CN106024422A - Method for preparing a capacitive electrode material by using domesticated activated sludge - Google Patents

Method for preparing a capacitive electrode material by using domesticated activated sludge Download PDF

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CN106024422A
CN106024422A CN201610355098.1A CN201610355098A CN106024422A CN 106024422 A CN106024422 A CN 106024422A CN 201610355098 A CN201610355098 A CN 201610355098A CN 106024422 A CN106024422 A CN 106024422A
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activated sludge
domestication
phenol
electrode material
capacitive electrode
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CN106024422B (en
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冯春华
雷振超
冯伟明
马萧萧
刘厚峰
郑嘉毅
伍兆基
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/02—Biological treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/20—Sludge processing

Abstract

The present invention discloses a method for preparing a capacitive electrode material by using domesticated activated sludge. The method comprises the following steps: (1) performing nitrification domestication or phenol domestication on activated sludge to obtain domesticated activated sludge, and (2) drying the resultant sludge in the step (1), performing grinding and sieving, performing calcination at the temperature of 700-1000 degrees centigrade for 1.5-4 hours in an inert gas atmosphere, performing acid treatment and then performing distilled water washing to neutral, performing drying at the temperature of 55-105 degrees centigrade and then performing sieving to obtain a self-doped porous sludge carbon material powder, that is, the capacitive electrode material. The method of the present invention increases the content of the nitrogen element in sludge carbon material, and the material has better capacitor performance.

Description

A kind of method utilizing acclimated activated sludge to prepare capacitive electrode material
Technical field
The invention belongs to capacitative materials technical field, be specifically related to one and utilize acclimated activated sludge preparation electricity The method of capacitive electrode material.
Background technology
Along with being on the rise of the energy and problem of environmental pollution, development new forms of energy or improve energy storage and conversion Mode gradually causes the interest of research worker.There is high power density, long service life and high security Ultracapacitor is a kind of ideal chose solving energy conversion and storage problem.Based on electric charge Ultrahigh, super Level capacitor can be divided into double layer capacitor and pseudocapacitors based on redox reaction.Electric double layer capacitance Device electrode material is mainly based on material with carbon element.In various pseudocapacitors materials, element doping, macromolecule Polymer, transition metal are high performance ultracapacitor active materials, therefore can be by adding in material with carbon element Add active material and improve capacitive property.
On the other hand, in sewage disposal, activated sludge process is stable to water quality and quantity because of it, and power consumption is few, purifies Sewage is effective and is widely used, but it can produce a large amount of activated sludge in running.These are lived Property sludge deposit a large amount of hardly degraded organic substances, microorganism, heavy metal and other toxic compounds.If processing Utilizing the improper risk of secondary pollution of bringing, therefore the disposal of activated sludge and utilization become Sewage Plant work A great problem.Activated sludge is mainly made up of compositions such as biomass, organic pollution and inorganic matters, and it is rich Containing organic elements such as C, H, N, O, S.Inorganic matter and filamentous bacteria constitute the skeleton of activated sludge, are micro- The template of biological attachment growth, it is bigger that the flocculant composition such as Fe, Al and filamentous bacteria make activated sludge have Specific surface area and loose pattern.As a example by coking chemical waste water activated sludge, it is rich in oxygen, nitrogen, ferrum, sulfur etc. Element, wherein the nitrogen-containing heterocycle compound such as pyridine, pyrroles is excellent electro-chemical activity composition.Thus, dirty Mud has the potentiality as good capacitive character energy storage material raw material, can be utilized and energy storage material by sludge treatment Preparation combine.
Summary of the invention
In order to overcome the disadvantages mentioned above of prior art with not enough, it is an object of the invention to provide a kind of utilization and tame and docile Change the method that activated sludge prepares capacitive electrode material, improve nitrogen element in mud material with carbon element by domestication Content and specific surface area, have more preferable capacitive property.
