CN110165225B - Modified anode nanocomposite material for SMFC and preparation method thereof - Google Patents

Modified anode nanocomposite material for SMFC and preparation method thereof Download PDF

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CN110165225B
CN110165225B CN201910431695.1A CN201910431695A CN110165225B CN 110165225 B CN110165225 B CN 110165225B CN 201910431695 A CN201910431695 A CN 201910431695A CN 110165225 B CN110165225 B CN 110165225B
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titanium dioxide
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邱峥辉
蔺存国
张宇
郑纪勇
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725th Research Institute of CSIC
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Abstract

The invention belongs to the technical field of microbial fuel cells, and particularly relates to a modified anode nanocomposite material for SMFC and a preparation method thereof, wherein the modified anode nanocomposite material for SMFC has larger specific surface area and can provide a large number of attachment sites for electrogenesis microorganisms, 1, 4-dihydroxy anthraquinone carried in mesopores can be used as an electronic mediator to attract the enrichment of the electrogenesis microorganisms and improve the electron transfer efficiency of the electrogenesis microorganisms, the starting time of a cell can be obviously shortened and the output voltage of the cell can be improved by coating the modified anode nanocomposite material for SMFC on the surface of an electrode material, compared with a bare carbon plate, the microbial fuel cell adopting the modified carbon plate anode has the advantages that the output voltage under the condition of adding 1000 omega resistance is improved by nearly 100 percent, meanwhile, the electrogenic microorganisms can be quickly attached to the surface of the electrode, and the output voltage is quickly increased and stabilized to about 300 mV.

Description

Modified anode nanocomposite material for SMFC and preparation method thereof
The technical field is as follows:
the invention belongs to the technical field of microbial fuel cells, and particularly relates to a modified anode nanocomposite material for SMFC and a preparation method thereof.
Background art:
the SMFC (microbial fuel cell of the seabed sediment type) uses the electricity-generating microbes in the seabed sediment to transfer electrons generated in the process of oxidizing organic matters to an electrode outside cells along a respiratory chain, then the electrons are transferred to a cathode and react with oxygen to form a whole loop. The natural anaerobic environment in subsea sediments, as well as the organic and mineral content present provide unique conditions for the growth of electrogenic microorganisms. The organic reserves in subsea sediments are huge and renewable and the long-term operation of SMFCs is not limited by the fuel supply. The electrode material of the SMFC is generally inert material such as graphite, so that the long-term operation of the SMFC is not restricted by battery material. Based on this, SMFC can be as providing the novel power of long-term stable normal position electric energy for underwater equipment.
The preparation method of the marine sediment microbial fuel cell modified anode disclosed in the Chinese patent 201410779536.8 comprises the following steps: (1) taking the sample with diameter of 1.6cm, length of 10cm, and surface area of 54cm2The graphite rod is used as a graphite anode, and the surface of the graphite is polished to be smooth by sand paper of 180, 360, 600 and 800 respectively; (2) mn is prepared by taking ferroferric oxide, manganese sulfate, graphite powder, kaolin and nickel chloride hexahydrate as raw materials2++Fe3O4+Ni2The graphite anode has the particle size of 500 meshes and the particle size of the kaolin of 400 meshes; mixing ferroferric oxide, manganese sulfate, graphite powder, kaolin and nickel chloride hexahydrate according to the mass ratio of 6%, 3%, 58%, 30% and 2% respectively, wherein the total mass is 4 g; (3) uniformly mixing, adding a certain amount of deionized water, coating the deionized water on four side surfaces of a graphite electrode, drying at the temperature of 80 ℃ for 45min, then placing the graphite electrode in a muffle furnace, and roasting at the temperature of 380-450 ℃ for 48 h; (4) drilling a small hole at one end of the pretreated graphite, adding conductive epoxy resin into the hole, and inserting the exposed part of the lead into the epoxy resin in the hole, but ensuring that the exposed part of the lead cannot be contacted with the graphite substrate; (5) after the conductive epoxy resin is solidified, testing whether the linkage between the electrode and the lead is good or not by using a universal meter, then filling the rest