CN209039169U - Bioelectrochemical system - Google Patents
Bioelectrochemical system Download PDFInfo
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- CN209039169U CN209039169U CN201821432766.7U CN201821432766U CN209039169U CN 209039169 U CN209039169 U CN 209039169U CN 201821432766 U CN201821432766 U CN 201821432766U CN 209039169 U CN209039169 U CN 209039169U
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- 230000005611 electricity Effects 0.000 claims abstract description 28
- 238000006385 ozonation reaction Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 244000005700 microbiome Species 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 58
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 55
- 239000004917 carbon fiber Substances 0.000 claims description 55
- 229910052799 carbon Inorganic materials 0.000 claims description 43
- 238000009792 diffusion process Methods 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 31
- -1 graphite Alkene Chemical class 0.000 claims description 20
- 239000006229 carbon black Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 60
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 49
- 238000007254 oxidation reaction Methods 0.000 abstract description 42
- 230000003647 oxidation Effects 0.000 abstract description 39
- 230000003197 catalytic effect Effects 0.000 abstract description 28
- 239000005416 organic matter Substances 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 12
- 238000011065 in-situ storage Methods 0.000 abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 75
- 239000000835 fiber Substances 0.000 description 52
- 239000000463 material Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 39
- 229910052742 iron Inorganic materials 0.000 description 32
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 32
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 28
- 229910052760 oxygen Inorganic materials 0.000 description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 26
- 239000001301 oxygen Substances 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 18
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- 238000009303 advanced oxidation process reaction Methods 0.000 description 9
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- 239000013153 zeolitic imidazolate framework Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
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- 239000002245 particle Substances 0.000 description 7
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
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- 238000007906 compression Methods 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011081 inoculation Methods 0.000 description 3
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- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
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- 239000010457 zeolite Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
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- 230000000903 blocking effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003013 cathode binding agent Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- HFWIMJHBCIGYFH-UHFFFAOYSA-N cyanoform Chemical compound N#CC(C#N)C#N HFWIMJHBCIGYFH-UHFFFAOYSA-N 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- CTHCTLCNUREAJV-UHFFFAOYSA-N heptane-2,4,6-trione Chemical compound CC(=O)CC(=O)CC(C)=O CTHCTLCNUREAJV-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C02F2201/002—Construction details of the apparatus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Biodiversity & Conservation Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
The utility model discloses bioelectrochemical system, which includes: shell, limits reaction compartment in the shell；Cathode, the cathode include that can be catalyzed the catalyst for generating hydrogen peroxide；Ozonation aerated mouth, the ozonation aerated mouth setting is on the housing；Anode, the anode and cathode electrical connection；And electricity-producing microorganism, the electricity-producing microorganism are attached to the outer surface of the anode.The cathode can generate hydrogen peroxide in situ as a result, and the hydrogen peroxide and ozone of generation can carry out advanced oxidation to the organic matter in sewage, improve the sewage treatment capacity of bioelectrochemical system；Also, catalytic ozonation reaction is used in bioelectrochemical system, the potential difference of system can be provided by the energy in sewage, eliminated external a large amount of electric energy investment, saved energy consumption, application is wide.
Description
Priority information
The application request on 06 15th, 2018 to China State Intellectual Property Office submit, number of patent application be
The priority and right of 201810620330.9 patent application, and by referring to being incorporated by herein.
Technical field
The utility model relates to environment, material, energy fields.In particular it relates to bioelectrochemical system.
Background technique
Environmental problem and energy problem are that contemporary society develops two hang-ups faced, take into account the energy while purifying sewage
Recycling is the new challenge that sewage disposal technology faces.It is one by the bioelectrochemical system of Typical Representative of microbiological fuel cell
The emerging sewage disposal technology of kind, can convert electric energy for the chemical energy in pollutant while handling sewage, utilization is attached
Anode electricity-producing microorganism by the oxidation operation in sewage, while cathode receives electronics and completes oxygen reduction reaction.
However, the performance of current bioelectrochemical system is still to be improved.
Utility model content
The utility model is intended to solve at least some of the technical problems in related technologies.
Continuous with population size expands and the sustainable development of social economy, city domestic sewage and trade effluent
Discharge amount also increases, and sewage treatment load persistently aggravates, this requirement to sewage treatment level is also higher and higher.Often at present
Bioremediation, substance processing of the, relative molecular mass poor to biodegradability from thousands of to tens of thousands of is more difficult, therefore,
Poor to biodegradability frequently with advanced oxidation processes at present, the biggish substance of relative molecular weight carries out degradation treatment.Advanced oxidation processes,
Refer to using the extremely strong hydroxyl radical free radical of oxidation susceptibility generated by series reaction, the mistake of oxidative degradation is carried out to pollutant
Journey.Advanced oxidation processes can make most organic permineralization or decomposition, have a good application prospect.Wherein, ozone
Catalysis oxidation is preferable to pollutant removal, is one of more common advanced oxidation processes, in catalytic ozonation reaction,
Ozone and hydroperoxidation generate removal or even mineralising that hydroxyl radical free radical is used for pollutant, have preferable sewage treatment effect
Fruit.Inventors have found that current advanced oxidation processes there are energy consumptions higher, the higher problem of cost of sewage disposal.It uses at present
Ozone and hydroperoxidation generate in the advanced oxidation processes of hydroxyl radical free radical, hydrogen peroxide as a kind of strong oxidizer,
Industrially mainly produced by anthraquinone oxidizing process, but due to its oxidisability and unstability, during transportation not only easily
It decomposes, and is easy explosion, cause potential environmental risk.Therefore, advanced oxidation processes can be applied in electro-chemical systems
In, using the oxygen reduction reaction of cathode in electro-chemical systems, hydrogen peroxide can be generated in situ, and is used for catalytic ozonation
In reaction, is added so as to avoid the outside of hydrogen peroxide, improve safety.However, inventor is had found by further investigation,
Although outside that this method avoids hydrogen peroxide adds, but the process of hydrogen peroxide is generated by the oxygen reduction reaction of cathode
In, biggish electric energy is needed, energy consumption is higher, is unfavorable for reducing cost of sewage disposal.
In view of this, the utility model proposes a kind of bioelectrochemical systems in the one aspect of the utility model.Tool
Body, which includes: shell, limits reaction compartment in the shell；Cathode, the cathode include that can urge
Change the catalyst for generating hydrogen peroxide；Ozonation aerated mouth, the ozonation aerated mouth setting is on the housing；Anode, the anode
It is electrically connected with the cathode；And electricity-producing microorganism, the electricity-producing microorganism are attached to the outer surface of the anode.As a result, should
Cathode can generate hydrogen peroxide in situ, and the hydrogen peroxide and ozone of generation can carry out advanced oxygen to the organic matter in sewage
Change, improves the sewage treatment capacity of bioelectrochemical system；Also, catalytic ozonation reaction is used for bioelectrochemistry system
In system, the potential difference of system can be provided by the energy in sewage, eliminated external a large amount of electric energy investment, saved energy consumption,
Application is wide.
Specifically, the cathode is air cathode, the cathode includes: catalyst layer, and the catalyst layer includes described
The catalyst for generating hydrogen peroxide can be catalyzed；Current collection layer；And diffusion layer.The straight of oxygen in air may be implemented in the cathode as a result,
Diffusion, mass transfer are connect, a large amount of aeration energy consumption is saved, and it is possible to which catalytic oxygen generates hydrogen peroxide, the hydrogen peroxide of generation
Can and ozonization, to organic matter carry out oxidative degradation, improve the service performance of the bioelectrochemical system.
Specifically, the catalyst includes: carbon black, graphene, carbon nanotube, carbon fiber or mesoporous carbon.As a result, into one
Step improves catalytic performance, improves the service performance of the bioelectrochemical system.
