CN106920982A - A kind of method of nanoporous molybdenum carbide in-situ modification three-dimensional carbonaceous anode of microbial fuel cell - Google Patents
A kind of method of nanoporous molybdenum carbide in-situ modification three-dimensional carbonaceous anode of microbial fuel cell Download PDFInfo
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- CN106920982A CN106920982A CN201710237125.XA CN201710237125A CN106920982A CN 106920982 A CN106920982 A CN 106920982A CN 201710237125 A CN201710237125 A CN 201710237125A CN 106920982 A CN106920982 A CN 106920982A
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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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- 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
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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
- H01M4/8605—Porous electrodes
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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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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- 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 invention discloses a kind of method of nanoporous molybdenum carbide in-situ modification three-dimensional carbonaceous anode of microbial fuel cell.The method is with carbon felt electrode as substrate, with phosphomolybdic acid as molybdenum source, by two processes of high temperature cabonization under electrostatic self-assembled and reducing atmosphere that diallyl dimethyl ammoniumchloride is mediated, so that the nano silicon carbide molybdenum of loose structure is in situ, homoepitaxial on carbon felt fiber, simple operating steps and controllable.Prepared three-dimensional combination electrode is applied to the anode of microbiological fuel cell, compared to unmodified carbon felt electrode, with bigger electrochemical surface area and more preferable biocompatibility, and the redox reaction to electron mediator has unique electro catalytic activity, anode activation overpotential is reduced, the electricity production power density of microbiological fuel cell is significantly improved.
Description
Technical field
The invention belongs to field of energy source materials, it is related to a kind of side of nanoporous molybdenum carbide in-situ modification three-dimensional carbon felt electrode
Method, further relates to the product obtained by the method and application of the product in anode of microbial fuel cell.
Background technology
With becoming increasingly conspicuous for global energy crisis and environmental degradation problem, can be organic in treatment sewage etc. as one kind
Discarded object produces the novel green sustainable energy technology of electric energy simultaneously, and microbiological fuel cell receives both domestic and external in recent years
Extensive concern.But, its relatively low electricity production power density and electric current output density be still limit the development of this emerging technology and
Where the bottleneck of application.Domestic and international scientist takes multiple technologies means to solve this problem, such as modified electrode material
Structure and surface nature so as to increase electrode active area and improve electrode affinity, micro- to producing electricity by genetic engineering means
Biology is transformed so as to improve its electricity generation ability, design optimization cell apparatus and operating parameter etc..Before compared to 5-10, to the greatest extent
The present microbiological fuel cell electricity production power output of pipe has the raising of conspicuousness, but still is difficult to meet wanting for practical application
Ask.The activation overpotential of microorganism anode is higher to be to restrict the principal element of microbiological fuel cell output power density, and drops
The activation overpotential of low anode it is critical only that and improve extracellular electron transport rate weaker between electricity-producing microorganism and electrode interface.
In recent years, nano structural material is in enhancing anode of microbial fuel cell interface electron transmission and then raising anode is micro-
Biological electro catalysis aspect of performance shows and reveals obvious advantage, and this is mainly attributed to the life that nanostructured superhigh specific surface area is become reconciled
Thing compatibility.Have concurrently high conductivity and structure-rich and it is controllable the features such as nanostructured carbon electrode material be Microbial fuel
The study hotspot of galvanic anode.At present, many documents and patent report nanostructured carbonaceous electrodes are had in enhancement microbiological
The application of anode of fuel cell aspect of performance.As document (Journal of Materials Chemistry A, 2016,4,
6342-6349) report the electricity production power density that three-dimensional bulk Graphene framework is used to be obtained during anode of microbial fuel cell
Up to 17.9W m-3.Chinese patent CN103985881A is prepared for micro- by the capillary polypropylene nitrile expanded material prepared by calcining
Biological fuel cell anode, effectively reduces production cost, but the electrode material macroporous structure is not enough, is unfavorable for producing electricity micro- life
The implantation growth of thing.Chinese patent CN104157884A proposes one kind and impregnated in graphene oxide by by three-diemsnional electrode brush
The method that vacuum freezedrying prepares three-dimensional anode of microbial fuel cell after in dispersion liquid, but the electrode prepared by the method
Graphene oxide contact between electrode brush in material is limited, is unfavorable for the efficient transmission of electronics.Correlative study it has been shown that
Preferable anode of microbial fuel cell material should be the composite porous electrode comprising macroporous structure and nano-pore structure simultaneously,
Wherein macroporous structure (more than micron order) can provide enough growing spaces and be grown for electricity-producing microorganism implantation and efficient
Mass transfer passage, and the specific surface area that nano-pore structure can provide superelevation is used for electrochemical reaction and coarse surface is used
In the adhesion (Advanced Energy Materials, 2016,6 (4) 1501535) of microorganism.It is worth noting that, electricity production
Extracellular electron transfer process between microorganism and anode is the interaction process between a biology-abiotic interface.Do not say and
Analogy, the chemical property of nanostructured anode material is also particularly significant to the efficiency of the extracellular electron transmission of microbiological fuel cell
's.
