CN114709426A - High-conductivity heteroatom-doped porous carbon nanoparticle composite material and application thereof in preparation of microbial fuel cell anode material - Google Patents

High-conductivity heteroatom-doped porous carbon nanoparticle composite material and application thereof in preparation of microbial fuel cell anode material Download PDF

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CN114709426A
CN114709426A CN202210329058.5A CN202210329058A CN114709426A CN 114709426 A CN114709426 A CN 114709426A CN 202210329058 A CN202210329058 A CN 202210329058A CN 114709426 A CN114709426 A CN 114709426A
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王志伟
刘令
覃程荣
梁辰
刘新亮
宋雪萍
朱凯莉
邹雪莲
袁金霞
韦丽萍
伍晓琪
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Guangxi University
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Abstract

The invention discloses a preparation method of a high-conductivity heteroatom-doped porous carbon nanoparticle composite material and application of the material in preparation of a microbial fuel cell anode material. The preparation method comprises the following steps: sequentially adding tannic acid, triethylamine and a solvent into an acetonitrile solution, performing a polycondensation reaction by ultrasonic waves, washing for several times after centrifuging, and drying to form covalent crosslinking Polyphosphazene (PSTA) nanospheres; adding the PSTA nanospheres into an ethanol solution mixed with Pluronic to obtain PSTA-Co nanospheres; and finally, heating the substances in a quartz tube to form heteroatom (N, P, S, Co) doped porous carbon nano particles. The invention obtains the nano-scale porous structure composite material with larger specific surface area, and the doping of the heteroatom ensures that the material has high conductivity, good biocompatibility and abundant electrochemical active centers, promotes the EET process and greatly improves the output power of Microbial Fuel Cells (MFCs).

Description

High-conductivity heteroatom-doped porous carbon nanoparticle composite material and application thereof in preparation of microbial fuel cell anode material
Technical Field
The invention belongs to the technical field of microbial fuel cells, and particularly relates to a high-conductivity heteroatom-doped porous carbon nanoparticle composite material and application thereof in preparation of a microbial fuel cell anode material.
Background
Microbial Fuel Cells (MFCs) are a green process technology that uses Electrochemically Active Microorganisms (EAMs) as biocatalysts to degrade organic compounds in wastewater and produce electrical energy. However, its low power consumption, high cost and lack of scalability have hindered the widespread practical use of MFCs. The performance of the anode, which is central to the operation of the MFC, determines the electrocatalytic activity of the electroactive biofilm and directly affects the EET process between the EAMs and the electrode. Therefore, the preparation of the high-performance anode material with high conductivity, a multi-layer pore structure and enough biocompatibility is a necessary condition for greatly improving the power generation performance efficiency of the MFC and enabling the MFC to be practically applied in the fields of sewage treatment, sustainable clean energy, environmental bioremediation and the like.
Conventional carbon-based anode materials, including Carbon Cloth (CC), carbon brush, carbon felt, and the like, generally exhibit low power output due to their low specific surface area, high internal resistance, weak adhesion to bacteria, and poor microbial selectivity. In contrast, many nanomaterials, such as carbon nanotubes, graphene, conducting polymers and metal compounds, have been widely used to modify MFC due to their excellent electrocatalytic activity. Nanomaterial modification can efficiently transfer electrons from bacteria to the surface of an electron acceptor. However, the preparation of carbon nanostructure materials is complicated and expensive, which is not conducive to mass production. Furthermore, the ability to tune existing material structures is often limited, resulting in poor MFC performance, and the preparation of many materials has not been adequately designed and optimized.
The N doping can improve the conductivity, the number of active sites and the biocompatibility of the material, form a microenvironment suitable for the growth of microorganisms and improve the electrocatalytic activity of the microorganisms. The S-and P-doping further optimizes the chemical state and surface hydrophobicity of the anode element, thereby improving the affinity of the electrode surface for bacteria, promoting the EET process, and even improving microbial activity. Co-doping provides additional active sites for oxygen reduction reactions. The nano-scale porous structure with large surface area not only promotes the formation of an electroactive biofilm, but also enables it to be inserted into a biocatalyst and contacted with active centers.
