WO2022111736A1 - Fe/fe₃c-embedded n-doped carbon composite material, preparation method for same, and applications thereof in microbial fuel cell - Google Patents

Fe/fe₃c-embedded n-doped carbon composite material, preparation method for same, and applications thereof in microbial fuel cell Download PDF

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WO2022111736A1
WO2022111736A1 PCT/CN2021/136209 CN2021136209W WO2022111736A1 WO 2022111736 A1 WO2022111736 A1 WO 2022111736A1 CN 2021136209 W CN2021136209 W CN 2021136209W WO 2022111736 A1 WO2022111736 A1 WO 2022111736A1
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composite material
carbon composite
doped carbon
embedded
intercalated
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French (fr)
Chinese (zh)
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路建美
陈冬赟
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苏州大学
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • 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
    • H01M2004/8684—Negative 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

Definitions

  • the invention belongs to the technology of microbial fuel cells, and relates to Fe/Fe 3 C intercalated N-doped carbon composite materials, a preparation method thereof, and the application of the composite materials as cathode catalysts in microbial fuel cells.
  • Microbial fuel cell uses the metabolism of microorganisms to directly convert chemical energy in organic wastewater into electrical energy, so as to generate electricity while removing pollutants in water. It is a zero pollution and low energy consumption. New sustainable energy technologies.
  • Single-chamber air cathode MFC is a type of MFC. Compared with dual-chamber MFC, its structure is simple, the electrode distance is short, the footprint is small, no proton exchange membrane is required, and the cathode mass transfer rate is improved, thereby reducing operating costs and improving The power generation capacity and power output of the MFC.
  • the cathodic oxygen reduction reaction (ORR) directly affects the power generation performance of the MFC.
  • the purpose of the present invention is to introduce and provide a preparation method of Fe/Fe 3 C intercalated N-doped carbon composite material and use it as a cathode catalyst to generate electricity in a microbial fuel cell.
  • An Fe/Fe 3 C embedded N-doped carbon composite material comprising the following steps: calcining carbon-based materials, nitrogen-containing polysaccharides, iron salts, and organic acids after solvothermal reaction to obtain Fe/Fe 3 C Embedded N-doped carbon composites.
  • a microbial fuel cell uses Fe/Fe 3 C intercalated N-doped carbon composite material as cathode catalyst, and the preparation method of Fe/Fe 3 C intercalated N-doped carbon composite material includes the following steps: carbon-based material, nitrogen-containing polysaccharide , iron salt and organic acid are calcined after solvothermal reaction to obtain Fe/Fe 3 C intercalated N-doped carbon composite material.
  • carbon-based materials and nitrogen-containing polysaccharides are dispersed in a solvent, and then iron salts and organic acids are added to obtain Fe/GO/CS composites through solvothermal reaction; the obtained Fe/GO/CS composites are placed in an inert gas atmosphere.
  • the MOF-derived Fe/Fe 3 C intercalated N-doped carbon composite (Fe/Fe 3 C/NC) was obtained by calcination at medium and high temperature; the Fe/Fe 3 C intercalated N-doped carbon composite was used as the cathode catalyst to assemble the MFC reactor , to obtain a microbial fuel cell to generate electricity.
  • the carbon-based material is graphene oxide or carbon nanotubes;
  • the nitrogen source is one of chitosan, melamine and urea;
  • the iron salt is ferric chloride hexahydrate (FeCl 3 ⁇ 6H 2 O);
  • the organic The acid was terephthalic acid;
  • the solvent was N,N-dimethylformamide (DMF).
  • the mass ratio of carbon-based material, nitrogen source, iron salt, and organic acid is 0.03: (0.05-0.3): 0.675: 0.207; the preferred mass ratio is 0.03: 0.1: 0.675: 0.207.
  • the temperature of the solvothermal reaction is 90 to 160° C. and the time is 5 to 40 hours, and the preferred temperature of the solvothermal reaction is 110° C. and the time is 20 hours.
  • the calcination temperature is 600-900°C
  • the calcination time is 1-4 hours
  • the heating rate is 5°C/min
  • the preferred calcination temperature is 800°C
  • the calcination time is 2 hours.
  • the invention adopts graphene oxide or carbon nanotube with good electrical conductivity as the substrate, uses ferric chloride hexahydrate and terephthalic acid as the precursor to provide a multi-faceted frame structure, and uses chitosan, melamine and urea as the precursors.
  • the invention further discloses the application of the above-mentioned Fe/Fe 3 C intercalated N-doped carbon composite material as a cathode catalyst in a microbial fuel cell, which can generate electricity.
  • the microbial fuel cell uses the Fe/Fe 3 C intercalated N-doped carbon composite material as the cathode catalyst, and specifically the Fe/Fe 3 C intercalated N-doped carbon composite material is coated on the conductive substrate as the cathode.
  • the activated sludge and anolyte are assembled to obtain a microbial fuel cell.
  • Fe/Fe 3 C derived from quantitative MOF after calcination treatment is embedded in the N-doped carbon composite material Fe/Fe 3 C/NC as the cathode catalyst, and the MFC is assembled.
  • the reactor is added with activated sludge and anolyte, and an external 1000 ⁇ resistor is used to generate electricity.
  • the data collector is used to collect data every 10 minutes, and the anolyte is replaced when the voltage drops below 20 mV.
  • the Fe/Fe 3 C intercalated N-doped carbon composite material disclosed in the present invention has a larger specific surface area and a mesoporous structure; Fe/Fe 3 C is uniformly supported in carbon nanotubes and graphene , a larger specific surface area can provide more active sites and mass transfer channels, which is beneficial to improve the performance of oxygen reduction reaction, and is a good catalyst material.
  • chitosan a cheap, environmentally friendly, renewable, and naturally abundant biomass material, is used as the N source to perform nitrogen doping on the material, increasing the The content of pyridine-N and graphite-N in the material is increased, and the performance of the catalyst for oxygen reduction reaction is further improved.
  • the present invention obtains electricity production performance and power output comparable to other microbial fuel cells with higher catalyst loading by reducing the cathode catalyst loading.
