CN114937781B - Modified carbon-based material, preparation method and application thereof - Google Patents
Modified carbon-based material, preparation method and application thereof Download PDFInfo
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- CN114937781B CN114937781B CN202210544747.8A CN202210544747A CN114937781B CN 114937781 B CN114937781 B CN 114937781B CN 202210544747 A CN202210544747 A CN 202210544747A CN 114937781 B CN114937781 B CN 114937781B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 58
- 150000001721 carbon Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 32
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 28
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 84
- 230000000813 microbial effect Effects 0.000 claims description 39
- 239000000446 fuel Substances 0.000 claims description 36
- 239000002689 soil Substances 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 71
- 230000000694 effects Effects 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 11
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 244000005700 microbiome Species 0.000 description 7
- 230000005611 electricity Effects 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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
- H01M4/96—Carbon-based electrodes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Sustainable Development (AREA)
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- Biotechnology (AREA)
- Materials Engineering (AREA)
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- Sustainable Energy (AREA)
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- General Health & Medical Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
A modified carbon-based material, a preparation method and application thereof belong to the technical field of material modification. The method comprises the following steps: preparing nano zero-valent iron; mixing the prepared nano zero-valent iron with polytetrafluoroethylene, polyvinyl alcohol and anaerobic water according to a proportion to obtain a mixed coating liquid; and coating the mixed coating liquid on the surface of the carbon-based material, and drying to obtain the modified carbon-based material. According to the preparation method, the nano zero-valent iron is dispersed by adopting the mixed solution of polytetrafluoroethylene, polyvinyl alcohol and anaerobic water in a specific proportion, so that the problem that the nano zero-valent iron is easy to oxidize and agglomerate is solved, the modification of the carbon-based material by directly utilizing the nano zero-valent iron is realized, and the oxidation-reduction capability, the electrical activity, the biological enrichment effect and the stability of the carbon-based material when the carbon-based material is used as an electrode are improved; the method has the advantages of low cost of raw materials, simple and environment-friendly preparation process, and considerable economic benefit and practicality.
Description
Technical Field
The invention relates to the technical field of material modification, in particular to a modified carbon-based material capable of being used as an anode of a microbial fuel cell, and a preparation method and application thereof.
Background
In the context of both environmental pollution and energy shortage, microbial fuel cell technology has been attracting attention because of its own two-sided significant advantages in degrading pollutants and generating electrical energy. To realize large-scale practical application of the technology, the power generation efficiency and the pollutant degradation rate of the microbial fuel cell are required to be improved together so as to optimize the overall performance of the microbial fuel cell.
The property of the two poles of the cell plays a decisive role in the overall performance of the microbial fuel cell, wherein the anode is used as a place for gathering and attaching electricity-generating microorganisms and participates in the process of carrying out electron transfer with the microorganisms, and the electron transfer efficiency is closely related to the performance of the cell, so that the microorganism attaching quantity of the anode is improved, the electron transfer efficiency is improved, the cost is reduced, and the popularization and the application of the microbial fuel cell can be further promoted.
The nano zero-valent iron is a metal material with high catalytic activity, green, low cost and easy obtainment, and has considerable economic benefit compared with metals such as Pd and the like. If the nano zero-valent iron is adopted to modify the anode of the microbial fuel cell, the microbial activity of the anode can be improved, the growth and propagation process of the microorganisms can be accelerated, the specific surface area and biocompatibility of the anode material can be increased, the microbial enrichment effect can be enhanced, the electron transfer rate of the anode can be promoted, the internal resistance of the cell can be reduced, the conductivity and the reactivity of the electrode can be improved, and the like, so that the microbial fuel cell can be very beneficial to electricity generation. However, nano zero-valent iron is easy to oxidize in air, has obvious passivation and corrosion problems, and is easy to agglomerate, so that the nano zero-valent iron is difficult to be used as a modification material to modify the surface of the electrode. At present, a learner tries to load nano zero-valent iron on montmorillonite to modify an electrode, but XRD test shows that the peak of the oxide of the iron is found by the prepared electrode material, and part of nano zero-valent iron is oxidized. The above problems with nano zero-valent iron limit its use in the field of microbial fuel cells.
