Phthalocyanine iron microwire or nanowire microbial fuel cell anode material and preparation method thereof

Abstract

The application discloses a kind of phthalocyanine iron microwire or nanowire microbial fuel cell anode material preparation and its application.Ordered accumulation nanowire or microwire can be in situ growth on the surface of carbon carrier such as carbon cloth, carbon felt, and phthalocyanine iron molecular accumulation spacing 1.6 nanometer.The application can promote the electron transfer between biological-nonbiological interface, improve the electron transfer rate between electricity-producing microorganism and phthalocyanine iron microwire or nanowire;The application can promote the effective enrichment of electricity-producing bacteria Geobacter in sludge, and the abundance ratio in microbial community is 87.5%, effectively improving the proportion of electricity-producing microorganism;The battery anode of the application has excellent biocompatibility, can guarantee the activity of biofilm in the long-term operation process of microbial fuel cell, can enrich electrically active bacteria, improve the long-term activity of biofilm, promote the interface extracellular electron transfer of microorganism, effectively solve the problem that the output power of microbial fuel cell is low and the long-term operation stability is poor.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of microbial fuel cells, and relates to a phthalocyanine iron microwire or nanowire microbial fuel cell anode material and a preparation method thereof. BACKGROUND

[0002] At present, energy shortage and water resource pollution have become a key concern, and the energy consumption required for sewage treatment accounts for 60%-70% of the entire sewage treatment system, so there is an urgent need for a technology that can reduce the cost of sewage treatment. A microbial fuel cell decomposes organic waste into water and carbon dioxide at the anode while releasing electrons, and the electrons are transmitted to the cathode through an external circuit, and oxygen, metals and inorganic salts on the cathode accept electrons as electron acceptors, thereby realizing sewage treatment and power generation, and no aeration is required during operation, which is a sewage treatment and synchronous power generation technology with important application prospects. However, the main reason why the microbial fuel cell cannot be put into actual production at present is that its long-term operation stability is poor and the power output is low. The main reasons are that the extracellular electron transfer process at the anode is slow, the conductivity of the anode material is poor, the electrogenic bacteria are not easy to adhere to the surface of the anode material, and the biocompatibility is poor. Therefore, researchers have improved the performance of the anode of the microbial fuel cell by using metal materials, carbon materials, and nano materials. However, due to the smooth surface of the metal material, it is difficult for bacteria to adhere, and some metal materials even have biological toxicity, which leads to a decrease in the activity of electrogenic bacteria and a decrease in the power generation efficiency; due to the complex microcosmic interaction between microorganisms and the electrode interface, the redox potential of some nano material anodes does not match the potential of c-type cytochrome (-400 mV~50 mV), and too high an electrode surface potential will lead to a decrease in microbial activity and a decrease in electron transfer efficiency, and too low a surface potential (lower than -400 mV) is not conducive to the secretion of proteins by microorganisms to participate in energy metabolism and increase the abundance of c-type cytochrome, thereby seriously limiting the energy conversion efficiency. Therefore, designing a nano material modified microbial fuel cell anode that can reduce the activation energy of microbial catalytic reaction from the thermodynamic aspect, improve the electron extraction and transfer rate from the kinetic aspect, and optimize the material diffusion path has important research significance for improving the output power of the microbial fuel cell.