  • the present invention overcomes the shortcomings of traditional use of platinum (Pt) and platinum-based nanomaterials as cathode materials, high cost, easy to be poisoned and biofilm pollution, resulting in rapid performance decay and poor durability.
  • the iron-based material with low price and good stability at the same time, the biomass material chitosan is used for nitrogen doping, and Fe/Fe 3 C/NC is used as the cathode catalyst with high oxygen reduction activity, and the 4-electron reduction path is carried out, and the product is harmless
  • the water is environmentally friendly, which greatly reduces the cost of the catalyst. At the same time, the cost of the catalyst is reduced, and the output voltage and power density of the MFC are improved, and it has better economic practicability.
  • Figure 1 shows the transmission electron microscope (TEM) image of the Fe frame.
  • Figure 2 is a scanning electron microscope (SEM) image of the Fe frame.
  • Figure 3 is the transmission electron microscope (TEM) image of Fe/GO/CS composite.
  • Figure 4 is the scanning electron microscope (SEM) image of Fe/GO/CS composite.
  • Figure 5 is the X-ray diffraction pattern (XRD) of Fe/Fe 3 C/NC-800 composite.
  • Fig. 6 is the transmission electron microscope (TEM) image of Fe/Fe 3 C/NC-800 composite.
  • Fig. 7 is the scanning electron microscope (SEM) image of Fe/Fe 3 C/NC-800 composite.
  • Figure 8 shows the voltage effect of Fe/Fe 3 C/NC composites obtained by calcination at different temperatures as MFC cathode materials.
  • Figure 9 shows the power density and polarization curves of Fe/Fe 3 C/NC composites obtained by calcination at different temperatures as MFC cathode materials.
  • the raw materials involved in the present invention are all commercially available products; unless otherwise specified, the specific preparation methods and testing methods adopted are conventional methods in the field.
  • the preparation method of the Fe/Fe 3 C embedded N-doped carbon composite material of the present invention is as follows: the carbon-based material and nitrogen-containing polysaccharide are dispersed in a solvent, then iron salt and organic acid are added, and Fe/GO/ CS composite; Fe/Fe 3 C intercalated N-doped carbon composite (Fe/Fe 3 C/NC) was obtained by calcining the obtained Fe/GO/CS composite at high temperature in an inert gas atmosphere.
  • the Fe/Fe 3 C was embedded in the N-doped carbon composite material as a cathode catalyst, and an MFC reactor was assembled to obtain a microbial fuel cell to generate electricity.
  • Example 1 Preparation of Fe framework, the specific steps are as follows: 0.675 g FeCl 3 ⁇ 6H 2 O and 0.207 g terephthalic acid were dispersed in 15 mL DMF, and then conventionally sonicated for 20 minutes. The obtained solution was poured into a 50 mL reaction kettle, moved to an oven, and heated to 110 °C for 20 h. Finally, the product was centrifuged and washed with DMF and hot ethanol, and dried under vacuum at 60 °C to obtain the Fe framework.
  • Figure 1 is a TEM image of the Fe frame
  • Figure 2 is a SEM image of the Fe frame. It can be seen from the figure that the as-prepared Fe framework exhibits a concave octahedral morphology with a uniform size of about 500 nm and a smooth surface.
  • Example 2 Preparation of Fe/GO/CS composites, the specific steps are as follows: an in-situ growth method is adopted. 0.03 g of carbon-based material graphene oxide and 0.1 g of nitrogen source chitosan were dispersed in 15 mL of DMF and conventionally sonicated for 1 h; 0.675 g of FeCl 3 6H 2 O and 0.207 g of terephthalic acid were added, and sonicated again. Treated for 20 min; then the resulting solution was transferred to the reactor and heated to 110 °C for 20 h; finally, the product was centrifuged and washed with DMF and hot ethanol, and dried at 60 °C under vacuum to obtain Fe/GO/CS Complex.
  • FIG. 3 is the TEM image of the Fe/GO/CS composite
  • FIG. 4 is the SEM image of the Fe/GO/CS composite. After the composite is formed, the surface becomes relatively rough.
  • Embodiment 3 The difference between this embodiment and the above-mentioned embodiment 2 is: the carbon-based material is carbon nanotubes, and the other is the same as the embodiment 2, and Fe/CN/CS composite is obtained.
  • Comparative example the difference with the above-mentioned second embodiment is: no carbon-based material is added, and the other is the same as the second embodiment to obtain Fe/CS composite.
  • Embodiment 4 The difference between this embodiment and the above-mentioned Embodiment 2 is: the nitrogen source is melamine, and the others are the same as in Embodiment 2 to obtain Fe/GO/S composite.
  • the nitrogen source is urea
  • other is the same as the second embodiment, to obtain Fe/GO/N composite.
  • Example 5 Preparation of Fe/Fe 3 C intercalated N-doped carbon composite material, the specific steps are as follows: In an argon atmosphere, the Fe/GO/CS composite obtained above was heated at 600°C, 700°C, 800°C, After calcination at 900 °C for 2 h, the heating rate was 5 °C/min, and the temperature was naturally lowered. Finally, the Fe/Fe 3 C/NC composite was prepared. Taking 800 ° C calcination as an example, it was named Fe/Fe 3 C/NC-800.
  • Figure 5 is the X-ray diffraction pattern (XRD) of the Fe/Fe 3 C/NC-800 composite material.
  • the samples all show a small diffraction peak at 26° 2 ⁇ , which points to the (002) of the amorphous graphitic carbon. noodle.
  • a large number of sharp diffraction peaks in the range of 35-55°2 ⁇ are produced by Fe 3 C and a small amount of Fe.
  • the two main diffraction peaks at 44.5° and 64.8° 2 ⁇ are the (110) and (200) characteristic diffraction peaks of Fe.
  • FIG. 6 is a TEM image of Fe/Fe 3 C/NC-800 composite material (calcined at 800° C.), and FIG.
  • FIG. 7 is a SEM image of Fe/Fe 3 C/NC-800 composite material. It can be seen from the figure that the mixed structure of two-dimensional graphene nanosheets and one-dimensional carbon nanotubes is displayed after calcination, and a large number of elliptical nanoparticles with a size of about 300 nm are uniformly embedded in carbon nanotubes or dispersed in graphene nanotubes. in the film.