Disclosure of Invention
The invention aims to provide a preparation method of a high-conductivity heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite material (N-HDPC) for a microbial fuel cell and a specific application of the composite material in preparation of an anode material of the microbial fuel cell.
The above object of the present invention is achieved by the following scheme:
a high-conductivity heteroatom-doped porous carbon nanoparticle composite material is prepared by the following steps:
the method comprises the following steps: dissolving tannic acid in acetonitrile, adding triethylamine, and performing ultrasonic treatment; dissolving hexachlorocyclotriphosphazene and 4, 4-dihydroxy diphenyl sulfone in acetonitrile, adding the acetonitrile into the solution after ultrasonic treatment, and continuing ultrasonic treatment; centrifuging and collecting precipitates, washing the precipitates with ethanol and deionized water, and drying the precipitates in vacuum at 50-90 ℃ to obtain covalent crosslinking polyphosphazene nanospheres;
step two: dissolving Pluronic in ethanol, adding the covalent cross-linked polyphosphazene nanospheres obtained in the step one, and performing ultrasonic uniform dispersion; mixing of Co (OAc)2·4H2Dissolving O in ethanol, adding the O into the solution after ultrasonic uniform dispersion, stirring at room temperature, centrifuging to collect a product, washing with ethanol and deionized water, and drying in vacuum at 50-90 ℃ to obtain PSTA-Co nanospheres;
step three: and (3) heating the PSTA-Co nanospheres obtained in the second step from room temperature to 750-900 ℃ in a quartz tube in the presence of constant argon, keeping the temperature constant for 3-6 h, washing with HCl solution and deionized water, drying in vacuum at 60-90 ℃, heating the dried black powder from room temperature to 800-1000 ℃ in the quartz tube, and keeping the temperature constant for 3-6 h to obtain the high-conductivity heteroatom doped porous carbon nanoparticle composite material (N-HDPC).
The mass ratio of the tannic acid to the hexachlorocyclotriphosphazene to the 4, 4-dihydroxy diphenyl sulfone in the first step is 1.5-2.4: 0.8-1.2, and the volume fraction of the triethylamine in the acetonitrile solution is 10-12%.
Pluronic, covalently cross-linked polyphosphazene nanospheres and Co (OAc) as described in step two2·4H2The mass ratio of O is 2:2: 3.
The ultrasonic power of the first step and the ultrasonic power of the second step are both 160-240W, and the ultrasonic frequency is both 50-90 Hz.
And in the second step, stirring time at room temperature is 24-36 h, and the centrifugal speed is 9000 rpm.
The two heating rates in the third step are both 10 ℃ and min-1。
The concentration of the HCl solution in the third step is 3 mol/L.
The high-conductivity heteroatom-doped porous carbon nanoparticle composite material can be applied to preparation of anode materials of microbial fuel cells, and specifically comprises the following steps: respectively ultrasonically cleaning the carbon cloth with acetone, absolute ethyl alcohol and deionized water for 20-40 min, and placing the carbon cloth in a tube furnace for N2Heating the mixture; sequentially adding deionized water and isopropyl to the high-conductivity heteroatom doped porous carbon nanoparticle composite materialAnd (2) uniformly coating the mixed solution obtained after uniform dispersion on two sides of the pretreated carbon cloth by using alcohol and 5% of Nafion solution in mass fraction, drying, and connecting titanium wires to the carbon cloth by using conductive silver adhesive to obtain the microbial fuel cell anode material (N-HDPC/CC) containing the high-conductivity heteroatom doped porous carbon nanoparticle composite material.
The temperature in the tubular furnace is 300-450 ℃, and the heating time is 3-6 h; the volume ratio of the deionized water to the isopropanol to the Nafion solution with the mass fraction of 5% is 5:10: 6.
The high-conductivity heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite material (N-HDPC) prepared by the preparation method has the excellent performance of graded nano-porous and the high stability of a carbon material, and the Co-doping of N, P, S and Co optimizes the chemical state and surface hydrophobicity of the material, improves the biocompatibility of the material, enhances the adhesion of cells, promotes the EET process and improves the power density of MFCs.
The high-conductivity heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite material (N-HDPC) obtained by the preparation method can be used as anode materials of Microbial Fuel Cells (MFCs) after being coated with carbon cloth.
