CN105870465B - A kind of preparation method of the auto-dope carbon catalysis material based on activated sludge acclimatization - Google Patents
A kind of preparation method of the auto-dope carbon catalysis material based on activated sludge acclimatization Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The preparation method of the invention discloses a kind of auto-dope carbon catalysis material based on activated sludge acclimatization, comprising the following steps: (1) nitrification domestication is carried out to activated sludge or phenol is tamed, the activated sludge after being tamed；(2) sludge that step (1) obtains is dried, is ground up, sieved, under atmosphere of inert gases, it is calcined 1.5~4 hours at 700~1000 DEG C, it is acid treated to be washed to neutrality with distillation, it is sieved after dry to obtain auto-dope carbon catalysis material powder at 55~105 DEG C.Method of the invention is simple, at low cost, and raw material sources are extensive, improves the content of nitrogen in catalysis material, and catalysis material has better hydrogen reduction catalytic performance.
Description
Technical field
The present invention relates to electrode catalytic materials technical field, in particular to a kind of auto-dope carbon based on activated sludge acclimatization
The preparation method of catalysis material.
Background technique
Fuel cell includes the emerging electricity production technology that microbiological fuel cell is clean and environmental protection, wherein a major class cell cathode
It directly participates in reacting by oxygen, the performance of cathodic oxygen reduction is to influence the major reason of battery efficiency of fuel cell generation, thus cathode oxygen is also
The performance of raw catalyst is the key factor of fuel cell practical application.Currently, platinum carbon catalyst is most efficient oxygen
Reduction catalysts material, but due to its cost height, place makes numerous researchers urgently find a kind of low price the deficiencies of low output
Efficient platinum carbon catalyst substitute.Wherein it was discovered by researchers that the doping carbon material through elements such as nitrogen, iron, hydrogen reduction are urged
Change activity to be significantly improved.
On the other hand, activated sludge process is a kind of most common method in processing life production waste water, and activated sludge is it
By-product is enriched a large amount of organic poisons, heavy metal and pathogen, if handling using the improper risk that will bring secondary pollution,
Therefore a great problem of activated sludge disposed with worked using sewage plant is become.
Activated sludge is mainly made of ingredients such as biomass, organic pollutant and inorganic matters.Wherein organic principle is mainly
Organic matter, microbial body and its extracellular polymeric and a small amount of primary, metazoa in sewage, C, H, N, O, S rich in
Equal elements；Inorganic constituents has the elements such as P, S, K, Ca, Mg, Na, Cl, B, Fe, Al, Cu, Co, Cr.Inorganic matter and der Pilz structure
The skeleton of Viability sludge, is the template of attached growth of microorganisms, and the flocculants such as Fe, Al ingredient and der Pilz make activated sludge
With biggish specific surface area and loose pattern.
Summary of the invention
In order to overcome the disadvantages mentioned above and deficiency of the prior art, the purpose of the present invention is to provide one kind to be based on activated sludge
The preparation method of the auto-dope carbon catalysis material of domestication improves the content of nitrogen in carbon material, ratio by acclimation early period
Surface area, electric conductivity, so that carbon material has similar graphene-structured, it is final to promote carbon material hydrogen reduction catalytic performance.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of the auto-dope carbon catalysis material based on activated sludge acclimatization, comprising the following steps:
(1) nitrification domestication is carried out to activated sludge or phenol is tamed, the activated sludge after being tamed；
The nitrification domestication, specifically:
Activated sludge is passed through the air that flow is 1~3L/min and carries out in the nitrification domestication liquid of pH=7.0~8.0
Oxygen nitrification domestication culture, controls MLSS in 3~6g/L, obtains the autotrophic type active pollution index using nitrobacteria as dominant bacteria；
The nitrification domestication liquid includes ammonia nitrogen；
The phenol domestication, specifically:
Activated sludge is passed through the air that flow is 1~3L/min and carries out in the phenol domestication liquid of pH=7.0~8.0
Oxy phenol domestication culture；MLSS is controlled in 3~6g/L；The heterotroph activated sludge that Phenol hydroxylase gene is dominant bacteria is obtained to wad a quilt with cotton
Body；The phenol domestication liquid includes phenol；
(2) sludge that step (1) obtains is dried, is ground up, sieved, under atmosphere of inert gases, in 700~1000
It is calcined 1.5~4 hours at DEG C, it is acid treated to be washed to neutrality with distillation, it is sieved after dry to obtain at 55~105 DEG C and mix certainly
Miscellaneous porous sludge carbon material powder, i.e. auto-dope carbon catalysis material.