Conventional carbonaceous material is typically electrochemicaUy inert, it is difficult to it is improved in unit catalytic levels to electronic media
The catalysis activity of body, the entirety of microorganism electro-catalysis ability is reached simply by electrochemical reaction quantity on increase electrode interface
The raising of level.If it is contemplated that electric to the three-dimensional carbonaceous macropore of high connductivity using the nano material with electro catalytic activity
Pole material carries out functional modification, perhaps can cooperate with enhancing micro- in two levels of unit catalysis activity and catalytic reaction total amount
Electron transmission ability on bioelectrode interface, so as to improve microorganism electrocatalytic reaction performance.The noble metals such as platinum have remarkable
Catalytic performance, and have been shown to significantly strengthen anode of microbial fuel cell microorganism electro-catalysis ability, but its
The factor such as expensive price and the scarcity of resource limits the application of these noble metals, so developing cheap, rich reserves and height
The functional modification that the non-precious metal catalyst of vigor is applied to three-dimensional macropore carbon-based electrode is extremely necessary.Molybdenum carbide has
There are the characteristic electron and catalysis characteristics similar to platinum, be studied and be applied to multiple catalytic fields such as desulfurization and hydrogenation.Compared with
In early research report, molybdenum carbide is tentatively proved to be able to be catalyzed some metabolic intermediates or product of microorganism so as to improving
The performance of microbiological fuel cell has a certain promotion, but the three-dimensional macropore carbon of the molybdenum carbide functional modification of nanoscale
Matter electrode has not been studied in reduction microorganism anode activation overpotential and raising microbiological fuel cell electricity generation ability.
The content of the invention
In view of this, it is an object of the invention to provide a kind of nanoporous molybdenum carbide in-situ modification three-dimensional carbonaceous microorganism
The method of anode of fuel cell.Mainly solving the technical problems that：A kind of system based on electrostatic self-assembled and high temperature cabonization is provided
Preparation Method, described anode is that, with three-dimensional carbon felt electrode as substrate, its carbon fiber diameter is about 15 microns, and growth in situ is fine in carbon
Nanoporous molybdenum carbide in dimension is trim, and its average pore size is 100 nanometers.
1st, the method for nanoporous molybdenum carbide in-situ modification three-dimensional carbon felt electrode provided by the present invention, concrete technical scheme
It is as follows：
1) by carbon felt be cut into it is appropriately sized after, be successively placed in acetone, watery hydrochloric acid and supersound washing 1 hour in distilled water,
The impurity on surface is removed, then is placed in distilled water and is boiled 30 minutes, drying for standby；
2) by step 1) handled by carbon felt be placed in horizontal oscillating reactions 12 in diallyl dimethyl ammoniumchloride solution
Hour, distilled water is cleaned 3 times；
3) by step 2) obtained by carbon felt be placed in 50mL 10-60mg mL-1In phosphorus molybdenum acid solution, horizontal oscillations reaction
12 hours, distilled water was cleaned 3 times, drying for standby；
4) by step 3) obtained by carbon felt be placed in vacuum tube furnace, it is small in reducing atmosphere high temperature carbonization treatment 3
When, that is, obtain the three-dimensional carbon felt electrode of nanoporous molybdenum carbide in-situ modification
Step 1) in the thickness of carbon felt be 3mm, be cut into the size of 1cm × 2cm, the concentration of watery hydrochloric acid is 1M, is dried
Temperature is 60 DEG C.
