CN110729487B - Microbial fuel cell based on molybdenum disulfide composite material as anode - Google Patents
Microbial fuel cell based on molybdenum disulfide composite material as anode Download PDFInfo
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 67
- CWQXQMHSOZUFJS-UHFFFAOYSA-N Molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000446 fuel Substances 0.000 title claims abstract description 33
- 230000000813 microbial Effects 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 92
- 239000004744 fabric Substances 0.000 claims abstract description 75
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- 239000002086 nanomaterial Substances 0.000 claims abstract description 15
- 229910015800 MoS Inorganic materials 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000005341 cation exchange Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 229920000767 polyaniline Polymers 0.000 claims description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 229920001940 conductive polymer Polymers 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229960001031 Glucose Drugs 0.000 claims description 9
- 238000002484 cyclic voltammetry Methods 0.000 claims description 9
- WQZGKKKJIJFFOK-VFUOTHLCSA-N β-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 230000001264 neutralization Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- 229940041514 Candida albicans extract Drugs 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L Mercury(I) chloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N Sodium molybdate Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N Thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940075397 calomel Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012138 yeast extract Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 229910052961 molybdenite Inorganic materials 0.000 abstract description 29
- 230000004048 modification Effects 0.000 abstract description 8
- 238000006011 modification reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000010923 batch production Methods 0.000 abstract 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000001580 bacterial Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001603 reducing Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 101700011027 GPKOW Proteins 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M Silver chloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- -1 and in the cathode Substances 0.000 description 1
- 244000052616 bacterial pathogens Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—BASIC ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—BASIC 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
-
- H—ELECTRICITY
- H01—BASIC 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
-
- H—ELECTRICITY
- H01—BASIC 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A high-performance microbial fuel cell based on a molybdenum disulfide composite material as an anode comprises an anode chamber and a cathode chamber, the maximum liquid filling volume of which is 20mL, and a double-chamber microbial fuel cell adopting a sandwich structure, wherein the two chambers are separated by a cation exchange membrane. The invention passes through MoS2The electrochemical performance of the carbon material is obviously improved by the modification of the nano material, and the MoS is shown by a test of a double-chamber microbial fuel cell2The modification of the nano material enables the internal resistance of the MFCs taking the carbon cloth as the anode to be reduced by 43 percent, the power to be improved by 60 percent, and the average coulombic efficiency to be 2.86 times that of the blank carbon cloth as the anode MFCs; the MoS can be further improved by compounding the conductive polymer2The conductivity of the carbon cloth electrode material reduces the charge transfer resistance and improves the electrocatalytic activity, and the whole anode based on the molybdenum disulfide composite material has low price, simple preparation and easy batch production, and can greatly reduce the operation cost of the microbial fuel cell.
Description
Technical Field
The invention relates to a microbial fuel cell, in particular to a high-performance microbial fuel cell based on a molybdenum disulfide composite material as an anode.
Background
Microbial Fuel Cell (MFCs) technology is a new type of device that can both treat wastewater containing organic pollutants and recover energy simultaneously. The basic principle is that in the anode chamber, microbe is used as catalyst to decompose organic matter under anaerobic condition, the produced electrons are transferred via external circuit, the produced protons are transferred to the cathode chamber via ion exchange membrane, and in the cathode, oxidant (electron acceptor) reacts with the arriving electrons and protons to produce reduction product. Because of good social and economic benefits, the method becomes a research hotspot in recent years.
However, the current battery has low output power density, which limits the wide application. The anode is a carrier attached to microorganisms and a current collector responsible for transferring electrons out, and the anode material plays an important role in the performance of power output of the MFCs and the like. The development of an anode material with good electrocatalytic performance, large specific surface area, high conductivity and good biocompatibility is one of the main strategies for improving the output power density of the MFCs.
Carbon materials are common anode materials because of the advantages of good conductivity, wide sources, low cost and the like, however, carbon elements have higher surface energy states and are easy to lose electronic reducibility, electrons need higher energy if the electrons directly jump to the surface of the carbon materials, so that the activation overpotential of an anode is larger, and the biocompatibility of the pure carbon materials is often poor. Therefore, the surface of the carbon material is subjected to various treatments and different nano materials are modified to increase the specific surface area of the anode and reduce the energy state, so that the activation overpotential and the like can be reduced, and the positive effect on the improvement of the power is achieved.