The nitrification domestication liquid includes phosphate buffer, mineral solution, vitamin solution, inorganic carbon source and ammonia nitrogen；Institute
Stating phenol domestication liquid includes phosphate buffer, mineral solution, vitamin solution, nitrogen source and phenol.
The concentration of ammonia nitrogen is 200~500mg/L in the nitrification domestication liquid.
The concentration of phenol is 500~1000mg/L in the phenol domestication liquid.
The aerobic nitrification domestication culture is by the way of gradient concentration culture；The aerobic phenol domestication culture is using ladder
Spend the mode of concentration culture.
Aerobic nitrification domestication culture using gradient concentration culture by the way of, specifically: successively ammonia nitrogen concentration be 50,
100, it 150,200,250,300,400, is tamed in the nitrification domestication liquid of 500mg/L.
The aerobic phenol domestication culture using gradient concentration culture by the way of, specifically: successively phenol concentration be 50,
100, it 200,300,400,600,800, is tamed in the phenol domestication liquid of 1000mg/L.
The activated sludge be rich in oxygen element, nitrogen, ferro element activated sludge.
The activated sludge is coking wastewater activated sludge.
The auto-dope carbon catalysis material powder includes N doping porous carbon, Fe2O3 doping porous carbon and surface rich in oxygen official
Porous carbon can be rolled into a ball.
The principle of the present invention are as follows:
The present invention is by taming activated sludge, during taming culture, the type of the microorganism in sludge
It is developed to the specific function type of selectivity, adapts to the micro organism quantity of specific environment, the micro- of specific nutrition substance cannot be utilized
It is biological then gradually dead, superseded.Microorganism in final activated sludge can form a large amount of and relatively stablize single dominant group.It is logical
Specific domestication culture is crossed, the nitrogen element content in sludge is further enriched with and is improved, and carbon-nitrogen ratio tends towards stability, in addition living
Property sludge in carbon abundant, oxygen, ferro element so that carbon material prepared by acclimated activated sludge should have stronger conductive energy
Power, oxygen reduction catalytic activity and the controllability for stablizing preparation.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) present invention improves nitrogen in catalysis material by carrying out nitrification domestication or phenol domestication to activated sludge
Content, have better hydrogen reduction catalytic performance.
(2) preparation method of the auto-dope carbon catalysis material of the invention based on activated sludge acclimatization, simple process, cost
Low, raw material sources are extensive.
(3) auto-dope carbon catalysis material powder prepared by the present invention has that pattern is loose porous, similar graphene-structured, and
The characteristic of the good and resistance to poisoning of specific surface area height, light specific gravity, cyclical stability.
(4) auto-dope carbon catalysis material prepared by the present invention institute doped chemical derives from activated sludge, nitrogen, iron member
The doping of element improves oxygen reduction activity.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of the porous sludge carbon material powder of auto-dope prepared by embodiment 1.
Fig. 2 is that the porous sludge carbon material powder x-ray photoelectron of auto-dope prepared by embodiment 1 can (XPS) spectrogram.
Fig. 3 is the nitrogen adsorption desorption test chart that embodiment 1 prepares the porous sludge carbon material powder of auto-dope.
Fig. 4 is the graph of pore diameter distribution of the porous sludge carbon material powder of auto-dope prepared by embodiment 1.
