CN115478364B - Preparation method and application of self-supporting electrospun carbon nanofiber composite membrane - Google Patents
Preparation method and application of self-supporting electrospun carbon nanofiber composite membrane Download PDFInfo
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Classifications
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- D—TEXTILES; PAPER
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a preparation method and application of a self-supporting electrospun carbon nanofiber composite membrane, wherein an MOF material and PAN spinning solution are subjected to electrostatic spinning, pre-oxidation and carbonization processes to prepare the composite membrane in situ, and the composite membrane has rich pore structures, high catalytic activity and microbial compatibility, and can effectively promote MFC power generation and sewage treatment efficiency.
Description
Technical Field
The invention belongs to the technical field of composite membrane material preparation, and particularly relates to a preparation method and application of a self-supporting electrospun carbon nanofiber composite membrane.
Background
Microbial Fuel Cells (MFCs) are a cost-effective system for wastewater treatment and energy recovery that can convert chemical energy in wastewater into electrical energy through microbial metabolism. However, the power generation performance of MFC is still not satisfactory, wherein the power generation performance of MFC is affected by the reactor structure, electrode materials, and electrolyte. The performance of MFC anodes, an important place for attachment and collection of electricity by the electrogenerating bacteria, greatly affects electrode electrocatalysis and bacterial Extracellular Electron Transfer (EET) rates, and is one of the key factors determining the overall performance of MFC. Therefore, development of a high-performance anode having a high specific area, a porous structure, good conductivity, and biocompatibility is imperative to improve the power generation performance of MFC.
Today, researchers have explored advanced anode materials with high conductivity, porosity, and biocompatibility to improve the electrogenic efficiency of MFCs. Metal-based materials (e.g., stainless steel mesh) are often used for MFC anodes, with high electrical conductivity and electrochemical properties. However, corrosion and low durability have limited their application to a large extent. Carbon-based materials, such as carbon cloth, carbon brush, carbon paper, etc., have good mechanical properties, durability and biocompatibility, but their electrical conductivity and electrochemical catalytic properties are not ideal. Nanomaterial (e.g., carbon nanotubes, graphene, nano-metal composites, etc.) modified electrodes generally achieve excellent electron transfer and electrocatalytic capabilities, with more bacterial adhesion, lower electron transfer resistance, and higher EET rates than conventional electrodes. However, they often require modification to the electrode surface with a conductive medium (e.g., carbon black) and a conductive binder (e.g., nafion), which often results in reduced catalyst conductivity and also suffers from reduced anode porosity due to nanomaterial aggregation. In addition, conductive adhesives are expensive, further affecting the further use of the material. Therefore, it is important to develop anode materials that are self-supporting, economical, porous, highly catalytic and stable.
Electrospun Carbon Nanofibers (CNF) have many unique characteristics, such as high specific area and graded porosity. CNF can be easily processed into 3D structures and decorated on electrodes without the need for conductive fillers like carbon black. Polyacrylonitrile (PAN) is the most widely used CNF precursor because of its high carbon content, ease of formation of uniform nanofibers and good commercial viability. Previous studies have shown that 3D CNFs attract electroactive biofilm formation on the MFC anode and achieve 21A/m 2 Is provided. In addition, chua et al manufactured a composition using CNF and carbonNanotube modified high performance MFC anode (highest power density 1.7W/m) 3 ). However, these studies all require modification of the nanomaterial to the electrode surface by means of a binder, affecting the pore structure of the nanofiber itself. These stable pore structures are critical to the efficiency of electron and substrate transport between the anode surface microorganisms and the electrode, and to ensure stability of the anode biofilm. Thus, the preparation of binder-free self-supporting PAN carbon nanofiber electrodes is important for forming good mechanical properties, stability and rich internal pore results.