Disclosure of Invention
The invention aims to provide a high-performance microbial fuel cell based on a molybdenum disulfide composite material as an anode, wherein a molybdenum disulfide nano material modified carbon material is adopted as the composite anode of the microbial fuel cell to improve the output power density of the microbial fuel cell.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-performance microbial fuel cell based on a molybdenum disulfide composite material as an anode adopts a sandwich type double-chamber structure comprising an anode chamber and a cathode chamber, and the anode chamber and the cathode chamber are separated by a cation exchange membrane;
the cathode chamber is used for storing cathode liquid, and the cathode immersed in the cathode liquid is carbon paper or carbon cloth;
the anode chamber is used for storing anolyte, and an anode immersed in the anolyte is molybdenum disulfide/carbon cloth or conductive polymer/molybdenum disulfide/carbon cloth (here, "/" refers to an interface existing between two different substances in a composite material, such as molybdenum disulfide/carbon cloth, and indicates that molybdenum disulfide grows on the carbon cloth, and "conductive polymer/molybdenum disulfide/carbon cloth, indicates that molybdenum disulfide grows on the carbon cloth, and conductive polymer is loaded on molybdenum disulfide.)
The catholyte stored in the cathode chamber was a pH-neutral PBS buffer solution (10.0 g/L sodium bicarbonate, 11.2g/L disodium hydrogen phosphate) containing 50mmol/L K3[Fe(CN)6]。
The anode is molybdenum disulfide/carbon cloth or conductive polymer/molybdenum disulfide/carbon cloth, and anolyte is stored in the anode chamber. The anolyte is PBS buffer solution (10.0 g/L sodium bicarbonate, 11.2g/L disodium hydrogen phosphate) with neutral pH, and contains 10.0g/L anhydrous glucose, 5g/L yeast extract and 0.8707 g/L2-hydroxy-1, 4-naphthoquinone (HNQ). The conductive polymer is molybdenum disulfide/carbon cloth which is also compounded with polyaniline, polypyrrole or polythiophene. In general, the maximum liquid-holding volumes of the anode chamber and the cathode chamber are both 20 mL.
Further, the preparation method of the molybdenum disulfide composite anode comprises the following steps: :
s1: ultrasonically cleaning a carbon cloth sold in the market for half an hour by using acetone, ethanol and deionized water in sequence, and then drying for later use;
s2: putting the cleaned carbon material into a solution containing 0.5-1.5g of thiourea, 1.0-1g of sodium molybdate, 0.2-0.6g of P123 and 30-70mL of deionized water, carrying out hydrothermal reaction for 4-6 hours at the temperature of 200 ℃ in a high-pressure reaction kettle, naturally cooling, then washing with the deionized water, and drying to obtain the grown MoS2Carbon material of nanomaterial.
Further, the preparation method of the composite polyaniline conductive polymer comprises the following steps:
s1: in the presence of 0.1mol L-1And 1mol L of aniline-1In the sulfuric acid solution, an electrode with hydrothermally grown molybdenum disulfide/carbon cloth is used as a working electrode;
s2: using Pt electrode as counter electrode and calomel electrode as reference, electroplating by cyclic voltammetry with scanning potential range of-0.2V-0.9V and scanning speed of 10mV s-1The number of scanning turns is 6-20.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention passes through MoS2The electrochemical performance of the carbon material is obviously improved by the modification of the nano material, a certain direct catalytic performance to substrate glucose is shown, and the maximum catalytic oxidation peak current of the carbon material in a solution containing the substrate glucose and an electron transfer mediator is 2.7 mA/cm2Far higher than that of blank carbon cloth by 0.37 mA/cm2。
2. The invention shows that MoS is prepared by testing the double-chamber microbial fuel cell2The modification of the nano material enables the internal resistance of the MFCs taking the carbon cloth as the anode to be reduced by 43 percent, the power to be improved by 60 percent, and the average coulombic efficiency to be 2.86 times that of the blank carbon cloth as the anode MFCs.
3. The invention can further improve MoS by the polymerization of polyaniline PANI2The conductivity of the carbon cloth electrode material reduces the charge transfer resistance and improves the electrocatalytic activity.
4. PANI/MoS of the invention2The maximum power density and the internal resistance of the battery with/carbon cloth as the anode MFCs are 42.13W m-3(135 omega) is far superior to 22.12W m of PANI/carbon cloth-MFC single material-3(180. OMEGA.), and MoS227.97W m for/carbon cloth-MFC-3(210 omega), therefore, the anode based on the molybdenum disulfide composite material is low in price, easy to produce in batches, capable of greatly reducing the running cost of the microbial fuel cell, simple to prepare and good in application prospect.