Fig. 5 is the porous sludge carbon material powder CV scanning curve figure of auto-dope prepared by embodiment 1.
Fig. 6 is the porous sludge carbon material powder LSV scanning curve figure of auto-dope prepared by embodiment 1.
Fig. 7 is the porous sludge carbon material powder CV scanning curve figure of auto-dope prepared by embodiment 2.
Fig. 8 is the porous sludge carbon material powder LSV scanning curve figure of auto-dope prepared by embodiment 2.
Fig. 9 is the porous sludge carbon material powder CV scanning curve figure of auto-dope prepared by embodiment 3.
Figure 10 is the porous sludge carbon material powder CV scanning curve figure of auto-dope prepared by embodiment 4.
Figure 11 is the porous sludge carbon material powder CV scanning curve figure of auto-dope of comparative example preparation.
Figure 12 is the porous sludge carbon material powder LSV scanning curve figure of auto-dope of comparative example preparation.
The porous sludge carbon material powder LSV scanning curve of auto-dope that Figure 13 is embodiment 1, prepared by embodiment 2, comparative example
Comparison diagram.
Figure 14 (a)~(c) be respectively embodiment 1, embodiment 2, in comparative example sludge scanning electron microscope (SEM)
Figure.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
10 grams are taken (to be somebody's turn to do by the nitrification domestication autotrophic type activated sludge of splendid steel coking wastewater project aerobic tank sludge acclimatization culture
The mass percent of carbon is 23.04% in sludge, and the mass percent of nitrogen is 6.39%, the quality percentage of oxygen element
Than grinding, sieving with 100 mesh sieve after taking-up, then under nitrogen atmosphere, with per minute 28.56%) to be dried 6 hours at 60 DEG C
10 degrees Celsius of heating rate calcines 2 hours at 800 DEG C, and resulting carbon dust is washed to after HCl treatment with distillation
Property, 300 meshes, which are crossed, after dry at 60 DEG C obtains the porous sludge carbon material powder of auto-dope, i.e. auto-dope carbon catalysis material.
The nitrification domestication, specifically:
Activated sludge is passed through the air that flow is 1~3L/min and carries out aerobic domestication culture, control in nitrification domestication liquid
MLSS obtains the autotrophic type active pollution index using nitrobacteria as dominant bacteria in 3~6g/L.
The nitrification domestication liquid (is equivalent to comprising 0.1mol/L pH=8.0 phosphate buffer, 1.91g/L ammonium chloride
500mg/L ammonia nitrogen), 3g/L sodium bicarbonate, 10mL mineral solution and 10mL vitamin solution is added in every liter of phosphate buffer.
The formula of 0.1mol/L pH=8.0 phosphate buffer is as shown in table 1.
Table 1
Mineral solution formula is as shown in table 2.
Table 2
Vitamin solution formula is as shown in table 3.
Table 3
Fig. 1 is the Scanning Electron microscope imaging figure of the porous sludge carbon material powder of auto-dope prepared by the present embodiment.It can
To find out, which has loose porous structure.
Fig. 2 is the full spectrogram of x-ray photoelectron spectroscopy of the porous sludge carbon material powder of auto-dope prepared by the present embodiment.It can
To find out, in addition to carbon, rich in elements such as nitrogen, oxygen, sulphur.After measured, nitrogen content 2.6%, the doping of nitrogen
Help to improve oxygen reduction catalytic activity.
Fig. 3 is the nitrogen adsorption desorption test chart of the porous sludge carbon material powder of auto-dope prepared by the present embodiment.After measured,
It can learn that its specific surface area is 609.4m2/g。
Fig. 4 is the graph of pore diameter distribution of the porous sludge carbon material powder of auto-dope prepared by the present embodiment.After measured, main aperture
Diameter concentrates on 12.13nm or so.