[0003] In order to solve such problems, some anodes modified by nano materials similar to the heme structure in cytochrome c become a new strategy to improve the performance of microbial fuel cells. Cheng et al. prepared amorphous iron porphyrin or phthalocyanine materials in the patent (a conjugated polymer biological catalytic material and its preparation method and application, patent number: CN202310550981.6), which showed enzyme-like catalytic activity in heterogeneous catalytic reaction, but its amorphous structure did not have high efficient electron transfer capacity, which was not conducive to the electron transfer at the anode interface of microbial fuel cells; In its patent, it is mentioned that natural porphyrin and metal porphyrin complex molecules have electron buffering properties, which can be used to stabilize the valence of the catalytic center, however, the anode of microbial fuel cell is a single-phase interface electron transfer from the electricity-producing microorganism to the anode, and the electron is quickly conducted to the cathode to form a closed loop to generate electricity, and the electron buffering property cannot promote the rapid interface electron transfer. Recently, Li et al. used disordered phthalocyanine iron loaded carbon cloth as the anode of microbial fuel cell, produced more active centers on the phthalocyanine iron loaded carbon cloth electrode by doping heteroatoms, and strengthened the affinity with outer membrane cytochrome c by using the structure similar to iron porphyrin, reduced the charge transfer resistance, improved the direct electron transfer process through the outer membrane cytochrome c, and the power density was increased by 4.32 times compared with carbon cloth. Li et al. used iron porphyrin-poly cationic ammonium salt to modify carbon cloth, improved the spatial structure of microbial membrane, accelerated the extracellular electron transfer by using the strong interaction between cytochrome c and FeN4 active site, and the power density was increased by 1.92 times compared with the control group. Jan et al. constructed a graphene / hematin coating, which replaced the role of extracellular cytochrome OmcZ, filled the gap of key electrochemistry at the microbial / anode interface, and restored the anode metabolic capacity of the mutant strain, and the maximum current density was 10.2 times higher than that of the control group. However, due to the serious self-aggregation of hematin or porphyrin, phthalocyanine and other molecules in the solution, the conductivity of the disordered accumulation and sedimentation or thin film is usually less than 10 -8 S / cm, which is far lower than the conductivity of microbial conductive hyphae (0.02-20 S / cm), and cannot be used as ideal artificial nano wires; and the above-mentioned anode materials cannot control the morphology and accumulation order of the aggregates, lack of electroactive bacteria enrichment ability, lack of rich electron transfer channels and ion diffusion paths, resulting in low extracellular electron transfer efficiency, and the toxic substances produced by long-term biofilm cannot be effectively diffused, causing the death of microorganisms, affecting the power generation and sewage treatment performance of microbial fuel cells.

[0004] In view of the above reasons, the present application provides a phthalocyanine iron microwire or nanowire microbial fuel cell anode material and a preparation method thereof. SUMMARY

[0005] The present application aims at overcoming the shortcomings of the existing microbial fuel cell anode technology, and provides a phthalocyanine iron microwire or nanowire microbial fuel cell anode material and a preparation method thereof.

[0006] The present application aims at overcoming the shortcomings of the existing microbial fuel cell anode technology, and provides a phthalocyanine iron microwire or nanowire microbial fuel cell anode material and a preparation method thereof.

[0007] The present application aims at overcoming the shortcomings of the existing microbial fuel cell anode technology, and provides a phthalocyanine iron microwire or nanowire microbial fuel cell anode material and a preparation method thereof.

[0008] The anode material is composed of phthalocyanine iron microwires or nanowires, and the microwires or nanowires are composed of ordered phthalocyanine iron molecules, and the one-dimensional artificial nanowires are grown in situ on the surface of the macroporous carbon cloth. The charge transfer resistance of the anode material is less than or equal to 12.5 ohms, which significantly reduces the internal resistance of the anode. Meanwhile, the abundance of Geobacter electroactive bacteria in the anode surface biofilm reaches 87.5%, and the long-term running biofilm activity can be effectively maintained. The anode material can be applied to microbial fuel cells and has the performance of enriching electroactive microorganisms and promoting extracellular electron transfer.

[0009] The preparation of the anode material includes the following steps:

[0010] (1) Washing the carbon cloth, placing the cut carbon cloth in acetone, and ultrasonic cleaning; then placing the carbon cloth in ethanol, and ultrasonic cleaning; and then placing the carbon cloth in deionized water, and ultrasonic cleaning. Placing the washed carbon cloth in an oven for drying, and waiting for use.

[0011] In this step, 5 mL of acetone is added for ultrasonic cleaning according to the proportion of 5 mL of acetone per 1 cm 2 of carbon cloth; 5 mL of ethanol is added for ultrasonic cleaning according to the proportion of 5 mL of ethanol per 1 cm 2 of carbon cloth, and 75%-99.5% concentration of ethanol can be used; and 5 mL of water is added for ultrasonic cleaning according to the proportion of 5 mL of water per 1 cm 2 of carbon cloth.

