CN105870462B - Preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material and products thereof and application - Google Patents
Preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material and products thereof and application Download PDFInfo
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- CN105870462B CN105870462B CN201610246282.2A CN201610246282A CN105870462B CN 105870462 B CN105870462 B CN 105870462B CN 201610246282 A CN201610246282 A CN 201610246282A CN 105870462 B CN105870462 B CN 105870462B
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- carbon nanotube
- phosphomolybdic acid
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 120
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 104
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 104
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000002604 ultrasonography Methods 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000020477 pH reduction Effects 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 7
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000000813 microbial effect Effects 0.000 claims description 8
- 239000010405 anode material Substances 0.000 abstract description 6
- 230000002906 microbiologic effect Effects 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract description 2
- 150000001721 carbon Chemical class 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- FVTCRASFADXXNN-SCRDCRAPSA-N flavin mononucleotide Chemical compound OP(=O)(O)OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O FVTCRASFADXXNN-SCRDCRAPSA-N 0.000 description 14
- 229940013640 flavin mononucleotide Drugs 0.000 description 14
- FVTCRASFADXXNN-UHFFFAOYSA-N flavin mononucleotide Natural products OP(=O)(O)OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O FVTCRASFADXXNN-UHFFFAOYSA-N 0.000 description 14
- 239000011768 flavin mononucleotide Substances 0.000 description 14
- 235000019231 riboflavin-5'-phosphate Nutrition 0.000 description 14
- 239000000243 solution Substances 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000008055 phosphate buffer solution Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- H01M4/8803—Supports for the deposition of the catalytic active composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
Preparation method the invention discloses carbon felt/carbon nanotube/phosphomolybdic acid composite material and products thereof and application, include the following steps：By carbon felt boiling, then the impurity for removing Carbon felt surface is washed with acetone and ethyl alcohol respectively, it is dry, pretreatment carbon felt is obtained, it is spare；Again by the effective HCl treatment of multi-wall carbon nano-tube, the carbon nanotube of acidification is obtained；Finally pretreatment carbon felt is placed in the mixed liquor of the carbon nanotube containing acidification and phosphomolybdic acid and is impregnated and after ultrasound, continue soaked overnight, take out drying, up to carbon felt/carbon nanotube/phosphomolybdic acid composite material, this method operating procedure is simple, resulting materials dispersion ratio in carbon felt is more uniform, compared to unmodified carbon felt, carbon felt/carbon nanotube/phosphomolybdic acid composite material has the active area of bigger, the charging current of bigger and higher power density, can be as the anode material application of microbiological fuel cell.
Description
Technical field
The invention belongs to field of material technology, and in particular to the preparation side of carbon felt/carbon nanotube/phosphomolybdic acid composite material
Method further relates to the application of product obtained by this method and the product.
Background technology
Basic motive of the energy as human survival, the material base of development and social development, exploitation and use are in people
Extremely important role is play always in the historical progress of class society.It is used with the exploitation of people, it is non-renewable on the earth
Fossil energy reserves it is fewer and fewer, global energy notch increases, problem of energy crisis is increasingly prominent.Master in the world
National all in the various new energy of active development, the development and utilization research of wherein biomass energy attracts attention.Currently with this
A little organic substances are as fuel, by handling, gasifying, burning, the technologies such as digesting and can generate energy.And microbiological fuel cell
Be exactly a kind of microbial bacterial by the use of in nature as biocatalyst, the chemical energy in organic matter is changed into electric energy
Device.Therefore, preparing high performance anode of microbial fuel cell material becomes the pass for improving its power density and discharge performance
Key.Make Microbial fuel by the two-dimentional carbon-based material of base stock, such as carbon paper, carbon cloth, carbon-point, carbon felt and glassy carbon electrode of carbon
The anode of battery is very universal, these materials have high conductivity and are very suitable for microbial cell in the growth of its surface, ratio
Surface area is big, and cheap and easy to get.Nevertheless, but all there are it is certain the defects of with it is insufficient.Carbon felt as selected by us, due to it
Hydrophily is bad, can hinder the transmission of electronics to a certain extent, and then influence the discharge performance and work(of microbiological fuel cell
Rate exports.Therefore, it is necessary to improve the hydrophily of carbon felt, to improve electric conductivity.