Using the porous sludge carbon material of auto-dope prepared by the present embodiment as oxygen reduction catalyst, using three-electrode system
Electrochemical workstation detects its hydrogen reduction catalytic capability.Wherein working electrode is the glass for loading carbon dust prepared by the present embodiment
Carbon electrode, reference electrode are saturated calomel electrode (SCE), are platinum filament to electrode, and electrolyte is 0.1mol/L KOH solution.CV is swept
Result is retouched as shown in figure 5, under the sweep speed of 20mV/s, in the comparison of nitrogen and oxygen atmosphere, prepared by the present embodiment
The porous sludge carbon material of auto-dope have apparent hydrogen reduction peak.LSV scanning result is as shown in fig. 6, pass through rotating circular disk electricity
Pole is respectively with the revolving speed of 400,625,900,1600,2500rpm, with 5mV/s in the 0.1mol/L KOH solution of oxygen saturation
Sweep speed under gained polarization curve.It is 3.89 through K-L equation model hydrogen reduction transfer electron number, illustrates it with excellent
Catalytic activity.
Embodiment 2
10 grams are taken (to be somebody's turn to do by the phenol domestication heterotroph activated sludge of splendid steel coking wastewater project aerobic tank sludge acclimatization culture
The mass percent of carbon is 24.06% in sludge, and the mass percent of nitrogen is 4.72%, the quality percentage of oxygen element
Than grinding, sieving with 100 mesh sieve after taking-up, then under nitrogen atmosphere, with per minute 5 29.16%) to be dried 6 hours at 60 DEG C
Degree Celsius heating rate, calcined 2 hours at 800 DEG C, be washed to neutrality with distillation after HCl treatment, it is dry at 60 DEG C
300 meshes are crossed afterwards obtains the porous sludge carbon material powder of auto-dope, i.e. auto-dope carbon catalysis material.
The phenol of the present embodiment is tamed, specifically:
Activated sludge is passed through the air that flow is 1~3L/min and carries out aerobic domestication culture in phenol domestication liquid；Control
MLSS is in 3~6g/L；Obtain the heterotroph active pollution index that Phenol hydroxylase gene is dominant bacteria.
The phenol domestication liquid includes 0.1mol/L pH=7.0 phosphate buffer, 800mg/L phenol, 0.2g/L chlorination
10mL mineral solution and 10mL vitamin solution are added in every liter of phosphate buffer for ammonium.Mineral solution and vitamin solution
Formula and embodiment 1 it is same.
The formula of 0.1mol/L pH=7.0 phosphate buffer is as shown in table 4.
Table 4
Subsequent experimental condition is same as Example 1, and CV scanning result is as shown in fig. 7, LSV scanning result such as Fig. 8, through K-L
It is 3.84 that electron number is shifted in equation model hydrogen reduction.Illustrate it with excellent oxygen reduction catalytic activity.
Embodiment 3
10 grams are taken (to be somebody's turn to do by the nitrification domestication autotrophic type activated sludge of splendid steel coking wastewater project aerobic tank sludge acclimatization culture
The mass percent of nitrogen is 6.39% in sludge, and the mass percent of oxygen element is that 28.56%) drying 6 is small at 60 DEG C
When, it grinds, sieves with 100 mesh sieve after taking-up, then under nitrogen atmosphere, with 10 degrees Celsius of heating rate per minute, at 900 DEG C
Calcining 2 hours is washed to neutrality with distillation after HCl treatment, and it is porous to obtain auto-dope for 300 meshes excessively after drying at 60 DEG C
Sludge carbon material powder, i.e. auto-dope carbon catalysis material.
Subsequent experimental condition is same as Example 1, and CV scanning result is as shown in figure 9, illustrate it with excellent hydrogen reduction
Catalytic activity.