  • Example 6 The solution obtained by ultrasonically mixing 14 mg of catalyst with 46.67 ⁇ L of isopropanol, 93.33 ⁇ L of Nafion adhesive, and 11.67 ⁇ L of deionized water was applied to carbon cloth (7 cm 2 ), and the catalyst loading was 2 mg/ cm 2 .
  • the microbial fuel cell consisted of carbon brushes at the anode, hydrophobic carbon cloth loaded with catalysts at the cathode, the anolyte of the MFC reactor contained 1 g/L sodium acetate, 50 mM PBS, and minerals and vitamins, and activated sludge was used to provide microorganisms.
  • FIG. 8 is a voltage effect diagram of Fe/Fe 3 C/NC composite materials obtained by calcination at different temperatures as MFC cathode materials.
  • the prepared Fe/Fe 3 C/NC composites calcined at different temperatures and the 20% Pt/C catalyst have good power generation capacity during MFC operation, especially Fe/Fe 3 C/NC-800 obtained the highest voltage output (540 mV) and maintained its superiority and good stability with little voltage drop after up to 70 days of operation, while the uncalcined Fe framework and Fe
  • the output voltage effect of the /GO/CS complex was less than 200 mV.
  • the Fe/CS composite calcined (800 °C) in Example 5 was used as a catalyst for the same test, and the voltage output was 390 mV; the Fe/GO/S composite was calcined (800 °C) in Example 5. Same test, voltage output is 450 mV.
  • FIG. 9 is a graph showing the power density and polarization curves of Fe/Fe 3 C/NC composites obtained by calcination at different temperatures as MFC cathode materials. It can be seen from the figure that the Fe/Fe 3 C/NC-800 catalyst obtained the highest power density of 1076.16 mW/m 2 , which is higher than other catalysts, showing its superior performance, as shown in the following table: .

Abstract

A Fe/Fe3C embedded N-doped carbon composite material, a preparation method for same, and applications thereof in a microbial fuel cell, serving as a cathode catalyst. With graphene oxide serving as a substrate, with chitosan serving as a nitrogen-doped precursor, and with ferric trichloride hexahydrate and terephthalic acid serving as precursors, a solvothermal reaction is carried out, then high-temperature pyrolysis is employed, and the Fe/Fe3C embedded N-doped carbon composite material, Fe/Fe3C/NC, is produced by calcination in an argon atmosphere. The Fe/Fe 3C embedded N-doped carbon composite material, Fe/Fe3C/NC, synthesized through a series of steps and serving as a cathode catalyst in a microbial fuel cell, provides an improved electricity generation performance, and has great research significance and a certain application prospect in the development of sustainable new energy.

Description

Fe/Fe3C嵌入N掺杂碳复合材料及其制备方法与其在微生物燃料电池中的应用Fe/Fe3C intercalated N-doped carbon composite and its preparation method and its application in microbial fuel cells 技术领域technical field
本发明属于微生物燃料电池技术，涉及Fe/Fe 3C嵌入N掺杂碳复合材料及其制备方法以及将其作为阴极催化剂在微生物燃料电池中的应用。 The invention belongs to the technology of microbial fuel cells, and relates to Fe/Fe 3 C intercalated N-doped carbon composite materials, a preparation method thereof, and the application of the composite materials as cathode catalysts in microbial fuel cells.
背景技术Background technique
随着现代科技和文明的快速发展，人口逐年增长，能源消耗日益增加，与此同时能源消耗所带来的环境污染问题也给人类以及自然界的生存与发展造成了一定的威胁，人们对能源危机也日渐关注，积极寻求或开发新型的可持续发展的能源生产技术是当务之急。With the rapid development of modern science and technology and civilization, the population is increasing year by year, and energy consumption is increasing day by day. At the same time, the environmental pollution caused by energy consumption also poses a certain threat to the survival and development of human beings and nature. People are concerned about the energy crisis. It is also increasingly concerned that it is imperative to actively seek or develop new sustainable energy production technologies.
微生物燃料电池(Microbial fuel cell, MFC)它利用微生物的代谢作用，将有机废水中的化学能直接转换为电能，从而实现在去除水中的污染物的同时产生电能，是一种零污染低能耗的新型可持续发展能源技术。单室空气阴极MFC是MFC的一种类型，相较于双室MFC，其结构简单，电极距离短，占地面积小，无需质子交换膜，阴极传质速率提高，进而降低了运行成本，提高了MFC的产电能力和功率输出。其中阴极氧还原反应(Oxygen reduction reaction, ORR) 直接影响MFC的产电性能。铂(Pt)和铂基纳米材料在ORR过程中具有高活性和理想的4电子转移路径，被广泛用作ORR催化剂，但由于其成本高、在实际运用中容易被毒化和生物膜污染而导致性能迅速衰减，耐久性不佳，使得其在MFC中的应用受到严重限制。因此，开发经济、高效、绿色、环保稳定的ORR催化剂替代Pt催化剂是实现MFC实际应用的前提。Microbial fuel cell (MFC) uses the metabolism of microorganisms to directly convert chemical energy in organic wastewater into electrical energy, so as to generate electricity while removing pollutants in water. It is a zero pollution and low energy consumption. New sustainable energy technologies. Single-chamber air cathode MFC is a type of MFC. Compared with dual-chamber MFC, its structure is simple, the electrode distance is short, the footprint is small, no proton exchange membrane is required, and the cathode mass transfer rate is improved, thereby reducing operating costs and improving The power generation capacity and power output of the MFC. The cathodic oxygen reduction reaction (ORR) directly affects the power generation performance of the MFC. Platinum (Pt) and platinum-based nanomaterials are widely used as ORR catalysts due to their high activity and ideal 4-electron transfer pathway during ORR process, but due to their high cost, susceptibility to poisoning and biofilm fouling in practical applications Rapid performance decay and poor durability make its application in MFC severely limited. Therefore, the development of economical, efficient, green, environmentally friendly and stable ORR catalysts to replace Pt catalysts is the premise for the practical application of MFCs.