part of the small hole with insulating epoxy resin, and airing, drying and storing; (6) preparing 45% of sulfuric acid and sulfuric acid with the volume ratio of 5: 2-5: 3A mixed solution of 36% concentrated nitric acid; (7) soaking the pretreated graphite anode in the solution for 30 minutes at the reaction temperature of 65 ℃; (8) removing the treated graphite anode, and repeatedly soaking with purified water until the pH value is unchanged; (9) putting the cleaned modified graphite anode into a forced air drying oven, and drying for 12 hours at 80 ℃; the preparation method of the anode material of the microbial fuel cell disclosed in the Chinese patent 201810941639.8 comprises the following specific preparation steps: (1) taking 5-10 parts of graphene oxide, 5-10 parts of thionyl chloride, 5-10 parts of propargyl alcohol and 5-10 parts of polystyrene in sequence, heating and refluxing the graphene oxide and the thionyl chloride for reaction for 24 hours, filtering, washing and drying the graphene oxide, heating and refluxing the graphene oxide and the propargyl alcohol for reaction for 24 hours, filtering, washing and drying the graphene oxide to obtain alkynyl graphene oxide, and reacting the alkynyl graphene oxide with the polystyrene to obtain polystyrene modified graphene oxide; (2) mixing carbon nanotubes and water according to a mass ratio of 1: 10-1: 20, performing mixed ultrasound, adding polyamine with the mass of 0.3-0.5 times that of the carbon nano tube, heating, stirring and mixing, adding carbomer, stirring for reaction, filtering and drying to obtain a modified carbon nano tube; (3) according to the weight parts, after 5-10 parts of polystyrene modified graphene oxide, 3-5 parts of modified carbon nano tubes, 5-10 parts of compound metal salt solution and 3-5 parts of nano metal powder are sequentially stirred and mixed, the pH value is adjusted to 8.0 by using urea solution, the mixture is subjected to hydrothermal reaction for 1-2 hours, and then the mixture is reduced by using hydrogen, filtered, washed and dried, so that the microbial dye battery anode material is obtained; the preparation method of the modified shaddock peel foam carbon microbial fuel cell anode material disclosed in the Chinese patent 201610173102.2 comprises the following specific preparation steps: (1) peeling 2-3 pomelos, cutting off yellow wax layers on the surfaces of the pomelo peels by using a cutter to obtain white skin and flesh with a spongy structure, soaking the white skin and flesh with deionized water for 3-5 hours, then putting the pomelo peels and flesh into a gauze bag, hanging the gauze bag in a hanging manner to enable water in the skin and flesh to naturally drip, taking out the pomelo skin and flesh when no water drips and falls in the gauze bag, and putting the pomelo skins and flesh into an oven to dry for 2-3 hours at 105-110 ℃; (2) putting the dried shaddock peel into a high-temperature carbonization furnace, introducing nitrogen into the furnace to replace all air in the shaddock peel, raising the temperature to 100 ℃ at a speed of 8 ℃/min under the protection of the nitrogen, pre-carbonizing the shaddock peel for 30-40 min, and then raising the temperature at a speed of 5 ℃/minRaising the temperature to 800-900 ℃, preserving heat, carbonizing for 1-2 h, and naturally cooling to room temperature to obtain the pomelo peel carbon foam; (3) crushing the prepared shaddock peel foamy carbon in a jet mill, sieving the crushed shaddock peel foamy carbon by a 200-mesh standard sieve, injecting sieved foamy carbon powder into a cylindrical mold with the diameter of 1-2 cm and the height of 5-6 cm, moving the cylindrical mold into a high-temperature sintering furnace, sintering the cylindrical mold at 500-600 ℃ for 2-3 hours, and removing the mold to obtain a cylindrical foamy carbon electrode for later use; (4) weighing 400-500 g of tourmaline, grinding by using an ultrafine grinding machine, sieving by using a standard sieve of 900-1000 meshes, and mixing the obtained tourmaline powder according to a solid-liquid ratio of 1: 50, pouring the mixture into a hydrochloric acid solution with the concentration of 0.5mol/L, stirring and soaking for 20-30 min, and then carrying out suction filtration and washing for 3-5 times by using deionized water; (5) pouring 100-120 g of washed superfine tourmaline powder and 5-8 g of polyvinyl butyral into 2-3L of acetone, placing the acetone and the superfine tourmaline powder into an ultrasonic dispersion machine for ultrasonic dispersion treatment for 10-20 min at the power of 200-300W, placing the acetone and the superfine tourmaline powder on a magnetic stirrer, and continuously stirring for 20-24 h to obtain a mixed tourmaline powder suspension; (6) pouring the obtained tourmaline powder suspension into a 5L beaker as electrolyte, taking