CN109879283A - A kind of preparation method of biomass porous carbon material and its application in anode of microbial fuel cell - Google Patents
A kind of preparation method of biomass porous carbon material and its application in anode of microbial fuel cell Download PDFInfo
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- CN109879283A CN109879283A CN201910174683.5A CN201910174683A CN109879283A CN 109879283 A CN109879283 A CN 109879283A CN 201910174683 A CN201910174683 A CN 201910174683A CN 109879283 A CN109879283 A CN 109879283A
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- 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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- 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
本发明公开了一种生物质多孔碳材料的制备方法及其在微生物燃料电池阳极的应用，包括如下步骤：(1)将收集到的一次性筷子破碎、洗涤、超声并干燥；(2)将破碎的一次性筷子在活化剂水溶液中活化处理，然后取出干燥；(3)将干燥后的产物在惰性气体分为下高温碳化，将碳化后的产物用酸洗涤，再用水洗涤，直到中性，将洗涤后的产物干燥，得到一次性筷子多孔碳材料。本发明通过碳化一次性筷子，得到多孔碳材料，制备方法简单廉价，为多孔碳材料的大批量制备提供参考。将一次性筷子多孔碳材料作为微生物燃料电池阳极有利于阳极室内产电微生物的附着，提供更多的活性位点，有利于提高微生物燃料电池的产电功率。
The invention discloses a preparation method of a biomass porous carbon material and its application in the anode of a microbial fuel cell, comprising the following steps: (1) crushing, washing, ultrasonicating and drying the collected disposable chopsticks; (2) making The broken disposable chopsticks are activated in the activator aqueous solution, and then taken out and dried; (3) the dried product is carbonized at high temperature under inert gas separation, and the carbonized product is washed with acid and then with water until it is neutral. , and drying the washed product to obtain the porous carbon material for disposable chopsticks. The invention obtains the porous carbon material by carbonizing the disposable chopsticks, the preparation method is simple and inexpensive, and provides a reference for the mass preparation of the porous carbon material. Using the disposable chopsticks porous carbon material as the anode of the microbial fuel cell is conducive to the attachment of electricity-generating microorganisms in the anode chamber, providing more active sites, which is beneficial to improve the electricity-generating power of the microbial fuel cell.
Description
Technical field
The present invention relates to technical field of material, and in particular to a kind of preparation method of biomass porous carbon material and its
In the application of anode of microbial fuel cell.
Background technique
Microbiological fuel cell (Microbial Fuel Cells, MFCs) is that one kind can be with direct oxidation waste water or deposition
Organic matter in object converts its chemical energy in the device of electric energy.Microbiological fuel cell is that 21 century field of environment engineering is emerging
The synchronous energy recovery technology of wastewater treatment, as a field brand-new and rich in challenge, therefore cause global pass
Note.But MFCs the problems such as that there is also output powers is lower, higher cost at present.Since the anode of MFCs is mainly used for growing
Microorganism, while by the electron transmission of generation to external circuits, therefore anode is an important original of MFCs power density size
Cause.There is the anode material of MFCs the delivery rate of effective specific surface area, mass-transfer efficiency and electronics to directly affect microorganism
The growing state of the stand density of film, microbial film directly affects the performance of anode, to directly affect the performance of MFCs.Therefore
Seek one kind can cheap, good conductivity, the preferable electrode material of biocompatibility it is particularly significant.
Biomass carbon material refers to by the biomass rich in carbon in the absence of oxygen, by one kind of Pintsch process generation
Solid, porous particles substance rich in carbon.Biomass carbon material contains a large amount of carbon, has gap structure abundant, biggish
More oxygen-content active gene is contained on specific surface area and surface, is a kind of very promising electrode material in MFCs.Using can
Regenerated biomass replaces increasingly depleted fossil fuel as carbon source, is the direction of the following whole nation or even global evolution, by
It is cheap in biomass, from a wealth of sources, so the raw material future porous carbon materials using biomass as porous carbon materials are led
The important component in domain.
Summary of the invention
Problem to be solved by this invention is: providing a kind of preparation method of biomass porous carbon material and its in microorganism
The application of anode of fuel cell, the present invention are directly biomass source using the discarded throwaway chopsticks in life, pass through letter
The method of single activation, carbonization prepares porous carbon materials, and the porous carbon of preparation is used as to the electrode material of microbiological fuel cell
Material, so that MFC produces higher electric energy.