Step 2) in diallyl dimethyl ammoniumchloride solution volume be 50mL, concentration be 10mg mL-1。
Step 3) in phosphorus molybdenum acid solution volume be 50mL, concentration be 10-60mg mL-1。
Step 4) in reducing atmosphere be hydrogen/argon gas mixed gas, its volume ratio be 1:9, carburizing temperature is 900 Celsius
Degree.
It is homoepitaxial fine in the carbon of carbon felt electrode according to the nano-porous structure molybdenum carbide obtained by above-mentioned preparation method
In dimension, its load capacity is controlled in 4.08-16.02wt%.
2nd, the three-dimensional carbon felt electrode of nanoporous molybdenum carbide in-situ modification of the present invention, its phase structure is by X-ray
Diffraction is characterized；Microscopic appearance is characterized by ESEM and transmission electron microscope；Specific surface area and nano-pore pore structure feature are by nitrogen thing
Reason adsorption analysis is characterized.
The three-dimensional carbon felt electrode of nanoporous molybdenum carbide in-situ modification of the present invention, be it is a kind of can be used directly from
The block electrode material of support.By X-ray diffraction map analysis, the crystal structure of the molybdenum carbide for being generated is hexagon carbonization two
Molybdenum.By scanning electron microscope (SEM) photograph and transmission electron microscope map analysis, the molybdenum carbide for being generated uniformly is given birth to by the nanometer sheet of about 100nm sizes
The nano-porous structure that the carbon felt fiber grown at about 15 microns is formed.By nitrogen physisorption isothermal curve and pore-size distribution
Map analysis, combination electrode of the present invention has the features such as specific surface area is big, pore-size distribution is wide.
3rd, the three-dimensional carbon felt electrode of nanoporous molybdenum carbide in-situ modification of the present invention as anode material in micro- life
Thing so expects the application in battery.Tested through three-electrode system, the three-dimensional carbon felt of described nanoporous molybdenum carbide in-situ modification is electric
Pole, compared to unmodified carbon felt electrode, passes with bigger capacitance current, catalytic current higher and smaller interface charge
The advantages of passing resistance, and the electro catalytic activity of uniqueness is shown to the electron mediator that electricity-producing microorganism is secreted.It is micro- through H type dual chambers
Biological fuel cell is tested, and the three-dimensional carbon felt electrode of described nanoporous molybdenum carbide in-situ modification has big electricity production power close
The advantages of degree, good stability and biocatalyst carrying capacity high, the output power density of the electrode of 8.31wt% load capacity is high
Up to 1025mW m-2。
The beneficial effects of the present invention are：The invention provides a kind of nanoporous molybdenum carbide in-situ modification three-dimensional carbon felt electricity
The method of pole, operating procedure is simple, controllable, and prepared combination electrode has the nanometer of carbonaceous macropore skeleton structure and molybdenum carbide concurrently
Loose structure, with electro-catalysis molybdenum carbide nano-porous structure high, equably growth in situ on carbon felt fiber, realizes nanometer
The pore structure regulation and control and the unification of surface chemical modification of structure electrode material；Electrochemical analysis and microbiological fuel cell test knot
Fruit shows that prepared functionalization combination electrode material has more preferable microorganism electro-catalysis compared to unmodified carbon felt electrode
The electricity production power density of ability and Geng Gao, has good application prospect as anode of microbial fuel cell.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below：
Fig. 1 is the carbon felt electrode (Mo of the gained nanoporous molybdenum carbide in-situ modification of embodiment 12C@CF) and unmodified carbon
The X-ray diffractogram of felt electrode (bare CF).
Fig. 2 is the carbon felt electrode (Mo of the gained nanoporous molybdenum carbide in-situ modification of embodiment 12C@CF) and unmodified carbon
Scanning electron microscope (SEM) photograph (a of felt electrode (bare CF)：bare CF；b-d：Mo2C@CF；Illustration is Mo in b2C@CF digital photographs).