Disclosure of Invention
Object of the invention
The invention aims to provide a modified carbon-based material and a preparation method and application thereof, wherein the preparation method adopts a mixed solution of polytetrafluoroethylene, polyvinyl alcohol and anaerobic water in a specific proportion to disperse nano zero-valent iron, so that the problem that the nano zero-valent iron is easy to oxidize and agglomerate is solved, the modification of the carbon-based material by the nano zero-valent iron is realized, and the oxidation-reduction capability, the electrical activity, the biological enrichment effect and the stability of the carbon-based material as an electrode are improved; the method has the advantages of low cost of raw materials, simple and environment-friendly preparation process, and considerable economic benefit and practicality.
(II) technical scheme
In order to solve the above problems, according to a first aspect of the present invention, there is provided a method for preparing a modified carbon-based material, comprising the steps of:
Preparing nano zero-valent iron;
mixing the prepared nano zero-valent iron with polytetrafluoroethylene, polyvinyl alcohol and anaerobic water according to the dosage ratio of 0.1-0.8: 1.5 to 4.3:1.5 to 4.0: 20-50, and obtaining a mixed coating liquid;
and coating the mixed coating liquid on the surface of the carbon-based material, and drying to obtain the modified carbon-based material.
Preferably, the dosage ratio of the nanometer zero-valent iron, polytetrafluoroethylene, polyvinyl alcohol and anaerobic water in the mixed coating liquid is 0.5-0.8: 1.5 to 3.5:1.5 to 2.5: 20-30 parts.
Specifically, the polytetrafluoroethylene is a polytetrafluoroethylene concentrated dispersion of 60 wt%; the polyvinyl alcohol is 1788 type, and the alcoholysis degree is 87.0% -89.0%.
Specifically, the carbon-based material is at least one selected from graphite felt, carbon fiber felt and carbon cloth, and preferably graphite felt.
In an alternative embodiment, the preparing nano zero-valent iron specifically includes:
and (3) dropwise adding a reducing agent into the iron source solution in an inactive atmosphere to obtain the nano zero-valent iron.
In an alternative embodiment, the specific conditions for mixing the prepared nano zero-valent iron with polytetrafluoroethylene, polyvinyl alcohol and oxygen-free water include:
Adding polyvinyl alcohol into oxygen-free water at 40-95 ℃ and stirring and mixing to obtain a colloid solution;
dripping polytetrafluoroethylene into the colloid solution, and stirring to obtain a mixed solution;
Adding nano zero-valent iron into the mixed solution, vibrating for 0.5-2 h, and performing ultrasonic treatment for 10-25 min.
In an alternative embodiment, the coating the mixed coating liquid onto the surface of the carbon-based material specifically includes:
and coating the mixed coating liquid on the surface of the carbon-based material in an inactive atmosphere in a dripping mode.
In a second aspect of the present invention, there is provided a modified carbon-based material produced by the production method of a modified carbon-based material as described in any one of the above.
In a third aspect of the present invention, there is provided a microbial fuel cell comprising a cathode and an anode, the anode being a modified carbon-based material prepared by the method for preparing a modified carbon-based material as described in any one of the above.
In a fourth aspect of the invention, there is provided the use of the microbial fuel cell for degrading organic matter in water and/or soil.
Wherein the organic matter comprises polycyclic aromatic hydrocarbon, petroleum hydrocarbon, antibiotics, polychlorinated biphenyl, pesticide and the like.