The purpose of the present invention is achieved through the following technical solutions:
A kind of method utilizing acclimated activated sludge to prepare capacitive electrode material, comprises the following steps:
(1) activated sludge is carried out nitrification domestication or phenol domestication, the activated sludge after being tamed；
Described nitrification is tamed, particularly as follows:
Activated sludge, in the nitrification domestication liquid of pH=7.0～8.0, is passed through the air that flow is 1～3L/min and enters The domestication of row aerobic nitrification is cultivated, and MLSS is 3～6g/L in control, obtains the autotrophy with nitrobacteria as dominant bacteria Type active pollution index；Described nitrification domestication liquid comprises ammonia nitrogen；
Described phenol is tamed, particularly as follows:
Activated sludge, in the phenol domestication liquid of pH=7.0～8.0, is passed through the air that flow is 1～3L/min and enters Oxy phenol of acting charitably domestication is cultivated；Control MLSS 3～6g/L；Obtaining Phenol hydroxylase gene is the different of dominant bacteria Support type active pollution index；Described phenol domestication liquid comprises phenol；
(2) mud that step (1) obtains is dried, grinds, sieves, under atmosphere of inert gases, Calcining 1.5～4 hours at 700～1000 DEG C, acid treated distilled water is washed till neutrality, at 55～105 DEG C Sieve the most after drying and obtain auto-dope porous mud material with carbon element powder, i.e. capacitive electrode material.
Described nitrification domestication liquid comprise phosphate buffer, mineral solution, vitamin solution, inorganic carbon source and Ammonia nitrogen；Described phenol domestication liquid comprises phosphate buffer, mineral solution, vitamin solution, nitrogen source and benzene Phenol.
In described nitrification domestication liquid, the concentration of ammonia nitrogen is 200～500mg/L.
In described phenol domestication liquid, the concentration of phenol is 500～1000mg/L.
The mode using gradient concentration to cultivate is cultivated in the domestication of described aerobic nitrification；The domestication of described good oxy phenol is cultivated Use the mode that gradient concentration is cultivated.
The mode using gradient concentration to cultivate is cultivated in the domestication of described aerobic nitrification: successively ammonia nitrogen concentration be 50, 100,150,200,250,300,400, the nitrification domestication liquid of 500mg/L is tamed.
The mode using gradient concentration to cultivate is cultivated in the domestication of described good oxy phenol, particularly as follows: dense at phenol successively Degree is 50,100,200,300,400,600,800, the phenol domestication liquid of 1000mg/L is tamed.
Described activated sludge is rich in oxygen element, nitrogen element, the activated sludge of ferrum element.
Described activated sludge is coking chemical waste water activated sludge.
Described auto-dope porous mud material with carbon element powder includes N doping porous carbon, Fe2O3 doping porous carbon and table Face richness oxygen-containing functional group porous carbon.
The principle of the present invention is:
The present invention is by taming activated sludge, during domestication is cultivated, and the microorganism in mud Kind develop to selective specific function kind, adapt to specific environment micro organism quantity, it is impossible to utilize The microorganism of specific nutrition material is the most dead, the most superseded.Microorganism in final activated sludge can be formed greatly Measure and relatively stablize single dominant group.By specifically taming cultivation, the nitrogen element content in mud obtains Further enrichment and improving, carbon-nitrogen ratio tends towards stability, and adds carbon abundant in activated sludge, oxygen, ferrum element, Make the material with carbon element prepared by acclimated activated sludge should have higher conductive capability, electro-chemical activity and stablize The controllability of preparation.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) present invention tames by activated sludge carries out nitrification domestication or phenol, improves mud material with carbon element The content of middle nitrogen element, has more preferable capacitive property.
(2) method preparing capacitive electrode material based on activated sludge of the present invention, technique is simple, cost Low, raw material sources are extensive.
(3) it is loose porous that the capacitive character mud material with carbon element powder that prepared by the present invention has pattern, and specific surface Long-pending height, light specific gravity, characteristic that cyclical stability is good.
(4) element that capacitative materials prepared by the present invention is adulterated derives from activated sludge.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) of the capacitive character mud material with carbon element powder of embodiment 1 preparation Figure.
Fig. 2 is that the capacitive character mud material with carbon element X-ray powder photoelectron of embodiment 1 preparation can (XPS) spectrum Figure.
Fig. 3 is the nitrogen adsorption desorption test figure that embodiment 1 prepares capacitive character mud material with carbon element powder.