a platinum sheet as a positive electrode and a spare cylindrical carbon foam electrode as a negative electrode, applying an electric field of 50-70V/cm between the positive electrode and the negative electrode by an electrophoretic deposition method, and carrying out electrophoretic deposition for 1-2 h; (7) after deposition is finished, taking out the carbon foam electrode on which the tourmaline is deposited, putting the carbon foam electrode into a vacuum drier, drying for 8-10 h, transferring the carbon foam electrode into a tubular resistance furnace, sintering at the high temperature of 1000-1200 ℃ for 1-2 h in the argon atmosphere, discharging, and naturally cooling to room temperature to obtain the modified shaddock peel carbon foam microbial fuel cell anode material; the anode material or the conductivity prepared by the method is remarkably improved, or the conductivity is remarkably improved, but the output power of the SMFC prepared by the method is very low, the operation stability is not ideal, as a key part of the SMFC, the anode is not only a living place of the electrogenesis microorganisms, but also plays a key role in transferring electrons to an external circuit, and the biocompatibility, the specific surface area, the conductivity and the like of the anode influence the output power of the SMFC to a great extent. Therefore, there is a need to develop an anode material with more excellent performance to improve the performance of SMFC.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, designs a modified anode nanocomposite material for SMFC and a preparation method thereof, shortens the starting time of a microbial fuel cell, improves the output voltage of the microbial fuel cell, and provides a new idea for improving the performance of the microbial fuel cell.
In order to achieve the purpose, the modified anode nano composite material for the SMFC is a reduced graphene oxide/titanium dioxide/1, 4-dihydroxy anthraquinone composite material; the main structure of the composite material comprises titanium dioxide microspheres, mesopores, 1, 4-dihydroxy anthraquinone and reduced graphene oxide; the titanium dioxide microspheres with the diameters of 400nm are provided with a plurality of mesopores, 1, 4-dihydroxy anthraquinone is filled in the mesopores, and the surfaces of the titanium dioxide microspheres are wrapped with a layer of reduced graphene oxide.
The modified anode nanocomposite material for SMFC can be mixed with a binder (Nafion) according to a set proportion and coated on the surface of a carbon-based material or a metal-based material to prepare a modified anode for SMFC.
The invention relates to a preparation method of a modified anode nano composite material for SMFC, which comprises the following five steps of preparing a mesoporous titanium dioxide precursor by a sol-gel method, heating and refluxing in a graphene oxide aqueous solution, carrying out hydrothermal reaction in an ethanol aqueous solution, calcining at high temperature under inert atmosphere and carrying 1, 4-dihydroxy anthraquinone under negative pressure:
(1) preparing a mesoporous titanium dioxide precursor by a sol-gel method: adding 4mL of tetrabutyl titanate into 200mL of ethylene glycol, stirring at the rotation speed of 400rpm for 6-24h at room temperature to form a mixed solution, adding the mixed solution into 340mL of acetone containing 1-2mL of deionized water, stirring at the rotation speed of 600rpm for 2h, and centrifuging to collect a white precipitate;
(2) heating and refluxing in a graphene oxide aqueous solution: adding 0.5g of the white precipitate obtained in the step (1) into 100mL of deionized water containing 0.125-0.05g of graphene oxide, refluxing for 4h at 90 ℃, centrifuging and collecting the gray precipitate;
(3) carrying out hydrothermal reaction in ethanol water solution: dispersing the gray precipitate obtained in the step (2) into a mixed solution consisting of 20mL of ethanol and 10mL of deionized water, carrying out hydrothermal reaction for 24h at 180 ℃, and centrifuging to collect black precipitate;
(4) high-temperature calcination under inert atmosphere: calcining black precipitate for 4 hours at 400 ℃ in the nitrogen atmosphere to obtain the graphene/titanium dioxide composite nano material;
(5) carrying 1, 4-dihydroxy anthraquinone under negative pressure: and (3) dispersing 0.2g of the graphene/titanium dioxide composite nano material obtained in the step (4) in 50mL of ethanol containing supersaturated 1, 4-dihydroxy anthraquinone, then transferring the mixture into a vacuum drying oven with the vacuum degree of 50mbar, standing for 15min, taking out, washing and drying, and repeatedly washing and drying for 3 times to obtain the graphene/titanium dioxide composite nano material loaded with the 1, 4-dihydroxy anthraquinone.