Metal-organic frameworks (MOFs) are mainly crystalline porous materials with periodic network structures formed by self-assembly of transition metal ions and organic ligands, and have been receiving considerable attention in recent years for applications in environmental remediation, catalysis, energy storage, and the like. Compared with the traditional porous material, the MOFs have the main advantage that the regulation and control of the catalytic performance, the structure and the porosity can be easily realized by adjusting the metal types and the organic connecting agent. Conventional MOFs are composed of organic linkers and metal centers, severely limiting their application due to poor carrier mobility and low conductivity. The thermal conversion of MOFs to carbon or metal carbon materials is a common method of improving their conductivity. The porous carbon material obtained after carbonization of MOFs can effectively improve the active site and the charge transmission path of the material. However, the scattered MOFs have weak interaction force and electric conductivity among carbonized particles, cannot meet application requirements, and are an effective way for improving the electron transmission and catalytic efficiency of the MOFs when the MOFs are introduced to the surface of the one-dimensional carbon nanofiber. Meanwhile, MOFs are introduced into the electrospun nanofiber in an in-situ blending or in-situ growth mode, and no additional adhesive is needed, so that the efficient and stable catalytic performance of the MOFs is ensured to be not influenced by an inactive adhesive. The introduction of MOFs can not only further improve the specific surface area and the catalytic performance of CNFs, but also compound various elements (such as Fe, N, S and the like) which are beneficial to improving the EET efficiency of bacteria, and can be used for preparing high-performance MFC anode materials based on CNFs. Based on the preparation method, the self-supporting electrospun carbon nanofiber composite electrode is obtained by regulating and controlling the preparation conditions of the PAN carbon nanofiber composite MOF material, so that the power generation efficiency and the sewage treatment efficiency of the MFC are enhanced.
At present, many researches have been developed around the electrospun carbon nanofiber modified electrode, but the electrode modification is mostly performed after the prepared carbon nanofibers are crushed, and the porosity between the nanofibers cannot be ensured. Meanwhile, the additionally added expensive conductive adhesive reduces the catalytic and conductive properties of the material and influences the overall catalytic efficiency of the carbon nanofiber. Carbon nanofibers are advantageous in terms of scale, however, the catalytic efficiency of pure carbon materials is still insufficient, and the addition of nano metal materials is needed to be considered for further improvement of the efficiency. The MOF has the advantages of high specific surface area, controllable structure, catalytic performance and the like, and has the prior advantage of strengthening the catalytic performance of the electrode material. Modification of MOFs alone to the electrode surface necessarily results in serious material aggregation and other problems, while traditional MOFs are poor in conductivity and require improvement in conductivity through carbonization. Currently, researchers combine MOFs with electrospun nanofibers by hot pressing, blending, in-situ growth, and the like, but there are few applications in MOF composite electrospun carbon nanofibers and performance optimization in MFC anodes. In addition, the application of self-supporting electrospun carbon nanofiber composite electrodes on MFC anodes has been reported very rarely.
Disclosure of Invention
The invention aims to obtain a self-supporting carbon nanofiber composite membrane electrode material, which has rich pore structures, high catalytic activity and microbial compatibility and promotes the efficiency of MFC electricity generation and sewage treatment.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the self-supporting electrospun carbon nanofiber composite membrane is characterized by comprising the following steps of:
step S1: 2-amino terephthalic acid, feCl 3 ˙6H 2 O is dissolved in DMF, then the mixed solution is placed in a reaction kettle to react for a period of time, and the reaction product is cleaned and dried to obtain MOF material;
step S2: and fully stirring Polyacrylonitrile (PAN) and N, N-Dimethylformamide (DMF) according to a certain proportion to prepare spinning solution, mixing the prepared MOF material with the PAN spinning solution according to a certain doping proportion, carrying out electrostatic spinning and pre-oxidation treatment on the mixture, and carbonizing the mixture in a protective atmosphere to prepare the self-supporting electrospun carbon nanofiber composite membrane.
Further, the method further comprises the step S3: in order to rapidly obtain the electrode material with more excellent electrochemical performance and higher mechanical strength, the carbon nanofiber composite films with different layers are obtained by superposing the carbon nanofiber composite films.
Further, the PAN in the spinning solution in the step S2 accounts for 5-16wt%.
Further, the doping proportion of the MOF material in the step S2 is 1-4wt%.
Further, in the step S2, the stirring rotation speed is 100-1750rpm.
Further, at least one layer of self-supporting electrospun nanofiber composite membrane is stacked in step S3.
Further, the pre-oxidation in the step S2 is carried out at 200-300 ℃ for 1-3h.
Further, the carbonization in the step S2 is to keep the temperature at 800-1000 ℃ for 1-3 hours.
The self-supporting electrospun nanofiber composite membrane is used for electrode materials of microbial fuel cells, in particular for manufacturing anode materials.