Fig. 4 is the graph of pore diameter distribution of the capacitive character mud material with carbon element powder of embodiment 1 preparation.
Fig. 5 is the capacitive character mud material with carbon element powder CV scanning curve figure of embodiment 1 preparation.
Fig. 6 is the capacitive character mud material with carbon element powder GCD curve chart of embodiment 1 preparation.
Fig. 7 is the capacitive character mud material with carbon element powder circulation stability test figure of embodiment 1 preparation
Fig. 8 is the capacitive character mud material with carbon element powder CV scanning curve figure of embodiment 2 preparation.
Fig. 9 is the capacitive character mud material with carbon element powder GCD curve chart of embodiment 2 preparation.
Figure 10 is capacitive character mud material with carbon element powder CV scanning curve figure prepared by comparative example.
Figure 11 is capacitive character mud material with carbon element powder GCD curve chart prepared by comparative example.
Figure 12 is that capacitive character mud material with carbon element powder GCD prepared by embodiment 1, embodiment 2, comparative example is bent Line comparison diagram.
Figure 13 (a)～(c) are respectively the scanning electron of mud in embodiment 1, embodiment 2, comparative example and show Micro mirror (SEM) figure.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not It is limited to this.
Embodiment 1
Take 10 grams of nitrification domestication autotrophic type activity cultivated by splendid steel coking chemical waste water project Aerobic Pond sludge acclimatization dirty Mud (in this mud, the mass percent of carbon is 23.04%, and the mass percent of nitrogen element is 6.39%, The mass percent of oxygen element is 28.56%) it is dried 6 hours at 60 DEG C, grind after taking-up, cross 100 mesh Sieve, the most under nitrogen atmosphere, with the heating rate of 10 degrees Celsius per minute, calcines 2 little at 800 DEG C Time, the carbon dust of gained is washed till neutrality with distilled water after HCl treatment, dried mistake 300 mesh at 60 DEG C Sieve obtains auto-dope porous mud material with carbon element powder, i.e. capacitive electrode material.
Described nitrification is tamed, particularly as follows:
Activated sludge, in nitrification domestication liquid, is passed through the air that flow is 1～3L/min and carries out aerobic domestication cultivation, MLSS is 3～6g/L in control, obtains the autotrophic type active pollution index with nitrobacteria as dominant bacteria.
Described nitrification domestication liquid comprises 0.1mol/L pH=8.0 phosphate buffer, 1.91g/L ammonium chloride (phase When in 500mg/L ammonia nitrogen), 3g/L sodium bicarbonate, it is molten that every liter of phosphate buffer adds 10mL mineral Liquid and 10mL vitamin solution
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 below.
Table 3
Fig. 1 is the Scanning Electron microscope imaging figure of capacitive character mud material with carbon element powder prepared by the present embodiment. It can be seen that this mud material with carbon element has loose porous structure.
Fig. 2 is the full spectrogram of x-ray photoelectron power spectrum of capacitive character mud material with carbon element powder prepared by the present embodiment. It can be seen that beyond de-carbon element, it is rich in elements such as nitrogen, oxygen, sulfur.After measured, its nitrogen content is 2.6%, The doping of nitrogen element is favorably improved material electrochemical activity, improves material capacitive property.
Fig. 3 is the nitrogen adsorption desorption test figure of capacitive character mud material with carbon element powder prepared by the present embodiment.Through surveying Fixed, it is appreciated that its specific surface area is 609.4m2/g。
Fig. 4 is the graph of pore diameter distribution of capacitive character mud material with carbon element powder prepared by the present embodiment.After measured, main Bore dia is wanted to concentrate on about 12.13nm.
