CN102728345A - Manganese dioxide catalyst, preparation method for same and application of same in microbial fuel cell treatment - Google Patents
Manganese dioxide catalyst, preparation method for same and application of same in microbial fuel cell treatment Download PDFInfo
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- CN102728345A CN102728345A CN2012101687727A CN201210168772A CN102728345A CN 102728345 A CN102728345 A CN 102728345A CN 2012101687727 A CN2012101687727 A CN 2012101687727A CN 201210168772 A CN201210168772 A CN 201210168772A CN 102728345 A CN102728345 A CN 102728345A
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- 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
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Abstract
The invention relates to a manganese dioxide catalyst, a preparation method for the same and application of the same in microbial fuel cell treatment. The preparation method comprises the following concrete steps: fully mixing manganese dioxide, a conductive carbon material and PVDF according to a mass ratio of 65: 20: 15; adding an N-methyl-2-pyrrolidone solvent into an obtained mixture until the mixture can turn into paste under stirring; adding an NaOH solution with a concentration of 8 to 12 mol/L, wherein the volume of the NaOH solution is identical with the volume of the N-methyl-2-pyrrolidone solvent; carrying out uniform stirring and placing an obtained mixture into a hydro-thermal reaction vessel for reaction for 1.5 to 12.5 h at a temperature of 105 to 115 DEG C under a pressure of 1.0 to 2.9 MPa; and carrying out cooling after the reaction is finished and taking out a pasty product which is the prepared manganese dioxide catalyst. Compared with conventional microbial fuel cells, output voltage of microbial fuel in a microbial fuel cell which uses the manganese dioxide catalyst provided in the invention as a catalyst for its cathode electrode is improved by the manganese dioxide catalyst, and removal efficiency of substances like the organic pollutant COD and ammonia nitrogen in leachate can be effectively enhanced by using the microbial fuel cell prepared in the invention to treat the leachate.
Description
Technical field:
The invention belongs to environmental protection and technical field of new energies, be specifically related to a kind of manganese dioxide-catalyst as the microorganism fuel cell cathode electrode catalyst and preparation method thereof and the application in percolate microbiological fuel cell treatment technology.
Background technology:
City garbage percolate is a kind of high concentrated organic wastewater; Metal and ammonia-nitrogen content are high; Water quality and quantity is unstable, nutrient is out of proportion, and contains a large amount of toxic organic pollutants, comprises VOC and half volatile organic compound; Concentration is all higher, and having many is pollutants of the preferential control of American National Bureau for Environmental Protection (USEPA).
Microbiological fuel cell (Microbial Fuel Cell; MFC); Be a kind ofly to utilize microorganism to make the desirable electrogenesis device that catalyst is converted into the chemical energy in the fuel electric energy; Can in electrogenesis, remove organic matter in the waste water, have the double effects of electrogenesis and waste treatment, be a debirs treatment technology that development potentiality is huge.Yet at present, the MFC power output is low and the organic pollutant removal rate is not high, is the bottleneck of its practical application of restriction.Through screening electrogenesis microorganism, improve battery structure, improve electrode material, optimize organic pollutant removal rate in power output and the waste water that approach such as service condition all can improve MFC.Wherein, improving the cathode reaction condition is effectively to improve the important method of output of MFC power and pollutants removal rate.
The potassium ferricyanide, potassium permanganate and potassium bichromate etc.; Because its high redox potential can significantly improve the power output of MFC as the cathode electronics acceptor time; But above-mentioned substance is non-renewable and have potential environmental hazard, and oxygen cheap and easy to get becomes desirable MFC cathode electronics acceptor owing to its environmental friendliness in the air.Yet the solubility of oxygen is low, there is big overpotential in negative electrode, needs to adopt cathod catalyst or other redox system to accelerate reaction rate, to improve the MFC performance.Metal platinum (Pt) has high electrocatalytic active and chemical stability, be preferably oxygen reduction reaction (oxygen reduction reaction, ORR) catalyst, but expensive price limit its be widely used; Transition metal macrocyclic complexes; Has catalytic activity preferably like pyrolysis FePC (pyr-FePc), durol Cobalt Porphyrin (CoTTMP) etc.; But stability is not high, the preparation process complicated; Practicality is not strong, and therefore adopting cheap metal oxide to replace precious metal is the important selection of oxidation-reduction electrode.