技术问题technical problem
本发明目的是介绍提供一种Fe/Fe 3C嵌入N掺杂碳复合材料的制备方法以及将其作为阴极催化剂在微生物燃料电池中进行产电。 The purpose of the present invention is to introduce and provide a preparation method of Fe/Fe 3 C intercalated N-doped carbon composite material and use it as a cathode catalyst to generate electricity in a microbial fuel cell.
技术解决方案technical solutions
为了达到上述目的，本发明采用如下具体技术方案：In order to achieve the above object, the present invention adopts following concrete technical scheme:
一种Fe/Fe 3C嵌入N掺杂碳复合材料，其制备方法包括以下步骤：将碳基材料、含氮多糖、铁盐、有机酸经溶剂热反应后进行煅烧，得到Fe/Fe 3C嵌入N掺杂碳复合材料。 An Fe/Fe 3 C embedded N-doped carbon composite material, the preparation method comprising the following steps: calcining carbon-based materials, nitrogen-containing polysaccharides, iron salts, and organic acids after solvothermal reaction to obtain Fe/Fe 3 C Embedded N-doped carbon composites.
一种微生物燃料电池，以Fe/Fe 3C嵌入N掺杂碳复合材料作为阴极催化剂，Fe/Fe 3C嵌入N掺杂碳复合材料的制备方法包括以下步骤：将碳基材料、含氮多糖、铁盐、有机酸经溶剂热反应后进行煅烧，得到Fe/Fe 3C嵌入N掺杂碳复合材料。 A microbial fuel cell uses Fe/Fe 3 C intercalated N-doped carbon composite material as cathode catalyst, and the preparation method of Fe/Fe 3 C intercalated N-doped carbon composite material includes the following steps: carbon-based material, nitrogen-containing polysaccharide , iron salt and organic acid are calcined after solvothermal reaction to obtain Fe/Fe 3 C intercalated N-doped carbon composite material.
本发明将碳基材料、含氮多糖在溶剂中分散，再加入铁盐、有机酸，经溶剂热反应得到Fe/GO/CS复合物；将得到的Fe/GO/CS复合物在惰性气体氛围中高温煅烧得MOF衍生的Fe/Fe 3C嵌入N掺杂碳复合材料（Fe/Fe 3C/NC）；将Fe/Fe 3C嵌入N掺杂碳复合材料做阴极催化剂，组装MFC反应器，得到微生物燃料电池，进行产电。 In the present invention, carbon-based materials and nitrogen-containing polysaccharides are dispersed in a solvent, and then iron salts and organic acids are added to obtain Fe/GO/CS composites through solvothermal reaction; the obtained Fe/GO/CS composites are placed in an inert gas atmosphere. The MOF-derived Fe/Fe 3 C intercalated N-doped carbon composite (Fe/Fe 3 C/NC) was obtained by calcination at medium and high temperature; the Fe/Fe 3 C intercalated N-doped carbon composite was used as the cathode catalyst to assemble the MFC reactor , to obtain a microbial fuel cell to generate electricity.
本发明中，碳基材料为氧化石墨烯或碳纳米管；氮源为壳聚糖、三聚氰胺、尿素中的一种；铁盐为六水合三氯化铁（FeCl 3·6H 2O）；有机酸为对苯二甲酸；溶剂为N,N-二甲基甲酰胺(DMF)。 In the present invention, the carbon-based material is graphene oxide or carbon nanotubes; the nitrogen source is one of chitosan, melamine and urea; the iron salt is ferric chloride hexahydrate (FeCl 3 ·6H 2 O); the organic The acid was terephthalic acid; the solvent was N,N-dimethylformamide (DMF).
本发明中，碳基材料、氮源、铁盐、有机酸的质量比为0.03: (0.05～0.3):0.675:0.207；优选的质量比为0.03:0.1:0.675:0.207。In the present invention, the mass ratio of carbon-based material, nitrogen source, iron salt, and organic acid is 0.03: (0.05-0.3): 0.675: 0.207; the preferred mass ratio is 0.03: 0.1: 0.675: 0.207.
本发明中，溶剂热反应的温度为90～160℃，时间为5～40小时，优选的溶剂热反应的温度为110℃，时间为20小时。In the present invention, the temperature of the solvothermal reaction is 90 to 160° C. and the time is 5 to 40 hours, and the preferred temperature of the solvothermal reaction is 110° C. and the time is 20 hours.
本发明中，煅烧温度为600～900℃，煅烧时间为1～4小时，升温速率为5℃/min，优选的煅烧温度为800℃，煅烧时间为2小时。In the present invention, the calcination temperature is 600-900°C, the calcination time is 1-4 hours, the heating rate is 5°C/min, the preferred calcination temperature is 800°C, and the calcination time is 2 hours.
本发明采用具有较好的导电性的氧化石墨烯或碳纳米管为基底，以六水合三氯化铁、对苯二甲酸为前躯体提供了多面框架结构，用壳聚糖、三聚氰胺、尿素作氮源对材料进行杂原子(N)掺杂，煅烧后所得的碳纳米管/石墨烯杂化结构具有较大的比表面积以及介孔结构，提供了大量的活性位点及传质通道，提高了复合材料的氧还原反应性能，有利于获得较高的电压及输出功率。The invention adopts graphene oxide or carbon nanotube with good electrical conductivity as the substrate, uses ferric chloride hexahydrate and terephthalic acid as the precursor to provide a multi-faceted frame structure, and uses chitosan, melamine and urea as the precursors. The nitrogen source doped the material with heteroatom (N), and the carbon nanotube/graphene hybrid structure obtained after calcination has a large specific surface area and a mesoporous structure, providing a large number of active sites and mass transfer channels, improving the The oxygen reduction reaction performance of the composite material is improved, which is beneficial to obtain higher voltage and output power.
本发明进一步公开了上述Fe/Fe 3C嵌入N掺杂碳复合材料作为阴极催化剂在微生物燃料电池中的应用，可进行产电。 The invention further discloses the application of the above-mentioned Fe/Fe 3 C intercalated N-doped carbon composite material as a cathode catalyst in a microbial fuel cell, which can generate electricity.