With the capacitive character porous carbon materials prepared by the present embodiment as electrode material for super capacitor, use three electricity The electrochemical workstation of polar body system detects its capacitive property.Wherein working electrode is prepared by load the present embodiment The glass-carbon electrode of carbon dust, reference electrode is saturated calomel electrode (SCE), is platinum filament to electrode, electrolysis Liquid is 1mol/L H2SO4Solution.CV scanning result is as it is shown in figure 5, capacitive character prepared by the present embodiment Mud material with carbon element 10,20,50,100, CV curve chart under the sweep speed of 200mV/s.GCD Dependence Results as shown in Figure 6, respectively the capacitive character mud material with carbon element prepared by the present embodiment 1,2,3, 5,10 the discharge and recharge charging and discharging curve, under 15A/g difference electric current density, under the electric current density of 1A/g, material The ratio capacitance of material is 889F/g.Cyclical stability is as it is shown in fig. 7, capacitive character prepared by the present embodiment Mud material with carbon element is the curve of discharge and recharge 10000 circle circulation gained, circulation under the conditions of electric current density is 20A/g After 10000 circles, electric capacity the most substantially reduces.
Embodiment 2
Take 10 grams of phenol domestication heterotroph activity cultivated by splendid steel coking chemical waste water project Aerobic Pond sludge acclimatization dirty (in this mud, the mass percent of carbon is 24.06% to mud, and the mass percent of nitrogen element is 4.72%, oxygen The mass percent of element is 29.16%) it is dried 6 hours at 60 DEG C, grind after taking-up, cross 100 mesh Sieve, the most under nitrogen atmosphere, with the heating rate of 5 degrees Celsius per minute, calcines 2 hours at 800 DEG C, Being washed till neutrality with distilled water after HCl treatment, at 60 DEG C, dried mistake 300 mesh sieve obtains auto-dope porous Mud material with carbon element powder, i.e. capacitive electrode material.
The phenol domestication of the present embodiment, particularly as follows:
Activated sludge, in phenol domestication liquid, is passed through the air that flow is 1～3L/min and carries out aerobic domestication cultivation； Control MLSS 3～6g/L；Obtain the heterotroph active pollution index that Phenol hydroxylase gene is dominant bacteria.
Described phenol domestication liquid comprise 0.1mol/L pH=7.0 phosphate buffer, 800mg/L phenol, 0.2 G/L ammonium chloride, adds 10mL mineral solution and 10mL vitamin solution in every liter of phosphate buffer. The formula of mineral solution and vitamin solution is same with embodiment 1.
The formula of 0.1mol/L pH=7.0 phosphate buffer is as shown in table 4 below.
Table 4
Subsequent experimental condition is same as in Example 1, and CV scanning result is as shown in Figure 8, made for the present embodiment Standby capacitive character mud material with carbon element sweeps CV curve under speed at 10mV/s；GCD curve is as it is shown in figure 9, be Capacitive character mud material with carbon element prepared by the present embodiment is 1A/g constant current charge-discharge curve chart in electric current density, It is 578F/g than capacitance.
Comparative example
This comparative example uses the activated sludge without domestication to prepare mud material with carbon element, specific as follows:
Take 10 grams of splendid steel coking chemical waste water project Aerobic Pond activated sludge (mass percent of carbon in this mud Being 21.62%, the mass percent of this nitrogen element is 4.01%, and the mass percent of oxygen element is 32.13%) It is dried 6 hours at 60 DEG C, grinds after taking-up, cross 100 mesh sieves, the most under nitrogen atmosphere, with every point The heating rate that clock is 5 degrees Celsius, calcines 2 hours, in being washed till with distilled water after HCl treatment at 800 DEG C Property, at 60 DEG C, dried mistake 300 mesh sieve obtains auto-dope porous mud material with carbon element powder, i.e. capacitive character electricity Pole material.
Subsequent experimental condition is same as in Example 1, CV scanning result such as Figure 10, prepared by the present embodiment Capacitive character mud material with carbon element GCD Dependence Results such as Figure 11 under conditions of electric current density is 1A/g, than electricity Capacitance is 146F/g.Capacitive character mud material with carbon element powder GCD prepared by embodiment 1, embodiment 2, comparative example Curve comparison figure such as Figure 12.
Figure 13 (a)～(c) are the scanning electron microscopy of mud in embodiment 1, embodiment 2, this comparative example Mirror figure, it can be seen that in non-acclimation sludge 13 (a), growth of microorganism ratio is sparse, acclimation sludge 13 (b), In 13 (c), growth fraction is denser, compact conformation.