[0012] The ultrasonic time in step (1) is 30-60 min, and the carbon cloth can be replaced by carbon carriers such as carbon felt and carbon paper according to actual needs.

[0013] (2) Preparation of phthalocyanine iron microwire / nanowire, 50-100 mg of phthalocyanine iron powder is placed on the upstream zone of a double-zone tube furnace, and heated to 450-500 DEG C at a heating rate of 1-10 DEG C / min; 3-5 pieces of 1 cm*1 cm cleaned carbon cloth are placed at a distance of 3-11 cm from the center of the downstream zone of the tube furnace, and heated to 200-250 DEG C at a heating rate of 1-10 DEG C / min. The process is carried out under vacuum and in a nitrogen atmosphere. After the temperature of the tube furnace decreases to room temperature, the phthalocyanine iron microwire / nanowire loaded carbon cloth anode is obtained.

[0014] The vacuum degree of step (2) is 10 -3 -10 -8 Pa, the holding time is 1-3 h, and the nitrogen gas flow rate is 5-10 sccm.

[0015] (3) The phthalocyanine iron microwire or nanowire modified carbon cloth is used as a microbial fuel cell anode, and after the cell is stably operated for several cycles, electrochemical impedance spectroscopy, power density test, scanning electron microscopy after inoculation, and anode microbial community analysis are used for characterization, which shows that the phthalocyanine iron microwire or nanowire loaded carbon cloth anode can effectively promote the effective enrichment of Geobacter and can effectively improve the performance of the microbial fuel cell.

[0016] Further, the ordered stacking distance of the phthalocyanine iron molecules is 1.6 nm; the diameter of the microwire is about 0.4-1.2 microns, and the diameter of the nanowire is about 10-100 nm; the microwire or nanowire is directly grown on the surface of the carbon cloth; and the carbon carrier includes carbon cloth, carbon felt and carbon paper, etc.

[0017] In the present application, the electrochemical impedance spectroscopy test after the bacterial film is attached is carried out after the cell is continuously operated for 4 cycles, and a stable bacterial film is formed on the surface of the anode. When the voltage of the microbial fuel electrode reaches the maximum value, the test is carried out in 50 mL of fresh anode liquid under a three-electrode system (saturated calomel electrode as reference electrode, platinum sheet electrode as counter electrode, and anode covered with biological film as working electrode).

[0018] In the present application, the power density curve is calculated by replacing the external resistance, and when the resistance value decreases to below 500 Ω, the resistance value decreases by less than 50 Ω, so as to prevent the power density curve from suddenly turning back and the maximum power density of the cell from being found.

[0019] In the present application, after inoculation, the anode scanning electron microscope observation is carried out, and after bacterial fixation and gradient dehydration, natural air drying is carried out at room temperature. Then, gold spraying treatment is carried out, so as to have a clear object image under the scanning electron microscope, and the gold spraying time is about 2 minutes.

[0020] In the present application, the anode microbial community analysis is carried out after inoculation and continuous stable operation of the battery for 40-50 days, the microorganisms on the anode surface are fully attached, and the biofilm is formed, and then DNA extraction and sequencing analysis are carried out.

[0021] Compared with the existing microbial fuel cell anode, the present application has the following advantages:

[0022] 1) The phthalocyanine iron microwire or nanowire anode can efficiently enrich Geobacter, and the proportion of Geobacter in the anode microbial community is as high as 87.5%.

[0023] 2) The phthalocyanine iron microwire or nanowire has excellent electrical conductivity and biocompatibility, and the microwire or nanowire generated in situ on the carbon cloth or carbon felt can well improve the roughness of the carbon cloth surface, facilitate bacterial adhesion, rapidly transfer the electrons transferred by bacteria through metabolism to the cathode, improve the extracellular electron transfer efficiency, and further improve the battery performance.

[0024] 3) The phthalocyanine iron microwire or nanowire has high electrical conductivity, and the synthesis process is simple and easy to prepare.