Specifically, the diameter of the carbon fiber is 0.1-5 μm.The catalyst and the biology are further improved as a result,
The service performance of electro-chemical systems.
Specifically, being free of binder in the catalyst layer.Avoid as a result, binder bring catalytic site blocking with
And the problems such as electric conductivity decline, and the cathode of binder free is also possible to prevent to fall off and band in long-term use due to binder
The cathode life problem come.
Specifically, the load capacity 2-30mg/cm of catalyst described in the catalyst layer2.Yin is further improved as a result,
The service performance of pole.
Specifically, the anode is formed by carbon brush, carbon cloth, carbon cloth or granular activated carbon.As a result, further
Improve the service performance of anode.
Specifically, the anode is plane-shape electrode, the electro-chemical systems further comprise: diaphragm, the diaphragm setting
Between the air cathode and the anode.The service performance of the bioelectrochemical system is further improved as a result,.
Detailed description of the invention
The above-mentioned and/or additional aspect and advantage of the utility model from the description of the embodiment in conjunction with the following figures will
Become obvious and be readily appreciated that, in which:
Fig. 1 shows the structural schematic diagram of the bioelectrochemical system according to the utility model one embodiment；
Fig. 2 shows the method flow diagram for preparing catalyst according to the utility model one embodiment；
Fig. 3 shows the structural schematic diagram of the air cathode according to the utility model one embodiment；
Fig. 4 shows the structural schematic diagram of the air cathode according to the utility model another embodiment；
Fig. 5 shows the structural schematic diagram of the air cathode according to the utility model another embodiment；
Fig. 6 shows the method flow diagram for preparing air cathode according to the utility model one embodiment；
Fig. 7 shows the structural schematic diagram of the bioelectrochemical system according to the utility model another embodiment；
Fig. 8 shows (A) carbon fiber under 5000 times of amplification factor, (B) carbon-iron composite fibre, (C) ZIF-8 modification carbon fiber
ZIF-8 modification PAN-Fe fiber (E) ZIF-8 modified carbon-iron fiber SEM photograph that dimension, (D) spinning obtain；
Fig. 9 shows (A) carbon fiber under 25000 times of amplification factor, (B) carbon-iron composite fibre, (C) ZIF-8 modification carbon fiber
ZIF-8 modification PAN-Fe fiber (E) ZIF-8 modified carbon-iron fiber SEM photograph that dimension, (D) spinning obtain；
Figure 10 is shown according to the MFC of the utility model one embodiment electrolysis, independent ozone and MFC ozone coupling
Methylene blue removal rate figure；
Figure 11 shows the methylene blue of independent ozone and MFC ozone coupling according to the utility model one embodiment
Removal rate figure；And
Figure 12 shows the power density curve graph of MFC, MFC ozone coupling.
Appended drawing reference:
10: catalyst layer；20: current collection layer；30: diffusion layer；40: supporting layer；100: shell；200: diaphragm；300: anode；
400: cathode；500: electricity-producing microorganism；600: ozonation aerated mouth.
Specific embodiment
The embodiments of the present invention are described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning
Same or similar element or element with the same or similar functions are indicated to same or similar label eventually.Below by ginseng
The embodiment for examining attached drawing description is exemplary, and is only used for explaining the utility model, and should not be understood as to the utility model
Limitation.
In the one aspect of the utility model, the utility model proposes a kind of bioelectrochemical system (MFC).According to this
The embodiment of utility model, the bioelectrochemical system include: shell 100, limit reaction compartment in shell 100；Cathode
400, cathode 400 includes that can be catalyzed the catalyst for generating hydrogen peroxide；Ozonation aerated mouth 600, ozonation aerated mouth 600 are used for cathode
400 provide ozone, and ozonation aerated mouth 600 is arranged on shell 100；Anode 300, anode 300 and cathode 400 are electrically connected；And
Electricity-producing microorganism 500, electricity-producing microorganism 500 are attached to the outer surface of anode 300.The cathode can generate peroxide in situ as a result,
Change hydrogen, the hydrogen peroxide and ozone of generation can produce the free radical that hydroxyl radical free radical etc. has Strong oxdiative function, can be with
Advanced oxidation is carried out to the organic matter in sewage, improves the sewage treatment capacity of bioelectrochemical system；Also, ozone is urged
Oxidation is in bioelectrochemical system, the potential difference of system can be provided by the energy in sewage, utilize anode
The electric energy of generation is supplied to cathode and reacts for electrochemical catalysis, eliminates external a large amount of electric energy investment, saves energy consumption, application
Property is wide.
In order to make it easy to understand, can be realized to the bioelectrochemical system according to the utility model embodiment above-mentioned has below
The principle of beneficial effect is briefly described:
On the one hand, as previously described, because hydrogen peroxide oxidation is high, stability is poor, transport is inconvenient, therefore, according to this reality
With novel embodiment, the advanced oxidation reaction and bioelectrochemical system of ozone and hydrogen peroxide are combined, can use life
The oxygen reduction reaction (two electronics oxygen reduction reactions) of cathode in object electro-chemical systems, it is in situ to generate hydrogen peroxide, so as to avoid
The outside of hydrogen peroxide adds, and improves safety, and the hydrogen peroxide of generation can enter the bioelectricity with from ozonation aerated mouth
The ozone reaction of chemical system generates the free radical with Strong oxdiative function such as hydroxyl radical free radical, to organic in sewage
Object carries out advanced oxidation removal；On the other hand, as previously mentioned, generating the process of hydrogen peroxide using the oxygen reduction reaction of cathode
In, need biggish electric energy, energy consumption is higher, and cost of sewage disposal is higher, and embodiment according to the present utility model, by ozone and
The advanced oxidation reaction of hydrogen peroxide is combined with bioelectrochemical system, and anode microorganism can be with while degradation of organic substances
It generates electronics (i.e. offer electric energy), which can carry out oxygen reduction reaction in cathode, therefore, according to this reality for delivery to cathode
With the bioelectrochemical system of new embodiment, cathode generates electric energy required for hydrogen peroxide in situ and can be confessed by anode
It gives, to dramatically save the power consumption of sewage treatment, has saved cost of sewage disposal, and pass through ozonation aerated mouth to yin
When pole provides ozone, the energy for needing to externally supply is less, therefore, generally, according to the bioelectricity of the utility model embodiment
Cathode advanced oxidation and bioelectrochemical system are coupled, not only increase the sewage of the bioelectrochemical system by chemical system
Processing capacity saves cost of sewage disposal moreover, reducing the energy consumption in sewage treatment, and application prospect is extensive.
Embodiment according to the present utility model, the type that can be catalyzed the catalyst of generation hydrogen peroxide are not particularly limited, only
It wants to be catalyzed and generates hydrogen peroxide (i.e. hydrogen peroxide).Hydrogen peroxide in conjunction with ozone or can be based on other in the cathode
Approach generate hydroxyl radical free radical, thus realize above-mentioned advanced oxidation processes (for example, when in the catalyst include ferrous iron when, two
With organic matter Fenton's reaction can occur for valence iron ion and hydrogen peroxide, so as to by organic matter, such as carboxylic acid, alcohol, esters
It is oxidized to inorganic matter, and then can be with many hardly degraded organic substances in oxidation removal sewage).Specifically, catalyst can be carbon
Base catalyst, such as at least one of carbon black, graphene, carbon nanotube, carbon fiber and mesoporous carbon；Alternatively, can also be miscellaneous original
The carbon-based material of son doping, such as the carbon-based material containing polyoxometallate, the carbon substrate containing active metal (such as Fe)
Material.