A microbial fuel cell using a self-supporting electrospun nanofiber composite membrane as an electrode material is used for sewage treatment.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that: the high-performance self-supporting carbon nanofiber composite membrane is obtained in situ by an electrospinning method, so that the use of an adhesive and the polymerization effect of a catalyst are well avoided. And by optimizing the stirring rotation speed, the PAN content, the MOF doping amount and the number of layers of the final PAN carbonized film, the composite film has better conductivity, porosity and high catalytic activity, can obviously strengthen the power generation and pollutant degradation efficiency of the MFC, and is beneficial to industrial mass production and popularization and use.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an electrochemical impedance spectrum of an electrospun PAN carbon nanofiber membrane obtained at different rotational speeds in example 1 of the present invention.
FIG. 2 shows the surface morphology (magnification 20,000 times) under different PAN addition amounts in example 1 of the present invention, wherein FIG. 2 (A) shows the PAN addition amount of 5wt%; FIG. 2 (B) shows the PAN addition amount of 8wt%; FIG. 2 (C) shows the PAN addition amount of 10wt%; FIG. 2 (D) shows the PAN addition amount of 12wt%; FIG. 2 (E) shows the PAN addition amount of 14wt%; fig. 2 (F) shows a PAN addition amount of 16wt%.
FIG. 3 is a cyclic voltammogram of a carbon nanofiber composite electrode with different MOF doping levels for different numbers of layers in example 2 of the present invention, wherein FIG. 3 (A) is a pure PAN film; FIG. 3 (B) is a doped 0.1gMOF-PAN composite membrane; FIG. 3 (C) is a doped 0.2gMOF-PAN composite membrane; FIG. 3 (D) is a doped 0.3g MOF-PAN composite membrane; FIG. 3 (E) is a doped 0.4gMOF-PAN composite membrane; fig. 3 (F) is a graph of the acclimated voltammograms of the carbon nanofiber composite electrode with different MOF doping amounts under two PAN membrane conditions.
Fig. 4 is a prepared self-supporting PAN carbon nanofiber composite electrode.
Fig. 5 shows MFC power density curves (a) and COD removal and coulombic efficiency (B) for different anode materials after acclimation.
FIG. 6 is a flow chart of the preparation of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
Example 1
Preparation of high-strength oriented nanofiber and PAN content optimization:
taking the addition amount of 12wt% PAN as a standard, fully mixing PAN and N, N-Dimethylformamide (DMF) to prepare spinning solution (10 g in total), and fully stirring for 24h under normal temperature. The obtained spinning solution is placed in a 10mL spinning injector, the injector is connected with a spinning needle head and then is arranged in a spinning machine, the distance between the needle head and a spinning shaft is 10cm, voltage of-2.0 kV is applied to the needle head in the spinning process, the voltage of the spinning shaft is 18kV, the advancing speed of the injector is set to be 1mL/min, the humidity is kept at about 10%, and the temperature is kept at 40 ℃. And then carrying out electrostatic spinning under different coaxial rotating speed conditions (100 rpm, 250rpm, 500rpm, 750rpm, 1000rpm, 1250rpm, 1500rpm, 1750 rpm), cutting the film into a certain size after obtaining a PAN nanofiber film, pre-oxidizing in a muffle furnace (heating rate of 1 ℃/min,250 ℃ for 1 h), and finally carbonizing in a tubular furnace (Ar gas atmosphere, heating rate of 2 ℃/min,900 ℃ for 1 h) to obtain the corresponding PAN carbon nanofiber. And (3) obtaining the PAN carbon nanofiber membrane at the optimal axis rotating speed by comparing parameters such as the film forming state, the conductivity and the like of the carbon nanofiber under different axis rotating speed conditions. As shown in fig. 1, the resistance of the electrode was minimized when the shaft speed reached 1500rpm, so 1500rpm was selected as the optimal shaft speed.
And (3) repeating the preparation process at 1500rpm, and comparing parameters such as diameter, orientation, mechanical strength, conductive performance and the like of the PAN carbon nanofiber obtained under different PAN adding ratios (5 wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16 wt%) to obtain the optimal PAN adding ratio. The appearance of the PAN nanofiber is shown in fig. 2, the diameter of the fiber is uneven when the PAN addition amount is lower than 10wt%, the pore size distribution difference is large, and when the PAN addition amount is higher than 10wt%, the fiber presents orientation regular distribution, but obvious beading appears on the surface of the fiber after the addition amount is higher than 14wt%. Therefore, the morphology and the electrochemical performance are comprehensively considered, and finally, the addition amount of 10wt% of PAN is adopted as the optimal addition amount.