Manganese dioxide has higher ORR catalytic activity and wide material sources, cheap, is a kind of cathod catalyst that relatively has application potential.Number of patent application is 200810198453.4 to disclose a kind of manganese dioxide in the application of preparation in the microorganism fuel cell cathode, is specifically related to manganese dioxide as application and the concrete proportioning thereof of catalyst in microorganism fuel cell cathode, or the like.Yet,, be that cathod catalyst is used for the percolate microbiological fuel cell and handles and do not see the correlation technique report as yet with manganese dioxide because manganese dioxide is as the shortcoming of cathod catalyst technology of preparing and the complexity of percolate composition.
Summary of the invention:
First purpose of the present invention provides simple, the excellent catalytic effect of a kind of preparation method, particularly with it as manganese dioxide-catalyst of catalyst excellent catalytic effect in handling percolate of microorganism fuel cell cathode electrode and preparation method thereof.
Manganese dioxide-catalyst of the present invention prepares through following method, and this method may further comprise the steps:
Manganese dioxide, conductive carbon material and PVDF (polyvinylidene fluoride) are compared mixing according to 65: 20: 15 quality; In mixture, add N-crassitude ketone solvent then until stirring into pasty state; Add 8 ~ 12mol/L NaOH solution again with N-crassitude ketone solvent equal volume; Putting into hydrothermal reaction kettle after stirring, is 105 ~ 115 ℃ in temperature, and pressure is to react 11.5 ~ 12.5 hours under the condition of 1.0 ~ 2.9MPa; Cooling after reaction finishes is taken out pastel and is the manganese dioxide-catalyst for preparing.
Described conductive carbon material is preferably graphite, acetylene black, carbon black or active carbon etc.
Described NaOH solution, the preferred 10mol/L of its concentration.
Preferably, the described hydrothermal reaction kettle of putting into is to be 110 ℃ in temperature, and pressure is to react 12h under the condition of 2.1MPa.
Second purpose of the present invention provides the application of above-mentioned manganese dioxide-catalyst in microbiological fuel cell.
Preferably, above-mentioned manganese dioxide-catalyst is in the application that is used for the disposal of refuse percolate as the microorganism fuel cell cathode electrode catalyst.
With the catalyst of manganese dioxide-catalyst of the present invention as the cathode electrode of microbiological fuel cell; Microbiological fuel cell than routine; This manganese dioxide-catalyst can improve the output voltage of microorganism fuel; And, can effectively improve the clearance of materials such as organic pollution COD, ammonia nitrogen in the percolate with this microbiological fuel cell Battery disposal percolate.
Description of drawings:
Fig. 1 is the structural representation of microbiological fuel cell of the present invention;
Fig. 2 is the cathode electrode cyclic voltammetry curve figure that the load of embodiment 1 has manganese dioxide-catalyst;
Fig. 3 is the output voltage figure that handles percolate with microbiological fuel cell;
Fig. 4 handles percolate COD, ammonia nitrogen removal frank figure after 7 days with microbiological fuel cell.
The specific embodiment:
Following examples are to further specify of the present invention, rather than limitation of the present invention.
Embodiment 1:
Take by weighing 130g manganese dioxide, 40g graphite powder and 30gPVDF (Kynoar) mixing respectively; In mixture, add 50mLN-methyl pyrrolidone stirring solvent then and become pasty state; Add 50mL 10mol/L NaOH solution again; Putting into hydrothermal reaction kettle after stirring, is 110 ℃ in temperature, and pressure is that 2.1MPa reacted 12 hours down.Be cooled to room temperature after hydro-thermal reaction finishes, take out pastel (manganese dioxide-catalyst), spread upon the surface of cathode electrode uniformly, 100 ℃ of oven dry obtain the cathode electrode that load has manganese dioxide-catalyst, and load factor is 0.5mg/cm
2
There is the cathode electrode of manganese dioxide-catalyst to carry out cyclic voltammetry scan (CV) above-mentioned load; Adopting three-electrode system, is to electrode with Pt, and sweep limits is-0.8 ~ 0.2V; Hg/HgO is a reference electrode; The NaCl of 1mol/L is an electrolyte, logical 15min nitrogen before the test, and keep aeration status in the test process.Sweep speed is 1mV/s, investigates the cyclic voltammetric performance that load has the cathode electrode of manganese dioxide-catalyst, and the result is as shown in Figure 2.Wherein, curve a representes that load has the cathode electrode of manganese dioxide-catalyst, and curve b representes that not load has the cathode electrode of manganese dioxide-catalyst.The result shows; Under all identical situation of other conditions; Curve a has the reduction peak that caused by manganese dioxide reduction at-0.2 ~ 0.3V place, and curve b does not produce obvious reduction peak, explain that the manganese dioxide-catalyst after hydro-thermal reaction prepares has stronger catalytic action to ORR.