The present invention in order to solve the above problem provided by technical solution are as follows: a kind of preparation side of biomass porous carbon material
Method the described method comprises the following steps,
(1), throwaway chopsticks are broken, washing, ultrasound and drying；
(2), broken throwaway chopsticks are activated in the aqueous solution of activator, then take out and dries；
(3), by dried product under inert gas range high temperature cabonization, by the product acid elution after carbonization, then
It is washed with deionized until the product drying after washing is obtained biomass porous carbon material by neutrality.
Preferably, the activator in the step (2) is ZnCl2Solution, the concentration of the ZnCl2 solution are 4mol/L.
Preferably, the temperature being activated in the step (2) is 150 DEG C, and the time of activation processing is 12h.
Preferably, the carburizing temperature of step (3) the high temperature carbonization is any one in 600 DEG C, 800 DEG C, 1000 DEG C
Kind.
Preferably, the carbonization time of step (3) the high temperature carbonization is 2h.
Preferably, the inert gas in the step (3) is N2 or Ar.
Preferably, the acid in the step (3) is hydrochloric acid, and the concentration of hydrochloric acid is 1mol/L.
A kind of biomass porous carbon material includes the following steps in the application of anode of microbial fuel cell,
A, slurries should be made by mixing into corresponding solvent cement and be coated in long 1cm, wide 1cm for the biomass carbon material
Carbon cloth on, be fabricated to anode of microbial fuel cell, be assembled in together with plain carbon cloth electrode in same anode chamber；
B, use carbon brush as microorganism fuel cell cathode, two pole room of yin-yang is linked by proton exchange membrane and is built into
For H-type microbial fuel cell unit, the microorganism growth-promoting media prepared need to be injected into anode chamber by temperature at 30 DEG C, and
Catholyte injects in cathode chamber；
C, link voltage data collector, the external resistance voltage value of acquisition in machine every five minutes, according to external resistance voltage
The variation of value regularly replaces catholyte and anolyte；
D, it cultivates two months, under conditions of reducing external resistance value, filters out the microbial flora that anti-current passes through,
Then the stable microbial film that grows into is carried on anode microorganism, can further progress correlated performance test.
Preferably, the pH value of catholyte and anolyte is neutrality in the step b.
Preferably, replacing external resistance value from big to small in the step c can resist high current to pass through to filter out
Microbial flora.
Compared with prior art, the invention has the advantages that
(1) using natural biomass castoff throwaway chopsticks as raw material, cheap, amount greatly, is had excellent performance the present invention,
It is environmentally protective, it is widely used.
(2) treatment process is simple, and a small amount of activator, which is added, by high-temperature calcination can be obtained the more of high specific surface area
Hole carbon material realizes the effective use of biomass resource.
(3) the biomass porous biocompatible carbon material of throwaway chopsticks is preferable, and specific surface area is larger, is conducive to anode production
The attachment and growth of electric microorganism, can effectively improve the electricity generation performance of microbiological fuel cell.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes a part of the invention, this hair
Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted improper limitations of the present invention.
Fig. 1 is the SEM figure of the biomass porous carbon material of 800 DEG C of the present invention；Using field emission microscopy observation sample
800 DEG C of product show shape appearance figure, it can be observed that material is made of cellular porous structure, pore structure is intensive and relatively
Even, surface is very coarse.The porous structure that 800 DEG C of sample can grow for microorganism provides place, and it is micro- to be conducive to increase anode
The load capacity of biology, to improve MFC electricity generation performance.
Fig. 2 is the BET figure of the biomass porous carbon material of 800 DEG C of the present invention；Specific surface area is up to 574cm2g, shows sample
There are many hole number of product.According to branch pore size distribution curve in figure, it can be seen that the aperture of sample is mainly distributed within 10nm, and
And 2nm distribution is also more concentrated, and shows that sample contains more micropore and mesoporous, more active sites can be provided for microorganism
Point, to influence the electricity generation performance of MFC.