Example 2
Preparing a self-supporting carbon nanofiber composite membrane electrode material:
225mg of 2-amino terephthalic acid, 675mg of FeCl are first reacted 3 ˙6H 2 O was dissolved in 60mL of DMF and allowed to dissolve well. Then the mixed solution is put into a reaction kettle to be subjected to hydrothermal reaction at the temperature of 110 ℃ for 10 hours, 15 hours, 20 hours and 24 hours, and then is put into an oven after being washed by DMF, ethanol and water in sequenceAnd (5) drying to obtain the MOF material. The MOF material was found to be more uniform, of a suitable size and with less impurities when the reaction time was 20 hours, as observed by scanning electron microscopy.
Mixing the prepared MOF material with 10wt% PAN (10 g) spinning solution, adjusting the doping proportion of MOF (doping amount of MOF is 0.1g (1 wt%), 0.2g (2 wt%), 0.3g (3 wt%), and 0.4g (4 wt%), then carrying out electrostatic spinning process under the optimal condition, pre-oxidizing in a muffle furnace (heating rate is 1 ℃/min, and maintaining at 250 ℃ for 1 h), and finally carbonizing in a tubular furnace (Ar gas atmosphere, heating rate is 2 ℃/min, and maintaining at 900 ℃ for 1 h), thereby obtaining PAN nanofibers with different MOF doping amounts. As shown in fig. 3F, the electrochemical performance is significantly improved after the PAN carbon nanofiber is compounded with the MOF, and the electrochemical performance shows an overall trend of increasing before decreasing, wherein the electrochemical performance is highest when the doping amount of the MOF is 0.3g (3 wt%).
The multilayer PAN composite carbonized film is obtained by superposing carbon nanofiber composite films (1 layer, 2 layers and 3 layers) with different layers. As shown in fig. 3, the PAN composite membranes with different MOF doping amounts show an overall trend of increasing and decreasing electrochemical performance when different layers are stacked, wherein the electrochemical performance is optimal when the layers are 2 layers. Figure 4 shows the morphology of the carbon nanofiber composite membrane after overall performance optimization.
Example 3
MFC reactor construction and application:
the MFC anode material is selected from: according to the above several optimization strategies, the performance of the double-layer PAN carbonized film, wherein the MOF doping ratio of the double-layer PAN carbonized film is 0.1g (1 wt%) and the composite double-layer carbonized film is 0.3g (1 wt%) in an MFC anode is examined, and the influence of different MOF doping amounts on the power generation of the MFC and the sewage treatment is explored.
Construction and domestication of the MFC reactor: the bipolar chamber organic glass MFC reactor is adopted, the cathode chamber and the anode chamber are separated by a proton exchange membrane, the external dimension of the single-chamber reactor is 6 multiplied by 7cm, the interior of the single-chamber reactor is cylindrical, and the effective volume of the single chamber is 108mL. The cathode was made of 2X 2cm carbon cloth, and was treated with 100mM potassium ferricyanide and 50mM phosphate buffer solution (PBS, 11.55g/L Na 2 HPO 4 ·12H 2 O、2.77g/L NaH 2 PO 4 ·2H 2 O) as catholyte. The anode material adopts a carbon nanofiber electrode with the length of 2 multiplied by 3cm, and the anode liquid comprises 0.41g/L sodium acetate, 50mM PBS, 0.13g/L KCl and 0.13g/L NH 4 Cl, vitamins and mineral elements. The MFC anolyte needs to be inoculated with 1mL of sludge (secondary sedimentation tank sludge of a sewage treatment plant) when the anolyte is changed in the domestication stage, the domestication stage takes 4 days as a period, and new anolyte needs to be subjected to nitrogen blowing to remove air in the solution, so that the anaerobic state of the anolyte is ensured. And the external circuit of the MFC is connected with a resistor of 1kΩ, and the voltages at two ends of the resistor are collected through a multichannel data collection system and used as the output voltage of the system. After the MFC system voltage reached the maximum and stabilized for 2 cycles, it was shown that the MFC system had stabilized. The change in the output voltage of the MFC was then observed, and when the voltage was below 0.05V, the anolyte and catholyte were replaced.