Drawings
FIG. 1 shows a blank carbon cloth and a MoS-loaded carbon cloth according to the present invention2 A cyclic voltammetry curve of carbon cloth of a nano valve in anolyte;
FIG. 2 is a plot of a polarization for various anode microbial fuel cells of the present invention; b power density graph;
FIG. 3 shows the PANI/carbon cloth, MoS, of the present invention2 Carbon cloth and PANI/MoS2A cyclic voltammogram of carbon cloth in anolyte;
FIG. 4 shows the PANI/carbon cloth, MoS, of the present invention2 Carbon cloth and PANI/MoS2A polarization curve of the carbon cloth anode microbial fuel cell; b power density plot.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment of the invention: a high-performance microbial fuel cell based on a molybdenum disulfide composite material as an anode is provided, wherein the preparation method of the molybdenum disulfide composite anode comprises the following steps: ultrasonically cleaning commercially available carbon cloth (not limited to carbon cloth, carbon paper, carbon felt and other carbon materials) by acetone, ethanol and deionized water for half an hour, and drying for later use; putting the cleaned carbon material into a solution containing 0.5-1.5g of thiourea, 1.0-1g of sodium molybdate, 0.2-0.6g of P123 and 30-70mL of deionized water, carrying out hydrothermal reaction for 4-6 hours at the temperature of 200 ℃ in a high-pressure reaction kettle, naturally cooling, then washing with the deionized water, and drying to obtain the grown MoS2Carbon material of nanomaterial.
In order to further increase the conductivity of the material, another embodiment of the present invention further includes compounding a conductive polymer such as polyaniline, polypyrrole, or polythiophene on the molybdenum disulfide/carbon material prepared above.
The preparation method of the composite Polyaniline (PANI) conductive polymer comprises the following steps: in the presence of 0.1mol L-1And 1mol L of aniline-1Sulfuric acid solution ofIn the liquid, an electrode with hydrothermally grown molybdenum disulfide/carbon cloth is used as a working electrode, a Pt electrode is used as a counter electrode, a calomel electrode is used as a reference, cyclic voltammetry is used for electroplating, the scanning potential range is-0.2V-0.9V, and the scanning speed is 10mV s-1The number of scanning turns is 6-20.
In conclusion, the high-performance microbial fuel cell based on the molybdenum disulfide composite material as the anode is a double-chamber microbial fuel cell, a sandwich structure is adopted, the maximum liquid filling volumes of an anode chamber and a cathode chamber are both 20mL, and the anode chamber and the cathode chamber are separated by a cation exchange membrane; wherein the cathode is carbon paper or carbon cloth, and the catholyte is pH neutral PBS buffer solution (10.0 g/L sodium bicarbonate, 11.2g/L disodium hydrogen phosphate) containing 50mmol/L K3[Fe(CN)6](ii) a The anode is molybdenum disulfide/carbon cloth or conductive polymer/molybdenum disulfide/carbon cloth, and the anolyte is PBS buffer solution (10.0 g/L sodium bicarbonate, 11.2g/L disodium hydrogen phosphate) with neutral pH and contains 10.0g/L anhydrous glucose, 5g/L yeast extract and 0.8707 g/L2-hydroxy-1, 4-naphthoquinone (HNQ).
Referring to fig. 4, based on the above cell structure, the start-up and power density polarization curves of the cell were determined: putting 18 mL of anolyte into a reactor, introducing high-purity nitrogen for 15 minutes, putting 2 mL of escherichia coli bacterial liquid into the reactor after the gas is introduced, and plugging an opening at the upper end of the reactor by using a rubber plug to enable the reactor to be in a sealed state; after the open-circuit voltage of the battery is stable, different resistors are sequentially loaded on the battery, and the system automatically records the voltage value, the power density and the current density output when the resistors are loaded at different loads.
The tests show that: (1) MoS2The modification of the nano material enables the internal resistance of MFCs based on carbon cloth as the anode to be reduced by 43 percent and the power to be improved by 60 percent; the average coulombic efficiency is 2.86 times that of the blank carbon cloth which is used as the anode MFCs; (2) polymerization of Polyaniline (PANI) may further enhance MoS2The conductivity of the carbon cloth electrode material reduces the charge transfer resistance and improves the electrocatalytic activity; (3) PANI/MoS2The maximum power density and the internal resistance of the battery with/carbon cloth as the anode MFCs are 42.13W m-3(135. OMEGA.) is far superior to the single one22.12W m for PANI/carbon cloth-MFC material-3(180. OMEGA.), and MoS227.97W m for/carbon cloth-MFC-3（210 Ω）。
Therefore, the anode based on the molybdenum disulfide composite material is low in price and easy to produce in batches, and therefore the operation cost of the microbial fuel cell can be greatly reduced.
