CN114772704A - Carbon-based electrode modified by nano iron oxide and macroscopic size large-scale preparation method and application thereof - Google Patents
Carbon-based electrode modified by nano iron oxide and macroscopic size large-scale preparation method and application thereof Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 139
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000000813 microbial effect Effects 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000011888 foil Substances 0.000 claims abstract description 8
- 238000000197 pyrolysis Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000004744 fabric Substances 0.000 claims description 27
- -1 iron ions Chemical class 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-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 2
- 229940079593 drug Drugs 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 235000013373 food additive Nutrition 0.000 claims description 2
- 239000002778 food additive Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 6
- 230000005518 electrochemistry Effects 0.000 abstract description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 210000001723 extracellular space Anatomy 0.000 abstract description 2
- 235000013980 iron oxide Nutrition 0.000 description 58
- 210000004027 cell Anatomy 0.000 description 10
- 239000000446 fuel Substances 0.000 description 10
- 238000007667 floating Methods 0.000 description 8
- 239000004098 Tetracycline Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 235000019364 tetracycline Nutrition 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229960005091 chloramphenicol Drugs 0.000 description 3
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
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- 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
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- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
A carbon-based electrode modified by nano iron oxide and a macroscopic size large-scale preparation method and application thereof belong to the technical field of microbial electrochemistry. The macroscopic size scale preparation method comprises the following steps: (1) weighing a carbon source and an iron source, and dissolving the carbon source and the iron source in deionized water to obtain an iron oxide precursor solution; (2) and (2) cleaning the carbon-based electrode by sequentially adopting acid and deionized water, naturally drying, soaking by adopting an iron oxide precursor solution, drying, wrapping and sealing by using aluminum foil paper, and placing in a muffle furnace for heat treatment to obtain the carbon-based electrode modified by the nano iron oxide. According to the invention, the surface of the carbon-based electrode is modified with the ferric oxide nano material, the electron transfer efficiency between the electrode and the microbial extracellular space is improved, the preparation process is simple, the ferric oxide and the surface of the electrode are tightly combined under the action of the carbon source under the high-temperature pyrolysis condition, the obtained electrode with a stable structure improves the electrochemical performance of microbial electrochemistry, promotes the enrichment of functional microbes, and enhances the removal effect of pollutants in the polluted water body.
Description
Technical Field
The invention belongs to the technical field of microbial electrochemistry, and particularly relates to a carbon-based electrode modified by nano iron oxide and a macroscopic size large-scale preparation method and application thereof.
Background
Microbial Electrochemical Technology (MET) is a novel water treatment Technology, and shows great application potential in water ecological remediation by virtue of the self-sustained operation characteristics and flexible construction mode of energy. At present, a Microbial Electrochemical System (MES) is difficult to be applied in a large scale in practical engineering, and is mainly limited by low efficiency of electron transfer between an electrode and a microorganism, so that the remediation efficiency of a polluted water body is low. The existing research shows that the electrode material is modified by using some nano materials, so that the enrichment of electroactive microorganisms can be promoted, and the electron transfer efficiency between the electrode and the microorganisms can be obviously improved.