Fig. 3 is the carbon felt electrode (Mo of the gained nanoporous molybdenum carbide in-situ modification of embodiment 12C@CF) transmission electron microscope
Figure.
Fig. 4 is the carbon felt electrode (Mo of the gained nanoporous molybdenum carbide in-situ modification of embodiment 12C@CF) and unmodified carbon
Nitrogen adsorption isothermal curve (a) and pore size distribution curve (b) of felt electrode (bare CF).
Fig. 5 is the carbon felt electrode (Mo of the gained nanoporous molybdenum carbide in-situ modification of embodiment 12C@CF) and unmodified carbon
Felt electrode (bare CF) is applied to the polarization curve and electricity production power density curve of anode of microbial fuel cell.
Fig. 6 is the carbon felt electrode (Mo of the gained nanoporous molybdenum carbide in-situ modification of embodiment 12C@CF) it is applied to microorganism
The discharge curve of anode of fuel cell.
Fig. 7 is the carbon felt electrode (Mo of the gained nanoporous molybdenum carbide in-situ modification of embodiment 12C@CF) and unmodified carbon
Felt electrode (bare CF) is applied to the cyclic voltammogram (a) and corresponding one mediation number curve of anode of microbial fuel cell
(b)。
Fig. 8 is the carbon felt electrode (Mo that the gained nanoporous molybdenum carbide in-situ modification of example 1 is not carried out2C@CF) and it is unmodified
Carbon felt electrode (bare CF) is applied to the electrochemical impedance collection of illustrative plates of anode of microbial fuel cell.
Fig. 9 is the carbon felt electrode (Mo of the gained nanoporous molybdenum carbide in-situ modification of embodiment 12C@CF) and unmodified carbon
Felt electrode (bare CF) is applied to anode of microbial fuel cell, the scanning electron microscope (SEM) photograph (a of electrode after discharge test：bare CF；
b-c：Mo2C@CF)。
Specific embodiment
Below in conjunction with accompanying drawing 1-9, nanoporous molybdenum carbide in-situ modification carbon felt electricity provided by the present invention is specifically described
The preparation and application of pole.The experimental technique of unreceipted actual conditions in embodiment, according to normal condition or according to institute of manufacturer
The condition of suggestion.
Embodiment 1：
1) carbon felt that thickness is 3 millimeters is cut into the strip of 1cm × 2cm sizes, is positioned in 50mL acetone solns
It is cleaned by ultrasonic 1 hour, is transferred in 50mL 1M watery hydrochloric acid that ultrasound is clear 1 hour, is transferred in 100mL distilled water and is cleaned by ultrasonic 1
Hour, the impurity on surface is removed, then be placed in and boiled in 100mL distilled water 30 minutes, drying for standby or as reference electrode；
2) by step 1) handled by sheet carbon felt be positioned over 50mL 10mg mL-1Diallyl dimethyl ammoniumchloride is molten
Horizontal oscillating reactions 12 hours in liquid, distilled water is cleaned 3 times after taking-up；
3) by step 2) obtained by carbon felt be positioned over 50mL 20mg mL-1In phosphorus molybdenum acid solution, horizontal oscillations reaction 12
Hour, distilled water is cleaned 3 times after taking-up, drying for standby；
4) by step 3) obtained by carbon felt be placed in vacuum tube furnace, in the hydrogen/argon gas mixed gas (body of reproducibility
Product is than being 1:9) 900 degrees Celsius of carbonization treatments 3 hours, that is, obtain the nanoporous carbon of molybdenum carbide load capacity about 8.31wt% in
Change the three-dimensional carbon felt electrode (Mo of molybdenum in-situ modification2C@CF)。
Three-dimensional carbon felt electrode (the Mo of the nanoporous molybdenum carbide in-situ modification of gained2C@CF) X-ray diffraction analysis such as
Shown in Fig. 1, it is pure dimolybdenum carbide as a result to show that the method generates molybdenum carbide.ESEM result (Fig. 2) shows to be generated
Molybdenum carbide homoepitaxial in carbon felt fiber surface, and in porous nanometer structure.Transmission electron microscope results (Fig. 3) show what is generated
Molybdenum carbide is for about the nanometer sheet of 100nm sizes.Isothermal nitrogen adsorption curve and pore size distribution curve (Fig. 4) show prepared
Mo2C@CF electrodes have specific surface area and pore size distribution wide higher.