Then; There is the cathode electrode of manganese dioxide-catalyst to be used for the single entry microbiological fuel cell load; The structure of the microbiological fuel cell that is adopted is as shown in Figure 1; Mainly be made up of anode chamber 1, anode electrode 2, cathode electrode 3 and external circuit, wherein manganese dioxide-catalyst 4 loads on the cathode electrode 3, the about 0.5mg/cm of load factor
2
At last, above-mentioned load there is the single entry microbiological fuel cell of the cathode electrode of manganese dioxide-catalyst be used for city garbage percolate processing, result such as Fig. 3 and shown in Figure 4.Cathode electrode is the single entry microbiological fuel cell of load manganese dioxide-catalyst not, and its maximum output voltage is merely 0.29V, and load has the single entry microbiological fuel cell of the cathode electrode of manganese dioxide-catalyst, and the maximum output voltage of battery can be up to 0.41V.And after city garbage percolate was handled 7 days through the single entry microbiological fuel cell, cathode electrode is the single entry microbiological fuel cell of load manganese dioxide-catalyst not, and the clearance of COD, ammonia nitrogen concentration is about 76.8% and 83.4% in the percolate; And load has the single entry microbiological fuel cell of the cathode electrode of manganese dioxide-catalyst, and after city garbage percolate was handled 7 days through it, the clearance of its COD, ammonia nitrogen concentration reached 87.2% and 96.1%, has improved 10.4% and 12.7% respectively.
This shows; With the catalyst of manganese dioxide-catalyst of the present invention as the cathode electrode of microbiological fuel cell; Microbiological fuel cell than routine; It can improve the output voltage of microorganism fuel, and handles percolate with this microbiological fuel cell, can effectively improve clearances such as organic pollution COD, ammonia nitrogen in the percolate.
Embodiment 2:
Take by weighing 130g manganese dioxide, 40g graphite powder and 30gPVDF (Kynoar) mixing respectively, in mixture, add 50mLN-methyl pyrrolidone stirring solvent then and become pasty state, add 50mL 12mol/L NaOH solution again; Put into hydrothermal reaction kettle after stirring; In temperature is 105 ℃, and pressure is that 2.9MPa reacted 11.5 hours down, is cooled to room temperature after hydro-thermal reaction finishes; Take out pastel (manganese dioxide-catalyst); Spread upon the surface of cathode electrode uniformly, 100 ℃ of oven dry obtain the cathode electrode that load has manganese dioxide-catalyst.This load there be the cathode electrode of the cathode electrode of manganese dioxide-catalyst as microbiological fuel cell; Microbiological fuel cell than routine; It can improve the output voltage of microorganism fuel; And handle percolate with this microbiological fuel cell, can effectively improve clearances such as organic pollution COD, ammonia nitrogen in the percolate.
Embodiment 3:
Take by weighing 130g manganese dioxide, 40g graphite powder and 30gPVDF (Kynoar) mixing respectively, in mixture, add 50mL N-methyl pyrrolidone stirring solvent then and become pasty state, add 50mL 8mol/L NaOH solution again; Put into hydrothermal reaction kettle after stirring; In temperature is 115 ℃, and pressure is that 1MPa reacted 12.5 hours down, is cooled to room temperature after hydro-thermal reaction finishes; Take out pastel (manganese dioxide-catalyst); Spread upon the surface of cathode electrode uniformly, 100 ℃ of oven dry obtain the cathode electrode that load has manganese dioxide-catalyst.This load there be the cathode electrode of the cathode electrode of manganese dioxide-catalyst as microbiological fuel cell; Microbiological fuel cell than routine; It can improve the output voltage of microorganism fuel; And handle percolate with this microbiological fuel cell, can effectively improve clearances such as organic pollution COD, ammonia nitrogen in the percolate.