The carbon material is one of the most widely applied electrode materials in the MES system by virtue of the advantages of good conductivity, high biocompatibility and environmental friendliness. Fe2O3And Fe3O4The carbon-based material modified by the iso-iron oxides can effectively improve the electrochemical performance of MES, and promote the extracellular electron transfer between microorganisms and electrodes, thereby improving the removal efficiency of the system to organic matters. Meanwhile, the iron oxide material widely exists in nature, has the characteristic of environmental friendliness, is often applied to MES coupled with ecological restoration technologies such as plant microbial fuel cells and constructed wetland microbial fuel cells, has a remarkable reinforcing effect on removal of organic matters, nitrogen, phosphorus and other pollutants in water and bottom sludge, and improves restoration efficiency of the water and the bottom sludge. The iron oxide modified electrode is mainly prepared by a hydrothermal method, a binder coating method and a pyrolysis method, wherein the size of the electrode prepared by the hydrothermal method is usually in the centimeter level and cannot meet the requirement of engineering on the size of the electrode; the use of the binder brings certain environmental risk problems in the water ecological restoration. And the iron oxide can be modified on the surface of the electrode in situ through a pyrolysis method, the risk of introducing organic matters into a water body is avoided, and meanwhile, the large-scale preparation of the electrode with the engineering size (meter size) can be realized. The carbon material electrode has low repair efficiency when being used in a microbial electrochemical system, and the nano material modified electrode for improving repair efficiency is difficult to prepare in a macroscopic scale. Therefore, the carbon-based electrode modified by the iron oxide prepared by the pyrolysis method can improve the running performance of MES and is suitable for restoring water ecology.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide a method for preparing iron oxide modified carbon-based electrodes in a large scale, and the method is applied to the performance enhancement of a microbial electrochemical system, solves the problem that the performance of the microbial electrochemical system is limited by the low efficiency of electron transfer between the electrodes and microbes, and realizes the application of the enhanced microbial electrochemical system in water ecological restoration. Specifically, the iron oxide nanoparticles are modified on the carbon-based electrode in situ through a dipping pyrolysis method, and the preparation and application of the carbon-based electrode applied to engineering level (meter-level size) are realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a macroscopic size large-scale preparation method of a carbon-based electrode modified by nano iron oxide is characterized by comprising the following steps:
(1) weighing a carbon source and an iron source, and dissolving the carbon source and the iron source in deionized water to obtain an iron oxide precursor solution;
(2) and (2) cleaning a carbon-based electrode by sequentially using acid and deionized water, naturally drying, soaking the carbon-based electrode by using the iron oxide precursor solution obtained in the step (1), drying, wrapping and sealing by using aluminum foil paper, and placing the aluminum foil paper in a muffle furnace for heat treatment to obtain the carbon-based electrode modified by the nano iron oxide.
The preparation method is characterized in that the iron source in the step (1) comprises FeCl2·4H2O，FeCl3·6H2O，Fe(NO3)3·9H2O，Fe(NO3)·6H2O,Fe2(SO4)3，FeSO4·6H2At least one of O.
The preparation method is characterized in that the carbon source in the step (1) comprises at least one of chitosan, polyethylene glycol, glucose and polyvinylpyrrolidone.
The preparation method is characterized in that in the step (1), the concentration of a carbon source of the iron oxide precursor solution calculated by carbon is 10-40 g/L, the concentration of an iron source of the iron oxide precursor solution calculated by iron ions is 5-15 g/L, and the molar ratio of the iron source calculated by iron ions to carbon in the carbon source is 1: 1-8.
The preparation method is characterized in that the carbon-based electrode in the step (2) comprises at least one of carbon cloth, carbon brush and carbon felt, and the acid comprises one or more of hydrochloric acid, sulfuric acid and nitric acid.
The preparation method is characterized in that the acid cleaning time in the step (2) is 10-60 min, the soaking time is 1-5 h, and the drying temperature is 10-80 ℃.
The preparation method is characterized in that the pH value of acid and deionized water in the step (2) is 4-7, and the heat treatment conditions are as follows: the pyrolysis temperature is 300-700 ℃, the heating rate is 1-20 ℃/min, and the time is 1-5 h.
A carbon-based electrode modified by nano iron oxide is characterized by being prepared by any one of the preparation methods. The carbon-based electrode modified by the nano iron oxide is applied to being used as a cathode and/or an anode of a microbial electrochemical system.
The constructed microbial electrochemical system is any one of a single-chamber microbial fuel cell, a double-chamber microbial fuel cell, a sediment microbial fuel cell, an artificial wetland coupling microbial electrochemical system and an ecological floating island coupling microbial electrochemical system. The constructed microbial electrochemical system has the action range from millilitre pollutant degradation of laboratory experiments to the remediation of polluted water bodies with tens of thousands of square meters for engineering application.
The application of the carbon-based electrode modified by the nano iron oxide in ecological restoration of polluted water bodies;
the pollutant in the polluted water body comprises at least one of nitrogen, phosphorus, food additives, organic synthetic raw materials, medicines, pesticides or dyes.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method is simple in preparation process, and the iron oxide nano material can be uniformly modified on the surface of the carbon-based electrode.