Specific embodiment according to the present utility model, can be catalyzed and generate the catalyst of hydrogen peroxide may include carbon fiber, carbon
Metal-organic framework compound and iron can be modified on fiber.Modified metal-organic frame chemical combination on carbon fiber as a result,
Object and iron can produce synergistic effect, can significantly improve the electrocatalysis characteristic of carbon fibre material, and therefore, which has excellent
Electrocatalysis characteristic, and the bioelectrochemical system have excellent service performance.Embodiment according to the present utility model, gold
Category-organic frame compound may include zeolite imidazole ester framework structured compound.The modification of zeolite imidazoles on carbon fiber as a result,
Ester framework structured compound and iron can produce synergistic effect, can significantly improve the electrocatalysis characteristic of carbon fibre material, therefore,
The catalyst has excellent electrocatalysis characteristic.Also, the iron in the catalyst can occur with the hydrogen peroxide generated in situ
Fenton's reaction, can be with degradation of organic substances, to further improve the sewage treatment performance of the bioelectrochemical system.It that is to say
It says, when including iron in cathod catalyst, on the cathode, ozone and hydrogen peroxide can interact and generate hydroxyl, can be to sewage
In organic matter carry out advanced oxidation, can also be in sewage moreover, iron and hydrogen peroxide can also interact and generate hydroxyl
Organic matter carries out advanced oxidation, i.e. generation Fenton's reaction, to further improve the sewage treatment of the bioelectrochemical system
Ability.The electro-chemical systems can generate hydrogen peroxide in situ as a result, certainly so as to easy utilization hydrogen peroxide manufacture hydroxyl
By the Strong oxdiatives group such as base, to realize the advanced oxidation to sewage.
Advanced oxidation processes, which refer to, generates the extremely strong hydroxyl radical free radical of oxidation susceptibility for pollutant by series reaction
The process of degradation, hydrogen peroxide/ozone, hydrogen peroxide/UV, catalytic ozonation, Fenton's reaction etc. are all common advanced oxygen
The method of change.Specifically, the electro-chemical systems can further have ozonation aerated unit, to cathode at ozone supply, utilize
Hydrogen peroxide/ozone generates hydroxyl radical free radical, realizes the advanced oxidation of sewage.
Inventor by further investigation and many experiments discovery, on carbon fiber simultaneously modified metal-organic frame
When closing object and iron, which has preferable catalytic performance, which has preferable electricity generation performance, not only
Can the fully oxidized pollutant decomposed in sewage, and can preferably recycle the energy resource in sewage.
On the one hand, modified metal-organic frame compound (the Metal-Organic Framework, MOF) on carbon fiber
When, since metal-organic framework compound has high specific surface area and Modulatory character, especially zeolite imidazole ester skeleton knot
Structure material (ZIF) have open skeleton structure, high stability, the specific surface area of super large and rule cellular structure (such as
The specific surface area of part ZIF member is up to 1970m2/ g, thermal decomposition temperature are up to 663K, flow back in vapor and organic solvent
In the case of be still able to maintain higher stability), therefore, the compound-modified carbon fiber of metal-organic framework have preferably urges
Change activity, also, there is novel topological structure, good catalytic activity during heterogeneous catalysis in ZIF family member.Root
According to the embodiments of the present invention, using monodispersed ZIF material (such as ZIF-8 particle, ZIF-8 are one kind of ZIF material,
Its synthesis condition is mild, easily prepared) modification carbon material when, can by the control to ZIF material (such as ZIF-8 particle) partial size
Easily to realize the control of the properties such as the partial size of nano carbon particle obtained for carbonization, the nanometer of obtained ZIF material modification
Carbon particle has excellent property, the catalytic performances such as specific surface area and the hole area of superelevation excellent.Also, according to the utility model
Embodiment, total carbonization will be carried out in ZIF-8 incorporation fibrous material, the carbon fibre material of obtained ZIF-8 modification can obtain
To better electrocatalysis characteristic.The carbon fiber for being modified with metal-organic framework compound is used for bioelectrochemical system as a result,
In cathode catalysis material when, the hydrogen reduction performance of cathode is higher (i.e. the electron acceptor concentration of cathode is higher), so as to promote
Electricity-producing microorganism into anode constantly decomposing organic matter and generates electronics, to improve at the sewage of bioelectrochemical system
Reason ability and electricity generation performance.
On the other hand, when modifying iron on carbon fiber, specifically, can be adulterated in the precursor solution for preparing carbon fiber
Iron, iron there may be there are three types of forms, respectively Fe7C3,Fe3Carbon-iron composite fibre of C and α-Fe, doping iron can be in electricity
Good electro-Fenton reaction performance is realized under electrochemical conditions.Embodiment according to the present utility model utilizes the carbon fiber for being modified with iron
When tieing up cathode catalysis material as bioelectrochemical system, the hydrogen peroxide that is generated due to Fenton's reaction, cathode electrocatalyst and
Fe2+Reaction generates Fe3+, the Fe of generation3+Electronics can be obtained on cathode be reduced to Fe2+, so that Fenton's reaction can be with
Circulation carries out, and improves Fenton's reaction to the oxidation removal efficiency of organic matter, meanwhile, increase containing for the electron acceptor of cathode
Amount；Also, the cathode aeration ozone generated and the hydroperoxidation generated in situ, the strong oxidizing property free radical OH of generation is not
The organic matter in sewage can only be aoxidized, also electronics is obtained on cathode and be reduced, thus further improve cathode electronics by
The concentration of body can also promote the electricity-producing microorganism of anode constantly to decompose so that the electro-catalysis electric current of cathode further increases
Organic matter simultaneously generates electronics, to improve the sewage treatment capacity and electricity generation performance of bioelectrochemical system.
In summary, carbon fiber is repaired due to incorporation iron and using metal-organic framework compound (such as ZIF-8)
Decorations, the sewage treatment capacity for improving bioelectrochemical system is different with the mechanism of electricity generation ability, therefore uses metal-organic framework
The synergistic effect that the two can be obtained when carbon-iron composite fibre of compound (such as ZIF-8) modification, i.e., work as in electro-chemical test
In, carbon-iron fiber of metal-organic framework compound (such as ZIF-8) modification shows optimal electrocatalysis characteristic.
Embodiment according to the present utility model, based on that can be catalyzed the gross mass for generating the catalyst of hydrogen peroxide, metal-is organic
The weight percent of frame compound can be 1%~50%, for example, can be 10%~20%.Metal-has machine frame as a result,
The weight percent of frame compound in the range when, can preferably improve the catalytic performance of the catalyst.Specifically, golden
Category-organic frame compound weight percent can be 3%, 5%-30%, 9%, 15%, 10%-20%, 12%, 15%,
17%.Embodiment according to the present utility model, based on the gross mass for the catalyst that can be catalyzed generation hydrogen peroxide, the weight percent of iron
It than being 1%~50%, such as can be 8%-20%.Specifically, the weight percent of iron can be 3%, 5%, 8%, 10%,
12%, 15%, 17%, 20%, 30%, 40%.The catalytic performance of the catalyst is further improved as a result,.Also, when gold
When the weight percent of category-organic frame compound and iron is distinguished within the above range, metal-organic framework compound and iron can
To have preferable synergistic effect, the sewage treatment capacity and electricity generation performance of bioelectrochemical system can be preferably improved.
Embodiment according to the present utility model, the diameter of carbon fiber can be 0.1-5 μm, such as can be 3-5 μm.By
This, the diameter of carbon fiber within this range when, specific surface area is larger, further improves the catalytic performance of the catalyst.Tool
Body, can be 1 μm, 2 μm, 0.5 μm, 3 μm, 4 μm.
Embodiment according to the present utility model, can be catalyzed generate hydrogen peroxide catalyst may include: carbon black, graphene,
At least one of carbon nanotube, carbon fiber and mesoporous carbon.Embodiment according to the present utility model, carbon fiber may include gold
The carbon fiber of at least one of category-organic frame compound, iron, carbon black, graphene, carbon nanotube and mesoporous carbon modification.By
This, further improves catalytic performance, improves the service performance of the bioelectrochemical system.
