CN113437313A - WO3-rGO nano particle synthesis method and microbial fuel cell constructed by same - Google Patents

WO3-rGO nano particle synthesis method and microbial fuel cell constructed by same Download PDF

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CN113437313A
CN113437313A CN202110716591.2A CN202110716591A CN113437313A CN 113437313 A CN113437313 A CN 113437313A CN 202110716591 A CN202110716591 A CN 202110716591A CN 113437313 A CN113437313 A CN 113437313A
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赵超越
刘丹青
于天池
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Harbin University of Science and Technology
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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
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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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

WO3A method for synthesizing rGO nano particles and a microbial fuel cell constructed by the same, belonging to the technical field of microbial fuel cells. The invention aims to solve the problems of high potential, low power, short period and the like of the anode of the conventional microbial fuel cell. WO3-rGO nanoparticle preparation method: firstly, mixing tartaric acid solution and sodium tungstate solution with the same volume, fully stirring, adjusting the pH value of the solution to 0.8-1.1, transferring the solution into a reaction kettle, transferring the mixed solution into the reaction kettle for hydrothermal reaction at the reaction temperature of 110-130 ℃ for 22-24 hours, centrifugally cleaning the solution for 3-5 times by using distilled water, centrifugally cleaning the solution for one time by using ethanol, and drying the solution in vacuum; secondly, adding isopropanol and Nafion solution into the materials and the reduced graphene with equal mass, carrying out ultrasonic treatment until the materials and the reduced graphene are completely and uniformly dispersed,and thirdly, coating the mixture on two sides of the pretreated carbon cloth, and naturally drying the mixture. The constructed microbial electrolysis cell is an H-type double-chamber MECs. The maximum voltage of the MFCs is 0.524V, the period is long, and the maximum power density is 1651.9mW/m2。

Description

WO3-rGO nano particle synthesis method and microbial fuel cell constructed by same
Technical Field
The invention belongs to the technical field of microbial fuel cells; in particular to WO for microbial fuel cells3-preparation method of rGO nano-particles and microbial fuel cell constructed by the same.
Background
A Microbial Fuel Cell (MFC) is a device that directly converts chemical energy in organic matter into electrical energy using microorganisms. The basic working principle is as follows: in the anaerobic environment of the anode chamber, organic matters are decomposed under the action of microorganisms to release electrons and protons, the electrons are effectively transferred between biological components and the anode by virtue of a proper electron transfer mediator and are transferred to the cathode through an external circuit to form current, the protons are transferred to the cathode through a proton exchange membrane, and the oxidant obtains the electrons at the cathode and is reduced to combine with the protons to form water. A Microbial Fuel Cell (MFC) is used as a device for utilizing biomass energy, and generates electricity by taking bacteria as a biocatalyst, and a phytologist Potter in the UK firstly discovers that microorganisms have the function of generating electricity in 1910, and proposes the concept of the MFC on the basis of the function. According to the working principle of the microbial fuel cell, the anode material of the microbial fuel cell has the advantages of large specific surface area, excellent biocompatibility and excellent electrochemical performance.
Tungsten nitride is a novel catalytic material, the surface property and the catalytic performance of the tungsten nitride are similar to those of noble metals, and sulfur pollution caused by industrial catalysts can be avoided by applying the tungsten nitride catalyst, so that the tungsten nitride catalyst is very environment-friendly as the catalyst. In addition, the tungsten nitride has several unique physical and chemical properties, such as high conductivity, corrosion resistance, good stability, etc., so that the tungsten nitride becomes an ideal material in the fields of photocatalysis and electrocatalysis.
Disclosure of Invention
The invention provides WO for a microbial fuel cell to solve the problems of high anode potential, low power, short period and the like of the conventional microbial fuel cell3-preparation method of rGO nano-particles and microbial fuel cell constructed by the same.