In order to further and better verify the invention, the following specific embodiments are also provided:
example 1:
MoS2study of electrocatalytic performance of/carbon cloth:
the first step is as follows: MoS2Preparation of carbon cloth: ultrasonically cleaning commercial carbon cloth with acetone, ethanol and deionized water for half an hour in sequence, and then drying for later use; MoS2The synthesis of the nano valve on the carbon cloth is carried out by putting the carbon cloth (2.5 cm multiplied by 5 cm) into the solution containing 0.9 g thiourea, 0.450 g sodium molybdate, 0.4 g P123 and 60 mL deionized water, hydrothermal reacting at 200 deg.C for 3-6 h in high pressure reactor, naturally cooling, washing with deionized water, drying to obtain the product2A carbon cloth of a nano material;
the second step is that: and testing the electrocatalytic performance.
MoS prepared as above2The/carbon cloth is used as a working electrode, the Ag/AgCl is used as a reference electrode, the platinum wire is used as a counter electrode, and a cyclic voltammogram of the anode is measured in anolyte.
Example 2:
MoS2research on microbial fuel cells with carbon cloth as the anode:
in MoS2The carbon cloth is taken as an anode, and the blank carbon paper is taken as a cathode; MoS2The carbon cloth anode was prepared as in example 1.
The cell adopts a sandwich structure, the maximum liquid filling volumes of an anode chamber and a cathode chamber are both 20mL, and the anode chamber and the cathode chamber are separated by a cation exchange membrane; the anolyte is PBS buffer solution (10.0 g/L sodium bicarbonate, 11.2g/L disodium hydrogen phosphate) with neutral pH, and contains 10.0g/L anhydrous glucose, 5g/L yeast extract and 0.8707 g/L2-hydroxy-1, 4-naphthoquinone (HNQ); the catholyte is PBS buffer with neutral pHThe extract solution (10.0 g/L sodium bicarbonate, 11.2g/L disodium hydrogen phosphate) contains 50mmol/L K3[Fe(CN)6]。
Starting of the cell and determination of the power density polarization curve: putting 18 mL of anolyte into a reactor, introducing high-purity nitrogen for 15 minutes, putting 2 mL of escherichia coli bacterial liquid into the reactor after the gas is introduced, and plugging an opening at the upper end of the reactor by using a rubber plug to enable the reactor to be in a sealed state; after the open-circuit voltage of the battery is stable, different resistors are sequentially loaded on the battery, and the system automatically records the voltage value, the power density and the current density output when the resistors are loaded at different loads.
Example 3:
PANI/MoS2study of a microbial fuel cell with carbon cloth as anode:
the synthesis method of PANI/MoS 2/carbon cloth is as follows: with PANI/MoS2The carbon cloth is taken as an anode, and the blank carbon paper is taken as a cathode; in the presence of 0.1mol L-1And 1mol L of aniline-1In the sulfuric acid solution, carbon cloth with hydrothermally grown molybdenum disulfide is used as a working electrode, a Pt electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, cyclic voltammetry is used for electroplating, the scanning potential range is-0.2V-0.9V, and the scanning speed is 10mV s-1。
The assembly of the microbial fuel cell, the power density and the polarization curve were measured as in example 2.
Example 4:
preparing and measuring a blank carbon cloth anode microbial fuel cell of a comparison system:
the assembly, power density and polarization curve of the microbial fuel cell were measured as in example 2, using a blank carbon cloth as the anode and a blank carbon paper as the cathode.
And (4) conclusion: referring to FIG. 1, a blank carbon cloth and grown MoS are shown2 The cyclic voltammogram of the carbon cloth of the nanomaterial in the anolyte shows that for MoS2 The carbon cloth electrode has obvious oxidation-reduction peak current for catalyzing glucose/HNQ in a range of-0.2V to-0.4V; shows the MoS2 The carbon cloth electrode shows excellent electrocatalysis performance in the anode system of the microbial fuel cellThe maximum catalytic oxidation peak current of the catalyst is 2.7 mA/cm2Far higher than that of blank carbon cloth by 0.37 mA/cm2。
Referring to FIG. 2, MoS is shown from a test of a two-compartment microbial fuel cell2The modification of the nano material enables the internal resistance of the MFCs based on the carbon cloth as the anode to be reduced by 43 percent, the power to be improved by 60 percent, and the result of periodic operation shows that the average coulombic efficiency of the MFCs is 2.86 times that of the MFCs of the blank carbon cloth.