Embodiment 4
(1) 10 grams of phenol by splendid steel coking wastewater project aerobic tank sludge acclimatization culture is taken to tame heterotroph activated sludge
(mass percent of nitrogen is 4.72% in the sludge, and the mass percent of oxygen element is 29.16%) to be put into vacuum refrigeration
It is 48 hours dry at -40 DEG C in drying machine, it grinds, sieves with 100 mesh sieve after taking-up, then under nitrogen atmosphere, with per minute 5
Degree Celsius heating rate, calcined 2 hours at 800 DEG C, be washed to neutrality with distillation after nitric acid treatment, it is dry at 60 DEG C
300 meshes are crossed afterwards obtains the porous sludge carbon material powder of auto-dope, i.e. auto-dope carbon catalysis material.
Subsequent experimental condition is same as Example 1, and CV scanning result is as shown in Figure 10, illustrates it with excellent hydrogen reduction
Catalytic activity.
Comparative example
This comparative example, which is used, prepares cathodic oxygen reduction C catalyst without the activated sludge of domestication, specific as follows:
Taking 10 grams of splendid steel coking wastewater project aerobic tank activated sludge, (mass percent of carbon is in the sludge
21.62%, the mass percent of the nitrogen is 4.01%, and the mass percent of oxygen element is 32.13%) dry at 60 DEG C
It 6 hours, grinds, sieves with 100 mesh sieve after taking-up, then under nitrogen atmosphere, with 5 degrees Celsius of heating rate per minute, in 800 DEG C
Lower calcining 2 hours, is washed to neutrality with distillation after HCl treatment, and it is more to obtain auto-dope for 300 meshes excessively after drying at 60 DEG C
Hole sludge carbon material powder, i.e. auto-dope carbon catalysis material.
Follow-up test condition is same as Example 1, and CV scanning result is as shown in figure 11.LSV scanning result such as Figure 12, through K-
It is 3.49 that electron number is shifted in L equation model hydrogen reduction.Illustrate it with certain oxygen reduction catalytic activity.Figure 13 be embodiment 1,
Compared in embodiment 2 and this comparative example with rotating disk electrode (r.d.e) revolving speed for the LSV scanning result of 2500rpm, it can be seen that through certainly
Compared with non-acclimation sludge, the porous sludge carbon of prepared auto-dope has better oxygen also for the type of supporting or the sludge of heterotroph domestication
Former catalytic performance.
Figure 14 (a)~(c) be embodiment 1, embodiment 2, in this comparative example sludge scanning electron microscope diagram, can see
Into non-acclimation sludge 14 (a), microorganism growth fraction is sparse, and 14 (b), 14 (c) middle growths are denser in acclimation sludge, knot
Structure is compact.
Table 5 is embodiment 1, sludge and sludge carbon organic element content in embodiment 2 and this comparative example, it can be seen that through from
The type of supporting or the sludge and non-acclimation sludge of heterotroph domestication, and the porous sludge carbon phase ratio of auto-dope accordingly prepared, have higher
Nitrogen element content and carbon-nitrogen ratio, nitrogen doped be conducive to oxygen reduction catalytic activity raising.
Table 5
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the auto-dope carbon catalysis material based on activated sludge acclimatization, which is characterized in that including following step
It is rapid:
(1) nitrification domestication is carried out to activated sludge or phenol is tamed, the activated sludge after being tamed；
The nitrification domestication, specifically:
Activated sludge is passed through the air that flow is 1~3L/min and carries out aerobic nitre in the nitrification domestication liquid of pH=7.0~8.0
Change domestication culture, controls MLSS in 3~6g/L, obtain the autotrophic type active pollution index using nitrobacteria as dominant bacteria；It is described
Nitrifying domestication liquid includes ammonia nitrogen；
The phenol domestication, specifically:
Activated sludge is passed through the air that flow is 1~3L/min and carries out aerobic benzene in the phenol domestication liquid of pH=7.0~8.0
Phenol domestication culture, controls MLSS in 3~6g/L；Obtain the heterotroph active pollution index that Phenol hydroxylase gene is dominant bacteria；Institute
Stating phenol domestication liquid includes phenol；
(2) sludge that step (1) obtains is dried, is ground up, sieved, under atmosphere of inert gases, at 700~1000 DEG C
Calcining 1.5~4 hours, it is acid treated to be washed to neutrality with distilling, it is sieved after dry to obtain auto-dope at 55~105 DEG C more
Hole sludge carbon material powder, i.e. auto-dope carbon catalysis material.