In order to make it easy to understand, simply being retouched to preparation according to the method for the catalyst of the utility model embodiment below
It states.
Embodiment according to the present utility model, which, which can be, utilizes electrostatic spinning shape
At, be made of fiber with self-supporting can layer structure.In order to further increase the catalytic performance of the catalyst, also
The carbon-based catalysis material with catalytic production hydrogen peroxide performance can be filled in the hole of the fiber with self-supporting energy.
Carbon-based catalysis material can be the upper of carbon black, active carbon, carbon dust, graphene, carbon nanotube and hetero atom (O, S, N etc.) doping
State material.
Embodiment according to the present utility model can be catalyzed and generate the catalyst of hydrogen peroxide and can be side by electrostatic spinning
Method preparation, with reference to Fig. 2, the method for electrostatic spinning may include:
S200: precursor solution is formed
In this step, carbon source is added, into solvent to form precursor solution.Implementation according to the present utility model
Example, solvent can be n,N-Dimethylformamide (DMF).Embodiment according to the present utility model, carbon source in precursor solution
Concentration can be greater than 5%.Thus, it is possible to the good flexible carbon fiber catalyst of processability.
Embodiment according to the present utility model, the concentration of carbon source described in precursor solution can be 5-15%, Ke Yi great
It can be 9-12% in 7%.Specifically, the concentration of carbon source can be 10%, 11%, 12% in precursor solution.As a result, may be used
With the good carbon fiber catalyst of processability.Embodiment according to the present utility model, carbon source may include polyacrylonitrile
(PAN), polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, carbon black, graphene, carbon nanotube and mesoporous carbon at least it
One.Thus, it is possible to the good carbon fiber catalyst of processability.
Embodiment according to the present utility model, when the carbon fiber for preparing metal-organic framework compound and/or iron modification
When, this method may further include: source of iron and metal-organic framework compound is added extremely in the solvent that carbon source is added
It is one of few, to form precursor solution.Embodiment according to the present utility model, source of iron may include praseodynium iron (Fe
(acac)3), diacetyl acetone ferrous iron, ferric trichloride, frerrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate and ferrous nitrate
At least one of.Thus, it is possible to the good carbon fiber catalyst of processability.
S300: electrostatic spinning processing is carried out
In this step, electrostatic spinning processing is carried out to precursor solution, to form fiber.It is according to the present utility model
Embodiment, the voltage of electrostatic spinning processing can be 5-30KV, specifically, the voltage of electrostatic spinning processing can be 8-12KV,
It can be 15KV, can be 20KV, can be 25KV.Thus, it is possible to the good carbon fiber catalyst of processability.According to this reality
With novel embodiment, in electrostatic spinning processing, distance of the electrospinning spinnerets away from receiver is 8-30cm, specifically, electrospinning spinnerets
Away from receiver away from can be 20cm, can be 25cm from that for 12-18cm, can be 15cm.Thus, it is possible to preparative
It can good carbon fiber catalyst.Embodiment according to the present utility model, electrostatic spinning processing in, to electrospinning spinnerets supply described in
The speed of precursor solution is 5-100 μ L/min, specifically, the speed of the precursor solution can be 7-15 μ L/min, it can
Think 20 μ L/min, can be 30 μ L/min.Thus, it is possible to the good carbon fiber catalyst of processability.
S400: pre-oxidation treatment is carried out
In this step, pre-oxidation treatment is carried out to the fiber that preceding step is formed.Embodiment according to the present utility model,
The macromolecular fibre that spinning terminates does not have electric conductivity, to prepare electrode, it is also necessary to be carbonized.Due to direct carbonization meeting
Fibre structure is destroyed, so that it is lost flexibility, preoxidation process is usually carried out before carbonization.Implementation according to the present utility model
Example, pre-oxidation treatment include: by carbon fiber or to have modified the fiber of metal-organic framework compound and iron and be placed in air atmosphere
In, the first heat treatment is carried out, the heating rate of the first heat treatment is 0.1-10 DEG C/min, specifically, the first heat treatment
Heating rate be 0.5-1.5 DEG C/min, can be 1 DEG C/min, can be 3 DEG C/min, can be 5 DEG C/min.Thus, it is possible to
Fibre structure caused by avoiding the rate of heat addition too fast destroys.It is heated to 220-400 degrees Celsius, is specifically heated to 250-300 DEG C
Afterwards, 1-3h is kept the temperature.Thus, it is possible to the good carbon fiber catalyst of processability.
S500: carbonization treatment is carried out
In this step, the fiber of the pre-oxidation treatment Jing Guo preceding step is subjected to carbonization treatment, to form carbon fiber
Dimension, to form catalyst.Embodiment according to the present utility model, carbonization treatment include: by the carbon fiber Jing Guo pre-oxidation treatment
The fiber for tieing up or having modified metal-organic framework compound and iron carries out the second heat treatment in nitrogen atmosphere, is warming up to
700-1300 DEG C, be carbonized 1-2h, and the heating rate of the second heat treatment is 0.1-10 DEG C/min, specifically, can be warming up to
1000 DEG C, be carbonized 1h, second heat treatment heating rate be 0.5-1.5 DEG C/min, can be 1 DEG C/min, can for 3 DEG C/
Min can be 5 DEG C/min.Thus, it is possible to fibre structure caused by avoiding the rate of heat addition too fast destroys, it can be good with processability
Good carbon fiber catalyst.
Specific embodiment according to the present utility model can prepare four kinds of carbon fibers using mentioned-above method of electrostatic spinning
Catalyst, i.e. pure carbon fiber, carbon-iron composite fibre, ZIF-8 modifying carbon fibers, ZIF-8 modified carbon-iron composite fibre.Specifically
, 1g polyacrylonitrile (carbon source) can be first dissolved in the precursor for being used as electrostatic spinning in 10mL DMF, be used to prepare soft
The carbon fibre material of property.Since there is no chemical changes for macromolecule in spinning process, therefore still maintain the knot of polyacrylonitrile
Structure.After spinning, carbon fibre material can just be obtained by needing for fibrous material to be carbonized.It is a large amount of due to containing in polyacrylonitrile
With nitrogen existing for cyano form, these nitrogens are largely scattered and disappeared in the form of nitrogen when high temperature cabonization, if directly
Carbonization is connect, then the structure that will lead to fibrous material is carbonized the gas generated in process and is destroyed, so as to cause fibrous material
Flexibility is lost, or even becomes powder.Generation in order to prevent this phenomenon needs to carry out before carbonization the pre- oxygen of fibrous material
Change, is heated in air to drive the cyano in fibrous material away.Fiber after pre-oxidation becomes dark-brown from yellow,
Represent the variation of wherein chemical composition.Fibrous material is carbonized again after pre-oxidation, so that it may avoid gas molecule
It discharges bring fibre structure to destroy, keeps flexible.It is also needed when pre-oxidation operation fine caused by preventing the rate of heat addition too fast
It ties up structure to destroy, therefore, the rate of heat addition can be 1 DEG C/min.
Embodiment according to the present utility model is available for the carbon of production electrode catalyst layer by pre-oxidizing and being carbonized
Fibrous material.Fibrous material is during pre-oxidation and carbonization, due to only remaining carbon atom during organic carbon, institute
To result in Mass lost, fiber size can there is a phenomenon where reduce.Inventors have found that pre-oxidation rate it is excessively high (such as higher than
10 DEG C/min), preferable flexible carbon fibre material cannot be prepared.Also, the concentration of precursor solution too low (such as less than 7%
When), liquid is unable to the preferably flexible carbon fibre material of processability.Specific embodiment according to the present utility model, when pre-oxidation
When heating rate is 0.5-1.5 DEG C/min, also, when precursor concentration is greater than 7% (such as 9%), it can obtain flexible good
Good carbon fibre material.As a result, utilize this method, based on electrostatic spinning technique can simple and quick preparation carbon fibre material.It removes
Except preparation is easy, have using mentioned-above electrostatic spinning-carbonization technique preparation monolith flexibility carbon fibre material good
Electric conductivity, high-specific surface area and excellent load performance.