[0025] 4) Phthalocyanine iron has good stability and can be applied to the anode of a microbial fuel cell, effectively improving the stability of long-term electrical energy output of the microbial fuel cell.

[0026] 5) Based on the excellent biocompatibility, good chemical stability, high electrical conductivity, and simple preparation of the phthalocyanine iron microwire or nanowire, the phthalocyanine iron microwire or nanowire efficiently enriches Geobacter, and the enrichment rate is as high as 87.5%, thereby effectively improving the output performance of the microbial fuel cell, and the maximum power density output is 3.02 W / m 2 , which is 2.19 times that of the control group anode, and the single cycle continuous discharge lasts for 7-9 days.

[0027] 6) The high-efficiency enrichment of Geobacter by the phthalocyanine iron microwire or nanowire anode overcomes the shortcomings of low output power and poor long-term running stability of the current microbial fuel cell. Therefore, the phthalocyanine iron microwire or nanowire can be applied to the anode of a microbial fuel cell, effectively improving the power generation and electrical energy output stability. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 X-ray powder diffraction patterns of phthalocyanine iron microwire modified carbon cloth (abbreviated as FePc-MW@CC) and carbon cloth (abbreviated as CC);

[0029] Figure 2 Scanning electron microscope images of phthalocyanine iron (a) microwire and (b) nanowire modified carbon cloth anodes;

[0030] Figure 3High resolution transmission electron microscopy image of phthalocyanine iron nanowires;

[0031] Figure 4 Scanning electron microscopy image of FePc-MW@CC anode after microorganism attachment;

[0032] Figure 5 Scanning electron microscopy image of bare carbon cloth anode after microorganism attachment;

[0033] Figure 6 Voltage output curve of the continuously running microbial fuel cell;

[0034] Figure 7 Polarization curve and power density curve of the microbial fuel cell;

[0035] Figure 8 Electrochemical impedance spectrogram of the microbial fuel cell anode after bacterial membrane attachment;

[0036] Figure 9 Sequencing graph of the microorganism on the anode of the microbial fuel cell at the species level. DETAILED DESCRIPTION

[0037] The present application will be further described below in conjunction with the accompanying drawings: the present embodiment is implemented on the premise of the technical solutions of the present application, and detailed implementation modes are given, but the protection scope of the present application is not limited to the following examples.

[0038] The present application provides preparation and application of phthalocyanine iron microwire or nanowire microbial fuel cell anode material, and the specific steps are as follows:

[0039] Step 1: Place the cut 1cm×1cm carbon cloth in 5mL acetone, ultrasonic clean for 30min, then place the carbon cloth in 5mL anhydrous ethanol, ultrasonic clean for 30min, and then place the carbon cloth in 5mL deionized water, ultrasonic clean for 30min. Place the cleaned carbon cloth in a 60℃ oven to dry, and wait for use.

[0040] Step 2: Place 50mg of phthalocyanine iron powder in the upstream area of the tube furnace and heat to 450℃ at a heating rate of 5℃ / min; place 3 pieces of 1cm×1cm cleaned carbon cloth at a distance of 3cm, 5cm and 7cm from the center of the tube furnace in the downstream area, and heat to 200℃ at a heating rate of 5℃ / min. The vacuum degree of this process is 10 -3 Pa, and the nitrogen flow is 5sccm. After the temperature of the tube furnace decreases to room temperature, the phthalocyanine iron microwire loaded carbon cloth anode is obtained.

[0041] Step 3: install the phthalocyanine iron micro-wire loaded carbon cloth anode to the microbial fuel cell, after the cell is stably operated for several cycles, the cell performance is tested by electrochemical impedance spectroscopy, power density test, scanning electron microscope after the bacteria are attached, and anode microbial community analysis, which shows that the phthalocyanine iron micro-wire or nano-wire loaded carbon cloth or carbon felt anode can effectively promote the effective enrichment of the electricity-producing bacteria Geobacter, and can effectively improve the performance of the microbial fuel cell.