Compared with the prior art, the modified anode nanocomposite material for the SMFC has a large specific surface area, can provide a large number of attachment sites for electrogenic microorganisms, the 1, 4-dihydroxy anthraquinone carried in the mesopores can be used as an electronic mediator to attract the enrichment of the electrogenic microorganisms, the electron transfer efficiency of the electrogenic microorganisms is improved, the starting time of the cell can be obviously shortened by coating the modified anode nanocomposite material for the SMFC on the surface of an electrode material, and the output voltage of the cell is improved.
Description of the drawings:
fig. 1 is a schematic diagram of the principle of the main structure of the modified anode nanocomposite material for SMFC according to the present invention.
Fig. 2 is a scanning electron microscope image of the graphene/titanium dioxide composite nanomaterial related to the present invention.
Fig. 3 is a nitrogen adsorption and desorption curve diagram of the graphene/titanium dioxide composite nanomaterial related to the invention.
FIG. 4 is a graph showing the release profile of 1, 4-dihydroxyanthraquinone according to the present invention in an aqueous solution of sodium chloride having a concentration of 3.5% by mass.
Fig. 5 is a graph showing output voltage curves of the modified carbon plate and the bare carbon plate according to the present invention under an applied resistance of 1000 Ω.
The specific implementation mode is as follows:
the following is a further description by way of example and with reference to the accompanying drawings.
Example 1:
this example relates to the release and characterization of 1, 4-dihydroxyanthraquinone in modified anode nanocomposites for SMFC: dispersing 50mg of the modified anode nanocomposite for the SMFC in 20mL of sodium chloride aqueous solution with the mass percent concentration of 3.5%, testing the absorbance value for 6 times at the frequency of testing once for 2h, wherein the scanning range is 200-900nm, drawing a standard curve of 1, 4-dihydroxyanthraquinone according to the test result, and converting the standard curve to obtain a release curve of the 1, 4-dihydroxyanthraquinone in the modified anode nanocomposite for the SMFC, which shows that the modified anode nanocomposite for the SMFC can carry the 1, 4-dihydroxyanthraquinone and release slowly, and the 1, 4-dihydroxyanthraquinone can be used as an electronic mediator to improve the electron transfer efficiency between an electrogenic microorganism and an electrode.
Example 2:
the embodiment relates to a method for preparing a modified anode of a submarine sediment type microbial fuel cell by using a modified anode nanocomposite material for SMFC, which comprises the following steps:
(1) taking a carbon plate with the length of 3cm, the width of 3cm and the height of 0.5cm as an anode, respectively polishing the carbon plate with 800-mesh, 1000-mesh and 1200-mesh sand paper until the surface is flat and smooth, and ultrasonically cleaning for 30 min;
(2) adding 25 mu L of Nafion aqueous solution and 125 mu L of deionized water into each 25mg of the modified anode nano composite material for the SMFC, mixing and stirring uniformly, and performing ultrasonic dispersion until uniform slurry is formed;
(3) the slurry was washed with a fine brush at 5mg/cm2The amount of the modified anode is uniformly coated on the surface of a carbon plate anode, and the modified anode is placed for 24 hours at room temperature to be dried, so that the modified anode of the submarine sediment type microbial fuel cell is obtained.
Example 3:
the embodiment relates to the construction and performance test of a seabed sediment type microbial fuel cell, the seabed sediment type microbial fuel cell consists of sea mud and seawater, the sea mud with the height of 20cm is arranged below the seabed sediment type microbial fuel cell, the anode of the modified carbon plate prepared in the embodiment 2 is placed at the position with the depth of 10cm of the sea mud, the natural seawater with the height of 10cm is arranged above the anode, the cathode of the modified carbon plate is placed in the natural seawater, and the cathode of the modified carbon plate is a carbon fiber brush with the length of 5 cm; after the submarine sediment type microbial fuel cell is assembled, an external resistance of 1000 ohms is additionally arranged between a cathode and an anode, a data acquisition system is used for recording output voltages of two ends of the submarine sediment type microbial fuel cell, the submarine sediment type microbial fuel cell prepared by a bare carbon plate anode is used as a comparison group for comparison, as shown in fig. 5, the output voltage of the submarine sediment type microbial fuel cell prepared by a modified carbon plate anode is rapidly increased and stabilized at about 300mV, the time for reaching the maximum voltage is 50h, the time for reaching the maximum voltage of the submarine sediment type microbial fuel cell prepared by the bare carbon plate anode is 70h, and the output voltage of the submarine sediment type microbial fuel cell prepared by the modified carbon plate anode is increased by nearly 100% compared with the output voltage of the submarine sediment type microbial fuel cell prepared by the bare carbon plate anode.