To solve the above problems, WO for a microbial fuel cell of the present invention3-the preparation of rGO nanoparticles is carried out as follows:
step one, mixing tartaric acid solution and sodium tungstate solution with equal volumes, adjusting the pH value of the solution, stirring for 1 hour, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the reaction temperature of 110-130 ℃ for 22-24 hours to obtain a turquoise solution after the reaction is finished, centrifuging and cleaning the turquoise solution for 3-5 times by using water, centrifuging and cleaning the turquoise solution for 1 time by using ethanol, and drying the turquoise solution in vacuum to obtain WO3Nanoparticles.
Step two, WO obtained in step one3Adding isopropanol, Nafion solution and rGO, and carrying out ultrasonic treatment until the mixture is completely dissolved.
Step three, coating the mixture on two sides of the pretreated carbon cloth, and naturally drying the mixture; to obtain WO3-rGO nanoparticles;
further, in the step one, the concentration of the tartaric acid solution is 0.4-0.6 mol/L, the concentration of the sodium tungstate solution is 0.4-0.6 mol/L, and the pH of the solution is adjusted to 0.8-1.1 by using hydrochloric acid.
Further limiting, the speed of magnetic stirring in the first step is controlled to be 300 r/min-800 r/min; the centrifugal rate is 9000 r/min-11000 r/min; the process conditions of vacuum drying are as follows: the temperature is 40-60 ℃, the vacuum degree is-25 kpa-30 kpa, and the time is 9-12 h.
Further limited, step two WO3The volume ratio of the mass of the-rGO nano particles to the isopropanol is 2-2.5 mg: 20-50 mu L.
Further limited, step two WO3The volume ratio of the mass of the rGO nano particles to the Nafion solution is 2-2.5 mg: 16-25 mu L.
Further defined, the pretreatment method of the carbon cloth in the fourth step is as follows: placing carbon cloth in a container, adding dilute hydrochloric acid, soaking, pouring out dilute hydrochloric acid, washing with distilled water, pouring out distilled water, adding acetone, soaking, pouring out acetone, sealing with sealing film, pricking multiple holes on the sealing film, vacuum drying, and sealing with sealing film.
WO obtained by the above process3-MFCs built with rGO nanoparticles are H-type dual-chamber MECs, the middle is separated by a pretreated Nafion membrane, the anode electrode prepared by the above preparation method is used as the anode material of the anode chamber, the pretreated carbon brush is used as the cathode material of the cathode chamber, the anolyte prepared from PBS, sodium acetate, a micro-biotin solution and a mineral solution is introduced into the anode chamber, the catholyte prepared from potassium chloride and potassium ferricyanide is introduced into the cathode chamber, and the cathode and the anode are connected together by an external resistor; completing construction to obtain a microbial electrolytic cell;
the carbon brush pretreatment method comprises the following steps: soaking the carbon cloth fiber side of the carbon brush in acetone for 30min, taking out the carbon cloth fiber side, putting the carbon cloth fiber side into a tubular furnace, sintering the carbon cloth fiber side at the temperature of 200-400 ℃ for 20-35 min, and naturally cooling the carbon cloth fiber side to room temperature to finish the pretreatment of the carbon brush;
further limited, the Nafion membrane pretreatment is completed by the following steps: soaking Nafion membrane in 3% H2O2(hydrogen peroxide solution with the mass percentage concentration of 3%) is put in a baking oven and treated for 20min to 35min (organic impurities are removed) at the temperature of 70 ℃ to 85 ℃, and 3% of H is poured off2O2Adding distilled water, placing in a drying oven, treating at 70-85 ℃ for 20-35 min, pouring out the distilled water, and then adding H with the concentration of 0.5moL/L2SO4Putting the mixture into an oven, treating the mixture for 20 to 35min at the temperature of between 70 and 85 ℃, and pouring off H2SO4Adding distilled water, placing in a baking oven, and treating at 70-85 ℃ for 20-35 min.
Further, the method for disposing the anolyte is as follows: adding 35 mL-70 mL of sodium acetate into 50 mg-85 mg of anhydrous sodium acetate, then adding 100 mu L-500 mu L of mineral solution and 500 mu L-650 mu L of trace element solution, and fully dissolving.