The principle of the invention is as follows: the Co-N with high specific surface area and good dispersion is obtained by ultrasonic polymerization and carbonization2P2The active center high conductivity heteroatoms (N, P, S, Co) are doped with porous carbon nanoparticle composites (N-HDPC). The nanoscale porous structure with large surface area not only promotes the formation of an electroactive biofilm, but also enables it to be inserted into a biocatalyst and contacted with an active center. The N-doping can improve the conductivity, the number of active sites and the biocompatibility of the material, form a microenvironment suitable for the growth of microorganisms and improve the electrocatalytic activity of the microorganisms. The chemical state and surface hydrophobicity of the anode element are further optimized by the S-and P-doping, so that the affinity of the electrode surface for bacteria is improved, the Co-doping provides additional active sites for oxygen reduction reaction, the microbial activity is improved, and the EET process is promoted.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method of the high-conductivity heteroatom (N, P, S, Co) doped porous carbon nanoparticle composite material is simple.
(2) The high-conductivity heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite material disclosed by the invention is coated on carbon cloth and then applied as a microbial fuel cell anode material, and the heteroatom doping enables the microbial fuel cell anode material to have high conductivity, good biocompatibility and abundant electrochemical active centers, promotes an EET process and greatly improves the output power of Microbial Fuel Cells (MFCs).
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a Carbon Cloth (CC) and a microbial fuel cell anode material (N-HDPC/CC) containing highly conductive heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite;
FIG. 2 is a full X-ray photoelectron spectrum of microbial fuel cell anode material (N-HDPC/CC) containing highly conductive heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite material;
FIG. 3 is a plot of Cyclic Voltammetry (CV) for CC and N-HDPC/CC anodes in fresh anode solution;
FIG. 4 is a graph of MFC output voltage for CC and N-HDPC/CC, respectively, as anodes for MFCs;
FIG. 5 is a MFC polarization curve and power density for CC and N-HDPC/CC, respectively, as anodes for MFCs;
FIG. 6 is an SEM image of CC and N-HDPC/CC anodes after 30 days of stable MFCs operation.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the experimental methods of the present invention in which specific conditions are not specified are generally performed under conventional conditions or under conditions recommended by manufacturers.
Example 1
The preparation method of the porous carbon nanoparticle composite material (N-HDPC) doped with high-conductivity heteroatoms (N, P, S and Co) comprises the following steps:
the method comprises the following steps: dissolving 1.2g of Tannic Acid (TA) in 400mL of acetonitrile, adding 40mL of Triethylamine (TEA), then performing ultrasonic treatment (160W, 90Hz) at 35 ℃ for 45min, dissolving 1g of Hexachlorocyclotriphosphazene (HCCP) and 1g of 4, 4-dihydroxydiphenylsulfone (BPS) in 600mL of acetonitrile, and adding the solution after ultrasonic treatment; continuing to perform ultrasonic treatment under the same condition, and performing polycondensation reaction for 1.5 h; the precipitate was collected by centrifugation (9000rpm), washed three times with 300mL of ethanol and deionized water, respectively, and vacuum-dried at 50 ℃ for 12h to obtain a light yellow powder, which was the covalently crosslinked polyphosphazene nanosphere (PSTA).
Step two: dissolving 2g of pluronic (F127) in 200mL of ethanol; then, 2g of PSTA is added into the solution and uniformly dispersed for 1h by ultrasonic (160W, 90 Hz); mixing 3gCo (OAc)2·4H2Dissolving O in 200mL of ethanol, adding the system, stirring at room temperature for 24h, centrifuging at 9000rpm, collecting the product, washing with 150mL of deionized water and ethanol respectively, and drying in vacuum at 50 ℃ for 12h to obtain the PSTA-Co nanospheres.
Step three: keeping the temperature of the PSTA-Co nanospheres constant for 6h at 750 ℃ in a quartz tube under constant argon flow, and increasing the temperature at 10 ℃ min-1Washing with 3mol/LHCl solution and deionized water for three times, and vacuum drying at 60 deg.C for 12 hr; heating the dried black powder in a quartz tube at 800 ℃ for 6h at a heating rate of 10 ℃ min-1And obtaining the high-conductivity heteroatom-doped porous carbon nanoparticle composite material (N-HDPC).