The iron oxide modified carbon-based electrode prepared by the method obviously improves the electrochemical efficiency of a microbial electrochemical system and improves the pollutant removal efficiency.
The invention can be suitable for large-scale carbon-based electrodes, large-scale production and preparation, and is suitable for the efficiency and application of a microbial electrochemical system in water ecological restoration. According to the invention, the surface of the carbon-based electrode is modified with the ferric oxide nano material, the electron transfer efficiency between the electrode and the microbial extracellular space is improved, the preparation process is simple, the ferric oxide and the surface of the electrode are tightly combined under the carbon source under the high-temperature pyrolysis condition, the obtained electrode with a stable structure improves the electrochemical performance of microbial electrochemistry, promotes the enrichment of functional microbes, enhances the removal effect of pollutants in the polluted water body, and has great engineering application value.
Drawings
FIG. 1 is a schematic representation of the utilization of FeCl3·6H2O is an iron source to obtain an iron oxide modified carbon cloth morphology structure;
FIG. 2 is a schematic representation of the utilization of FeCl3·6H2O is an iron source to obtain an iron oxide modified carbon brush morphology structure;
FIG. 3 shows the utilization of Fe (NO)3)3·6H2O is the carbon cloth morphology structure modified by the iron oxide obtained by the iron source;
FIG. 4 shows the utilization of Fe (NO)3)3·6H2O is the carbon brush shape structure modified by the iron oxide obtained by the iron source;
FIG. 5 shows the effect of the ecological floating island coupled microbial electrochemical system constructed with iron oxide modified electrodes on the removal of chloramphenicol;
FIG. 6 shows the effect of an ecological floating island coupled microbial electrochemical system constructed with iron oxide modified electrodes on the removal of tetracycline;
fig. 7 is a power density plot for an engineering scale ecological floating island coupled microbial fuel cell system.
Detailed Description
The invention will be further illustrated by the following figures and examples.
Example 1:
a macroscopic size large-scale preparation method of a carbon-based electrode modified by nano iron oxide is completed according to the following steps:
adding FeCl to the solvent3·6H2O and polyvinylpyrrolidone (PVPK30) are fully dissolved to obtain an iron oxide precursor solution;
the concentration of an iron source (calculated by iron ions) in the iron oxide precursor solution is 100 mM;
the concentration of the carbon source in the iron oxide precursor solution is 20 g/L;
second, high temperature heat treatment of the electrode
Fully cleaning the carbon cloth by using 10 percent hydrochloric acid and deionized water in sequence, and fully soakingAnd (5) moistening the precursor solution prepared in the step (I) and fully drying. Wrapping and sealing the dipped and dried carbon cloth by using aluminum foil paper, putting the wrapped and sealed carbon cloth into a muffle furnace, and performing heat treatment to obtain the carbon cloth modified by the nano iron oxide, which is marked as FeCl3-a carbon cloth.
The temperature of the heat treatment is 500 ℃, the heating rate is 10 ℃/min, and the time of the heat treatment is 3 h.
As shown in fig. 1, the morphology structure and surface element analysis of the carbon cloth modified with iron oxide obtained in the first embodiment are shown, and the iron oxide nano-material modified on the surface of the carbon cloth is uniformly distributed on the surface of the carbon cloth.
Example 2:
a macroscopic size large-scale preparation method of a carbon-based electrode modified by nano iron oxide is completed according to the following steps:
adding FeCl to the solvent3·6H2Fully dissolving O and polyvinylpyrrolidone (PVPK30) to obtain an iron oxide precursor solution;
the concentration of an iron source (calculated by iron ions) in the iron oxide precursor solution is 100 mM;
the concentration of the carbon source in the iron oxide precursor solution is 20 g/L;
second, high temperature heat treatment of the electrode
And (4) fully cleaning the carbon brush by using 10% hydrochloric acid and deionized water in sequence, fully soaking the carbon brush in the precursor solution prepared in the step (I), and fully drying. Wrapping and sealing the dipped and dried carbon brush by using aluminum foil paper, putting the carbon brush into a muffle furnace, and carrying out heat treatment to obtain the carbon brush modified by the nano iron oxide, and marking the carbon brush as FeCl3-a carbon brush.