本发明中，微生物燃料电池以Fe/Fe 3C嵌入N掺杂碳复合材料作为阴极催化剂，具体将Fe/Fe 3C嵌入N掺杂碳复合材料涂覆在导电基底上作为阴极，在与常规活性污泥、阳极液组装，得到微生物燃料电池。 In the present invention, the microbial fuel cell uses the Fe/Fe 3 C intercalated N-doped carbon composite material as the cathode catalyst, and specifically the Fe/Fe 3 C intercalated N-doped carbon composite material is coated on the conductive substrate as the cathode. The activated sludge and anolyte are assembled to obtain a microbial fuel cell.
本发明公开的催化剂在微生物燃料电池中进行产电方法中，将煅烧处理后的定量MOF衍生的Fe/Fe 3C嵌入N掺杂碳复合材料Fe/Fe 3C/NC作阴极催化剂，组装MFC反应器，加入活性污泥、阳极液，外接1000 Ω电阻进行产电，利用数据采集器每隔10分钟采集一次数据，待电压降至20 mV以下更换阳极液。 In the method for generating electricity in the microbial fuel cell with the catalyst disclosed in the invention, Fe/Fe 3 C derived from quantitative MOF after calcination treatment is embedded in the N-doped carbon composite material Fe/Fe 3 C/NC as the cathode catalyst, and the MFC is assembled. The reactor is added with activated sludge and anolyte, and an external 1000 Ω resistor is used to generate electricity. The data collector is used to collect data every 10 minutes, and the anolyte is replaced when the voltage drops below 20 mV.
有益效果beneficial effect
本发明的优点：1、本发明公开的Fe/Fe 3C嵌入N掺杂碳复合材料具有较大的比表面积以及介孔结构；Fe/Fe 3C均一地负载在碳纳米管和石墨烯中，较大的比表面积可以提供了较多的活性位点以及传质通道，有利于提高氧还原反应性能，是一种良好的催化剂材料。 Advantages of the present invention: 1. The Fe/Fe 3 C intercalated N-doped carbon composite material disclosed in the present invention has a larger specific surface area and a mesoporous structure; Fe/Fe 3 C is uniformly supported in carbon nanotubes and graphene , a larger specific surface area can provide more active sites and mass transfer channels, which is beneficial to improve the performance of oxygen reduction reaction, and is a good catalyst material.
2、本发明公开的Fe/Fe 3C嵌入N掺杂碳复合材料的制备方法中，采用便宜，环保，可再生，自然丰富生物质材料壳聚糖作为N源对材料进行氮掺杂，增加了材料中吡啶-N，石墨-N的含量，进一步提高了催化剂的氧还原反应的性能。 2. In the preparation method of Fe/Fe 3 C embedded N-doped carbon composite material disclosed in the present invention, chitosan, a cheap, environmentally friendly, renewable, and naturally abundant biomass material, is used as the N source to perform nitrogen doping on the material, increasing the The content of pyridine-N and graphite-N in the material is increased, and the performance of the catalyst for oxygen reduction reaction is further improved.
3、本发明通过减少阴极催化剂负载量获得了可以与其他较高催化剂负载量的微生物燃料电池相媲美的产电性能和功率输出。3. The present invention obtains electricity production performance and power output comparable to other microbial fuel cells with higher catalyst loading by reducing the cathode catalyst loading.
4、本发明克服了传统的使用铂(Pt)和铂基纳米材料作阴极材料成本高、易被毒化和生物膜污染而导致性能迅速衰减，耐久性不佳的缺点，选择了自然资源丰富，价格低廉，稳定性好的铁基材料，同时选用生物质材料壳聚糖进行氮掺杂，Fe/Fe 3C/NC作阴极催化剂具有高氧还原活性，进行4电子还原路径，产物为无害的水，环境友好，极大的降低了催化剂成本降低了催化剂成本的同时，提高了MFC的输出电压和功率密度，具有更好的经济实用性。 4. The present invention overcomes the shortcomings of traditional use of platinum (Pt) and platinum-based nanomaterials as cathode materials, high cost, easy to be poisoned and biofilm pollution, resulting in rapid performance decay and poor durability. The iron-based material with low price and good stability, at the same time, the biomass material chitosan is used for nitrogen doping, and Fe/Fe 3 C/NC is used as the cathode catalyst with high oxygen reduction activity, and the 4-electron reduction path is carried out, and the product is harmless The water is environmentally friendly, which greatly reduces the cost of the catalyst. At the same time, the cost of the catalyst is reduced, and the output voltage and power density of the MFC are improved, and it has better economic practicability.
附图说明Description of drawings
图1 为Fe框架的透射电镜图（TEM）。Figure 1 shows the transmission electron microscope (TEM) image of the Fe frame.
图2 为Fe框架的扫描电镜图（SEM）。Figure 2 is a scanning electron microscope (SEM) image of the Fe frame.
图3 为Fe/GO/CS复合物的透射电镜图（TEM）。Figure 3 is the transmission electron microscope (TEM) image of Fe/GO/CS composite.
图4 为Fe/GO/CS复合物的扫描电镜图（SEM）。Figure 4 is the scanning electron microscope (SEM) image of Fe/GO/CS composite.
图5 为Fe/Fe 3C/NC-800复合材料的X-射线衍射图（XRD）。 Figure 5 is the X-ray diffraction pattern (XRD) of Fe/Fe 3 C/NC-800 composite.
图6 为Fe/Fe 3C/NC-800复合材料的透射电镜图（TEM）。 Fig. 6 is the transmission electron microscope (TEM) image of Fe/Fe 3 C/NC-800 composite.
图7 为Fe/Fe 3C/NC-800复合材料的扫描电镜图（SEM）。 Fig. 7 is the scanning electron microscope (SEM) image of Fe/Fe 3 C/NC-800 composite.
图8 为不同温度煅烧获得的Fe/Fe 3C/NC复合材料作MFC阴极材料的电压效果图。 Figure 8 shows the voltage effect of Fe/Fe 3 C/NC composites obtained by calcination at different temperatures as MFC cathode materials.
图9 为不同温度煅烧获得的Fe/Fe 3C/NC复合材料作MFC阴极材料的功率密度与极化曲线图。 Figure 9 shows the power density and polarization curves of Fe/Fe 3 C/NC composites obtained by calcination at different temperatures as MFC cathode materials.