Invention content
In view of this, one of the objects of the present invention is to provide the preparation sides of carbon felt/carbon nanotube/phosphomolybdic acid composite material
Method；The second object of the present invention is to provide carbon felt/carbon nanotube/phosphomolybdic acid composite material as made from the above method；This hair
The bright third purpose is to provide the application of carbon felt/carbon nanotube/phosphomolybdic acid composite material.
For achieving the above object, the present invention provides following technical solution：
1st, the preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material, includes the following steps：
A. the pretreatment of carbon felt：By carbon felt boiling, then the impurity for removing Carbon felt surface is washed with acetone and ethyl alcohol respectively,
It is dry, it is spare；
B. it is acidified carbon nanotube：By the effective HCl treatment of multi-wall carbon nano-tube, the carbon nanotube of acidification is obtained；
C. the preparation of carbon felt/carbon nanotube/phosphomolybdic acid composite material：It will be placed on and contain through the pretreated carbon felts of step A
After impregnating ultrasound in the carbon nanotube and the mixed liquor of phosphomolybdic acid that are acidified obtained by step B, then soaked overnight, takes out drying, i.e.,
Obtain carbon felt/carbon nanotube/phosphomolybdic acid composite material.
Preferably, the step A is that carbon felt is cut into bulk, is boiled in water to 4~5h of boiling, then taken out, then according to
Secondary to impregnate simultaneously ultrasound 0.5h with acetone and ethyl alcohol respectively, be finally soaked in water ultrasound 3 times, each 30min, and then 60 DEG C of vacuum are done
It is dry, it is spare.
Preferably, the step B is to add in multi-walled carbon nanotube in concentrated hydrochloric acid (hydrochloric acid mass fraction is 37%), fully
After mixing, 5h is stirred at 18~25 DEG C, separating carbon nano-tube is washed with water, 80 DEG C of vacuum drying, obtains the carbon nanometer of acidification
Pipe.
Preferably, the step C is that the carbon felt pre-processed through step A is cut into 1cm × 2cm sizes, is then being acidified
Carbon nanotube and phosphomolybdic acid mass ratio be 1:5~10:Immersion ultrasound 2h in 1 mixed solution, then soaked overnight, then 60 DEG C
It is taken out after vacuum drying, unadsorbed firm carbon nanotube and phosphomolybdic acid residue on Carbon felt surface is washed with water, continue 60
DEG C vacuum drying, that is, obtain carbon felt/carbon nanotube/phosphomolybdic acid composite material.
It is furthermore preferred that carbon nanotube concentration is 10mg/mL and a concentration of 20mg/mL of phosphomolybdic acid in the mixed solution.
2nd, carbon felt/carbon nanotube/phosphomolybdic acid composite material made from the method.
3rd, the carbon felt/carbon nanotube/phosphomolybdic acid composite material answering in anode of microbial fuel cell material is prepared
With.
In the present invention, concentrated hydrochloric acid refers to the hydrochloric acid that hydrochloric acid mass fraction is more than 37%.
The beneficial effects of the present invention are：The present invention provides a kind of systems of carbon felt/carbon nanotube/phosphomolybdic acid composite material
Preparation Method, operating procedure is simple, and there is resulting materials good hydrophily and carbon nanotube can be good at point in Carbon felt surface
It dissipates, is shown through electric discharge and power density test result, which, which compares the carbon felt handled under the same conditions, has preferably
Discharge performance and higher power density can be used as anode of microbial fuel cell material application.
Description of the drawings
In order to make the purpose of the present invention, technical solution and advantageous effect clearer, the present invention provides drawings described below：
Fig. 1 be carbon felt (CF) and carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material scanning electron microscope (SEM) photograph with
Partial enlargement scanning electron microscope (SEM) photograph (A：Carbon felt (CF) partial enlarged view；B：Carbon felt (CF) scanning electron microscope (SEM) photograph；C：Carbon felt/carbon nanotube/
Phosphomolybdic acid (CF/CNT/PMo) composite material partial enlarged view；D：Carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite wood
Expect scanning electron microscope (SEM) photograph).
Fig. 2 is the x-ray photoelectron of carbon felt (CF) and carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material
Spectrogram.