The temperature of the heat treatment is 500 ℃, the heating rate is 10 ℃/min, and the time of the heat treatment is 3 h.
As shown in fig. 2, the morphology structure and the surface element analysis of the carbon brush modified by the iron oxide prepared in the second embodiment are shown, and the iron oxide nano material is uniformly modified on the surface of the carbon brush.
Example 3:
a macroscopic size large-scale preparation method of a carbon-based electrode modified by nano iron oxide is completed according to the following steps:
adding Fe (NO) to the solvent3)3·9H2O and polyvinylpyrrolidone (PVPK30) are fully dissolved to obtain an iron oxide precursor solution;
the concentration of an iron source (calculated by iron ions) in the iron oxide precursor solution is 100 mM;
the concentration of the carbon source in the iron oxide precursor solution is 20 g/L;
secondly, high-temperature heat treatment of the electrode
And (2) fully cleaning the carbon cloth by using 10% hydrochloric acid and deionized water in sequence, fully soaking the carbon cloth in the precursor solution prepared in the step (I), and fully drying. Wrapping and sealing the dipped and dried carbon cloth by using aluminum foil paper, putting the wrapped and sealed carbon cloth into a muffle furnace, and performing heat treatment to obtain the carbon cloth modified by the nano iron oxide, which is marked as Fe (NO)3)3-a carbon cloth.
The temperature of the heat treatment is 500 ℃, the heating rate is 10 ℃/min, and the time of the heat treatment is 3 h.
As shown in fig. 3, the carbon cloth morphology structure modified by the iron oxide prepared in the third embodiment uniformly modifies the iron oxide nano material on the surface of the carbon cloth.
Example 4:
a macroscopic size large-scale preparation method of a carbon-based electrode modified by nano iron oxide is completed according to the following steps:
adding Fe (NO) to the solvent3)3·9H2Fully dissolving O and polyvinylpyrrolidone (PVPK30) to obtain an iron oxide precursor solution;
the concentration of an iron source (calculated by iron ions) in the iron oxide precursor solution is 100 mM;
the concentration of the carbon source in the iron oxide precursor solution is 20 g/L;
second, high temperature heat treatment of the electrode
And (3) fully cleaning the carbon brush by using 10% hydrochloric acid and deionized water in sequence, fully soaking the carbon brush in the precursor solution prepared in the step (I), and fully drying. Drying the impregnated solutionWrapping and sealing the carbon brush by using aluminum foil paper, putting the carbon brush into a muffle furnace, and performing heat treatment to obtain the carbon brush modified by the nano iron oxide, and marking the carbon brush as Fe (NO)3)3-a carbon cloth.
The temperature of the heat treatment is 500 ℃, the heating rate is 10 ℃/min, and the time of the heat treatment is 3 h.
As shown in fig. 4, the morphology structure of the carbon brush modified by the iron oxide prepared in the fourth embodiment is obtained, and the iron oxide nano material is uniformly modified on the surface of the carbon brush.
Example 5:
the carbon brushes and carbon cloths prepared in the examples 1 and 2 are applied to the cathode and the anode (CC-CB: carbon cloth anode and carbon brush cathode; Fe/CC-Fe/CB: iron oxide modified carbon cloth anode and iron oxide modified carbon brush cathode) of the constructed ecological floating island microbial fuel cell system respectively, and the effect evaluation of the tetracycline and chloramphenicol content in the polluted water body is carried out.
Fig. 5 shows the degradation effect of the iron oxide-modified electrode constructed by the ecological floating island-coupled microbial fuel cell system prepared in examples 1 and 2 on tetracycline, which indicates that the iron oxide-modified carbon-based electrode can improve the degradation effect on tetracycline by 61.64% in the first day, which is 28.84% higher than that of the control group; fig. 6 shows that the degradation effect of the electrode modified by iron oxide prepared in examples 1 and 2 on chloramphenicol in the first day can reach 96.88%, which is 23.74% higher than that of the control group.