Specific embodiment
Carry out the embodiment that the present invention will be described in detail below in conjunction with accompanying drawings and embodiments, how the present invention is applied whereby
Technological means solves technical problem and reaches the realization process of technical effect to fully understand and implement.
Embodiment 1
A kind of preparation method of biomass porous carbon material, the described method comprises the following steps,
(1), throwaway chopsticks are broken, washing, ultrasound and drying；
(2), broken throwaway chopsticks are activated in the aqueous solution of activator, then take out and dries；
(3), by dried product under inert gas range high temperature cabonization, by the product acid elution after carbonization, then
It is washed with deionized until the product drying after washing is obtained biomass porous carbon material by neutrality.
Activator in the step (2) is ZnCl2Solution, the concentration of the ZnCl2 solution are 4mol/L.
The temperature being activated in the step (2) is 150 DEG C, and the time of activation processing is 12h.
The carburizing temperature of step (3) the high temperature carbonization is any in 600 DEG C, 800 DEG C, 1000 DEG C.
The carbonization time of step (3) the high temperature carbonization is 2h.
Inert gas in the step (3) is N2 or Ar.
Acid in the step (3) is hydrochloric acid, and the concentration of hydrochloric acid is 1mol/L.
A kind of biomass porous carbon material includes the following steps in the application of anode of microbial fuel cell,
A, slurries should be made by mixing into corresponding solvent cement and be coated in long 1cm, wide 1cm for the biomass carbon material
Carbon cloth on, be fabricated to anode of microbial fuel cell, be assembled in together with plain carbon cloth electrode in same anode chamber；
B, use carbon brush as microorganism fuel cell cathode, two pole room of yin-yang is linked by proton exchange membrane and is built into
For H-type microbial fuel cell unit, the microorganism growth-promoting media prepared need to be injected into anode chamber by temperature at 30 DEG C, and
Catholyte injects in cathode chamber；
C, link voltage data collector, the external resistance voltage value of acquisition in machine every five minutes, according to external resistance voltage
The variation of value regularly replaces catholyte and anolyte；
D, it cultivates two months, under conditions of reducing external resistance value, filters out the microbial flora that anti-current passes through,
Then the stable microbial film that grows into is carried on anode microorganism, can further progress correlated performance test.
The pH value of catholyte and anolyte is neutrality in the step b.
External resistance value is replaced in the step c from big to small to filter out the microorganism that high current can be resisted to pass through
Flora.
Embodiment 2
The preparation of biomass porous carbon material: impregnating supersound washing in deionized water for the throwaway chopsticks being collected into,
It dries for 24 hours and is crushed under the conditions of 60 DEG C；The material being crushed is put into the ZnCl2 solution of 4mol/L, mixed liquor capacity does not surpass
Cross inner liner of reaction kettle capacity 70% carries out 12 hours of 150 DEG C of hydro-thermal reactions, filters after reaction and under the conditions of 60 DEG C
Drying is for 24 hours；Product after drying is calcined under atmosphere of inert gases, from room temperature with 5 DEG C/min be warming up to 600 DEG C, 800 DEG C,
1000 DEG C, and 2h is kept at a temperature of its respectively, cooled to room temperature is black cellular solid after taking-up, grinds alternative.
The removal of biomass porous carbon material impurity: the product ultimately generated in (1) is successively used to the dilute hydrochloric acid of 1mol/L
And deionized water is rinsed, and filters and drying for 24 hours, finally obtains the biomass porous carbon of throwaway chopsticks under 60 DEG C of vacuum conditions
Material.
Application of the biomass porous carbon material in terms of anode of microbial fuel cell: by carbon material and corresponding solvent with
And adhesive mixing is made into slurries and is applied to surplus uniformly to be fabricated to electrode on the carbon cloth of 2*1cm, assembles with plain carbon cloth
In in same anode of microbial fuel cell room.Common carbon brush is cathode, and it is micro- that two pole room of yin-yang with proton exchange membrane is assembled into H-type
Biological fuel cell device, external circuit chain connecting resistance.Under the conditions of 30 DEG C of room temperature or so, by configured catholyte and anolyte
Corresponding yin, yang pole room is injected respectively.The voltage value that an external resistance was acquired by voltage data collector every five minutes, according to
The variation of external resistance voltage value regularly replaces catholyte and anolyte, until microorganism, which stablizes growth, can carry out correlated performance
Test.