Fig. 3 is carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material anode of carbon felt (CF) and different proportion
Cycle in germy lactate solution and in the phosphate buffer solution containing 10 μM of flavin mononucleotide (FMN)
Voltammogram (a：Carbon nanotube is 10 with phosphomolybdic acid mass ratio：1 carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo a) is compound
Material anode is containing the cyclic voltammogram in germy lactate solution；b：Carbon nanotube is 1 with phosphomolybdic acid mass ratio：2
Carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo b) composite material anode is containing the cycle in germy lactate solution
Voltammogram；c：Carbon nanotube is 1 with phosphomolybdic acid mass ratio：5 carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo c) is compound
Material anode is containing the cyclic voltammogram in germy lactate solution；d：Carbon nanotube is 10 with phosphomolybdic acid mass ratio：1
Carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo a) composite material anode is in the flavin mononucleotide (FMN) containing 10 μM
The cyclic voltammogram of phosphate buffer solution；e：Carbon nanotube is 1 with phosphomolybdic acid mass ratio：2 carbon felt/carbon nanotube/phosphorus molybdenum
Sour (CF/CNT/PMo b) composite material anode is followed in the phosphate buffer solution of the flavin mononucleotide (FMN) containing 10 μM
Ring voltammogram；f：Carbon nanotube is 1 with phosphomolybdic acid mass ratio：5 carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo c) is multiple
Condensation material anode is in the cyclic voltammogram of the phosphate buffer solution of the flavin mononucleotide (FMN) containing 10 μM).
Fig. 4 is fired for carbon felt (CF) and carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material anode in microorganism
Expect the electric discharge figure in battery.
Fig. 5 is that bacterium is swept on carbon felt (CF) and carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material anode
Retouch electron microscope (a：Carbon felt (CF)；b：Carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material).
Fig. 6 is fired for carbon felt (CF) and carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material anode in microorganism
Expect the power density curve in battery.
Specific embodiment
Below in conjunction with attached drawing, the preferred embodiment of the present invention is described in detail.It is not specified in embodiment specific
The experimental method of condition, usually according to normal condition or according to the normal condition proposed by manufacturer.
The preparation method of embodiment 1, carbon felt/carbon nanotube/phosphomolybdic acid composite material
The preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material, includes the following steps：
A. the pretreatment of carbon felt：Carbon felt is cut into bulk, is boiled in water to boiling 4-5h, then taken out, then divide successively
Not Yong acetone and ethyl alcohol impregnate and ultrasound 0.5h, be finally soaked in water ultrasound 3 times, each 30min, is then dried in vacuo for 60 DEG C,
It is spare；
B. it is acidified carbon nanotube：Multi-walled carbon nanotube is added in concentrated hydrochloric acid (37%), after being sufficiently mixed, in room temperature (18
~25 DEG C) under stir 5h, separating carbon nano-tube is washed with water, and 80 DEG C of vacuum drying obtain the carbon nanotube of acidification；
C. the preparation of carbon felt/carbon nanotube/phosphomolybdic acid composite material：By the carbon felt pre-processed through step A be cut into 1cm ×
Then 2cm sizes impregnate ultrasound 2 in the carbon nanotube being acidified containing 10mg/mL and mixed solution containing 20mg/mL phosphomolybdic acids
H, then soaked overnight then take out after 60 DEG C of vacuum drying, and washing away unadsorbed firm carbon on Carbon felt surface with secondary water receives
Mitron and phosphomolybdic acid residue continue 60 DEG C of vacuum drying, that is, obtain carbon felt/carbon nanotube/phosphomolybdic acid composite material (CF/
CNT/PMo).The scanning electron microscope (SEM) photograph of gained carbon felt/carbon nanotube/phosphomolybdic acid composite material, can from figure as shown in C in Fig. 1 and D
Clearly to find out, one layer of carbon nanotube can be adsorbed, and carbon nanotube thereon is evenly distributed in Carbon felt surface, adsorbance
It is more.
Embodiment 2
Embodiment 2 is same as Example 1, difference lies in carbon felt acidification carbon nanotube and phosphomolybdic acid mass ratio be 10：1
Mixed solution in impregnate ultrasound (carbon nanotube and the concentration of phosphomolybdic acid being acidified in mixed solution be respectively 100mg/mL with
10mg/mL)。
Embodiment 3
Embodiment 2 is same as Example 1, difference lies in carbon felt acidification carbon nanotube and phosphomolybdic acid mass ratio be 1：5
Mixed solution in impregnate ultrasound (carbon nanotube and the concentration of phosphomolybdic acid being acidified in mixed solution be respectively 10mg/mL with
50mg/mL)。
Comparative example 1：The pretreatment of carbon felt
The pretreatment of carbon felt, includes the following steps：Carbon felt is cut into bulk, is boiled in water to boiling 4~5h, Ran Houqu
Go out, then impregnated respectively with acetone and ethyl alcohol, ultrasonic 0.5h, finally impregnate 30min with a water ultrasound, repeatedly for three times, take out, 60
DEG C vacuum drying, it is spare；The pretreated carbon felt scanning electron microscope (SEM) photograph of gained is as shown in A in Fig. 1 and B.