本发明的实施方式Embodiments of the present invention
本发明涉及的原料都是市售产品；如无特殊说明，采用的具体制备方法以及测试方法都为本领域常规方法。The raw materials involved in the present invention are all commercially available products; unless otherwise specified, the specific preparation methods and testing methods adopted are conventional methods in the field.
本发明的Fe/Fe 3C嵌入N掺杂碳复合材料的制备方法如下：将碳基材料、含氮多糖在溶剂中分散，再加入铁盐、有机酸，经溶剂热反应得到Fe/GO/CS复合物；将得到的Fe/GO/CS复合物在惰性气体氛围中高温煅烧得Fe/Fe 3C嵌入N掺杂碳复合材料（Fe/Fe 3C/NC）。将Fe/Fe 3C嵌入N掺杂碳复合材料做阴极催化剂，组装MFC反应器，得到微生物燃料电池，进行产电。 The preparation method of the Fe/Fe 3 C embedded N-doped carbon composite material of the present invention is as follows: the carbon-based material and nitrogen-containing polysaccharide are dispersed in a solvent, then iron salt and organic acid are added, and Fe/GO/ CS composite; Fe/Fe 3 C intercalated N-doped carbon composite (Fe/Fe 3 C/NC) was obtained by calcining the obtained Fe/GO/CS composite at high temperature in an inert gas atmosphere. The Fe/Fe 3 C was embedded in the N-doped carbon composite material as a cathode catalyst, and an MFC reactor was assembled to obtain a microbial fuel cell to generate electricity.
实施例一：Fe框架的制备，具体步骤如下：将0.675 g FeCl 3·6H 2O和0.207 g 对苯二甲酸分散在15 mL DMF中，然后常规超声处理20分钟。将获得的溶液倒入50 mL反应釜中，移至烘箱，加热至110℃保持20 h。 最后，将产物离心并用DMF和热乙醇洗涤，并在真空下于60℃干燥，得到Fe框架。附图1为Fe框架的TEM图，附图2为Fe框架的SEM图。从图中可以看出，制备得到的Fe框架呈现凹面八面体形态，大小均一，尺寸约为500 nm，并且表面光滑。 Example 1: Preparation of Fe framework, the specific steps are as follows: 0.675 g FeCl 3 ·6H 2 O and 0.207 g terephthalic acid were dispersed in 15 mL DMF, and then conventionally sonicated for 20 minutes. The obtained solution was poured into a 50 mL reaction kettle, moved to an oven, and heated to 110 °C for 20 h. Finally, the product was centrifuged and washed with DMF and hot ethanol, and dried under vacuum at 60 °C to obtain the Fe framework. Figure 1 is a TEM image of the Fe frame, and Figure 2 is a SEM image of the Fe frame. It can be seen from the figure that the as-prepared Fe framework exhibits a concave octahedral morphology with a uniform size of about 500 nm and a smooth surface.
实施例二：Fe/GO/CS复合物的制备，具体步骤如下：采用原位生长法。将0.03 g 碳基材料氧化石墨烯和0.1 g氮源壳聚糖分散在15 mL DMF中并常规超声处理1 h；再加入0.675 g FeCl 3·6H 2O和0.207 g 对苯二甲酸，再超声处理20分钟；随后将所得溶液转移至反应釜中，并加热至110℃保持20 h；最后，将产物离心并用DMF和热乙醇洗涤，并在真空下于60℃干燥，得到Fe/GO/CS复合物。附图3为Fe/GO/CS复合物的TEM图，附图4为Fe/GO/CS复合物的SEM图，形成复合物后表面变得相对粗糙。 Example 2: Preparation of Fe/GO/CS composites, the specific steps are as follows: an in-situ growth method is adopted. 0.03 g of carbon-based material graphene oxide and 0.1 g of nitrogen source chitosan were dispersed in 15 mL of DMF and conventionally sonicated for 1 h; 0.675 g of FeCl 3 6H 2 O and 0.207 g of terephthalic acid were added, and sonicated again. Treated for 20 min; then the resulting solution was transferred to the reactor and heated to 110 °C for 20 h; finally, the product was centrifuged and washed with DMF and hot ethanol, and dried at 60 °C under vacuum to obtain Fe/GO/CS Complex. FIG. 3 is the TEM image of the Fe/GO/CS composite, and FIG. 4 is the SEM image of the Fe/GO/CS composite. After the composite is formed, the surface becomes relatively rough.
实施例三：本实施方式与上述实施例二的不同点是:所述碳基材料为碳纳米管，其他与实施例二相同，得到Fe/CN/CS复合物。Embodiment 3: The difference between this embodiment and the above-mentioned embodiment 2 is: the carbon-based material is carbon nanotubes, and the other is the same as the embodiment 2, and Fe/CN/CS composite is obtained.
对比例：与上述实施例二的不同点是:不加入碳基材料，其他与实施例二相同，得到Fe/CS复合物。Comparative example: the difference with the above-mentioned second embodiment is: no carbon-based material is added, and the other is the same as the second embodiment to obtain Fe/CS composite.
实施例四：本实施方式与上述实施例二的不同点是:所述的氮源为三聚氰胺，其他与实施例二相同，得到Fe/GO/S复合物。Embodiment 4: The difference between this embodiment and the above-mentioned Embodiment 2 is: the nitrogen source is melamine, and the others are the same as in Embodiment 2 to obtain Fe/GO/S composite.
本实施方式与上述实施例二的不同点是:所述的氮源为尿素，其他与实施例二相同，得到Fe/GO/N复合物。The difference between this embodiment and the above-mentioned second embodiment is: the nitrogen source is urea, and other is the same as the second embodiment, to obtain Fe/GO/N composite.
实施例五：Fe/Fe 3C嵌入N掺杂碳复合材料的制备，具体步骤如下： 在氩气气氛下，将上述所得Fe/GO/CS复合物分别于600℃、700℃、800℃、900℃煅烧2 h，升温速率为5°C / min，自然降温，最终制备得到Fe/Fe 3C/NC复合材料，以800℃煅烧为例，命名为Fe/Fe 3C/NC-800。 Example 5: Preparation of Fe/Fe 3 C intercalated N-doped carbon composite material, the specific steps are as follows: In an argon atmosphere, the Fe/GO/CS composite obtained above was heated at 600°C, 700°C, 800°C, After calcination at 900 °C for 2 h, the heating rate was 5 °C/min, and the temperature was naturally lowered. Finally, the Fe/Fe 3 C/NC composite was prepared. Taking 800 ° C calcination as an example, it was named Fe/Fe 3 C/NC-800.