Step four: the pretreatment method of the carbon cloth comprises the following steps: cutting carbon cloth into 1cm × 2cm, ultrasonic cleaning with acetone, anhydrous ethanol, and deionized water for 20min, cleaning surface oil, and heating in a tubular furnace at 300 deg.C to N2Heating for 6h under the atmosphere.
Step five: weighing 9.2mg of N-HDPC, placing the N-HDPC into a 5mL centrifuge tube, sequentially adding 49.6 mu L of deionized water, 100 mu L of isopropanol and 57.12 mu L of Nafion solution with the mass fraction of 5%, carrying out ultrasonic treatment for 30min to uniformly disperse the mixture, and uniformly coating the dispersed mixture on two sides of the pretreated carbon cloth. Drying at normal temperature overnight for 12h, connecting the titanium wires to carbon cloth by conductive silver adhesive, and finally obtaining the microbial fuel cell anode material (N-HDPC/CC) containing the high-conductivity heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite material. The scanning electron micrograph of the obtained microbial fuel cell anode material (N-HDPC/CC) containing the high-conductivity heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite material is shown in figure 1b, and the material still maintains uniform size and pore structure after carbonization at 900 ℃.
Example 2
The preparation method of the porous carbon nanoparticle composite material (N-HDPC) doped with high-conductivity heteroatoms (N, P, S and Co) comprises the following steps:
the method comprises the following steps: dissolving 2.4g of Tannic Acid (TA) in 800mL of acetonitrile, adding 80mL of Triethylamine (TEA), then performing ultrasonic treatment (240W, 50Hz) at 35 ℃ for 45min, dissolving 2g of Hexachlorocyclotriphosphazene (HCCP) and 2g of 4, 4-dihydroxydiphenylsulfone (BPS) in 1200mL of acetonitrile, and adding the mixture into the ultrasonic solution; continuing to perform ultrasonic treatment under the same condition, and performing polycondensation reaction for 1.5 h; the precipitate was collected by centrifugation (9000rpm), washed three times with 600mL of ethanol and deionized water, respectively, and vacuum dried at 90 ℃ for 12h to give a pale yellow powder, i.e., PSTA nanospheres.
Step two: 4g of pluronic (F127) was dissolved in 400mL of ethanol; then 4g of PSTA was added to the above solution and dispersed homogeneously by sonication (240W, 50Hz) for 1h, 6g of Co (OAc)2·4H2Dissolving O in 400mL of ethanol, adding the system, stirring at room temperature for 36h, centrifuging at 9000rpm, collecting the product, washing with 300mL of deionized water and ethanol for three times respectively, and drying in vacuum at 90 ℃ for 12h to obtain the PSTA-Co nanospheres.
Step three: keeping the temperature of the PSTA-Co nanospheres in a quartz tube at 900 ℃ for 3h under constant argon flow, wherein the heating rate is 10 ℃ min-1Washed three times with 3mol/LHCl solution and deionized water and dried under vacuum at 90 ℃ for 12 h. Heating the dried black powder in a quartz tube at 1000 ℃ for 3h at a constant temperature of 10 ℃ min-1And obtaining the porous carbon nano particle composite material (N-HDPC) doped with the high-conductivity heteroatom.
Step four: the pretreatment method of the Carbon Cloth (CC) comprises the following steps: cutting carbon cloth into 1cm × 2cm, ultrasonic cleaning with acetone, anhydrous ethanol, and deionized water for 40min, cleaning surface oil, and heating in a tubular furnace at 450 deg.C to N2In the atmosphereHeating for 3 h.
Step five: weighing 18.4mg of N-HDPC, placing the N-HDPC into a 10mL centrifuge tube, sequentially adding 99.2 muL of deionized water, 200 muL of isopropanol and 114.24 muL of Nafion solution with the mass fraction of 5%, carrying out ultrasonic treatment for 30min to uniformly disperse the mixture, and uniformly coating the dispersed mixture on two sides of the pretreated carbon cloth. Drying at normal temperature for 12h, connecting the titanium wires to carbon cloth by conductive silver adhesive, and finally obtaining the microbial fuel cell anode material (N-HDPC/CC) containing the high-conductivity heteroatom doped porous carbon nano-particle composite material.