Further defined, the mineral element solution is prepared by the following steps: mixing 1.0-2.0 g of nitrilotriacetic acid, 80-100 mg of zinc sulfate, 2-5 mg of magnesium sulfate, 5-15 mg of copper sulfate, 200-700 mg of molybdenum sulfate, 5-15 mg of aluminum potassium sulfate, 80-150 mg of sodium chloride, 10-30 mg of boric acid, 60-100 mg of ferrous sulfate, 100-150 mg of cobalt chloride, 100-120 mg of calcium chloride and 5-25 mg of sodium molybdate, adding a proper amount of distilled water, fully dissolving, adjusting the pH to 6-8 by using a saturated sodium hydroxide solution, adding the distilled water to a constant volume of 1L, uniformly mixing, sealing and sterilizing.
Further defined, the trace element solution is prepared by the following steps: 0.5mg to 1mg of beta-glycerol, 0.5mg to 1mg of folic acid, 1mg to 3mg of pyridoxine hydrochloride (octyl), 1mg to 5mg of thiamine hydrochloride, 1mg to 5mg of riboflavin, 1mg to 5mg of nicotinic acid, 1mg to 5 mgD-calcium pantothenate and 0.02mg to 0.03mg of vitamin B12Mixing 1-5 mg of p-aminobenzoic acid and 1-5 mg of sulfuric acid, adding a proper amount of distilled water, fully dissolving, adding distilled water to a constant volume of 0.25L, uniformly mixing, sealing and sterilizing.
Further defined, the preparation method of the catholyte is as follows: mixing 200-300 mg of potassium chloride and 800-1000 mg of potassium ferricyanide, and adding 50-60 ml of distilled water for full dissolution.
In the present invention, WO is used3-rGO nano-particles as anode electrode material, is a WO modified by carbon cloth electrode and coated rGO3The composite material strengthens the graphitization degree of the electrode material, thereby reducing the electron transfer resistance, promoting the connection between bacteria and the electrode, and further improving the power generation rate of the MFC. The invention utilizes WO3The nano-particles have excellent electrocatalytic performance and good biocompatibility, and are beneficial to the large-scale enrichment of microorganisms on the surface of an electrode, so that the electricity generation rate of the MFC is improved.
The maximum voltage of the double-chamber microbial fuel cell formed by the anode electrode is 0.524V, the single cycle period reaches 5 days, and the double-chamber microbial fuel cell is still in a stable state for 140 days;
the maximum power density of the double-chamber microbial fuel cell formed by the anode electrode is 1651.9mW/m2。
The anode of the invention has good biocompatibility.
The COD removal rate of the invention reaches 88.5427% +/-3.4766%.
The coulombic efficiency of the invention reaches 9.5531% +/-0.5416%.
Drawings
FIG. 1 is WO3TEM images of the nanoparticles;
FIG. 2 is WO3XRD pattern of the nanoparticles;
FIG. 3 is a time-voltage graph;
FIG. 4 is a graph of power density and polarization;
FIG. 5 is a scanning electron micrograph of bacterial attachment after 140 days of culture.
Detailed Description
Implementation 1:
WO for microbial Fuel cell in the present example3-the preparation of rGO nanoparticles is carried out as follows:
step one, WO3Preparing nano particles: weighing 0.1667g of sodium tungstate dihydrate and 0.1000g of tartaric acid in a 100mL beaker, adding 50mL of deionized water, stirring for 10min, dropwise adding 6mol/L hydrochloric acid into the solution, adjusting the pH of the solution to be 0.9 to generate yellow precipitate, stirring for 30min again, putting the solution into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 24 h in an oven at 130 ℃. Centrifuging at 9600r/min after the reaction is finished, centrifugally cleaning the obtained green solid with deionized water for 3 times, cleaning with ethanol for 1 time, and drying in a vacuum drying oven at 60 ℃ and under-25 kPa for 12 hours to obtain WO3And (3) nanoparticles.
Step two, taking the WO obtained in the step one31.25mg of nano particles, adding 1.25mg of rGO, 50 mu L of isopropanol and 20 mu L of dispersions D520 Nafion solution, and carrying out ultrasonic treatment until the nano particles are completely dissolved to obtain a mixture A.
