CN104466201A - Preparation method of modified anode of marine sediment microbial fuel cell - Google Patents
Preparation method of modified anode of marine sediment microbial fuel cell Download PDFInfo
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- CN104466201A CN104466201A CN201410779536.8A CN201410779536A CN104466201A CN 104466201 A CN104466201 A CN 104466201A CN 201410779536 A CN201410779536 A CN 201410779536A CN 104466201 A CN104466201 A CN 104466201A
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- 239000000446 fuel Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000013049 sediment Substances 0.000 title claims abstract description 14
- 230000000813 microbial effect Effects 0.000 title abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 35
- 239000010439 graphite Substances 0.000 claims abstract description 35
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 9
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 9
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000002906 microbiologic effect Effects 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 abstract 3
- 239000002131 composite material Substances 0.000 abstract 1
- 238000005498 polishing Methods 0.000 abstract 1
- 239000013535 sea water Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a preparation method of a modified anode of a marine sediment microbial fuel cell, and belongs to the technical field of a microbial fuel cell. The method comprises the steps: selecting a graphite rod with the diameter being 1.6cm, the length being 10cm and the surface area being 54cm<2> as a graphite anode, polishing the surface of the graphite to be smooth by respectively utilizing abrasive paper of 180, 360, 600 and 800, preparing a Mn<2+>+Fe3O4+Ni<2+>graphite anode from ferroferric oxide, manganese sulfate, graphite powder, kaoline and nickel chloride hexahydrate as raw materials, wherein the particle size of the graphite powder is 500 meshes, the particle size of the kaoline is 400 meshes, mixing the ferroferric oxide, the manganese sulfate, the graphite powder, the kaoline and the nickel chloride hexahydrate respectively according to a mass ratio of 6 percent, 3 percent, 58 percent, 30 percent and 2 percent, wherein the total mass of the ferroferric oxide, the manganese sulfate, the graphite powder, the kaoline and the nickel chloride hexahydrate is 4g. The method has advantages that the conductivity of a composite cathode prepared by adopting the method is obviously improved.
Description
Technical field
The present invention relates to a kind of preparation method of marine sediment microbiological fuel cell modification anode, belong to technical field of microbial fuel battery.
Background technology
Deposit microbiological fuel cell (SMFCs) is a kind of typical membraneless microbiological fuel cell, its mechanism of action is: be positioned over by anode material in the deposit of anaerobism, cathode material is arranged in the aerobic aqueous phase in upper strata, be connected with resistance by wire between negative electrode and anode, in deposit, organic substance is deposited indigenous microorganism oxidation Decomposition in thing near anode region, the electron transmission produced is to anode, negative electrode is arrived again through external circuit, oxygen in cathodic region and the proton transmitted from anode region are combined and generate water, thus realize removing in deposit the object of generation current again while organic pollution.
Deposit microbiological fuel cell (SMFCs) not only can provide lower wattage power supply for the long term monitoring instrument of ocean or Inland Water, can be used for the reparation of deposit biology in situ simultaneously.Hong etc. adopt graphite as the SMFCs made by electrode, and through the operation of 5 months, average current density was 20.4mA/m
2, in deposit, TOC have dropped 21.9%, and oxidizable organic content have dropped 32.7% (Hong
et al., 2008); Yan etc. adopt SMFCs to add the combination technique of unformed iron (FeOOH), study the effect of its degraded lake sediment China and Philippines and pyrene, result shows it and is respectively 99.47 ± 0.15%, 94.79 ± 0.63% to the clearance of deposit China and Philippines, pyrene, has significant control and recovery dynatron effect for polycyclic aromatic hydrocarbons contaminated in lake sediment.
SMFCs applies a very favorable condition in ocean in addition, and the conductivity being exactly seawater is strong, more easily plays the effect of SMFCs.The research of Holmes etc. finds, seawater SMFCs maximum current density is 20 mA/m
2, and fresh water SMFCs maximum current density only has 10 mA/m
2, its reason mainly seawater than the good conductivity (Holmes of fresh water
et al, 2004).At 20 DEG C, the electric conductivity of seawater is 50000 uS/cm, and the electric conductivity of fresh water only has 500 uS/cm, seawater has corrosiveness for deposit fuel battery negative pole simultaneously, the corrosiveness of negative electrode can improve its specific area on the one hand, secondly can form the raising (Bergel that biomembrane is conducive to cathodic oxygen reduction performance
et al, 2005).The people such as Tender have carried out SMFCs field experiment in two places, sabkha area near the river mouth in Oregonian Yaquina gulf and the Tuckerton in New York respectively, organic carbon content in two place deposits is respectively 2-6% and 4-6%, and power density curve shows that the power density that can continue to export at Yaquina and Tuckerton two places deposit fuel cell is respectively 28 mW/m
2with 27 mW/m
2, the microbe species of anode surface enrichment is mainly ground Bacteriaceae (Tender
et al, 2002).The people such as Ryckelynck have installed the bottom sediment microbiological fuel cell of identical type in Ya Kuina gulf, battery system outputs about 33 mW/m
2continuous power density, the numerical value of people's reports such as this and Tende is close (Ryckelynck
et al, 2005).Therefore utilize deposit microbiological fuel cell to carry out electrogenesis and have advantageous advantage.