Example 3
The preparation method of the porous carbon nanoparticle composite material (N-HDPC) doped with high-conductivity heteroatoms (N, P, S and Co) comprises the following steps:
the method comprises the following steps: dissolving 1.8g of Tannic Acid (TA) in 600mL of acetonitrile, adding 60mL of Triethylamine (TEA), then performing ultrasonic treatment (200W, 70Hz) at 35 ℃ for 45min, dissolving 1.5g of Hexachlorocyclotriphosphazene (HCCP) and 1.5g of 4, 4-dihydroxydiphenylsulfone (BPS) in 800mL of acetonitrile, and adding the mixture to the ultrasonic solution; continuing to perform ultrasonic treatment under the same condition, and performing polycondensation reaction for 1.5 h; the precipitate was collected by centrifugation (9000rpm), washed three times with 450mL of ethanol and deionized water, respectively, and vacuum dried at 70 ℃ for 12h to give a pale yellow powder, i.e., PSTA nanospheres.
Step two: dissolving 3g of pluronic (F127) in 300mL of ethanol; then 3g of PSTA was added to the above solution and dispersed homogeneously by sonication (200W, 70Hz) for 1h, 4.5g of Co (OAc)2·4H2Dissolving O in 300mL of ethanol, adding the system, stirring for 30h at room temperature, centrifuging at 9000rpm, collecting the product, washing with 225mL of deionized water and ethanol for three times respectively, and drying in vacuum at 70 ℃ for 12h to obtain the PSTA-Co nanospheres.
Step three: keeping the temperature of the PSTA-Co nanospheres in a quartz tube at 825 deg.C under constant argon flow for 4.5h, and increasing the temperature at 10 deg.C/min-1Washed three times with 3mol/LHCl solution and deionized water and dried in vacuum at 75 ℃ for 12 h. Heating the dried black powder in a quartz tube at 900 ℃ for 4.5h, wherein the heating rate is 10 ℃ min-1To obtain the highly conductive impurityAn atom-doped porous carbon nanoparticle composite (N-HDPC).
Step four: the pretreatment method of the Carbon Cloth (CC) comprises the following steps: cutting carbon cloth into 1cm × 2cm, ultrasonic cleaning with acetone, anhydrous ethanol, and deionized water for 30min, cleaning surface oil, and heating in tubular furnace at 375 deg.C under N2Heating for 4.5h under the atmosphere.
Step five: weighing 13.8mg of N-HDPC, placing the N-HDPC into a 10mL centrifuge tube, sequentially adding 74.4 muL of deionized water, 150 muL of isopropanol and 85.68 muL of Nafion solution with the mass fraction of 5%, carrying out ultrasonic treatment for 30min to uniformly disperse the mixture, and uniformly coating the dispersed mixture on two sides of the pretreated carbon cloth. Drying at normal temperature for 12h, connecting titanium wires to carbon cloth by conductive silver adhesive, and finally obtaining the microbial fuel cell anode material (N-HDPC/CC) containing the high-conductivity heteroatom doped porous carbon nanoparticle composite material.
The properties of the material prepared in the present invention were verified by using the material prepared in example 1 as a representative, and the same technical effects were obtained in examples 2 and 3.
The pretreatment of the carbon cloth comprises the following steps: cutting Carbon Cloth (CC) into pieces of 1cm x 2cm, ultrasonic cleaning with acetone, anhydrous ethanol, and deionized water for 20min, cleaning surface oil, and heating in a tubular furnace at 350 deg.C to N2Heating for 3h under the atmosphere. The scanning electron microscope of the pretreated carbon cloth is shown in FIG. 1b, and the CC material is not beneficial to bacterial adhesion due to hydrophobicity and smooth surface.
To further verify the doping of the heteroatoms (N, P, S and Co) on the carbon cloth, the anode material (N-HDPC/CC) of the microbial fuel cell containing the porous carbon nanoparticle composite material doped with the high conductive heteroatoms (N, P, S and Co) prepared in example 1 was subjected to X-ray detection, and the result is shown in fig. 2. The results show that N, P, S and Co atoms are incorporated into the graphitic carbon structure.