MFC electricity generation and sewage treatment efficiency analysis: in a stable MFC system after the acclimation is finished, detecting COD removal rate, coulomb efficiency and the like in the system, detecting electrochemical properties of electrodes and suspension after the acclimation of the MFC is finished, evaluating electron transfer efficiency and existing electron transfer intermediaries in the surfaces of the electrodes and the suspension by means of an electrochemical workstation test cyclic voltammogram, an electrochemical impedance spectrum and a current-time curve, comparing EET rates of different systems, and analyzing a mechanism of the composite material for strengthening the electricity generation efficiency of the MFC by combining microbiological molecular means such as a microbiological protein test, a high-throughput test, a metagenome and the like. As shown in FIG. 5, when the carbon nanofiber composite using 0.1g MOF has optimal electricity generation efficiency, COD removal efficiency and coulombic efficiency, and electricity generation amount is as high as 2286.9mW/m 2 Compared with the traditional carbon-based electrode (such as carbon cloth and carbon felt), the self-supporting carbon nanofiber composite electrode has great promotion, shows that the self-supporting carbon nanofiber composite electrode is effective for strengthening MFC power generation and sewage treatment, and has a certain application prospect. The preparation flow of the invention is shown in FIG. 6 for clarity of the overall process of the invention.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (6)
1. A preparation method of a self-supporting electrospun carbon nanofiber composite membrane is characterized by comprising the following steps of: the method comprises the following steps:
step S1: 2-amino terephthalic acid, feCl 3 ˙6H 2 O is dissolved in DMF, then the mixed solution is put into a reaction kettle for hydrothermal reaction for a period of time, and the reaction product is cleaned and dried to obtain MOF material;
step S2: fully stirring polyacrylonitrile and N, N-dimethylformamide according to a certain proportion to prepare spinning solution, mixing the prepared MOF material with the spinning solution according to a certain doping proportion, carrying out electrostatic spinning and pre-oxidation treatment on the mixture, and carbonizing the mixture in a protective atmosphere to prepare the self-supporting electrospun carbon nanofiber composite membrane;
step S3: superposing the carbon nanofiber composite membrane to obtain a self-supporting electrospun carbon nanofiber composite membrane superposed by 2 layers of carbon nanofiber composite membranes;
in the step S2, the proportion of polyacrylonitrile in the spinning solution is 5-16wt% and the doping proportion of the MOF material is 1-4wt%;
the carbonization in the step S2 is to keep the temperature at 800-1000 ℃ for 1-3h.
2. The method according to claim 1, characterized in that: in the step S2, the stirring rotation speed is 100-1750rpm.
3. The method according to claim 1, characterized in that: the pre-oxidation in the step S2 is carried out at 200-300 ℃ for 1-3h.
4. A self-supporting electrospun nanofiber composite membrane prepared by the method of any one of claims 1-3.
5. Use of the self-supporting electrospun nanofiber composite membrane according to claim 4 for the manufacture of anode materials for microbial fuel cells.