The beneficial effects of the present invention are:
(1) using natural biomass castoff throwaway chopsticks as raw material, cheap, amount greatly, is had excellent performance the present invention,
It is environmentally protective, it is widely used.
(2) treatment process is simple, and a small amount of activator, which is added, by high-temperature calcination can be obtained the more of high specific surface area
Hole carbon material realizes the effective use of biomass resource.
(3) the biomass porous biocompatible carbon material of throwaway chopsticks is preferable, and specific surface area is larger, is conducive to anode production
The attachment and growth of electric microorganism, can effectively improve the electricity generation performance of microbiological fuel cell.
Only highly preferred embodiment of the present invention is described above, but is not to be construed as limiting the scope of the invention.This
Invention is not only limited to above embodiments, and specific structure is allowed to vary.All protection models in independent claims of the present invention
Interior made various change is enclosed to all fall in the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of biomass porous carbon material, it is characterised in that: it the described method comprises the following steps,
(1), throwaway chopsticks are broken, washing, ultrasound and drying；
(2), broken throwaway chopsticks are activated in the aqueous solution of activator, then take out and dries；
(3), by dried product under inert gas range high temperature cabonization, by the product acid elution after carbonization, then spend
Ion water washing is dry by the product after washing until neutrality, obtains biomass porous carbon material.
2. a kind of preparation method of biomass porous carbon material according to claim 1, it is characterised in that: the step
(2) activator in is ZnCl2Solution, the concentration of the ZnCl2 solution are 4mol/L.
3. a kind of preparation method of biomass porous carbon material according to claim 1, it is characterised in that: the step
(2) temperature being activated in is 150 DEG C, and the time of activation processing is 12h.
4. a kind of preparation method of biomass porous carbon material according to claim 1, it is characterised in that: the step
(3) carburizing temperature of high temperature carbonization is any in 600 DEG C, 800 DEG C, 1000 DEG C.
5. a kind of preparation method of biomass porous carbon material according to claim 1, it is characterised in that: the step
(3) carbonization time of high temperature carbonization is 2h.
6. a kind of preparation method of biomass porous carbon material according to claim 1, it is characterised in that: the step
(3) inert gas in is N2 or Ar.
7. a kind of preparation method of biomass porous carbon material according to claim 1, it is characterised in that: the step
(3) acid in is hydrochloric acid, and the concentration of hydrochloric acid is 1mol/L.
8. a kind of biomass porous carbon material is in the application of anode of microbial fuel cell, it is characterised in that: include the following steps,
A, slurries should be made by mixing into corresponding solvent cement and be coated in long 1cm, the carbon of wide 1cm for the biomass carbon material
On cloth, it is fabricated to anode of microbial fuel cell, is assembled in together with plain carbon cloth electrode in same anode chamber；
B, use carbon brush as microorganism fuel cell cathode, two pole room of yin-yang is linked by proton exchange membrane and builds as H
The microorganism growth-promoting media prepared need to be injected into anode chamber and cathode by type microbial fuel cell unit, temperature at 30 DEG C
Liquid injects in cathode chamber；
C, link voltage data collector, the external resistance voltage value of acquisition in machine every five minutes, according to external resistance voltage value
Variation regularly replaces catholyte and anolyte；
D, it cultivates two months, under conditions of reducing external resistance value, filters out the microbial flora that anti-current passes through, micro- life
Then the stable microbial film that grows into is carried on anode object, can further progress correlated performance test.
9. a kind of biomass porous carbon material according to claim 8 is in the application of anode of microbial fuel cell, spy
Sign is: the pH value of catholyte and anolyte is neutrality in the step b.
10. a kind of biomass porous carbon material according to claim 8 is in the application of anode of microbial fuel cell, spy
Sign is: external resistance value is replaced in the step c from big to small to filter out the microorganism that high current can be resisted to pass through
Flora.
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Cited By (2)
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| CN111009648A (en) * | 2019-12-10 | 2020-04-14 | 华南农业大学 | Silicon-carbon composite material and preparation method thereof |
| CN113666355A (en) * | 2021-07-28 | 2021-11-19 | 新疆大学 | Preparation method of porous carbon material derived from tomato peel residue |
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