Carbon nanotube/phosphomolybdic acid has been adsorbed in carbon felt further to verify, carbon of the pretreated carbon felt in acidification has been received
Mitron and phosphomolybdic acid mass ratio are 2：Carbon felt/carbon nanotube/phosphomolybdic acid composite material is made under the conditions of 1 and carries out X-ray detection, knot
Fruit is as shown in Figure 2.The results show that adsorbed really in the carbon felt of carbon felt/carbon nanotube/phosphomolybdic acid composite material carbon nanotube/
Phosphomolybdic acid.
Fig. 2 is the carbon nanotube of acidification and phosphomolybdic acid ratio is 2：The X of 1 carbon felt/carbon nanotube/phosphomolybdic acid composite material
Ray Photoelectron spectrogram.It can be seen from the figure that carbon nanotube/phosphomolybdic acid is adsorbed in carbon felt.
Application Example：Carbon felt/carbon nanotube/application of the phosphomolybdic acid composite material as microorganism anode material
Carbon felt/carbon nanotube/phosphomolybdic acid composite material made from Examples 1 to 3 is tested for microbiological fuel cell,
And it is compared with pretreated carbon felt as anode.
Fig. 3 is respectively 10 in the carbon nanotube and phosphomolybdic acid mass ratio of acidification for carbon felt：1,1：2 and 1：5 carbon felt/carbon is received
Mitron/phosphomolybdic acid composite material anode is in germy lactate solution and contains 10 μM of flavin mononucleotide (FMN)
Cyclic voltammogram in phosphate buffer solution.From figure 3, it can be seen that the carbon nanotube in acidification is with phosphomolybdic acid mass ratio
10：When 1, using carbon felt/carbon nanotube/phosphomolybdic acid composite material material as anode to bacterium and flavin mononucleotide (FMN)
There is good volt-ampere to respond, and its capacitance improves a lot, show that carbon nanotube/phosphomolybdic acid modification can improve anode material
Capacitance, and when carbon nanotube and the phosphomolybdic acid mass ratio of acidification increase to 1：It is multiple with carbon felt/carbon nanotube/phosphomolybdic acid when 5
The condensation material material still has bacterium and flavin mononucleotide (FMN) as anode good volt-ampere to respond, and shows be acidified
Carbon nanotube and phosphomolybdic acid mass ratio control 1：5~10：Anode material can be used as by meeting material made from the range of 1
Material.
Carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material sun is made for carbon felt (CF) and embodiment 1 in Fig. 4
Electric discharge figure of the pole in microbiological fuel cell.From fig. 4, it can be seen that with carbon felt/carbon nanotube/phosphomolybdic acid composite material material
Expect that the discharge performance as anode significantly improves, show that carbon nanotube/phosphomolybdic acid modification can improve the electric discharge of anode material
Energy.
Carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material sun is made for carbon felt (CF) and embodiment 1 in Fig. 5
The scanning electron microscope (SEM) photograph of extremely upper bacterium.From figure 5 it can be seen that using for bacterial number on material of the pretreatment carbon felt as anode compared with
It is few, it is more as bacterial number on the material of anode using carbon felt/carbon nanotube/phosphomolybdic acid composite material, show to adsorb carbon nanotube/
After phosphomolybdic acid, it can significantly increase bacterial adsorption quantity.
Carbon felt/carbon nanotube/phosphomolybdic acid (CF/CNT/PMo) composite material sun is made for carbon felt (CF) and embodiment 1 in Fig. 6
Power density curve of the pole in microbiological fuel cell.From fig. 6, it can be seen that after absorption carbon nanotube/phosphomolybdic acid, most
High power density (937.4mW cm-2) it is unmodified carbon felt anode (98.8mW cm-2) more than 9 times, show carbon nanotube/phosphorus molybdenum
Acid modification improves the power density of anode material.