Inventors have found that cathode is the central factor for influencing electrozone catalysis oxidation and bioelectricity catalytic ozonation performance
One of.But oxygen needed for cathode used at present provides hydrogen reduction by aeration, energy consumption are higher.Reality according to the present utility model
Example is applied, the cathode in bioelectrochemical system can be air cathode, and the direct of oxygen in air may be implemented in the cathode as a result,
Diffusion, mass transfer, save a large amount of aeration energy consumption, and it is possible to effectively be catalyzed two electronics oxygen reduction reactions and ozone in-situ is urged
Oxidation carries out oxidative degradation to organic matter, improves the service performance of the bioelectrochemical system, realizes to sewage
Deep purifying.
Embodiment according to the present utility model, cathode are air cathode, and with reference to Fig. 3, which includes: catalyst layer
10, current collection layer 20 and diffusion layer 30, catalyst layer 10 include the catalyst that catalytic oxygen generates hydrogen peroxide.The cathode as a result,
Can with catalytic oxygen generate hydrogen peroxide, also, generate hydrogen peroxide can and ozonization, oxidation drop is carried out to organic matter
Solution, improves the service performance of the bioelectrochemical system.Specifically, the catalyst layer can be through mentioned-above electrostatic
The material with self-supporting energy of spin processes preparation, further improves the service performance of the air cathode as a result,.According to this
The embodiment of utility model, current collection layer 20 improve the conductive capability of the air cathode for collected current；Diffusion layer 30 is used for
Promote the transmission of oxygen and prevents liquid water from overflowing from air cathode.
Specifically, embodiment according to the present utility model, with reference to Fig. 3, the diffusion layer 30 of the air cathode can be with air
Be in contact (not shown), so that reduction reaction occurs using the oxygen in air, and then realizes the use of the air cathode
Function.Current collection layer 20 is formed in side of the diffusion layer 30 far from air, and catalyst layer 10 is formed in current collection layer 20 far from diffusion layer
30 side, and with electrolyte contacts (not shown).Diffusion layer 30 is contacted with air as a result, so that oxygen can be spread
Into the air cathode, while current collection layer 20 is used to be enriched with electric current, and improves the electric conductivity of air cathode, and catalyst layer 10 is being urged
Under agent effect, reduction reaction occurs using electronics and oxygen, and then the using effect of the air cathode can be improved.
In addition, embodiment according to the present utility model, with reference to Fig. 4, which can also have a structure that diffusion
Layer 30 is in contact (not shown) with air, and catalyst layer 10 is positioned at being formed in side of the diffusion layer 30 far from air, current collection
Layer 20 is formed in side of the catalyst layer 10 far from diffusion layer 30, and with electrolyte contacts (not shown).And then it can mention
The using effect of the high air cathode.
In addition, the air cathode can also further have branch in order to further increase the using effect of the air cathode
Support layer.Embodiment according to the present utility model, with reference to Fig. 5, supporting layer 40 is formed between catalyst layer 10 and diffusion layer 30, and
And supporting layer 40 can be formed by stainless (steel) wire.Thus, it is possible to be provided by supporting layer 40 for the air cathode more good
Support construction, and supporting layer 40 and current collection layer 20 are located at the two sides of catalyst layer 10, and then can be catalyst layer 10
Good protection is provided, prevent 10 dusting of catalyst layer in actual use lose and to the using effect of the air cathode
It adversely affects.In addition, the supporting layer 40 being made of stainless (steel) wire can also further increase the electric conductivity of the air cathode,
And then it can be further improved the performance of the air cathode.
Embodiment according to the present utility model is free of binder in catalyst layer 10.It avoids and is brought by binder as a result,
Catalytic site blocking and electric conductivity the problems such as declining, and the air cathode of binder free is also possible to prevent due to binder
It falls off and bring cathode life problem in long-term use.Embodiment according to the present utility model, catalyst in catalyst layer
Load capacity can be 2-30mg/cm2, specifically, can be 2-6mg/cm2.Making for air cathode is further improved as a result,
Use performance.Embodiment according to the present utility model, catalytic current density of the air cathode under -0.4V current potential are not less than 15A/
m2.The air cathode has good service performance as a result,.Also, the characteristic of the air cathode binder free, so that Gao Bibiao
The advantage of the catalysis material of area is fully utilized, and excellent load performance enables fibrous material to load various other urge
Agent carries out advanced optimizing for material, therefore the catalyst layer has two excellent electronics hydrogen reduction catalytic capabilities.
In order to make it easy to understand, simply being retouched to preparation according to the method for the air cathode of the utility model embodiment below
It states.Specifically, mentioned-above air cathode can be through following methods preparation, with reference to Fig. 6, this method comprises:
S10: current collection layer is provided
In this step, current collection layer is provided.Embodiment according to the present utility model, current collection layer, which can be, to be formed by stainless steel
, to utilize the good electric conductivity of stainless steel, by electron rich on the air cathode, and then air yin can be improved
The performance of pole.Specifically, embodiment according to the present utility model, current collection layer can be formed by stainless (steel) wire.
S20: diffusion layer is formed
In this step, diffusion layer is formed.Embodiment according to the present utility model, diffusion layer can be by following steps systems
It is standby: carbon black to be mixed with 60 mass % polytetrafluoroethylene (PTFE) (PTFE) dispersion liquids, the quality of carbon black and 60 mass %PTFE dispersion liquids
Than for 2:3.Ethyl alcohol is added in the mixture of carbon black and 60 mass %PTFE dispersion liquids to increase the viscosity of said mixture,
Then, ultrasonic mixing 10-30 minutes in 80 degrees Celsius of water-bath, so that said mixture forms sticky mass.Finally, will
Above-mentioned sticky mass carries out forming processes, to obtain diffusion layer.Specifically, embodiment according to the present utility model, by this
Sticky mass quickly rubs pressure under 80 degrees Celsius, the pressure less than 0.5MPa by kneading, to make ethyl alcohol volatilize, and
Keep carbon black even closer in conjunction with PTFE during rubbing pressure.It then repeats above-mentioned rub and presses through journey 3-5 times, to improve preparation
The compressive property of diffusion layer in use.Then, will lead at 80 degrees Celsius, 1.5MPa by the mixture for rubbing pressure repeatedly
Vertical compression machine vertical compression 10 seconds are crossed, to obtain sticky solid tabletting.The sticky solid tabletting is placed on the second stainless (steel) wire,
80 degrees Celsius, under conditions of 4.5MPa by the pressure maintaining of vertical compression machine 1 minute, so that the sticky solid tabletting is closely tied with stainless (steel) wire
It closes.Then the stainless (steel) wire containing sticky solid tabletting is put into Muffle furnace, is heat-treated 15-20 minutes under 340 degrees Celsius
Make its curing molding, to obtain diffusion layer.In addition, another embodiment according to the present utility model, is preparing diffusion layer
In the process, sticky solid tabletting can not be compressed on the second stainless (steel) wire, and diffusion layer is directly obtained by vertical compression process.
It will be appreciated by those skilled in the art that stainless (steel) wire can be played and be supported in tableting processes during preparing diffusion layer
The effect of diffusion layer, to reach better tabletting effect.Therefore, the specific area of the second stainless (steel) wire and mesh number be not by spy
It does not limit, as long as can play the role of supporting diffusion layer.For example, one embodiment according to the present utility model, second
Stainless (steel) wire can be that area is 11.3cm250 mesh stainless (steel) wires.