(III) beneficial effects
The technical scheme of the invention has the following beneficial technical effects:
According to the preparation method of the modified carbon-based material, the mixed solution of polytetrafluoroethylene, polyvinyl alcohol and anaerobic water in a specific proportion is adopted to disperse the nano zero-valent iron, so that the agglomeration phenomenon of the nano zero-valent iron can be effectively reduced, the nano zero-valent iron is ensured to be uniformly distributed on the surface of the carbon-based material under the condition of not depending on a solid phase carrier, the problem that the nano zero-valent iron is easy to passivate and corrode when being directly exposed in the air can be avoided, the nano zero-valent iron is ensured to have stable performance, and the reaction rate and efficiency of the material used as an electrode can be effectively improved, and the service life of the electrode can be prolonged; meanwhile, the method has the advantages of low cost of raw materials, simple preparation process and considerable economic benefit and practicality;
The nano zero-valent iron loaded on the modified carbon-based material can exist in the air stably, the electrochemical activity of the material is enhanced, the anode microorganism enrichment effect is improved when the modified carbon-based material is applied to a microbial fuel cell, the electron transfer is promoted, and the comprehensive performance of electricity generation and pollutant removal of the microbial fuel cell is optimized; meanwhile, the modified carbon-based material contains iron element which is closely related to the growth and propagation of microorganisms, and the iron element participates in the formation of the ferrohemoglobin so as to improve the activity of the microorganisms and reduce secondary pollution to the environment.
Drawings
FIG. 1 is an electron microscope (SEM) image of an unmodified graphite felt material used in examples 2 and 3;
FIG. 2 is an electron microscope (SEM) image of the modified graphite felt material 1 provided in example 2;
FIG. 3 is an XRD pattern of an unmodified graphite felt material and modified graphite felt material 1 provided in example 2;
FIG. 4 is a graph of the voltammetric properties of the unmodified graphite felt materials employed in examples 2 and 3;
FIG. 5 is a graph of the volt-ampere characteristic of the modified graphite felt material 1 provided in example 2;
FIG. 6 is a graph of the volt-ampere characteristic of the modified graphite felt material 2 provided in example 3;
FIG. 7 is a graph showing the change in the power generation voltage output of a microbial fuel cell constructed with unmodified graphite felt material, modified graphite felt material 1, modified graphite felt material 2 as anodes, respectively;
FIG. 8 is a graph showing the effect of a microbial fuel cell constructed with unmodified graphite felt material, modified graphite felt material 1, modified graphite felt material 2 as anodes on removal of α -hexa in soil, respectively;
FIG. 9 is a graph showing the effect of a microbial fuel cell constructed with unmodified graphite felt material, modified graphite felt material 1, modified graphite felt material 2 as anodes on removal of γ -hexa in soil, respectively;
Fig. 10 is a physical view of the modified graphite felt material 3.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
An embodiment of the invention provides a preparation method of a modified carbon-based material, which comprises the following steps:
step 1: preparing nano zero-valent iron;
Step 2: mixing the prepared nano zero-valent iron with polytetrafluoroethylene, polyvinyl alcohol and anaerobic water according to the dosage ratio of 0.1-0.8: 1.5 to 4.3:1.5 to 4.0: 20-50, and obtaining a mixed coating liquid; wherein the anaerobic water is water without oxygen, and can be prepared by deoxidizing ultrapure water;
Step 3: and coating the mixed coating liquid on the surface of the carbon-based material, and drying to obtain the modified carbon-based material.
According to the preparation method of the modified carbon-based material, the mixed solution of polytetrafluoroethylene, polyvinyl alcohol and anaerobic water in a specific proportion is adopted to disperse the nano zero-valent iron, so that the agglomeration phenomenon of the nano zero-valent iron can be effectively reduced, the nano zero-valent iron is ensured to be uniformly distributed on the surface of the carbon-based material without depending on a solid phase carrier, the problem that the nano zero-valent iron is easy to passivate and corrode when being directly exposed to the air can be avoided, the nano zero-valent iron is ensured to have stable performance, and the reaction rate and efficiency when being used as a material electrode can be effectively improved, and the service life of the electrode can be prolonged; meanwhile, the method has the advantages of low cost of raw materials, simple preparation process and considerable economic benefit and practicality.