Referring to FIG. 3, it can be seen from the cyclic voltammetry and impedance tests that polymerization of PANI can greatly improve MoS2The conductivity of the carbon cloth electrode material reduces the charge transfer resistance and improves the electrocatalytic activity; PANI/MoS2The maximum power density and the internal resistance of the battery with/carbon cloth as the anode MFCs are 42.13W m-3(135 omega) is far superior to 22.12W m of PANI/carbon cloth-MFC single material-3(180. OMEGA.), and MoS227.97W m for/carbon cloth-MFC-3（210 Ω）。
Therefore, the anode based on the molybdenum disulfide composite material is low in price and easy to produce in batches, and the operation cost of the microbial fuel cell can be greatly reduced.
In summary, the following steps: the invention provides a high-performance microbial fuel cell based on a molybdenum disulfide composite material as an anode, which is prepared by MoS2The modification of the nano material obviously improves the electrochemical performance of the carbon material, shows certain direct catalytic performance to substrate glucose, and is 2.7 mA/cm in solution containing the substrate glucose and an electron transfer mediator2Far higher than that of blank carbon cloth by 0.37 mA/cm2(ii) a Second, testing of a two-compartment microbial fuel cell showed that MoS2The modification of the nano material enables the internal resistance of the MFCs taking the carbon cloth as the anode to be reduced by 43 percent, the power to be improved by 60 percent, the average coulombic efficiency is 2.86 times that of the blank carbon cloth as the anode MFCs, and meanwhile, the polymerization of PANI can further improve MoS2The conductivity of the carbon cloth electrode material reduces the charge transfer resistance and improves the electrocatalytic activity; in addition, PANI/MoS2The maximum power density and the internal resistance of the battery with/carbon cloth as the anode MFCs are 42.13W m-3(135 omega) is far superior to 22.12W m of PANI/carbon cloth-MFC single material-3(180. OMEGA.), and MoS227.97W m for/carbon cloth-MFC-3(210 omega), therefore, the anode based on the molybdenum disulfide composite material is low in price and easy to produce in batches, and the running cost of the microbial fuel cell can be greatly reduced.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (1)
1. A microbial fuel cell based on a molybdenum disulfide composite material as an anode is characterized in that a sandwich type double-chamber structure comprising an anode chamber and a cathode chamber is adopted, and the anode chamber and the cathode chamber are separated by a cation exchange membrane;
the cathode chamber is used for storing cathode liquid, and the cathode immersed in the cathode liquid is carbon paper or carbon cloth;
the anode chamber is internally stored with anolyte, and the anode immersed in the anolyte is conductive polymer/molybdenum disulfide/carbon cloth;
the catholyte is PBS buffer solution with neutral pH, is prepared by mixing 10.0g/L sodium bicarbonate and 11.2g/L disodium hydrogen phosphate, and contains 50mmol/L K3[Fe(CN)6]；
The anolyte is PBS buffer solution with neutral pH, is formed by mixing 10.0g/L sodium bicarbonate and 11.2g/L disodium hydrogen phosphate, and contains 10.0g/L anhydrous glucose, 5g/L yeast extract and 0.8707 g/L2-hydroxy-1, 4-naphthoquinone HNQ;
the conductive polymer is a conductive polymer which is formed by compounding polyaniline, polypyrrole or polythiophene on molybdenum disulfide/carbon cloth;
the preparation method of the conductive polymer/molybdenum disulfide/carbon cloth comprises the following steps:
ultrasonically cleaning a carbon cloth sold in the market for half an hour by using acetone, ethanol and deionized water in sequence, and then drying for later use;
placing the cleaned carbon material in a container containing0.5 to 1.5g of thiourea, 1.0 to 1g of sodium molybdate, 0.2 to 0.6g of P123 and 30 to 70mL of deionized water, placing the solution in a high-pressure reaction kettle, carrying out hydrothermal reaction for 4 to 6 hours at the temperature of 150 plus 200 ℃, naturally cooling, washing the solution with the deionized water, and drying the solution to obtain the MoS grown on the surface of the substrate2A carbon material of a nanomaterial;
in the presence of 0.1mol L-1And 1mol L of aniline-1In the sulfuric acid solution, an electrode with hydrothermally grown molybdenum disulfide/carbon cloth is used as a working electrode;
using Pt electrode as counter electrode and calomel electrode as reference, electroplating by cyclic voltammetry with scanning potential range of-0.2V-0.9V and scanning speed of 10mV s-1The number of scanning turns is 6-20.
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