S30: catalyst is compressed between current collection layer and diffusion layer, to form air cathode
In this step, catalyst is compressed between current collection layer and diffusion layer, to form air cathode.According to this reality
With novel embodiment, as previously mentioned, catalyst prepared by the method for using electrostatic spinning can be the layer structure of self-supporting,
It is therefore not necessary to other auxiliary supporting materials, can easily by catalyst direct pressing obtained current collection layer and diffusion layer it
Between, to form air cathode.The catalyst of the layer structure can be directly pressed together on branch by embodiment according to the present utility model
On support structure, to obtain cathode.
Embodiment according to the present utility model, with reference to Fig. 3, firstly, diffusion layer 30 is prepared according to previously described method,
In, diffusion layer 30 is compressed on the side of the second stainless (steel) wire.Then, catalyst layer 10 is prepared using previously described method,
Also, catalyst layer 10 is compressed on the side of the first stainless (steel) wire.To be compressed on the diffusion layer on the second stainless (steel) wire 30 with
It is compressed together by vertical compression machine under the pressure of 10~40MPa to be formed in the catalyst layer 10 on the first stainless (steel) wire, straight
During pressure, catalyst layer 10 is contacted with the second stainless (steel) wire.The first stainless (steel) wire can be as the collection of the air cathode as a result,
Electric layer 20, meanwhile, supporting layer 40 of second stainless (steel) wire as the air cathode.Then, above-mentioned pressure is kept 20 minutes, so as to
Above-mentioned four-layer structure can be combined closely.Finally, it is 30 minutes dry under 80 degrees Celsius in Muffle furnace, on removing
State the moisture in structure.Thus, it is possible to easily obtain the air cathode according to the utility model embodiment.
Thus, it is possible to easily prepare mentioned-above cathode, and the cathode performance is good.
Embodiment according to the present utility model, anode be by carbon brush, carbon cloth, carbon cloth and granular activated carbon at least
One of formed.Thus, it is possible to further save the cost of the bioelectrochemical system, and the electricity production bacterium is improved in anode
Adhesive ability.
Embodiment according to the present utility model, with reference to Fig. 7, when anode is plane-shape electrode, which can be with
Further comprise: diaphragm 200, diaphragm 200 are arranged between air cathode 400 and anode 300.It further improves as a result,
The service performance of the bioelectrochemical system.Embodiment according to the present utility model, barrier material, that is, diaphragm 200 can for sun from
Proton exchange or ceramic membrane.Thus, it is possible to realize microorganism to sewage degradation, synchronous electrogenesis and cathode generate hydrogen peroxide and
Fenton's reaction in situ carries out the deep purifying of sewage.
Embodiment according to the present utility model, with reference to Figure 10 and Figure 11, when which runs 2 hours pair
The removal rate of methylene blue is not less than 90%.The electro-chemical systems have good sewage treatment capacity as a result,.
Embodiment according to the present utility model, with reference to Figure 12, when which is 100 ohm, power
Density is not less than 135mW/m2.The electro-chemical systems have good electricity generation performance as a result,.
In summary, the utility model provides one kind suitable for electro-catalysis production hydrogen peroxide and situ catalytic electrozone is urged
The cathode of oxidation, the advanced treating etc. for sewage.Embodiment according to the present utility model, catalyst can be use
Electrostatic spinning-pre-oxidation-carbonization technique preparation carbon fiber-based material, the material is conductive well, specific surface area is larger
The features such as, applied to the catalysis for being catalyzed two electronics oxygen reduction reactions and ozone in-situ catalytic oxidation in bioelectrochemical system
Performance is high, stability is good, and raw material sources are extensive；Embodiment according to the present utility model, cathode can be air cathode, air yin
Level Four layer structure can be extremely used, is divided into Catalytic Layer, current collection layer, diffusion layer and supporting layer, preparation process is succinct.According to this reality
With the bioelectrochemical system of new embodiment, there is good sewage treatment capacity and electricity generation performance, also, by ozone catalytic
Oxidation reaction is in bioelectrochemical system, the potential difference of system can be provided by the energy in sewage, be produced using anode
Raw electric energy is supplied to cathode and reacts for electrochemical catalysis, eliminates external a large amount of electric energy investment, saves energy consumption, application
Extensively.
Catalyst and air cathode described in the utility model have the advantage that
1) using specific surface area, larger, conductive black material with good conductivity turns electronics as oxygen reduction catalyst
Shifting is more likely to two electronic mechanisms, generates hydrogen peroxide.
2) carbon black materials obtain be easy, cost is relatively low, substantially reduces the cost of air cathode, facilitate electro-chemical systems and
Popularization and use of the bioelectrochemical system in terms of sewage treatment and recycling.
3) method made using Catalytic Layer, current collection layer, diffusion layer, the lamination of supporting layer four prepares air cathode, technique letter
Just, condition is simple, and the air cathode prepared is functional, is suitble to large area production.
It should be noted that concrete type is not by special according to the bioelectrochemical system of the utility model embodiment
Limitation, as long as oxygen reduction reaction occurs for its cathode.It such as can be microbiological fuel cell, microorganism electrolysis cell or micro-
Biological desalination cell etc., and according to the bioelectrochemical system of the utility model embodiment, application scenarios are very extensive, example
It such as can be used for handling sanitary sewage, trade effluent, and the organic matter in sewage is electric energy by microorganism conversion by it,
While eliminating pollution, available energy is generated, low energy consumption and high-efficient.
The embodiment of the utility model is explained below in conjunction with embodiment.Under it will be understood to those of skill in the art that
The embodiment in face is merely to illustrate the utility model, and should not be regarded as limiting the scope of the utility model.It is not specified in embodiment
Particular technique or condition, it described technology or conditions or is carried out according to the literature in the art according to product description.
Reagents or instruments used without specified manufacturer is that can purchase the conventional products obtained by market.
Embodiment 1 prepares pure carbon fiber
Embodiment according to the present utility model prepares carbon fiber-based material by electrostatic spinning-pre-oxidation-Carbonation process,
Wherein the presoma of electrostatic spinning is polyacrylonitrile (PAN).The production process of pure carbon fiber catalyst are as follows: take 1g polyacrylonitrile molten
In 10mL dimethylformamide (DMF), left and right is made it completely dissolved for 24 hours for stirring, then carries out Static Spinning using this solution
Silk obtains fiber, and positive voltage and negative voltage are respectively 10kV in spinning process, and using metal plate as receiver, syringe needle distance is connect
The distance for receiving device is 15cm, and the flow velocity of syringe is adjusted to 10 μ L/min.After spinning, the fiber that spinning is obtained is placed in sky
Atmosphere heats one hour at 280 DEG C in enclosing, and heating rate is 1 DEG C/min, and after its natural cooling, color becomes dark brown
Color indicates that pre-oxidation is completed.It is then warming up to 1000 DEG C of carbonization 1h in nitrogen atmosphere, heating rate is 2 DEG C/min,
The carbon fiber-based material of black can be obtained.
Embodiment 2 prepares carbon-iron composite fibre
Other preparation methods with embodiment 1, unlike, 1g Fe is added in 10mL spinning precursor solution
(acac)3, iron can be mixed in final fibrous material.
Embodiment 3 prepares the carbon fiber of ZIF-8 modification
Other preparation methods with embodiment 1, unlike: take 0.59g zinc nitrate hexahydrate to be dissolved in 4mL deionized water；
11.35g2- methylimidazole is dissolved in 40mL deionized water；5 minutes synthesis ZIF-8 are mixed in the two.It is carried out after synthesis with DMF
Washing-centrifugation 2~3 times, washing takes the obtained white powder ultrasonic disperse of 0.2g in DMF after finishing, to its formation
Uniform suspension, then weigh 1g PAN dissolution and carry out spinning in the solution.