In a preferred embodiment, the dosage ratio of the nanometer zero-valent iron, the polytetrafluoroethylene, the polyvinyl alcohol and the anaerobic water in the mixed coating liquid is 0.5-0.8: 1.5 to 3.5:1.5 to 2.5: 20-30 parts.
When the substances in the coating liquid are proportioned according to the proportion, the uniform dispersion of the nano zero-valent iron can be further ensured, the occurrence of agglomeration phenomenon can be further reduced, the oxidation of the nano zero-valent iron can be further effectively avoided, and meanwhile, the electrode has better removal effect on organic matters such as polycyclic aromatic hydrocarbon, petroleum hydrocarbon, antibiotics, polychlorinated biphenyl, pesticides and the like.
Specifically, the polytetrafluoroethylene is a polytetrafluoroethylene concentrated dispersion of 60 wt%; the polyvinyl alcohol is 1788 type, and the alcoholysis degree is 87.0% -89.0%.
Specifically, the carbon-based material is preferably a porous material, and the porous carbon-based material may be at least one selected from a graphite felt, a carbon fiber felt, and a carbon cloth, preferably a graphite felt.
In an alternative embodiment, the preparing nano zero-valent iron comprises:
and (3) dropwise adding a reducing agent into the iron source solution in an inactive atmosphere to obtain the nano zero-valent iron.
Wherein:
The inactive atmosphere is inert gases such as nitrogen or argon;
The iron source is a soluble salt of iron such as FeSO 4、FeCl2、FeCl3、Fe(NO3)2, preferably FeSO 4; the concentration of the iron source solution is 0.05-1 mol/L in terms of the mole number of iron ions;
The reducing agent is aqueous solution of NaBH 4、KBH4 and the like; the concentration of the reducing agent is 0.1-0.3 mol/L;
the speed of dripping reducing agent into the iron source solution is 20-60 drops/min.
The embodiment of the invention can also adopt other existing modes to prepare nano zero-valent iron, and the grain diameter of the nano zero-valent iron is preferably smaller than 100nm.
In an alternative embodiment, the specific conditions for mixing the prepared nano zero-valent iron with polytetrafluoroethylene, polyvinyl alcohol and oxygen-free water include:
Adding polyvinyl alcohol into oxygen-free water at 40-95 ℃ and stirring and mixing to obtain a colloid solution;
dripping polytetrafluoroethylene into the colloid solution, and stirring to obtain a mixed solution;
Adding nano zero-valent iron into the mixed solution, vibrating for 0.5-2 h, and performing ultrasonic treatment for 10-25 min.
The mixing method ensures that the nano zero-valent iron particles are fully wrapped and mixed with the mixed solution of polytetrafluoroethylene and polyvinyl alcohol to the greatest extent uniformly.
In an alternative embodiment, the coating the mixed coating liquid onto the surface of the carbon-based material specifically includes:
and coating the mixed coating liquid on the surface of the carbon-based material in an inactive atmosphere in a dripping mode.
Wherein the inactive atmosphere is inert gases such as nitrogen or argon;
the dripping is to apply the coating while dripping until the coating liquid is covered on the surface of the carbon-based material.
In an alternative embodiment, the drying of step 3 includes:
Under the vacuum condition, the drying temperature is 40-80 ℃ and the drying time is 10-16 h.
Another embodiment of the present invention provides a modified carbon-based material prepared by the method for preparing a modified carbon-based material described in the above embodiment.
The specific description and effects of the modified carbon-based material are described in detail in the preparation method, and are not repeated here.
The invention also provides a microbial fuel cell, which comprises a cathode and an anode, wherein the anode is the modified carbon-based material prepared by the embodiment of the preparation method, and the cathode is carbon-based materials such as graphite felt, carbon fiber felt, carbon cloth and the like.