[0042] The cell performance test in step 3 above includes output voltage curve and power density curve. Figure 6 It is known from the output voltage curve that the highest output voltage of the phthalocyanine iron micro-wire loaded carbon cloth anode is 0.617V, which is significantly higher than 0.473V of the carbon cloth, and the continuous power output lasts for 7-9 days. The cell power density test method is: when the cell is replaced with anode liquid and cathode liquid, the cell voltage is raised to the highest, and then the external resistance is removed to keep open circuit state for about 2h, and then the resistance box is connected. The resistance is reduced from 2000, 1750, 1500, 1250, 1000, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400Ω to 350Ω, and the corresponding voltage value under each resistance is recorded, and the corresponding current and power are calculated by I=U / R and P=UI. Then, the electrode area is 2×10 -4 m 2 The corresponding current density and power density are obtained. Figure 7 It is known from the power density curve that the maximum power density of the phthalocyanine iron micro-wire modified carbon cloth anode is 3.02W / m 2 , which is 2.19 times of that of the carbon cloth (1.41W / m 2 ).

[0043] In order to reveal the reason for the high power output realized by the phthalocyanine iron micro-wire loaded carbon cloth anode, the present application characterizes the adhesion speed of microorganisms on the anode, the anode electrochemical impedance spectrum after the adhesion of the bacterial film, and the anode microbial community composition. Figure 4 is the scanning electron microscope graph of the phthalocyanine iron micro-wire modified carbon cloth anode after inoculation for 3-4 days, Figure 5 is the scanning electron microscope graph of the bare carbon cloth anode after inoculation for 5-6 days. It can be seen that a large number of bacteria have been attached to the surface of the phthalocyanine iron micro-wire anode, and the bacteria tend to adhere to the micro-wire, while only a small amount of bacteria are attached to the carbon cloth anode. This is consistent with Figure 6 the phthalocyanine iron micro-wire anode has a shorter voltage starting time. Figure 8is the electrochemical impedance spectrogram measured after the battery is stably operated for 4 cycles, and it can be seen that the charge transfer impedance (12.08 Ω) of the phthalocyanine iron microwire modified carbon cloth anode is significantly lower than the charge transfer impedance (33.97 Ω) of the carbon cloth anode, which is consistent with the excellent electric energy output result thereof. Figure 9 is the microbial community sequencing result of the anode when the battery is stably operated for 40 days, and it can be seen that the proportion of Geobacter on the phthalocyanine iron microwire anode is as high as 87.5%, which is significantly higher than that (58.3%) of the carbon cloth anode. Due to the efficient enrichment of Geobacter electrogenic bacteria on the phthalocyanine iron microwire anode, the phthalocyanine iron microwire anode has stable high electric energy output.

[0044] The application will be further described below in combination with specific examples, but the content of the application is not limited thereto:

[0045] Example 1

[0046] Step one: cut 1 cm x 1 cm carbon felt into 5 mL acetone, ultrasonic cleaning for 30 min, then place the carbon cloth in 5 mL of absolute ethanol, ultrasonic cleaning for 30 min, and then place the carbon cloth in 5 mL of deionized water, ultrasonic cleaning for 30 min. Place the washed carbon felt in a 60°C oven to dry.

[0047] Step two: place 50 mg of phthalocyanine iron powder in the upstream zone of the tube furnace and heat to 450°C at a rate of 5°C / min; place three 1 cm x 1 cm washed carbon felts at a distance of 3 cm, 5 cm and 7 cm from the center of the tube furnace in the downstream zone and heat to 200°C at a rate of 5°C / min. The process is carried out in a vacuum and a nitrogen atmosphere, and the nitrogen flow is 5 sccm. After the temperature of the tube furnace decreases to room temperature, the phthalocyanine iron microwire loaded carbon felt anode is obtained.

[0048] Example 2

[0049] Step one: cut 1 cm x 1 cm carbon felt into 5 mL acetone, ultrasonic cleaning for 60 min, then place the carbon cloth in 5 mL of absolute ethanol, ultrasonic cleaning for 60 min, and then place the carbon cloth in 5 mL of deionized water, ultrasonic cleaning for 60 min. Place the washed carbon felt in a 60°C oven to dry.