Therefore, the carbon felt/carbon nanotube/phosphomolybdic acid composite material obtained has better discharge performance and higher work(
Rate density can be used as anode of microbial fuel cell material application.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (6)
1. the preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material, which is characterized in that include the following steps：
A. the pretreatment of carbon felt：By carbon felt boiling, then the impurity for removing Carbon felt surface is washed with acetone and ethyl alcohol respectively, done
It is dry, it is spare；
B. it is acidified carbon nanotube：Multi-walled carbon nanotube is added in concentrated hydrochloric acid, after being sufficiently mixed, 5h is stirred at 18 ~ 25 DEG C,
Separating carbon nano-tube is washed with water, 80 DEG C of vacuum drying, obtains the carbon nanotube of acidification；
C. the preparation of carbon felt/carbon nanotube/phosphomolybdic acid composite material：It will be placed on through the pretreated carbon felts of step A containing step
The carbon nanotube being acidified obtained by B is 1 with phosphomolybdic acid mass ratio:5~10:After impregnating ultrasound 2h in 1 mixed solution, then impregnate
Overnight, it takes out dry to get carbon felt/carbon nanotube/phosphomolybdic acid composite material.
2. the preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material according to claim 1, it is characterised in that：It is described
Step A is that carbon felt is cut into bulk, is boiled in water to 4 ~ 5h of boiling, then taken out, then is soaked respectively with acetone and ethyl alcohol successively
Simultaneously ultrasound 0.5h is steeped, be finally soaked in water ultrasound 3 times, each 30min, and then 60 DEG C of vacuum drying, spare.
3. the preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material according to claim 1, it is characterised in that：It is described
Step C is that the carbon felt pre-processed through step A is cut into 1cm × 2cm sizes, then in the carbon nanotube of acidification and phosphomolybdic acid matter
Amount is than being 1:5~10:Ultrasound 2h, then soaked overnight are impregnated in 1 mixed solution, then takes out, is washed with water after 60 DEG C of vacuum drying
Unadsorbed firm carbon nanotube and phosphomolybdic acid residue on Carbon felt surface are removed, continues 60 DEG C of vacuum drying, that is, obtains carbon felt/carbon
Nanotube/phosphomolybdic acid composite material.
4. the preparation method of carbon felt/carbon nanotube/phosphomolybdic acid composite material according to claim 3, it is characterised in that：It is described
Carbon nanotube concentration is 10mg/mL and a concentration of 20mg/mL of phosphomolybdic acid in mixed solution.
5. carbon felt/carbon nanotube/phosphomolybdic acid composite material made from any one of claim 1 ~ 4 the method.
6. carbon felt/carbon nanotube/phosphomolybdic acid composite material is in anode of microbial fuel cell material is prepared described in claim 5
Application.
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| CN107774264A (en) * | 2017-09-19 | 2018-03-09 | 浙江工商大学 | Load composite oxides magnetic nanometer and the electrode of CNT and its preparation and application |
| CN109546163B (en) * | 2018-11-15 | 2021-09-24 | 电子科技大学 | Modification method of graphite felt electrode for organic flow battery |
| CN110993963B (en) * | 2019-11-25 | 2021-01-05 | 河北科技大学 | Phosphomolybdic acid/reduced graphene oxide/polyaniline composite material and preparation method and application thereof |
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| CN1624963A (en) * | 2004-10-20 | 2005-06-08 | 华南理工大学 | Fuel cell anode catalyst using heteropolyacid as promoter and preparation method thereof |
| CN101170175A (en) * | 2006-10-26 | 2008-04-30 | 三星Sdi株式会社 | Electrode for fuel cell, membrane-electrode assembly for fuel cell including same, and fuel cell system including the same |
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| CN102658201A (en) * | 2012-05-09 | 2012-09-12 | 福建师范大学 | Preparation method of direct methanol fuel cell anode composite membrane catalyst |
| CN102751513A (en) * | 2012-07-24 | 2012-10-24 | 浙江师范大学 | Anode catalyst of methanol fuel cell and preparation method of anode catalyst |
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| CN1624963A (en) * | 2004-10-20 | 2005-06-08 | 华南理工大学 | Fuel cell anode catalyst using heteropolyacid as promoter and preparation method thereof |
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| CN101847459A (en) * | 2009-03-27 | 2010-09-29 | 中国科学院物理研究所 | Composite carbon nanotube conductive thin film and preparation method and preparation device thereof |
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| CN102751513A (en) * | 2012-07-24 | 2012-10-24 | 浙江师范大学 | Anode catalyst of methanol fuel cell and preparation method of anode catalyst |
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