In a further embodiment, the invention provides the use of the microbial fuel cell provided in the above embodiment for degrading organic matter in water and/or soil. Wherein the organic matter comprises polycyclic aromatic hydrocarbon, petroleum hydrocarbon, antibiotics, polychlorinated biphenyl, pesticide and the like.
The following are specific embodiments of the present invention:
the raw materials used in the embodiments of the invention are all commercial products, wherein:
The graphite felt is a micro-hydrophilic graphite felt with the thickness of 3mm purchased from Jing Zhouhao new materials limited company;
Polytetrafluoroethylene is 60wt% polytetrafluoroethylene concentrated dispersion;
the polyvinyl alcohol is 1788 type, and the alcoholysis degree is 87.0% -89.0%.
Example 1
Preparing nano zero-valent iron:
100mL of FeSO 4·7H2 O solution with the concentration of 0.08mol/L is taken to be placed in a four-necked flask which is continuously filled with nitrogen, 25 drops/min of NaBH 4 solution with the concentration of 0.2mol/L is dripped, the prepared black nanometer zero-valent iron is washed for a plurality of times by absolute ethyl alcohol, acetone and deionized water, then the solution is dried for 24 hours in a freeze dryer, and the solution is stored in a sealed plastic bottle filled with nitrogen.
Example 2
The embodiment provides a modified graphite felt material which can be used as an anode of a microbial fuel cell, the modified graphite felt material uses a graphite felt as a basic carbon-based material, the modified graphite felt material is modified by using the nano zero-valent iron provided in the embodiment 1, and the specific preparation steps of the modified graphite felt material are as follows:
Firstly, soaking and cleaning a graphite felt by using acetone, repeatedly washing by using ethanol and deionized water, and drying at the temperature of 60 ℃ for later use.
1.9625G of polyvinyl alcohol is taken in 25mL of deoxidized ultrapure water, stirred and heated in a water bath magnetic stirrer at 60 ℃ until solid is melted, the heating is turned off after a colloid solution is formed, 1mL of 60wt% polytetrafluoroethylene concentrate is dripped into a glass bottle, the stirring is continued for half an hour, the ultrasonic mixing is carried out for 15min, the mixed solution is obtained, and 0.785g of nano zero-valent iron is added into the mixed solution. And sealing the glass bottle added with the nano zero-valent iron powder, oscillating for 1h in a constant-temperature oscillating box, and then performing ultrasonic treatment for 15min, so that the nano zero-valent iron particles are fully wrapped and uniformly mixed with the mixed solution of polytetrafluoroethylene and polyvinyl alcohol to the greatest extent, and an anaerobic environment is maintained in the whole electrode preparation process. And (3) dripping the white emulsion containing the nano zero-valent iron after uniform vibration and mixing on the surface of the graphite felt under the nitrogen atmosphere, uniformly coating by using a coating rod, immediately drying in a vacuum drying oven at the drying temperature of 60 ℃ for 12 hours, taking out the dried graphite felt material, and marking the modified graphite felt material as a modified graphite felt material 1.
Example 3
The embodiment provides a modified graphite felt material which can be used as an anode of a microbial fuel cell, and the preparation method of the modified graphite felt material is basically the same as that of the embodiment 2, except that the nano zero-valent iron load is adjusted from 0.785g to 0.3925g, and the obtained electrode is named as modified graphite felt material 2.
Comparative example 1
The embodiment provides a modified graphite felt material which can be used as an anode of a microbial fuel cell, and the preparation method of the modified graphite felt material is basically the same as that of the embodiment 2, except that the nano zero-valent iron load is adjusted from 0.785g to 1g, and the obtained electrode is denoted as modified graphite felt material 3.
The graphite felt material 3 obtained after vacuum drying was found to exhibit a significant large piece of red rust a, as shown in fig. 10.