Embodiment 2：
By step 3 in embodiment 1) the concentration of phosphorus molybdenum acid solution be adjusted to 10mg mL-1, other the step of same embodiment
1, that is, obtain the three-dimensional carbon felt electrode of the nanoporous molybdenum carbide in-situ modification of molybdenum carbide load capacity about 4.08wt%.
Embodiment 3：
By step 3 in embodiment 1) the concentration of phosphorus molybdenum acid solution be adjusted to 40mg mL-1, other the step of same embodiment
1, that is, obtain the three-dimensional carbon felt electrode of the nanoporous molybdenum carbide in-situ modification of molybdenum carbide load capacity about 12.36wt%.
Embodiment 4：
By step 3 in embodiment 1) the concentration of phosphorus molybdenum acid solution be adjusted to 60mg mL-1, other the step of same embodiment
1, that is, obtain the three-dimensional carbon felt electrode of the nanoporous molybdenum carbide in-situ modification of molybdenum carbide load capacity about 16.02wt%.
Embodiment 5：
Using the three-dimensional carbon felt electrode (Mo of nanoporous molybdenum carbide in-situ modification obtained in embodiment 12C@CF,
8.31wt%) be used for H type double-chamber microbiological fuel cells anode tested, and with unmodified carbon felt electrode (bare
CF) it is compared.Microbiological fuel cell runs the polarization curve and electricity production power density curve drawn to stable case
As shown in figure 5, as a result showing the three-dimensional carbon felt electrode of the nanoporous molybdenum carbide in-situ modification of the gained of embodiment 1 than unmodified
Carbon felt electrode has open-circuit voltage and power output density higher.The nanoporous molybdenum carbide in-situ modification of the gained of embodiment 1
As a result discharge curve of the three-dimensional carbon felt electrode under the conditions of constant external resistance (1500 ohm) as shown in fig. 6, show that it has
The discharge cycle of stabilization, disclosure satisfy that long-term reusable demand.
Embodiment 6：
To the anode of microbial fuel cell in embodiment 5 it is nanoporous molybdenum carbide in-situ modification using three-electrode system
Three-dimensional carbon felt electrode and unmodified carbon felt electrode be circulated voltammetric scan and electrochemical analysis, with Microbial fuel
Galvanic anode is that the three-dimensional carbon felt electrode or unmodified carbon felt electrode of nanoporous molybdenum carbide in-situ modification are working electrode, micro-
Biofuel battery cathode is that, to electrode, saturated calomel electrode is reference electrode.Fig. 7 is cyclic voltammetry scan figure (a) and correspondence
Mediation number figure (b), as a result show the three-dimensional carbon felt electrode ratio of nanoporous molybdenum carbide in-situ modification of the gained of embodiment 1 not
The carbon felt electrode of modification has bigger capacitance current and catalytic current, and can make the redox peaks of flavin electron mediator
Current potential is negative to be moved, and reduces the overpotential of the anode-catalyzed reaction of microorganism.Fig. 8 is electrochemical impedance figure, as a result shows the institute of embodiment 1
The three-dimensional carbon felt electrode of the nanoporous molybdenum carbide in-situ modification for obtaining has smaller interface charge to turn than unmodified carbon felt electrode
Move resistance.
Embodiment 7：
It is the three-dimensional carbon felt electrode of nanoporous molybdenum carbide in-situ modification by the anode of microbial fuel cell in embodiment 5
Taken out after discharge test with unmodified carbon felt electrode, after formaldehyde is fixed and ethanol dehydration is processed, entered using ESEM
Row observation, refers to Fig. 9.Result shows, on the three-dimensional carbon felt electrode of the nanoporous molybdenum carbide in-situ modification of the gained of embodiment 1
Bacterial growth amount is that biocatalyst carrying capacity is significantly higher than unmodified carbon felt electrode, with more preferable biocompatibility.