[0050] Step 2: Place 100 mg of iron phthalocyanine powder in the upstream section of a tube furnace and heat it to 450°C at a rate of 5°C / min. In the downstream section, place five 1 cm x 1 cm pieces of clean carbon felt at locations 3 cm, 5 cm, 7 cm, 9 cm, and 11 cm from the center of the tube furnace and heat it to 200°C at a rate of 5°C / min. This process is performed under vacuum conditions for 3 hours in a nitrogen atmosphere at a flow rate of 10 sccm. After the tube furnace temperature cools to room temperature, the carbon felt anode loaded with iron phthalocyanine microwires is obtained.

[0051] Example 3

[0052] Step 1: Place the cut 1cm x 1cm carbon in 5mL of acetone and ultrasonically clean it for 30 minutes. Then, place the carbon in 5mL of anhydrous ethanol and ultrasonically clean it for 30 minutes. Then, place the carbon in 5mL of deionized water and ultrasonically clean it for 30 minutes. Dry the cleaned carbon in a 60°C oven until ready for use.

[0053] Step 2: Place 50 mg of iron phthalocyanine powder in the upstream section of a tube furnace and heat it to 450°C at a rate of 5°C / min. In the downstream section, place three 1 cm x 1 cm pieces of clean carbon cloth at 7 cm, 9 cm, and 11 cm from the center of the tube furnace and heat it to 250°C at a rate of 5°C / min. This process is performed under vacuum conditions for 1 hour in a nitrogen atmosphere with a nitrogen flow rate of 5 sccm. After the tube furnace temperature cools to room temperature, the carbon cloth anode loaded with iron phthalocyanine nanowires is obtained.

[0054] Example 4

[0055] Step 1: Place the cut 1cm x 1cm carbon in 5mL of acetone and ultrasonically clean it for 60 minutes. Then, place the carbon in 5mL of anhydrous ethanol and ultrasonically clean it for 60 minutes. Then, place the carbon in 5mL of deionized water and ultrasonically clean it for 60 minutes. Dry the cleaned carbon in a 60°C oven until ready for use.

[0056] Step 2: Place 100 mg of iron phthalocyanine powder in the upstream section of a tube furnace and heat it to 450°C at a rate of 5°C / min. In the downstream section, place three 1 cm x 1 cm pieces of clean carbon cloth at 7 cm, 9 cm, and 11 cm from the center of the tube furnace and heat it to 200°C at a rate of 5°C / min. This process is performed under vacuum conditions for 3 hours in a nitrogen atmosphere at a flow rate of 10 sccm. After the tube furnace temperature cools to room temperature, the carbon cloth anode loaded with iron phthalocyanine nanowires is obtained.

[0057] Example 5

[0058] Step one: cut 1cm*1cm carbon cloth and clean it in 5mL acetone for 60min, then clean it in 5mL absolute ethanol for 60min, and then clean it in 5mL deionized water for 60min. Dry the cleaned carbon cloth in 60℃ oven and wait for use.

[0059] Step two: put 100mg of iron phthalocyanine powder in the upstream zone of the tube furnace and heat it to 500℃ at a heating rate of 5℃ / min; put 3 pieces of cleaned carbon cloth (1cm*1cm) in the downstream zone of the tube furnace at 7cm, 9cm, 11cm from the center of the tube furnace and heat them to 200℃ at a heating rate of 5℃ / min. The process is carried out in vacuum and nitrogen atmosphere, and the nitrogen flow rate is 5sccm. After the temperature of the tube furnace decreases to room temperature, the carbon cloth anode loaded with iron phthalocyanine nanowires is obtained.