Characterization of the modified graphite felt material:
And (3) placing the unmodified graphite felt material, the obtained modified graphite felt material 1 and the modified graphite felt material 2 in a natural air environment for more than a month, and observing the morphology of the modified graphite felt material and analyzing the element content of the modified graphite felt material by using a scanning electron microscope (SEM-EDS). As represented by modified graphite felt material 1, referring to fig. 1 and 2, it can be seen that the unmodified graphite felt material is a carbon fiber with distinct roots, the surface state is smooth, and no load is present; the carbon fiber with distinct electrode roots of the modified graphite felt is successfully loaded with spherical nano zero-valent iron particles, and the carbon fiber is uniformly loaded and has lighter agglomeration phenomenon. The change of elements in the material before and after modification was observed by using an X-ray diffractometer (XRD), and also represented by modified graphite felt material 1, referring to fig. 3, it was found that the nano zero-valent iron was still in a zero-valent iron state after being supported on the surface of the graphite felt substrate, and was not oxidized.
Electrochemical performance test is carried out on the modified graphite felt material:
And (3) performing electrochemical performance tests on the unmodified graphite felt material, the modified graphite felt material 1 and the modified graphite felt material 2 by using a cyclic voltammetry. Referring to fig. 4-6, the graphite felt material modified by the nano zero-valent iron has a larger response current peak value, so that the specific surface area of the material is effectively improved; meanwhile, the corresponding closed curve area is increased, the charge transfer capacity of the modified electrode is enhanced, and the conductivity is improved.
The modified graphite felt material is used as an anode of a microbial battery, and the treatment effect of the modified graphite felt material on organic pollutants is tested:
and respectively taking the unmodified graphite felt, the modified graphite felt material 1 and the modified graphite felt material 2 as anodes, and respectively building soil microbial fuel cells, wherein the soil microbial fuel cells are marked according to the adopted anodes. Three soil microbial fuel cells are adopted to remove the organic chlorine pesticide alpha-hexa in the soil and to carry out the electricity generation experiment of the microbial fuel cells, and the specific construction method of the cells and the specific steps of the experiment comprise:
Firstly, 100g of moist contaminated soil is filled at the bottom of a cylinder container, an anode graphite felt (an unmodified graphite felt, a modified graphite felt material 1 or a modified graphite felt material 2 respectively) is paved on the upper surface of a soil layer at the bottom, then 400g of contaminated soil is continuously added on the anode graphite felt, a proper amount of tap water is added to keep the soil moist, and finally, a cathode graphite felt material is paved on the upper surface of the soil layer. The cathode and the anode are connected by using titanium wires (diameter is 1 mm) sleeved with an anti-oxidation material, and are connected with an external resistor with a resistance value of 1000 omega, so that a closed loop is formed by combination. Each device is added with a certain overlying water submerged cathode, and simultaneously an overlying water layer with the thickness of 15mm is kept, and the device operates at the temperature of 28 ℃ to collect the output voltage change of the microbial fuel cell in real time. After 101 days of operation, the content of the organic chlorine pesticide alpha-hexa in the soil is measured by adopting a gas chromatography for measuring organic chlorine pesticide of soil and sediment (HJ 921-2017) issued by the ecological environment department of the people's republic of China, and the removal rate of the organic chlorine pesticide alpha-hexa in microbial fuel cells with different anode materials is calculated.
As shown in fig. 7 and 8, the output voltage value of the microbial fuel cell assembled by the modified graphite felt material 1 and the modified graphite felt material 2 is obviously higher than that of the unmodified graphite felt, the removal rate of pesticide alpha-hexa is improved by more than 2 times, and the highest removal rate can reach more than 75%.
