purpose schorl powder, the mass ratio that 0.6mL aniline and 1.5g ammonium persulfate make MWNT, tourmaline, PANI is the catalysis electrode of 24: 12: 72.After domestication biofilm in MFC, as MEC modification biological negative electrode, carry out MEC and produce the hydrogen test, when applied voltage is 0.9V, obtain maximum current density 189Am
-3, COD clearance 91.7%, hydrogen yield 1.53m
3m
3d
-1.This modified biological negative electrode is carried out to electrochemical property test, adopt three electrode test systems, acquired results as shown in Figure 4.
Differently from embodiment 1 be in the first step to get respectively carbon nano-tube after the 0.6g purifying, 0.15g8000 purpose schorl powder, the mass ratio that 0.2mL aniline and 0.5g ammonium persulfate make MWNT, tourmaline, PANI is the catalysis electrode of 24: 6: 8.After domestication biofilm in MFC, as MEC modification biological negative electrode, carry out MEC and produce the hydrogen test, when applied voltage is 0.9V, obtain maximum current density 178Am
-3, COD clearance 91.2%, hydrogen yield 1.34m
3m
3d
-1.This modified biological negative electrode is carried out to electrochemical property test, adopt three electrode test systems, acquired results as shown in Figure 4.
Differently from embodiment 1 be in the first step to get respectively carbon nano-tube after the 0.6g purifying, 0.3g8000 purpose schorl powder, the mass ratio that 0.2mL aniline and 0.5g ammonium persulfate make MWNT, tourmaline, PANI is the catalysis electrode of 24: 12: 8.After domestication biofilm in MFC, as MEC modification biological negative electrode, carry out MEC and produce the hydrogen test, when applied voltage is 0.9V, obtain maximum current density 158Am
-3, COD clearance 90.1%, hydrogen yield 1.20m
3m
3d
-1.This modified biological negative electrode is carried out to electrochemical property test, adopt three electrode test systems, acquired results as shown in Figure 4.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improve and conversion all should belong to the protection range of claims of the present invention.
Claims (10)
1. microorganism electrolysis cell modification biological cathode preparation method is characterized in that: take MWNT, tourmaline and PANI combination electrode prepares MEC modification biological negative electrode as base material; At first MWNT and tourmaline powder ball milling are mixed, add solvent, aniline and ammonium persulfate, stirring reaction under condition of ice bath, washing and drying obtains MWNT/ tourmaline/PANI compound; Compound and binding agent and acetone are mixed with and obtain MWNT/ tourmaline/PANI combination electrode, after natural air drying, according to conventional method, tame biofilm as the MFC anode, then move to the MEC negative electrode, finally construct MWNT/ tourmaline/PANI modification biological negative electrode.
2. preparation method as claimed in claim 1, it is characterized in that: it specifically comprises the following steps:
(1) purifying of carbon nano-tube;
(2) by carbon nano-tube after purifying and tourmaline powder ball milling mixing in proportion;
(3) in mixture, add in proportion surfactant, HCl and H
2O, stir under ice bath;
(4), under the ice bath stirring condition, in said mixture, add in proportion aniline, the ammonium persulfate that is dissolved in HCl after decompression distillation, and continue ice bath stirring reaction a few hours;
(5) said mixture washing, centrifugal, suction filtration are obtained to MWNT/ tourmaline/PANI composite material;
(6) to above-mentioned composite material add in proportion binding agent and solvent even, and ultrasonic dispersion;
(7) ultrasonic mixture is coated in to conductive substrates equably, natural air drying obtains MWNT/ tourmaline/PANI combination electrode;
(8) above-mentioned combination electrode is tamed to biofilm as for the MFC anode;
(9), after taming successfully, move to the MEC negative electrode.
3. preparation method as claimed in claim 2, it is characterized in that: the purification process of described carbon nano-tube is: under 50-80 ℃ of condition, ultrasonic 12-24 hour in sulfuric acid/nitric acid mixed liquor (3: 1).
4. preparation method as claimed in claim 2, it is characterized in that: described tourmaline powder is 325-8000 purpose schorl powder or dravite powder; Described surfactant is DBSA or kayexalate.
5. preparation method as claimed in claim 2, it is characterized in that: the mass ratio of described MWNT/ tourmaline/PANI is 24: 3-12: 8-72.
6. preparation method as claimed in claim 2, it is characterized in that: the HCl solution amount of substance concentration of described step (3) and (4) is 0.5-1mol/L, and condition of ice bath is 0-5 ℃; In described step (4), the stirring reaction time is 12-24 hour.
7. preparation method as claimed in claim 2, it is characterized in that: described binding agent is polytetrafluoroethylene or 5%Nafion solution; Described conductive substrates is carbon cloth, carbon felt or carbon paper.
8. preparation method as claimed in claim 2, it is characterized in that: the natural air drying time in described step (7) is 24-48 hour.
9. preparation method as claimed in claim 2, is characterized in that: in described step (9), tame successfully stable for Voltage-output in MFC.
10. the application of microorganism electrolysis cell modification biological negative electrode in microorganism electrolysis cell that prepare of described method as arbitrary as claim 1-9.
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| CN113764682A (en) * | 2021-09-11 | 2021-12-07 | 东莞理工学院 | SMFC (surface Mount fiber channel) mangano-manganic oxide/tourmaline composite cathode and preparation method thereof |
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