Table 1 is mud and mud carbon organic element content in embodiment 1, embodiment 2 and this comparative example, permissible See the mud and non-acclimation sludge tamed through autotrophic type or heterotroph, and the mud material with carbon element phase of corresponding preparation Ratio, has higher nitrogen element content and carbon-nitrogen ratio, the raising doped with beneficially capacitive property of nitrogen element.
Table 5
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by described reality Execute the restriction of example, the change made under other any spirit without departing from the present invention and principle, modification, Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.

Claims (10)

1. one kind utilizes the method that acclimated activated sludge prepares capacitive electrode material, it is characterised in that include Following steps:
(1) activated sludge is carried out nitrification domestication or phenol domestication, the activated sludge after being tamed；
Described nitrification is tamed, particularly as follows:
Activated sludge, in the nitrification domestication liquid of pH=7.0～8.0, is passed through the air that flow is 1～3L/min and enters The domestication of row aerobic nitrification is cultivated, and MLSS is 3～6g/L in control, obtains the autotrophy with nitrobacteria as dominant bacteria Type active pollution index；Described nitrification domestication liquid comprises ammonia nitrogen；
Described phenol is tamed, particularly as follows:
Activated sludge, in the phenol domestication liquid of pH=7.0～8.0, is passed through the air that flow is 1～3L/min and enters Oxy phenol of acting charitably domestication is cultivated, and controls MLSS 3～6g/L；Obtaining Phenol hydroxylase gene is the different of dominant bacteria Support type active pollution index；Described phenol domestication liquid comprises phenol；
(2) mud that step (1) obtains is dried, grinds, sieves, under atmosphere of inert gases, Calcining 1.5～4 hours at 700～1000 DEG C, acid treated distilled water is washed till neutrality, at 55～105 DEG C Sieve the most after drying and obtain auto-dope porous mud material with carbon element powder, i.e. capacitive electrode material.
The method utilizing acclimated activated sludge to prepare capacitive electrode material the most according to claim 1, It is characterized in that, described nitrification domestication liquid comprises phosphate buffer, mineral solution, vitamin solution, nothing Machine carbon source and ammonia nitrogen；Described phenol domestication liquid comprise phosphate buffer, mineral solution, vitamin solution, Nitrogen source and phenol.
The method utilizing acclimated activated sludge to prepare capacitive electrode material the most according to claim 1, It is characterized in that, in described nitrification domestication liquid, the concentration of ammonia nitrogen is 200～500mg/L.
The method utilizing acclimated activated sludge to prepare capacitive electrode material the most according to claim 1, It is characterized in that, in described phenol domestication liquid, the concentration of phenol is 500～1000mg/L.
The method utilizing acclimated activated sludge to prepare capacitive electrode material the most according to claim 1, It is characterized in that, the mode using gradient concentration to cultivate is cultivated in the domestication of described aerobic nitrification；Described good oxy phenol The mode using gradient concentration to cultivate is cultivated in domestication.
The method utilizing acclimated activated sludge to prepare capacitive electrode material the most according to claim 5, It is characterized in that, the mode using gradient concentration to cultivate is cultivated in the domestication of described aerobic nitrification: dense at ammonia nitrogen successively Degree is 50,100,150,200,250,300,400, the nitrification domestication liquid of 500mg/L is tamed.
The method utilizing acclimated activated sludge to prepare capacitive electrode material the most according to claim 5, It is characterized in that, the mode using gradient concentration to cultivate is cultivated in the domestication of described good oxy phenol, particularly as follows: successively Phenol concentration be 50,100,200,300,400,600,800, in the phenol domestication liquid of 1000mg/L Domestication.
The method utilizing acclimated activated sludge to prepare capacitive electrode material the most according to claim 1, It is characterized in that, described activated sludge is rich in oxygen element, nitrogen element, the activated sludge of ferrum element.
The method utilizing acclimated activated sludge to prepare capacitive electrode material the most according to claim 1, It is characterized in that, described activated sludge is coking chemical waste water activated sludge.
The method utilizing acclimated activated sludge to prepare capacitive electrode material the most according to claim 1, It is characterized in that, described auto-dope porous mud material with carbon element powder includes N doping porous carbon, Fe2O3 doping porous Carbon and rich surface oxygen-containing functional group porous carbon.
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