Embodiment 4 prepares the carbon fiber of ZIF-8 and Fe modification
Other preparation methods with embodiment 3, unlike: PAN and Fe is added simultaneously in ZIF-8 dispersion liquid
(acac)3?.
Morphology of carbon fibers structural characterization:
The carbon fibre material of embodiment 1-4 preparation is characterized using scanning electron microscope.Fig. 8 and Fig. 9 are respectively
Each fibrous material amplifies 5000 times and 25000 times of SEM photograph, wherein (A) is carbon fiber, (B) be carbon-iron composite fibre,
It (C) be ZIF-8 modifying carbon fibers, (D) is the ZIF-8 modification PAN-Fe fiber and (E) ZIF-8 modified carbon-iron that spinning obtains
The SEM photograph of fiber.Good, uniform fibre is presented in the product that different precursors carry out that spinning obtains it can be seen from Fig. 8
Pattern is tieed up, is not in the presence of hanging " drop ".Iron-carbon composite fibre and the pattern of pure carbon fiber are slightly different, fiber table
It looks unfamiliar and has particulate matter and warty object, for the iron material in incorporation carbon fiber.The preceding body of the iron used in the present embodiment
Body is trivalent iron salt, ferric acetyl acetonade, i.e. Fe (acac)3, with the organic ligand of molysite during pre-oxidation and carbonization
Volatilization is carbonized, and iron is transformed to the form of oxide from the form of salt, exists in the form of di-iron trioxide.Due to pre-
The chemical environment of iron ion changes greatly in oxidation and carbonisation, can not carry out normal crystal growing process, therefore present
The irregular form such as warty and fine granularity.And in the PAN-Fe fiber of ZIF-8 modification, then it can be seen that square block
Particulate matter, for the ZIF-8 particle of paddling process synthesis.Electrostatic spinning synthesis is carried out again later due to synthesizing ZIF-8 in the application
Fibrous material, therefore ZIF-8 particle is different from iron particle, has not only maintained good crystal morphology, but also do not have in embedded fiber, and
It is to exist in a mixed way in fiber.Comparison diagram 8 (D) and Fig. 8 (E) are it can be found that fine by the PAN-Fe of ZIF-8 modification
After dimension is carbonized, the density of crystal has sharp fall.This may be in carbonisation organic backbone contraction become smaller, together
When part ZIF-8 crystal structure destroyed caused by.Fig. 9 further explains the microscopic feature of fibrous material.By Fig. 9
(A) as can be seen that the diameter of carbon fiber is about at 1~2 μm, and in contrast, carbon-iron composite fibre diameter then can achieve
Between 3~5 μm, illustrate remove outside knob except, the iron of incorporation also be closely adhered in carbon fiber.By Fig. 9
(D) and Fig. 9 (E) it can also be seen that for ZIF-8 modification carbon-iron composite fibre diameter then can achieve between 3~5 μm,
In carbonisation, the size of ZIF-8 crystal is significantly changed, but still maintains original ZIF structure.
Embodiment 5 prepares air cathode
Diffusion layer is prepared first.On diffusion layer the mass ratio of carbon black and PTFE control 3:10, the i.e. load capacity of carbon black about
For 13mg/cm2, and the load capacity of PTFE is about 44mg/cm2, according to 11.34cm2Size weigh carbon black and PTFE, be added suitable
Ethyl alcohol is measured, mixture viscosity is increased.Ultrasonic mixing 1min or so forms sticky mass in a water bath.Sticky mass passes through
It is rolled 2-3 times repeatedly on plate, then by its vertical compression on stainless (steel) wire or titanium net, suppresses 10min under conditions of 4.5MPa.
The diffusion layer suppressed is put into Muffle furnace, makes its curing molding in 340 DEG C of heat treatment 20min.
The flexible carbon fibre material 40mg for ZIF-8 and the Fe modification that embodiment 4 is prepared directly is pressed as catalyst layer
Between current-collecting member and the backing material of diffusion layer, cathode forms system.Attached drawing 5 is seen in each layer relative position.
Electrochemical cathode system testing: double chamber type reactor is built, anode chamber is having a size of 4cm × 5cm × 5cm, cathode chamber
Having a size of 2cm × 5cm × 5cm, it is used as using platinum guaze to electrode, cation-exchange membrane is as barrier material.Anolyte uses
50mM phosphate buffer, catholyte is using the sodium sulphate of 50mM and the methylene blue mixed solution of 20mg/L, control cathode electricity
Gesture measures the degradation rate that cathode works as Methylene Blue to run 15,30,60min under the conditions of -0.4V (vs.SCE) respectively.
Embodiment 6 constructs microbiological fuel cell (i.e. bioelectrochemical system, MFC)
Build double chamber type reactor, anode chamber having a size of 4cm × 5cm × 5cm, cathode chamber having a size of 2cm × 5cm × 5cm,
Using air cathode prepared by embodiment 5 as cathode, and the bottom of reactor cathode is by ozonation aerated mouth, can be to yin
Pole provides ozone.Using carbon brush as anode, using cation-exchange membrane as barrier material, carbon brush is before the use in Muffle
30min is heat-treated at 450 DEG C in furnace.By above-mentioned anode be fitted into as electro-chemical systems test reactor in as anode (instead of
Gauze platinum electrode), bioelectrochemical system water outlet (bacterium containing electricity production) in inoculation continuous operation 1 year or more connects external circuit.Using out
Water is mixed with the PBS of equivalent, then adds the sodium acetate of 1g/L, the vitamin of 5mg/L and the mine with 12.5mg/L thereto
Substance, the inoculation liquid as microbiological fuel cell.In inoculation startup stage, microbiological fuel cell reactor connects 1000 Ω
Extrernal resistance operation, and reactor is placed in 30 DEG C of incubator.
Comparative example 1 constructs ozone oxidation electro-chemical systems
Build double chamber type reactor, anode chamber having a size of 4cm × 5cm × 5cm, cathode chamber having a size of 2cm × 5cm × 5cm,
It is used as using platinum guaze to electrode, saturated calomel electrode is as reference electrode, and cation-exchange membrane is as barrier material.Using implementation
Air cathode prepared by example 5 is as cathode.
Comparative example 2 constructs biological electrolysis system
Other structures with embodiment 6, unlike, in the comparative example, using common platinum carbon electrode as cathode.
Sewage treatment capacity test:
To the ozone of the microbiological fuel cell (i.e. microbiological fuel cell ozone coupling system) of embodiment 6, comparative example 1
Biological electrolysis system (i.e. MFC electrolysis system) in oxidizing and electrochemical system (i.e. independent ozone coupling system) and comparative example 2
Carry out sewage treatment capacity test.Methylene blue is selected to pass through the methylene blue in catholyte as the model substrate of reaction
Concentration is catalyzed two electronics oxygen reducing abilities to characterize different air cathodes.The condition of electro-chemical test is the electrical potential conditions of -0.4V,
Therefore the method that test is selected is potentiostatic method.Using containing 20mgL-1The mixed solution of methylene blue and 50mM sodium sulphate is as yin
Pole liquid is packed into electrochemical reactor, the performance of air cathode is characterized by the removal rate of methylene blue.In methylene blue
Measurement aspect, is measured using spectrophotometry, and directly absorbance of the measurement solution under 664nm wavelength, reflection solution are worked as
In methylene blue concentration.
In the microbiological fuel cell (i.e. microbiological fuel cell ozone coupling system) of embodiment 6, the ozone of comparative example 1
Biological electrolysis system (i.e. MFC electrolysis system) in oxidizing and electrochemical system (i.e. independent ozone coupling system) and comparative example 2
In, anolyte uses 50mM phosphate buffer, and catholyte is molten using the methylene blue mixing of the sodium sulphate and 20mg/L of 50mM
Liquid, control cathode potential measure cathode respectively and work as Methylene Blue to run 15,30,60min under the conditions of -0.4V (vs.SCE)
Degradation rate.Test result is as shown in figs.10 and 11.