[0060] Based on the good biocompatibility, high conductivity, excellent chemical stability of iron phthalocyanine aggregates, and the similar structure with the heme in the outer membrane protein of the electricity-producing bacteria, the electron transfer between the biological and non-biological interfaces can be promoted, and the electron transfer rate between the electricity-producing microorganisms and the iron phthalocyanine microwires or nanowires can be improved; the carbon cloth anode modified with iron phthalocyanine microwires or nanowires can promote the effective enrichment of Geobacter in the sludge, and the abundance ratio in the microbial community is 87.5%, effectively improving the proportion of electricity-producing microorganisms; the carbon cloth anode modified with iron phthalocyanine microwires or nanowires has excellent biocompatibility, which can ensure the activity of the biofilm during the long-term operation of the microbial fuel cell. The application of iron phthalocyanine microwires or nanowires to the anode of the microbial fuel cell can enrich the electroactive bacteria, improve the long-term activity of the biofilm, promote the extracellular electron transfer of the microbial interface, and effectively solve the problems of low output power and poor long-term operation stability of the microbial fuel cell.

[0061] The above merely illustrates the preferred embodiments of the present application, which are different implementations based on the overall concept of the present application, and the protection scope of the present application is not limited thereto. Any changes or replacements easily conceived by those skilled in the art within the technical scope disclosed by the present application should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for preparing a microbial fuel cell anode material of iron phthalocyanine microwires or nanowires modified carbon cloth, characterized in that: The anode material is composed of iron phthalocyanine microwires or nanowires, which are composed of orderly stacked iron phthalocyanine molecules. One-dimensional artificial nanowires are in situ grown on the surface of a macroporous carbon cloth. The charge transfer resistance of the anode material is ≤12.5 Ω. The preparation method of the anode material is as follows: Step 1: Cleaning of carbon cloth: Place the cut carbon cloth in acetone and ultrasonically clean it; then place the carbon cloth in ethanol and ultrasonically clean it; then place the carbon cloth in deionized water and ultrasonically clean it. Place the cleaned carbon cloth in an oven and dry it for later use. In this step, the 2 The carbon cloth was ultrasonically cleaned by adding acetone in a ratio of 5 mL acetone; 2 Add 5 mL of ethanol to the carbon cloth and ultrasonically clean it with ethanol. 75%-99.5% concentration of ethanol can be used. 2 The carbon cloth was ultrasonically cleaned by adding 5 mL of water. The cleaned carbon cloth was dried in an oven at 50°C for 6 hours before use. The ultrasonic time in step 1 is 30 to 60 minutes, and the carbon cloth can be replaced with other carbon supports according to actual needs; Step 2: Preparation of iron phthalocyanine microwires / nanowires: 50-100 mg of iron phthalocyanine powder is placed in the upstream zone of a dual-temperature zone tubular furnace and heated to 450-500°C at a heating rate of 1-10°C / min. In the downstream zone, 3-5 pieces of 1 cm×1 cm clean carbon cloth are placed 3-11 cm away from the center of the tubular furnace and heated to 200-250°C at a heating rate of 1-10°C / min. This process is carried out under vacuum conditions and in a nitrogen atmosphere. After the tubular furnace temperature drops to room temperature, a carbon cloth anode loaded with iron phthalocyanine microwires / nanowires is obtained. The vacuum degree of step 2 is 10 -3 -10 -8 Pa, the holding time is 1~3h, and the nitrogen gas flow rate is 5~10 sccm.

2. A composite anode material for a microbial fuel cell using an iron phthalocyanine microwire or nanowire prepared by the method of claim 1, characterized in that: The ordered stacking distance of the iron phthalocyanine molecules is 1.6 nanometers.

3. A composite anode material for a microbial fuel cell using an iron phthalocyanine microwire or nanowire as claimed in claim 2, characterized in that: The diameter of the microwire is 0.4 micrometers to 1.2 micrometers, and the diameter of the nanowire is 10 nanometers to 100 nanometers.

4. The iron phthalocyanine microwire or nanowire microbial fuel cell composite anode material according to claim 3, characterized in that: The micron wires or nanowires are directly grown on the surface of the carbon cloth.

5. The iron phthalocyanine microwire or nanowire microbial fuel cell composite anode material according to claim 4, characterized in that: The carbon support includes carbon cloth, carbon felt and carbon paper.

6. An application of the iron phthalocyanine microwire or nanowire microbial fuel cell composite anode material as claimed in claim 5, characterized in that: The iron phthalocyanine microwire or nanowire anode grown directly on the surface of any carbon support can be directly used as the anode of a microbial fuel cell.

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