Although deposit microbiological fuel cell (SMFCs) has good application prospect in multiple fields such as contaminated environment process, electrogenesis, but the conductivity of existing microbiological fuel cell is usually lower, larger conductive current and voltage is often needed to obtain expected effect, its power loss is comparatively large, and the Choice and design of different anode material and structure has important impact for the electricity generation ability of SMFCs and clean effect.In order to solve above-mentioned difficulties, need to develop a kind of preparation method that can promote the marine sediment microbiological fuel cell modification anode of anode conductivity.
Summary of the invention
The object of this invention is to provide a kind of preparation method of marine sediment microbiological fuel cell modification anode.
The technical problem that the present invention mainly solves is the problem that the conductivity of the anode that existing preparation method obtains can not meet the demands.
In order to realize object of the present invention, the technical solution used in the present invention is:
A preparation method for marine sediment microbiological fuel cell modification anode, comprises the following steps:
(1) cut-off footpath is 1.6 cm, and long 10 cm, surface area is 54 cm
2graphite rod as graphite anode, use the sand papering graphite surface of 180,360,600,800 to smooth respectively;
(2) with tri-iron tetroxide, manganese sulfate, graphite powder, kaolin and six water nickel chlorides for raw material makes Mn
2++ Fe
3o
4+ Ni
2+graphite anode, wherein the particle diameter of graphite powder is 500 orders, and kaolinic particle diameter is 400 orders; Tri-iron tetroxide, manganese sulfate, graphite powder, kaolin and six water nickel chlorides are mixed according to the mass ratio of 6%, 3%, 58%, 30% and 2% respectively, gross mass is 4 grams;
(3) add a certain amount of deionized water after mixing, be applied to graphite electrode four sides, at 80 DEG C of temperature, dry 45 min, are then placed in Muffle furnace by graphite electrode, at 380 DEG C ~ 450 DEG C roasting temperature 48 h;
(4) make a call to an aperture in graphite one end that preliminary treatment is good, Xiang Kongzhong adds conductive epoxy resin, in the epoxy resin insert in the hole, but will ensure that the exposed part of wire can not contact with graphite matrix by wire exposed part;
Etc. (5) after conductive epoxy resin has solidified, whether good with the link between universal instrument test electrode and wire, then with the epoxy resin insulated, the part of aperture remainder is filled up, dry kept dry;
(6) dose volume is than being the sulfuric acid of 45% of 5:2 ~ 5:3 and the mixed solution of the red fuming nitric acid (RFNA) of 36%;
(7) graphite anode good for pre-treatment is soaked 30 minutes in the solution, reaction temperature is 65 DEG C;
(8) removed by the graphite anode handled well, pure water soaks repeatedly, until pH value does not change;
(9) cleaned modified graphite anode is put into air dry oven, 80 DEG C of dryings 12 hours.
Described muffle furnace is 400 degrees Celsius.
The mixed liquor volume of described 45% sulfuric acid and 36% red fuming nitric acid (RFNA) is than being 5:2.
Advantage of the present invention is: compared to prior art, the conductivity of the modification anode that preparation method of the present invention obtains obviously is promoted, improve anode microbial kinetics active, accelerate born of the same parents' exoelectron transfer rate, improve chemical property and the power output of microbiological fuel cell, this preparation method's technique is simple, and cost of material is low, obtained modification positive pole machinery intensity is high, is suitable for the through engineering approaches application of microbiological fuel cell.
Embodiment
Illustrate to the technical scheme in the embodiment of the present invention clearly and completely below.
A preparation method for marine sediment microbiological fuel cell modification anode, comprises the following steps:
(1) cut-off footpath is 1.6 cm, and long 10 cm, surface area is 54 cm
2graphite rod as graphite anode, use 180 respectively, 360,600, the sand papering graphite surface of 800 is to smooth;
(2) with tri-iron tetroxide, manganese sulfate, graphite powder, kaolin and six water nickel chlorides for raw material makes Mn
2++ Fe
3o
4+ Ni
2+graphite anode, wherein the particle diameter of graphite powder is 500 orders, and kaolinic particle diameter is 400 orders; Tri-iron tetroxide, manganese sulfate, graphite powder, kaolin and six water nickel chlorides are mixed according to the mass ratio of 6%, 3%, 58%, 30% and 2% respectively, gross mass is 4 grams;
(3) a certain amount of deionized water is added after mixing, be applied to graphite electrode four sides, at 80 DEG C of temperature, dry 45 min, are then placed in Muffle furnace by graphite electrode, at 380 DEG C ~ 450 DEG C roasting temperature 48 h, preferred muffle furnace is 400 degrees Celsius;
(4) make a call to an aperture in graphite one end that preliminary treatment is good, Xiang Kongzhong adds conductive epoxy resin, in the epoxy resin insert in the hole, but will ensure that the exposed part of wire can not contact with graphite matrix by wire exposed part;
Etc. (5) after conductive epoxy resin has solidified, whether good with the link between universal instrument test electrode and wire, then with the epoxy resin insulated, the part of aperture remainder is filled up, dry kept dry;
(6) dose volume is than being the sulfuric acid of 45% of 5:2 ~ 5:3 and the mixed solution of the red fuming nitric acid (RFNA) of 36%, and preferably the mixed liquor volume of 45% sulfuric acid and 36% red fuming nitric acid (RFNA) is than being 5:2;
(7) graphite anode good for pre-treatment is soaked 30 minutes in the solution, reaction temperature is 65 DEG C;
(8) removed by the graphite anode handled well, pure water soaks repeatedly, until pH value does not change;
(9) cleaned modified graphite anode is put into air dry oven, 80 DEG C of dryings 12 hours.