In order to distinguish ozone decolorization and microbiological fuel cell coupled system for methylene blue decolorizing effect, specifically in fact
It tests design parameter and is shown in Table 1.
1 MFC of table electrolysis, independent ozone and MFC ozone coupling condition setting
As seen from Figure 10, the sewage treatment capacity of the bioelectrochemical system is than individual ozone oxidation electrochemistry system
The sewage treatment capacity of system is strong, also, is not less than after bioelectrochemical system operation 2 hours to the removal rate of methylene blue
90%.The electro-chemical systems have good sewage treatment capacity as a result,.
Microbiological fuel cell ozone coupling system, MFC electrolysis and independent ozone coupling system remove pollutant
Division result is as shown in Figure 10.As seen from Figure 10, compared to MFC electrolysis system, independent ozone coupling system and MFC coupling
The sewage treatment capacity of system is stronger.
Independent ozone coupling system and MFC coupled system are as shown in figure 11 for the decoloration result of methylene blue, the life
The sewage treatment capacity of object electro-chemical systems is stronger than the sewage treatment capacity of individual ozone oxidation electro-chemical systems, also, should
Bioelectrochemical system is not less than 90% to the removal rate of methylene blue after running 2 hours.The electro-chemical systems have good as a result,
Good sewage treatment capacity.
Electricity generation performance test
Microbiological fuel cell (i.e. microbiological fuel cell ozone coupling system) and comparative example 1 to embodiment 6
Ozone oxidation electro-chemical systems (i.e. independent ozone coupling system) carry out electricity generation performance test, measure the specific of power density curve
Step are as follows: at the end of a cycle of operation of microbiological fuel cell, culture solution is replaced, and extrernal resistance is adjusted to 5000 Ω,
Start to measure after stablizing one hour, records the output voltage and anode potential under 5000 Ω.As soon as every record data point is adjusted
Low extrernal resistance records next data point after 20min.The range for adjusting extrernal resistance is 5000 Ω, 1000 Ω, 500 Ω, 300 Ω, 200
Ω,100Ω,50Ω,30Ω,20Ω,10Ω.A series of output voltages are recorded in test process.Electric current by output voltage with
Extrernal resistance acquires, and cathode is the disk of diameter 3cm in this research, and area is about 7cm2, thus acquire current density.It is close by electric current
Degree finds out power density with voltage.Above data is sought to carry out mapping analysis after finishing.The function of independent ozone coupling system
The test method of rate density curve is identical as microbiological fuel cell.Test result is as shown in figure 12.
With reference to Figure 12, from polarization curve as can be seen that in MFC ozone coupling system, exposed in cathode chamber into a small amount of smelly
Oxygen helps to promote the electricity generation performance of microbiological fuel cell.MFC ozone coupling system and MFC electrolysis reach most in 100 Ω
Big current density is consistent with the extrernal resistance of selection.Compared in 0.05M Na2SO4Mode is added in the MFC run under electrolyte
Substrate methylene blue internal resistance improves.When the microbiological fuel cell internal resistance is 100 ohm, power density is not less than 135mW/m2。
The microbiological fuel cell has good electricity generation performance as a result,.
The orientation or positional relationship of the instructions such as term " on ", "lower" is based on attached drawing institute in the description of the present invention,
The orientation or positional relationship shown is merely for convenience of description the utility model rather than requires the utility model must be with specific
Orientation construction and operation, therefore should not be understood as limiting the present invention.
In the description of this specification, the description of reference term " one embodiment ", " another embodiment " etc. means to tie
The embodiment particular features, structures, materials, or characteristics described are closed to be contained at least one embodiment of the utility model.
In the present specification, the schematic representation of the above terms does not necessarily have to refer to the same embodiment or example.Moreover, description
Particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more of the embodiments or examples.
In addition, without conflicting with each other, those skilled in the art can by different embodiments described in this specification or
The feature of example and different embodiments or examples is combined.
Although the embodiments of the present invention have been shown and described above, it is to be understood that above-described embodiment is
Illustratively, it should not be understood as limiting the present invention, those skilled in the art are in the scope of the utility model
Inside it can make changes, modifications, alterations, and variations to the above described embodiments.
Claims (8)
1. a kind of bioelectrochemical system characterized by comprising
Shell limits reaction compartment in the shell；
Cathode, the cathode include that can be catalyzed the catalyst for generating hydrogen peroxide；
Ozonation aerated mouth, the ozonation aerated mouth setting is on the housing；
Anode, the anode and cathode electrical connection；And
Electricity-producing microorganism, the electricity-producing microorganism are attached to the outer surface of the anode.
2. bioelectrochemical system according to claim 1, which is characterized in that the cathode is air cathode, the yin
Pole includes:
Catalyst layer, the catalyst layer include the catalyst that can be catalyzed and generate hydrogen peroxide；
Current collection layer；And
Diffusion layer.
3. bioelectrochemical system according to claim 2, which is characterized in that the catalyst includes: carbon black, graphite
Alkene, carbon nanotube, carbon fiber or mesoporous carbon.
4. bioelectrochemical system according to claim 3, which is characterized in that the diameter of the carbon fiber is 0.1-5 μm.
5. bioelectrochemical system according to claim 2, which is characterized in that be free of binder in the catalyst layer.
6. bioelectrochemical system according to claim 2, which is characterized in that the load capacity 2-30mg/ of the catalyst
cm2。
7. bioelectrochemical system according to claim 1, which is characterized in that the anode is by carbon brush, carbon cloth, carbon fiber
What Wei Bu or granular activated carbon were formed.
8. bioelectrochemical system according to claim 1, which is characterized in that the anode is plane-shape electrode, the electricity
Chemical system further comprises:
Diaphragm, the diaphragm are arranged between the cathode and the anode.
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| CN110776087A (en) * | 2019-11-07 | 2020-02-11 | 大连理工大学 | Circulating culture system comprising microbial electrochemical water purifying device |
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| US11180870B2 (en) * | 2018-08-17 | 2021-11-23 | Cence Inc. | Carbon nanofiber and method of manufacture |
| CN111302448B (en) * | 2019-11-26 | 2021-12-10 | 东北师范大学 | Method for treating high-concentration industrial sewage by Shewanella driving electro-Fenton reaction |
| CN110790436A (en) * | 2019-12-12 | 2020-02-14 | 西安热工研究院有限公司 | Treatment system and method for power station boiler composite organic acid cleaning wastewater |
| CN113089002A (en) * | 2021-03-18 | 2021-07-09 | 重庆大学 | Selective oxidation device and method for coupling organic matters through electrocatalysis hydrogen peroxide production |
| CN116177689B (en) * | 2023-04-20 | 2023-12-19 | 中国科学院地球化学研究所 | Four-layer structure electro-Fenton cathode, preparation method and application thereof |
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| GB201515869D0 (en) * | 2015-09-08 | 2015-10-21 | Johnson Matthey Fuel Cells Ltd | Oxygen reduction reactor catalyst |
| CN105161730B (en) * | 2015-09-28 | 2017-07-28 | 清华大学 | Air cathode and microbiological fuel cell |
| CN107381725B (en) * | 2017-06-26 | 2023-03-31 | 清华大学 | Air cathode, preparation method and sewage treatment system |
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| CN109081427B (en) * | 2018-06-15 | 2024-01-09 | 清华大学 | Bioelectrocatalysis ozone oxidation system |
| CN110776087A (en) * | 2019-11-07 | 2020-02-11 | 大连理工大学 | Circulating culture system comprising microbial electrochemical water purifying device |
| CN110776087B (en) * | 2019-11-07 | 2021-09-24 | 大连理工大学 | Circulating culture system comprising microbial electrochemical water purifying device |
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