6. The use of the anode material of claim 5 in microbial fuel cell energy recovery and sewage treatment.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007050460A2 (en) * | 2005-10-25 | 2007-05-03 | Inorganic Specialists, Inc. | Carbon nanofiber paper and applications |
| CN102576877A (en) * | 2009-08-10 | 2012-07-11 | ***纪念研究院 | Self assembled multi-layer nanocomposite of graphene and metal oxide materials |
| KR20160083321A (en) * | 2014-12-30 | 2016-07-12 | 현대자동차주식회사 | Multilayer electrode for polymer electrolyte membrane fuel cell and method for preparing the same |
| CN105829593A (en) * | 2013-12-27 | 2016-08-03 | 东丽株式会社 | Carbon fiber nonwoven fabric, production method for carbon fiber nonwoven fabric, and nonwoven fabric of carbon fiber precurser fibers |
| KR20190091615A (en) * | 2018-01-29 | 2019-08-07 | 한국세라믹기술원 | Piezoelectric ceramic material for Macro Fiber Composite |
| EP3539644A1 (en) * | 2018-03-13 | 2019-09-18 | Gaznat SA | Graphene membrane filter for gas separation |
| CN111081995A (en) * | 2019-11-07 | 2020-04-28 | 东北大学 | Preparation method of metal oxide carbon nanofiber electrode material based on MOFs derivation |
| CN111354929A (en) * | 2019-12-30 | 2020-06-30 | 中国计量大学 | Preparation of carbon fiber-tin disulfide electrode material with multilayer core-shell structure |
| CN113005568A (en) * | 2021-02-24 | 2021-06-22 | 北京科技大学 | Method for preparing porous Co/C nano fiber by PVP (polyvinyl pyrrolidone) assisted ZIF (zinc-doped carbon) growth |
| CN113054207A (en) * | 2021-03-02 | 2021-06-29 | 北京科技大学 | Preparation method of metal salt assisted rapid growth metal organic framework derivative |
| CN113178606A (en) * | 2021-04-19 | 2021-07-27 | 中山大学 | Flexible wearable composite energy collecting device and manufacturing method and application thereof |
| CN114447291A (en) * | 2021-12-22 | 2022-05-06 | 西安理工大学 | Self-supporting ferric trifluoride-carbon nanofiber cathode material and preparation method thereof |
| CN115000343A (en) * | 2022-05-30 | 2022-09-02 | 三峡大学 | Preparation method of flexible double-layer self-supporting electrode |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5648785B2 (en) * | 2010-07-29 | 2015-01-07 | 日清紡ホールディングス株式会社 | Fuel cell electrode |
| KR20220067896A (en) * | 2020-11-18 | 2022-05-25 | 현대자동차주식회사 | Carbon metal-organic framework composite, manufacturing method thereof, and lithium air battery comprising the same |
-
2022
- 2022-09-26 CN CN202211173442.7A patent/CN115478364B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007050460A2 (en) * | 2005-10-25 | 2007-05-03 | Inorganic Specialists, Inc. | Carbon nanofiber paper and applications |
| CN102576877A (en) * | 2009-08-10 | 2012-07-11 | ***纪念研究院 | Self assembled multi-layer nanocomposite of graphene and metal oxide materials |
| CN105829593A (en) * | 2013-12-27 | 2016-08-03 | 东丽株式会社 | Carbon fiber nonwoven fabric, production method for carbon fiber nonwoven fabric, and nonwoven fabric of carbon fiber precurser fibers |
| KR20160083321A (en) * | 2014-12-30 | 2016-07-12 | 현대자동차주식회사 | Multilayer electrode for polymer electrolyte membrane fuel cell and method for preparing the same |
| KR20190091615A (en) * | 2018-01-29 | 2019-08-07 | 한국세라믹기술원 | Piezoelectric ceramic material for Macro Fiber Composite |
| EP3539644A1 (en) * | 2018-03-13 | 2019-09-18 | Gaznat SA | Graphene membrane filter for gas separation |
| CN111081995A (en) * | 2019-11-07 | 2020-04-28 | 东北大学 | Preparation method of metal oxide carbon nanofiber electrode material based on MOFs derivation |
| CN111354929A (en) * | 2019-12-30 | 2020-06-30 | 中国计量大学 | Preparation of carbon fiber-tin disulfide electrode material with multilayer core-shell structure |
| CN113005568A (en) * | 2021-02-24 | 2021-06-22 | 北京科技大学 | Method for preparing porous Co/C nano fiber by PVP (polyvinyl pyrrolidone) assisted ZIF (zinc-doped carbon) growth |
| CN113054207A (en) * | 2021-03-02 | 2021-06-29 | 北京科技大学 | Preparation method of metal salt assisted rapid growth metal organic framework derivative |
| CN113178606A (en) * | 2021-04-19 | 2021-07-27 | 中山大学 | Flexible wearable composite energy collecting device and manufacturing method and application thereof |
| CN114447291A (en) * | 2021-12-22 | 2022-05-06 | 西安理工大学 | Self-supporting ferric trifluoride-carbon nanofiber cathode material and preparation method thereof |
| CN115000343A (en) * | 2022-05-30 | 2022-09-02 | 三峡大学 | Preparation method of flexible double-layer self-supporting electrode |
Non-Patent Citations (1)
| Title |
|---|
| 阳极碳纸叠加层数对微生物燃料电池产电性能的影响;钟丽萍等;化工新型材料;第43卷(第3期);126-129 * |
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