Fig. 1 shows SEM images of Carbon Cloth (CC) and microbial fuel cell anode material (N-HDPC/CC) containing highly conductive heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite, CC material is not favorable for bacterial adhesion due to hydrophobicity and smooth surface (fig. 1 a). For the N-HDPC/CC anode, the presence of N-HDPC increased the roughness and hydrophilicity of the CC surface, which favoured bacterial adhesion and the formation of thick biofilm (FIG. 1 b).
Fig. 2 shows the full X-ray photoelectron spectrum of the microbial fuel cell anode material (N-HDPC/CC) containing the highly conductive heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite, confirming that N, P, S and Co atoms were incorporated into the graphitic carbon structure.
FIG. 3 shows Cyclic Voltammograms (CV) of CC and N-HDPC/CC anodes in fresh anode solution, FIG. 3a is CV plot before inoculation, FIG. 3b is CV plot under turnaround conditions (with sodium acetate) after 30 days of operation, and FIG. 3c is CV plot under non-turnaround conditions (without sodium acetate) after 30 days of operation. The N-HDPC modified electrode in fig. 3a shows higher capacitive current than the CC anode, which means that there are more electrocatalytically active sites. After 1 month of stable operation of the MFCs, a typical sigmoidal curve appeared in all anode curves (fig. 3b), indicating the electro-activity and electrocatalytic oxidation of the bacteria on sodium acetate. The peak current density of the N-HDPC/CC anode is 10.85 A.m-2Much higher than CC (1.61A · m)-2). Thus, the above results show that the N-HDPC/CC anode improves the electrocatalytic activity of EAMs, thereby improving the power generation performance of MFCs. The curve area of N-HDPC/CC is also higher than that of CC, and further proves that HPCN modification is beneficial to adhesion of electroactive bacteria and provides more active sites for electrocatalytic oxidation-reduction reaction.
FIG. 4 is a graph of MFC output voltage for CC and N-HDPC/CC, respectively, as the anode of the MFC. Wherein, the MFC voltage of the two anodes in the first cycle is irregular or unstable, which indicates that the microorganism does not form a stable colony, the microbial colony is stable after the first cycle, and the MFC output voltage (523mV) of the N-HDPC/CC anode is higher than the MFC (310mV) of the CC anode. This result indicates that N-HDPC improves the EET process between the anode and the microorganism because heteroatom doping provides more active sites, and higher biocompatibility.
FIG. 5 shows the MFC polarization curve and power density for CC and N-HDPC/CC anodes as MFC anodes, respectively, and it can be seen from the graph that the MFC open-circuit voltage (0.78v) of N-HDPC/CC anode is larger than the MFC open-circuit voltage of CC anodeThe voltage (0.695v) is high, and the absolute value of the slope is low, which shows that N-HDPC reduces the electrocatalytic overpotential of the anode electroactive biomembrane. The power density of the MFC using the N-HDPC/CC anode was 1.72 W.m-2The current density was 4.52A · m-2Respectively, CC anode (power density of 0.945 W.m)-2The current density is 3.12 A.m-2) 1.82 times and 1.44 times, indicating that MFC at the N-HDPC/CC anode performs better than MFC at the CC.
FIG. 6 shows SEM images of (a, b, c) CC and (d, e, f) N-HDPC/CC anodes after stable operation of the MFCs for 30 days. The results show that, as shown in fig. 6a-c, only a small part of the carbon fiber surface on the CC anode is attached by microorganisms, and microorganisms are difficult to attach due to the smooth surface, low hydrophobicity and porosity, and small specific surface area of the CC anode. Furthermore, low CC anode porosity does not guarantee internal microbial activity when biofilm thickness increases, leading to reduced colony activity or apoptosis. In contrast, most of the N-HDPC/CC electrode surface was covered with microbes, all carbon cloth fibers were coated with rod-shaped bacteria, and the electrodes were not clogged (fig. 6d and 6 e). In the biofilm, viable bacterial cells were tightly attached to the anode surface, and microbial nanowires (or conductive pili) were visible between bacteria (fig. 6f), indicating that N-HDPC has sufficient biocompatibility.
Therefore, the prepared microbial fuel cell anode material (N-HDPC/CC) containing the high-conductivity heteroatom (N, P, S and Co) doped porous carbon nanoparticle composite material has better biocompatibility and higher power density, and is suitable for being applied as the anode material of the microbial fuel cell.