And respectively converting the soil organic pollutant objects into organic chlorine pesticides gamma-hexa, beta-hexa and delta-hexa, and respectively adopting three soil microbial fuel cells to perform experiments of removing the organic chlorine pesticides in the soil and generating electricity of the microbial fuel cells. After the operation is carried out for 101 days, the removal rate of the organic chlorine pesticide in the microbial fuel cells with different anode materials is calculated, and as can be seen from the graph 9, the removal rate of the microbial fuel cells assembled by the modified graphite felt material 1 and the modified graphite felt material 2 on the pesticide gamma-hexa is improved by more than 2 times, and the highest removal rate can reach about 85%; the removal rates of the modified graphite felt material 1, the modified graphite felt material 2 and the microbial fuel cell assembled by the unmodified graphite felt on the beta-hexa are respectively as follows: 55.52%, 12.38%, 6.42%; the removal rates of delta-hexa are respectively as follows: 82.27%, 63.12%, 38.45%.
In conclusion, the modified graphite felt material prepared by the embodiment of the invention can stably exist in air, nano zero-valent iron is not easy to oxidize, and compared with the common unmodified graphite felt material, the modified graphite felt material is applied to the microbial fuel cell technology, can more effectively remove various organic chlorine pesticide pollutants in polluted soil, realizes higher-efficiency electricity generation output, and has small secondary pollution to the environment.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (9)
1. The preparation method of the modified carbon-based material is characterized by comprising the following steps of:
Preparing nano zero-valent iron;
Mixing the prepared nano zero-valent iron with polytetrafluoroethylene, polyvinyl alcohol and anaerobic water according to the mass ratio of 0.1-0.8: 1.5 to 4.3:1.5 to 4.0: 20-50, and obtaining a mixed coating liquid;
Coating the mixed coating liquid on the surface of a carbon-based material, and drying to obtain a modified carbon-based material;
The carbon-based material is at least one selected from graphite felt, carbon fiber felt and carbon cloth.
2. The method for preparing a modified carbon-based material according to claim 1, wherein the dosage ratio of nano zero-valent iron, polytetrafluoroethylene, polyvinyl alcohol and anaerobic water in the mixed coating solution is 0.5-0.8: 1.5 to 3.5:1.5 to 2.5: 20-30 parts.
3. The method for producing a modified carbon-based material according to claim 1, characterized in that:
The polytetrafluoroethylene is a polytetrafluoroethylene concentrated dispersion with the weight percentage of 60 percent;
the polyvinyl alcohol is 1788 type, and the alcoholysis degree is 87.0% -89.0%.
4. The method for preparing a modified carbon-based material according to claim 1, wherein the preparing of nano zero-valent iron specifically comprises:
and (3) dropwise adding a reducing agent into the iron source solution in an inactive atmosphere to obtain the nano zero-valent iron.
5. The method for preparing the modified carbon-based material according to claim 1, wherein the specific conditions for mixing the prepared nano zero-valent iron with polytetrafluoroethylene, polyvinyl alcohol and oxygen-free water include:
Adding polyvinyl alcohol into oxygen-free water at 40-95 ℃ and stirring and mixing to obtain a colloid solution;
dripping polytetrafluoroethylene into the colloid solution, and stirring to obtain a mixed solution;
Adding nano zero-valent iron into the mixed solution, vibrating for 0.5-2 h, and performing ultrasonic treatment for 10-25 min.
6. The method for producing a modified carbon-based material according to claim 1, wherein the coating of the mixed coating liquid onto the surface of the carbon-based material specifically comprises:
and coating the mixed coating liquid on the surface of the carbon-based material in an inactive atmosphere in a dripping mode.
7. A modified carbon-based material produced by the production method of a modified carbon-based material as claimed in any one of claims 1 to 6.
8. A microbial fuel cell comprising a cathode and an anode, wherein the anode is a modified carbon-based material prepared by the method for preparing a modified carbon-based material according to any one of claims 1 to 6.
9. Use of the microbial fuel cell according to claim 8 for degrading organic matter in water and/or soil.
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