Claims (7)
1. the method for a kind of nanoporous molybdenum carbide in-situ modification three-dimensional carbonaceous anode of microbial fuel cell, it is characterised in that：
Prepared there is provided a kind of easy and controllable electrostatic self-assembled and high temperature cabonization method, specifically include following steps：
1) by carbon felt be cut into it is appropriately sized after, be placed in acetone, watery hydrochloric acid and supersound washing 1 hour in distilled water, remove surface
Impurity, then be placed in distilled water and boil 30 minutes, drying for standby；
2) by step 1) handled by carbon felt be placed in horizontal oscillating reactions 12 hours in diallyl dimethyl ammoniumchloride solution,
Distilled water is cleaned 3 times；
3) by step 2) obtained by carbon felt be placed in 50mL 10-60mg mL-1In phosphorus molybdenum acid solution, horizontal oscillations reaction 12 is small
When, distilled water is cleaned 3 times, drying for standby；
4) by step 3) obtained by carbon felt be placed in vacuum tube furnace, in reducing atmosphere high temperature carbonization treatment 3 hours, obtain
To the three-dimensional carbon felt electrode of nanoporous molybdenum carbide in-situ modification.
2. the method for nanoporous molybdenum carbide in-situ modification according to claim 1 three-dimensional carbon felt electrode, it is characterised in that：
The step 1) in the thickness of carbon felt be 3mm, be cut into the size of 1cm × 2cm, the concentration of watery hydrochloric acid is 1M, drying temperature
It is 60 DEG C.
3. the method for nanoporous molybdenum carbide in-situ modification according to claim 1 three-dimensional carbon felt electrode, it is characterised in that：
The step 2) in diallyl dimethyl ammoniumchloride solution volume be 50mL, concentration be 10mg mL-1。
4. the method for nanoporous molybdenum carbide in-situ modification according to claim 1 three-dimensional carbon felt electrode, it is characterised in that：
The step 3) in phosphorus molybdenum acid solution volume be 50mL, concentration be 10-60mg mL-1。
5. the method for nanoporous molybdenum carbide in-situ modification according to claim 1 three-dimensional carbon felt electrode, it is characterised in that：
The step 4) in reducing atmosphere be hydrogen/argon gas mixed gas, its volume ratio be 1:9, carburizing temperature is 900 degrees Celsius.
6. the method for nanoporous molybdenum carbide in-situ modification according to claim 1 three-dimensional carbon felt electrode, it is characterised in that：
Described molybdenum carbide is nano-porous structure of the homoepitaxial on carbon felt carbon fiber, and its load capacity is controlled in 4.08-
16.02wt%.
7. the method for a kind of nanoporous molybdenum carbide in-situ modification three-dimensional carbonaceous anode of microbial fuel cell, it is characterised in that：
The application of anode of microbial fuel cell material.
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| CN108172852A (en) * | 2018-01-29 | 2018-06-15 | 广东工业大学 | A kind of anode of microbial fuel cell, preparation method and microbiological fuel cell |
| CN109136973A (en) * | 2018-08-28 | 2019-01-04 | 南京工业大学 | A kind of base metal doping molybdenum carbide hydrogen-precipitating electrode and its preparation method and application |
| CN109244423A (en) * | 2018-10-23 | 2019-01-18 | 大连交通大学 | A kind of preparation method with porous spongy carbon-based nano electrode material |
| CN110380028A (en) * | 2019-07-08 | 2019-10-25 | 武汉理工大学 | A kind of CNT/MoS2Lithium ion battery negative material and preparation method thereof |
| CN110993963A (en) * | 2019-11-25 | 2020-04-10 | 河北科技大学 | Phosphomolybdic acid/reduced graphene oxide/polyaniline composite material and preparation method and application thereof |
| CN111081983A (en) * | 2019-12-26 | 2020-04-28 | 陕西科技大学 | Co9S8Preparation method of self-supporting cathode of carbon felt sodium ion battery |
| CN111564642A (en) * | 2020-05-29 | 2020-08-21 | 哈尔滨工业大学 | Preparation method and application of niobium carbide nanoparticle modified carbon cloth electrode |
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| CN104143644A (en) * | 2014-07-31 | 2014-11-12 | 东莞理工学院 | Microbial fuel cell, anode, anode catalyst and preparation method thereof |
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