Claims (7)
1. the preparation method of a manganese dioxide-catalyst is characterized in that, may further comprise the steps:
Manganese dioxide, conductive carbon material and PVDF are compared mixing according to 65: 20: 15 quality; In mixture, add N-crassitude ketone solvent then until stirring into pasty state; Add 8 ~ 12mol/L NaOH solution again with N-crassitude ketone solvent equal volume; Putting into hydrothermal reaction kettle after stirring, is 105 ~ 115 ℃ in temperature, and pressure is to react 11.5 ~ 12.5 hours under the condition of 1.0 ~ 2.9MPa; Cooling after reaction finishes is taken out pastel and is the manganese dioxide-catalyst for preparing.
2. the preparation method of manganese dioxide-catalyst according to claim 1 is characterized in that, described conductive carbon material is graphite, acetylene black, carbon black or active carbon.
3. the preparation method of manganese dioxide-catalyst according to claim 1 is characterized in that, described NaOH solution, and its concentration is 10mol/L.
4. the preparation method of manganese dioxide-catalyst according to claim 1 is characterized in that, the described hydrothermal reaction kettle of putting into is 110 ℃ in temperature, and pressure is to react 12h under the condition of 2.1MPa.
5. manganese dioxide-catalyst for preparing according to the preparation method of the described manganese dioxide-catalyst of claim 1.
6. the application of the described manganese dioxide-catalyst of claim 5 in microbiological fuel cell.
7. application according to claim 6 is characterized in that, described manganese dioxide-catalyst is in the application that is used for the disposal of refuse percolate as the microorganism fuel cell cathode electrode catalyst.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104617312A (en) * | 2015-01-29 | 2015-05-13 | 黑龙江大学 | Microbial fuel cell cathode catalyst material with bacteriostatic function and preparation method thereof |
| CN105776502A (en) * | 2016-01-06 | 2016-07-20 | 浙江工商大学 | Method for reducing CO2 by virtue of metal oxide modified biofilm electrode |
| CN108808015A (en) * | 2018-05-21 | 2018-11-13 | 南昌航空大学 | A kind of polyaniline/reduced graphene/TiO2The synthetic method of material and its application |
| CN112978867A (en) * | 2021-02-24 | 2021-06-18 | 重庆建深环境科技有限公司 | Method for electrolyzing ammonia nitrogen wastewater by using manganese-containing catalyst |
| CN113005467A (en) * | 2021-02-24 | 2021-06-22 | 重庆大学 | Method for producing hydrogen by electrolyzing ammonia by using manganese-containing catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101355170A (en) * | 2008-09-11 | 2009-01-28 | 广东省生态环境与土壤研究所 | Application of manganese dioxide in preparation of microbial fuel cell cathode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101355170A (en) * | 2008-09-11 | 2009-01-28 | 广东省生态环境与土壤研究所 | Application of manganese dioxide in preparation of microbial fuel cell cathode |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104617312A (en) * | 2015-01-29 | 2015-05-13 | 黑龙江大学 | Microbial fuel cell cathode catalyst material with bacteriostatic function and preparation method thereof |
| CN105776502A (en) * | 2016-01-06 | 2016-07-20 | 浙江工商大学 | Method for reducing CO2 by virtue of metal oxide modified biofilm electrode |
| CN105776502B (en) * | 2016-01-06 | 2019-04-16 | 浙江工商大学 | A kind of metal oxide modified electrode biomembrane reduction CO2Method |
| CN108808015A (en) * | 2018-05-21 | 2018-11-13 | 南昌航空大学 | A kind of polyaniline/reduced graphene/TiO2The synthetic method of material and its application |
| CN112978867A (en) * | 2021-02-24 | 2021-06-18 | 重庆建深环境科技有限公司 | Method for electrolyzing ammonia nitrogen wastewater by using manganese-containing catalyst |
| CN113005467A (en) * | 2021-02-24 | 2021-06-22 | 重庆大学 | Method for producing hydrogen by electrolyzing ammonia by using manganese-containing catalyst |
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