Claims (4)

1. A modified anode nano composite material for SMFC is characterized in that the modified anode nano composite material is a reduced graphene oxide/titanium dioxide/1, 4-dihydroxy anthraquinone composite material; the main structure comprises titanium dioxide microspheres, mesopores, 1, 4-dihydroxy anthraquinone and reduced graphene oxide; the titanium dioxide microspheres with the diameters of 400nm are provided with a plurality of mesopores, 1, 4-dihydroxy anthraquinone is filled in the mesopores, and the surfaces of the titanium dioxide microspheres are wrapped with reduced graphene oxide.
2. The modified anode nanocomposite for SMFC according to claim 1, which is capable of being mixed with a binder and applied to the surface of a carbon-based material or a metal-based material for preparing a modified anode for SMFC.
3. The modified anode nanocomposite material for the SMFC according to claim 1 or 2, wherein the preparation method comprises the following five steps of preparing a mesoporous titanium dioxide precursor by a sol-gel method, heating and refluxing in a graphene oxide aqueous solution, carrying out a hydrothermal reaction in an ethanol aqueous solution, calcining at a high temperature under an inert atmosphere, and carrying 1, 4-dihydroxy anthraquinone under negative pressure.
4. The method for preparing the modified anode nanocomposite material for the SMFC according to claim 3, wherein the method comprises the following steps:
(1) preparing a mesoporous titanium dioxide precursor by a sol-gel method: adding 4mL of tetrabutyl titanate into 200mL of ethylene glycol, stirring at the rotation speed of 400rpm for 6-24h at room temperature to form a mixed solution, adding the mixed solution into 340mL of acetone containing 1-2mL of deionized water, stirring at the rotation speed of 600rpm for 2h, and centrifuging to collect a white precipitate;
(2) heating and refluxing in a graphene oxide aqueous solution: adding 0.5g of the white precipitate obtained in the step (1) into 100mL of deionized water containing 0.125-0.05g of graphene oxide, refluxing for 4h at 90 ℃, centrifuging and collecting the gray precipitate;
(3) carrying out hydrothermal reaction in ethanol water solution: dispersing the gray precipitate obtained in the step (2) into a mixed solution consisting of 20mL of ethanol and 10mL of deionized water, carrying out hydrothermal reaction for 24h at 180 ℃, and centrifuging to collect black precipitate;
(4) high-temperature calcination under inert atmosphere: calcining black precipitate for 4 hours at 400 ℃ in the nitrogen atmosphere to obtain the graphene/titanium dioxide composite nano material;
(5) carrying 1, 4-dihydroxy anthraquinone under negative pressure: and (3) dispersing 0.2g of the graphene/titanium dioxide composite nano material obtained in the step (4) in 50mL of ethanol containing supersaturated 1, 4-dihydroxy anthraquinone, then transferring the mixture into a vacuum drying oven with the vacuum degree of 50mbar, standing for 15min, taking out, washing and drying, and repeatedly washing and drying for 3 times to obtain the graphene/titanium dioxide composite nano material loaded with the 1, 4-dihydroxy anthraquinone.
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Title
A novel anode modified by 1,5-dihydroxyanthraquinone/multiwalled carbon nanotubes composite in marine sediment microbial fuel cell and its electrochemical performance;Haoshuang Zhang;《INTERNATIONAL JOURNAL OF ENERGY RESEARCH》;20180610;第42卷(第7期);第2574-2582页 *
Nanostructured Graphene/TiO 2 Hybrids as High-Performance Anodes for Microbial Fuel Cells;Cui-e Zhao等;《CHEMELECTROCHEM》;20171231;第4卷(第12期);第3068-3074页 *

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