Example 6:
the carbon brushes (diameter 5cm, length 1m) and carbon cloth (length 5m, width 1m) of meter scale modified by the iron oxides prepared in the examples 2 and 4 were applied to the cathode and anode of the constructed engineering scale ecological floating island coupling microbial fuel cell system, respectively, to construct the ecological floating island coupling microbial fuel cell system (CC-CB: carbon cloth anode, carbon brush cathode; Fe/CC-CB: iron oxide modified carbon cloth anode, cathode carbon brush; CC-Fe/CB: carbon cloth anode, iron oxide modified carbon brush cathode), and the electrochemical density of long-term operation was evaluated, as shown in fig. 7.
Claims (10)
1. A macroscopic scale preparation method of a carbon-based electrode modified by nano iron oxide is characterized by comprising the following steps:
(1) weighing a carbon source and an iron source, and dissolving the carbon source and the iron source in deionized water to obtain an iron oxide precursor solution;
(2) and (2) taking a carbon-based electrode, sequentially cleaning the carbon-based electrode by using acid and deionized water, naturally drying the carbon-based electrode, soaking the carbon-based electrode in the iron oxide precursor solution obtained in the step (1), drying the carbon-based electrode, wrapping and sealing the carbon-based electrode by using aluminum foil paper, and placing the carbon-based electrode in a muffle furnace for heat treatment to obtain the carbon-based electrode modified by the nano iron oxide.
2. The method according to claim 1, wherein the iron source in step (1) comprises FeCl2·4H2O，FeCl3·6H2O，Fe(NO3)3·9H2O，Fe(NO3)·6H2O，Fe2(SO4)3，FeSO4·6H2At least one of O.
3. The method according to claim 1, wherein the carbon source in the step (1) comprises at least one of chitosan, polyethylene glycol, glucose and polyvinylpyrrolidone.
4. The method according to claim 1, wherein the concentration of the carbon source in the iron oxide precursor solution in step (1) is 10g/L to 40g/L in terms of carbon, and the concentration of the iron source in the iron oxide precursor solution is 5g/L to 15g/L in terms of iron ions.
5. The method according to claim 1, wherein the carbon-based electrode in the step (2) comprises at least one of a carbon cloth, a carbon brush and a carbon felt, and the acid comprises one or a combination of hydrochloric acid, sulfuric acid and nitric acid.
6. The method according to claim 1, wherein the acid cleaning in step (2) is performed for 10-60 min, the soaking time is 1-5 h, and the drying temperature is 10-80 ℃.
7. The preparation method according to claim 1, wherein the pH of the acid and the deionized water in the step (2) is 4 to 7, and the heat treatment conditions are as follows: the pyrolysis temperature is 300-700 ℃, the heating rate is 1-20 ℃/min, and the time is 1-5 h.
8. A carbon-based electrode modified by nano iron oxide, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. Use of the nano-iron oxide modified carbon-based electrode of claim 8 as a cathode and/or anode of a microbial electrochemical system.
10. The application of the carbon-based electrode modified by nano iron oxide as claimed in claim 8 in the ecological restoration of polluted water;
the pollutant in the polluted water body comprises at least one of nitrogen, phosphorus, food additives, organic synthetic raw materials, medicines, pesticides or dyes.
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| CN109713328A (en) * | 2019-02-19 | 2019-05-03 | 东华大学 | A kind of carbon felt load iron oxide electrode and its preparation and application |
| CN111613802A (en) * | 2020-06-10 | 2020-09-01 | 中国船舶重工集团公司第七二五研究所 | Modified carbon brush electrode and preparation method thereof |
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| CN109713328A (en) * | 2019-02-19 | 2019-05-03 | 东华大学 | A kind of carbon felt load iron oxide electrode and its preparation and application |
| CN111613802A (en) * | 2020-06-10 | 2020-09-01 | 中国船舶重工集团公司第七二五研究所 | Modified carbon brush electrode and preparation method thereof |
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