Experimentally result verification, compared to prior art, the conductivity of the modification anode that preparation method of the present invention obtains obviously is promoted, and improves anode microbial kinetics active, accelerate born of the same parents' exoelectron transfer rate, improve chemical property and the power output of microbiological fuel cell.
Claims (3)
1. a preparation method for marine sediment microbiological fuel cell modification anode, is characterized in that, comprise the following steps:
(1) cut-off footpath is 1.6 cm, and long 10 cm, surface area is 54 cm
2graphite rod as graphite anode, use the sand papering graphite surface of 180,360,600,800 to smooth respectively;
(2) with tri-iron tetroxide, manganese sulfate, graphite powder, kaolin and six water nickel chlorides for raw material makes Mn
2++ Fe
3o
4+ Ni
2+graphite anode, wherein the particle diameter of graphite powder is 500 orders, and kaolinic particle diameter is 400 orders; Tri-iron tetroxide, manganese sulfate, graphite powder, kaolin and six water nickel chlorides are mixed according to the mass ratio of 6%, 3%, 58%, 30% and 2% respectively, gross mass is 4 grams;
(3) add a certain amount of deionized water after mixing, be applied to graphite electrode four sides, at 80 DEG C of temperature, dry 45 min, are then placed in Muffle furnace by graphite electrode, at 380 DEG C ~ 450 DEG C roasting temperature 48 h;
(4) make a call to an aperture in graphite one end that preliminary treatment is good, Xiang Kongzhong adds conductive epoxy resin, in the epoxy resin insert in the hole, but will ensure that the exposed part of wire can not contact with graphite matrix by wire exposed part;
Etc. (5) after conductive epoxy resin has solidified, whether good with the link between universal instrument test electrode and wire, then with the epoxy resin insulated, the part of aperture remainder is filled up, dry kept dry;
(6) dose volume is than being the sulfuric acid of 45% of 5:2 ~ 5:3 and the mixed solution of the red fuming nitric acid (RFNA) of 36%;
(7) graphite anode good for pre-treatment is soaked 30 minutes in the solution, reaction temperature is 65 DEG C;
(8) removed by the graphite anode handled well, pure water soaks repeatedly, until pH value does not change;
(9) cleaned modified graphite anode is put into air dry oven, 80 DEG C of dryings 12 hours.
2. the preparation method of a kind of marine sediment microbiological fuel cell modification anode according to claim 1, is characterized in that: described muffle furnace is 400 degrees Celsius.
3. the preparation method of a kind of marine sediment microbiological fuel cell modification anode according to claim 1, is characterized in that: the mixed liquor volume of described 45% sulfuric acid and 36% red fuming nitric acid (RFNA) is than being 5:2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410779536.8A CN104466201A (en) | 2014-12-16 | 2014-12-16 | Preparation method of modified anode of marine sediment microbial fuel cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410779536.8A CN104466201A (en) | 2014-12-16 | 2014-12-16 | Preparation method of modified anode of marine sediment microbial fuel cell |
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| Publication Number | Publication Date |
|---|---|
| CN104466201A true CN104466201A (en) | 2015-03-25 |
Family
ID=52911882
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|---|---|---|---|
| CN201410779536.8A Pending CN104466201A (en) | 2014-12-16 | 2014-12-16 | Preparation method of modified anode of marine sediment microbial fuel cell |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034321A (en) * | 2019-02-21 | 2019-07-19 | 浙江海洋大学 | A kind of microbial fuel cell unit for marine culture wastewater of degrading |
| CN113921800A (en) * | 2021-10-11 | 2022-01-11 | 吉林大学 | Preparation of porous silicon as lithium ion battery cathode material by using ocean clay magnesium thermal reduction |
-
2014
- 2014-12-16 CN CN201410779536.8A patent/CN104466201A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034321A (en) * | 2019-02-21 | 2019-07-19 | 浙江海洋大学 | A kind of microbial fuel cell unit for marine culture wastewater of degrading |
| CN113921800A (en) * | 2021-10-11 | 2022-01-11 | 吉林大学 | Preparation of porous silicon as lithium ion battery cathode material by using ocean clay magnesium thermal reduction |
| CN113921800B (en) * | 2021-10-11 | 2024-01-09 | 吉林大学 | Preparation of porous silicon as lithium ion battery anode material by magnesian clay magnesian reduction |
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Application publication date: 20150325 |
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