2. the preparation method of the auto-dope carbon catalysis material according to claim 1 based on activated sludge acclimatization, feature
It is, the nitrification domestication liquid includes phosphate buffer, mineral solution, vitamin solution, inorganic carbon source and ammonia nitrogen；The benzene
Phenol domestication liquid includes phosphate buffer, mineral solution, vitamin solution, nitrogen source and phenol.
3. the preparation method of the auto-dope carbon catalysis material according to claim 1 based on activated sludge acclimatization, feature
It is, the concentration of ammonia nitrogen is 200~500mg/L in the nitrification domestication liquid.
4. the preparation method of the auto-dope carbon catalysis material according to claim 1 based on activated sludge acclimatization, feature
It is, the concentration of phenol is 500~1000mg/L in the phenol domestication liquid.
5. the preparation method of the auto-dope carbon catalysis material according to claim 1 based on activated sludge acclimatization, feature
It is, the aerobic nitrification domestication culture is by the way of gradient concentration culture；The aerobic phenol domestication culture uses gradient
The mode of concentration culture.
6. the preparation method of the auto-dope carbon catalysis material according to claim 5 based on activated sludge acclimatization, feature
Be, aerobic nitrification domestication culture using gradient concentration culture by the way of, specifically: successively ammonia nitrogen concentration be 50,
100, it 150,200,250,300,400, is tamed in the nitrification domestication liquid of 500mg/L.
7. the preparation method of the auto-dope carbon catalysis material according to claim 5 based on activated sludge acclimatization, feature
Be, the aerobic phenol domestication culture using gradient concentration culture by the way of, specifically: successively phenol concentration be 50,
100, it 200,300,400,600,800, is tamed in the phenol domestication liquid of 1000mg/L.
8. the preparation method of the auto-dope carbon catalysis material according to claim 1 based on activated sludge acclimatization, feature
Be, the activated sludge be rich in oxygen element, nitrogen, ferro element activated sludge.
9. the preparation method of the auto-dope carbon catalysis material according to claim 1 based on activated sludge acclimatization, feature
It is, the activated sludge is coking wastewater activated sludge.
10. the preparation method of the auto-dope carbon catalysis material according to claim 1 based on activated sludge acclimatization, feature
It is, the auto-dope carbon catalysis material powder includes N doping porous carbon, Fe2O3 doping porous carbon and surface rich in oxygen function
Group's porous carbon.
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| CN103779111A (en) * | 2014-01-27 | 2014-05-07 | 华南理工大学 | Method for manufacturing electrode materials of super-capacitors by using surplus sludge |
| CN104150607A (en) * | 2014-07-30 | 2014-11-19 | 华南理工大学 | Device and method for degrading phenol and ammonia nitrogen simultaneously by virtue of microbial fuel cell |
| CN104681307A (en) * | 2015-03-20 | 2015-06-03 | 金小娟 | Preparation method of oxygen and nitrogen co-supported activated carbon electrode |
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|---|---|---|---|---|
| CN102267695A (en) * | 2011-07-25 | 2011-12-07 | 中国石油天然气集团公司 | Method for preparing super activated charcoal from oily sludge |
| CN103779111A (en) * | 2014-01-27 | 2014-05-07 | 华南理工大学 | Method for manufacturing electrode materials of super-capacitors by using surplus sludge |
| CN104150607A (en) * | 2014-07-30 | 2014-11-19 | 华南理工大学 | Device and method for degrading phenol and ammonia nitrogen simultaneously by virtue of microbial fuel cell |
| CN104681307A (en) * | 2015-03-20 | 2015-06-03 | 金小娟 | Preparation method of oxygen and nitrogen co-supported activated carbon electrode |
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