Claims (10)

1. A high-conductivity heteroatom-doped porous carbon nanoparticle composite material is characterized by comprising the following steps:
the method comprises the following steps: dissolving tannic acid in acetonitrile, adding triethylamine, and performing ultrasonic treatment; dissolving hexachlorocyclotriphosphazene and 4, 4-dihydroxy diphenyl sulfone in acetonitrile, and adding the acetonitrile into the solution after ultrasonic treatment for continuous ultrasonic treatment; centrifuging and collecting precipitates, washing the precipitates with ethanol and deionized water, and drying the precipitates in vacuum at 50-90 ℃ to obtain covalent crosslinking polyphosphazene nanospheres;
step two: dissolving Pluronic in ethanol, adding the covalent cross-linked polyphosphazene nanospheres obtained in the step one, and performing ultrasonic uniform dispersion; general formula (Co), (OAc)2·4H2Dissolving O in ethanol, adding the O into the solution after ultrasonic uniform dispersion, stirring at room temperature, centrifuging to collect a product, washing with ethanol and deionized water, and drying in vacuum at 50-90 ℃ to obtain PSTA-Co nanospheres;
step three: and (3) heating the PSTA-Co nanospheres obtained in the second step from room temperature to 750-900 ℃ in a quartz tube under the existence of constant argon, keeping the temperature constant for 3-6 hours, washing with HCl solution and deionized water, drying in vacuum at 60-90 ℃, heating the dried black powder in the quartz tube from room temperature to 800-1000 ℃, and keeping the temperature constant for 3-6 hours to obtain the high-conductivity heteroatom doped porous carbon nanoparticle composite material.
2. The porous carbon nanoparticle composite material with high conductivity and heteroatom doping content as claimed in claim 1, wherein the mass ratio of the tannic acid, the hexachlorocyclotriphosphazene and the 4, 4-dihydroxydiphenylsulfone in the step one is 1.5-2.4: 0.8-1.2, and the volume fraction of the triethylamine in the acetonitrile solution is 10-12%.
3. The porous carbon nanoparticle composite material with high conductivity and heteroatom doping as claimed in claim 1, wherein the Pluronic, the covalently cross-linked polyphosphazene nanospheres and Co (OAc) in step two2·4H2The mass ratio of O is 2:2: 3.
4. The highly conductive heteroatom-doped porous carbon nanoparticle composite material as claimed in claim 1, wherein the ultrasonic power in the first step and the ultrasonic frequency in the second step are both 160-240W and 50-90 Hz.
5. The highly conductive heteroatom-doped porous carbon nanoparticle composite material according to claim 1, wherein in the second step, the stirring time at room temperature is 24-36 h, and the centrifugal speed is 9000 rpm.
6. The porous carbon nanoparticle composite material with high conductivity and heteroatom doping according to claim 1, wherein the temperature rise rate of two times in the third step is 10 ℃ min-1。
7. The porous carbon nanoparticle composite material with high conductivity and heteroatom doping according to claim 1, wherein the concentration of HCl solution in the third step is 3 mol/L.
8. The application of the high-conductivity heteroatom-doped porous carbon nanoparticle composite material disclosed by any one of claims 1-7 in preparation of anode materials of microbial fuel cells.
9. The application of claim 8, wherein the carbon cloth is ultrasonically cleaned with acetone, absolute ethyl alcohol and deionized water for 20-40 min in a tube furnace for N2Heating the mixture; sequentially adding a Nafion solution containing deionized water, isopropanol and 5% by mass into the high-conductivity heteroatom-doped porous carbon nanoparticle composite material, uniformly coating the uniformly-dispersed mixed solution on two sides of the pretreated carbon cloth, drying, and connecting titanium wires to the carbon cloth by using conductive silver adhesive to obtain the microbial fuel cell anode material containing the high-conductivity heteroatom-doped porous carbon nanoparticle composite material.
10. The use according to claim 9, wherein the temperature in the tube furnace is 300-450 ℃ and the heating time is 3-6 h; the volume ratio of the deionized water to the isopropanol to the Nafion solution with the mass fraction of 5% is 5:10: 6.
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