附图5为Fe/Fe 3C/NC-800复合材料的X-射线衍射图（XRD），样品在26°2θ处均显示出小的衍射峰，该峰指向无定形石墨碳的（002）面。35-55°2θ范围内的大量尖锐衍射峰是由Fe 3C和少量Fe产生的。44.5°和64.8° 2θ处的两个主要衍射峰是Fe的（110）和（200）特征衍射峰。图6为Fe/Fe 3C/NC-800复合材料（800℃煅烧）的TEM图，附图7为Fe/Fe 3C/NC-800复合材料的SEM图。从图中可以看出煅烧后显示出二维石墨烯纳米片和一维碳纳米管的混合结构，大量的尺寸约300 nm大小的椭圆形纳米颗粒均匀嵌入碳纳米管中或分散在石墨烯纳米片中。 Figure 5 is the X-ray diffraction pattern (XRD) of the Fe/Fe 3 C/NC-800 composite material. The samples all show a small diffraction peak at 26° 2θ, which points to the (002) of the amorphous graphitic carbon. noodle. A large number of sharp diffraction peaks in the range of 35-55°2θ are produced by Fe 3 C and a small amount of Fe. The two main diffraction peaks at 44.5° and 64.8° 2θ are the (110) and (200) characteristic diffraction peaks of Fe. FIG. 6 is a TEM image of Fe/Fe 3 C/NC-800 composite material (calcined at 800° C.), and FIG. 7 is a SEM image of Fe/Fe 3 C/NC-800 composite material. It can be seen from the figure that the mixed structure of two-dimensional graphene nanosheets and one-dimensional carbon nanotubes is displayed after calcination, and a large number of elliptical nanoparticles with a size of about 300 nm are uniformly embedded in carbon nanotubes or dispersed in graphene nanotubes. in the film.
实施例六：将14 mg的催化剂与46.67 μL异丙醇、93.33 μLNafion粘接剂、11.67 μL去离子水超声混合得到的溶液涂至碳布上（7 cm 2），催化剂负载量为2 mg/cm 2。微生物燃料电池包括阳极碳刷，阴极负载有催化剂的疏水碳布，MFC反应器的阳极液包含1g/L的乙酸钠，50mM PBS以及矿物质和维生素，活性污泥用于提供微生物。MFC反应器外接1000 Ω电阻进行产电，利用数据采集器每隔10分钟采集一次D次电压数据。以现有20% Pt/C催化剂作为对比，进行平行实验。附图8为不同温度煅烧获得的Fe/Fe 3C/NC复合材料作MFC阴极材料的电压效果图。从图中可以看出，所制备的不同温度煅烧的Fe/Fe 3C/NC复合材料与20% Pt/C催化剂都在MFC运行过程中具有较好的产电能力，尤其是Fe/Fe 3C/NC-800获得了最高的电压输出（540 mV）且经过长达70天的运行后电压少有降低但依旧保持其优越性以及良好的稳定性，而未经煅烧处理的Fe框架以及Fe/GO/CS复合物的输出电压效果不尽人意，不到200 mV。Fe/CS复合物经过实施例五煅烧（800℃）的产物作为催化剂进行同样的测试，电压输出为390 mV；Fe/GO/S复合物经过实施例五煅烧（800℃）的产物作为催化剂进行同样的测试，电压输出为450 mV。 Example 6: The solution obtained by ultrasonically mixing 14 mg of catalyst with 46.67 μL of isopropanol, 93.33 μL of Nafion adhesive, and 11.67 μL of deionized water was applied to carbon cloth (7 cm 2 ), and the catalyst loading was 2 mg/ cm 2 . The microbial fuel cell consisted of carbon brushes at the anode, hydrophobic carbon cloth loaded with catalysts at the cathode, the anolyte of the MFC reactor contained 1 g/L sodium acetate, 50 mM PBS, and minerals and vitamins, and activated sludge was used to provide microorganisms. The MFC reactor was connected with an external 1000 Ω resistor to generate electricity, and the data collector was used to collect D times of voltage data every 10 minutes. Parallel experiments were carried out with the existing 20% Pt/C catalyst as a comparison. FIG. 8 is a voltage effect diagram of Fe/Fe 3 C/NC composite materials obtained by calcination at different temperatures as MFC cathode materials. It can be seen from the figure that the prepared Fe/Fe 3 C/NC composites calcined at different temperatures and the 20% Pt/C catalyst have good power generation capacity during MFC operation, especially Fe/Fe 3 C/NC-800 obtained the highest voltage output (540 mV) and maintained its superiority and good stability with little voltage drop after up to 70 days of operation, while the uncalcined Fe framework and Fe The output voltage effect of the /GO/CS complex was less than 200 mV. The Fe/CS composite calcined (800 °C) in Example 5 was used as a catalyst for the same test, and the voltage output was 390 mV; the Fe/GO/S composite was calcined (800 °C) in Example 5. Same test, voltage output is 450 mV.
待微生物燃料电池运行稳定后测试，测试前需更换新鲜阳极液使反应器开路稳定后，从大到小依次外接不同电阻（10000Ω～50Ω），待每个电阻运行稳定后记录电压值，再根据以下公式计算得到电流密度及功率密度。Test after the microbial fuel cell runs stably. Before the test, it is necessary to replace the fresh anolyte to make the reactor open and stable, and then connect different resistances (10000Ω~50Ω) in order from large to small. After each resistance is stable, record the voltage value, and then according to The following formulas are used to calculate the current density and power density.
Figure 461819dest_path_image001
；
Figure 541770dest_path_image002
。
Figure 461819dest_path_image001
;
Figure 541770dest_path_image002
.
附图9为不同温度煅烧获得的Fe/Fe 3C/NC复合材料作MFC阴极材料的功率密度与极化曲线图。从图中可以看出Fe/Fe 3C/NC-800催化剂获得了最高的功率密度1076.16 mW/m 2，高于其他的催化剂，表现出其优越的性能，见下表：
Figure 629812dest_path_image003
。 FIG. 9 is a graph showing the power density and polarization curves of Fe/Fe 3 C/NC composites obtained by calcination at different temperatures as MFC cathode materials. It can be seen from the figure that the Fe/Fe 3 C/NC-800 catalyst obtained the highest power density of 1076.16 mW/m 2 , which is higher than other catalysts, showing its superior performance, as shown in the following table:
Figure 629812dest_path_image003
.
通过以上分析，说明采用本发明的技术方案成功制备了由MOF衍生的Fe/Fe 3C嵌入N掺杂碳复合材料Fe/Fe 3C/NC，并且作为阴极催化剂在MFC运行过程中具有较好的氧还原反应性能获得了较高且稳定的电压输出以及较高的功率密度，具有很好的应用前景。 The above analysis shows that the Fe/Fe 3 C-intercalated N-doped carbon composite Fe/Fe 3 C/NC derived from MOF has been successfully prepared by the technical solution of the present invention, and it has good performance as a cathode catalyst during the operation of the MFC. High and stable voltage output and high power density are obtained with the excellent oxygen reduction reaction performance, which has a good application prospect.

Claims (10)

  1. 一种Fe/Fe 3C嵌入N掺杂碳复合材料，其特征在于，所述Fe/Fe 3C嵌入N掺杂碳复合材料的制备方法包括以下步骤：将碳基材料、氮源、铁盐、有机酸经溶剂热反应后进行煅烧，得到Fe/Fe 3C嵌入N掺杂碳复合材料。 An Fe/Fe 3 C embedded N-doped carbon composite material, characterized in that, the preparation method of the Fe/Fe 3 C embedded N-doped carbon composite material comprises the following steps: mixing a carbon-based material, a nitrogen source, an iron salt , the organic acid is calcined after solvothermal reaction to obtain Fe/Fe 3 C intercalated N-doped carbon composite material.
  2. 根据权利要求1所述Fe/Fe 3C嵌入N掺杂碳复合材料，其特征在于，碳基材料为氧化石墨烯或碳纳米管；铁盐为六水合三氯化铁；有机酸为对苯二甲酸；氮源为壳聚糖、三聚氰胺、尿素中的一种。 The Fe/Fe 3 C embedded N-doped carbon composite material according to claim 1, wherein the carbon-based material is graphene oxide or carbon nanotubes; the iron salt is ferric trichloride hexahydrate; the organic acid is p-benzene Diformic acid; nitrogen source is one of chitosan, melamine and urea.
  3. 根据权利要求1所述Fe/Fe 3C嵌入N掺杂碳复合材料，其特征在于，碳基材料、氮源、铁盐、有机酸的质量比为0.03: (0.05～0.3):0.675:0.207。 The Fe/Fe 3 C embedded N-doped carbon composite material according to claim 1, wherein the mass ratio of carbon-based material, nitrogen source, iron salt, and organic acid is 0.03: (0.05-0.3): 0.675: 0.207 .
  4. 根据权利要求3所述Fe/Fe 3C嵌入N掺杂碳复合材料，其特征在于，碳基材料、含氮多糖、铁盐、有机酸的质量比为0.03:0.1:0.675:0.207。 The Fe/Fe 3 C embedded N-doped carbon composite material according to claim 3, wherein the mass ratio of carbon-based material, nitrogen-containing polysaccharide, iron salt, and organic acid is 0.03:0.1:0.675:0.207.
  5. 根据权利要求1所述Fe/Fe 3C嵌入N掺杂碳复合材料，其特征在于，溶剂热反应的温度为90～160℃，时间为5～40小时；煅烧温度为600～900℃，煅烧时间为1～4小时。 The Fe/Fe 3 C intercalated N-doped carbon composite material according to claim 1, wherein the temperature of the solvothermal reaction is 90-160° C., and the time is 5-40 hours; the calcination temperature is 600-900° C., The time is 1 to 4 hours.
  6. 根据权利要求5所述Fe/Fe 3C嵌入N掺杂碳复合材料，其特征在于，溶剂热反应的温度为110℃，时间为20小时；煅烧温度为800℃，煅烧时间为2小时。 The Fe/Fe 3 C intercalated N-doped carbon composite material according to claim 5, wherein the temperature of the solvothermal reaction is 110°C and the time is 20 hours; the calcination temperature is 800°C and the calcination time is 2 hours.
  7. 一种微生物燃料电池，以Fe/Fe 3C嵌入N掺杂碳复合材料作为阴极催化剂，其特征在于，所述Fe/Fe 3C嵌入N掺杂碳复合材料的制备方法包括以下步骤：将碳基材料、含氮多糖、铁盐、有机酸经溶剂热反应后进行煅烧，得到Fe/Fe 3C嵌入N掺杂碳复合材料。 A microbial fuel cell uses Fe/Fe 3 C intercalated N-doped carbon composite material as a cathode catalyst, characterized in that the preparation method of Fe/Fe 3 C intercalated N-doped carbon composite material comprises the following steps: The base material, nitrogen-containing polysaccharide, iron salt, and organic acid are calcined after solvothermal reaction to obtain Fe/Fe 3 C intercalated N-doped carbon composite material.
  8. 根据权利要求7所述微生物燃料电池，其特征在于，Fe/Fe 3C嵌入N掺杂碳复合材料粘接在导电基底上作为微生物燃料电池的阴极。 The microbial fuel cell according to claim 7, wherein the Fe/Fe 3 C intercalated N-doped carbon composite material is bonded on the conductive substrate as the cathode of the microbial fuel cell.
  9. 权利要求7所述微生物燃料电池在制备能源材料中的应用。The application of the microbial fuel cell of claim 7 in the preparation of energy materials.
  10. 权利要求1所述Fe/Fe 3C嵌入N掺杂碳复合材料在制备微生物燃料电池中的应用。 Application of the Fe/Fe 3 C intercalated N-doped carbon composite material of claim 1 in the preparation of microbial fuel cells.
PCT/CN2021/136209 2020-11-30 2021-12-07 Fe/fe₃c-embedded n-doped carbon composite material, preparation method for same, and applications thereof in microbial fuel cell WO2022111736A1 (en)

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