Step three, a pretreatment method of the carbon cloth: cutting the carbon cloth into 1 × 1cm with scissors2And (2) placing the carbon cloth in a 50mL beaker, adding 30mL of dilute HCl with the mass concentration of 10% and soaking for 15min, pouring out the dilute HCl solution, washing with distilled water for several times, pouring out the distilled water, adding 15mL of acetone and soaking for 15min, pouring out the acetone solution, sealing the beaker with a sealing film, pricking holes with a syringe needle, finally placing the beaker in a vacuum drying box, carrying out vacuum drying at the vacuum degree of-25 kpa and the temperature of 40 ℃ for 9h, sealing the beaker with the sealing film after drying, and reserving for later use, uniformly coating the mixture A obtained in the step (three) on a pretreated substrate, and then uniformly coating the mixture A on the pretreated substrateNaturally drying both sides of the carbon cloth to obtain the WO3-rGO nanoparticles.
Implementation 2: WO obtained by the preparation method described in example 13-rGO nanoparticle-constructed microbial fuel cells:
firstly, pretreatment of required materials:
the carbon brush pretreatment method comprises the following steps: the carbon cloth fiber side of 10 carbon brushes is downwards put into a beaker of 0.5L, then 0.45L of acetone is added, after being soaked for 30min, the carbon cloth fiber is taken out and directly put into a large tube furnace, then the carbon cloth fiber is sintered for 30min at 350 ℃, after naturally cooling to room temperature, the carbon cloth fiber is taken out and put into the beaker of 0.5L, and the carbon cloth fiber is sealed by a sealing film for standby.
The pretreatment method of the Nafion membrane comprises the following steps: mixing 10X 10cm2The Nafion membrane was divided into 9 portions on average, and the cut Nafion membrane was placed in a 100mL beaker, to which was added 100mL of 3% H2O2Placing into a drying oven, treating at 80 deg.C for 30min, and removing organic impurities; 100mL 3% H2O2Pouring out, adding 100mL of distilled water, placing into an oven, and treating at 80 ℃ for 30 min; then 100mL of the solution was poured off, and 0.5moL/LH was added2SO4Placing into an oven, and treating at 80 deg.C for 30 min; finally, 100mL0.5mol/LH is added2SO4Poured off, added with 100mL of distilled water, put into an oven and treated at 80 ℃ for 30 min. After all the liquid is treated, the liquid in the liquid is poured out, new distilled water is added, and the liquid is sealed by a sealing film for later use.
The 3% H2O2Refers to hydrogen peroxide solution with the mass percentage concentration of 3 percent.
The microbial fuel cell constructed in this example was an H-type dual-chamber MEC, the middle was separated by a pre-treated perfluorosulfonic acid ionic membrane, a 50mL double-ear glass bottle was used as the reactor, and WO prepared by the preparation method described in example 1 was used3-rGO nanoparticles are used as anode material in the anode compartment, pretreated carbon brushes are used as cathode material in the cathode compartment, anolyte prepared from PBS, sodium acetate, a micronutrient solution and a mineral solution is introduced into the anode compartment, catholyte prepared from potassium chloride and potassium ferricyanide is introduced into the cathode compartment, and the cathode and the anode are connected together by an additional 1000 Ω resistor; complete the buildObtaining a microbial electrolysis cell; the voltage changes are recorded in multiple data acquisition channels.
Wherein the formula of the mineral element solution is as follows: 1.5g of nitrilotriacetic Acid (NTA) and 100mg of zinc sulfate (ZnSO) were precisely weighed4·7H2O), 3mg magnesium sulfate (MgSO)4·7H2O), 10mg copper sulfate (CuSO)4·5H2O), 500mg of molybdenum sulfate (MuSO)4·H2O), 10mg of aluminum potassium sulfate (AlK (SO)4)2·12H2O), 100mg of sodium chloride (NaCl), 10mg of boric acid (H)3BO3) 100mg ferrous sulfate (FeSO)4·7H2O), 100mg of cobalt chloride (CoCl)2·7H2O), 100mg of calcium chloride (CaCl)2) And 10mg of sodium molybdate (Na)2MoO4·2H2O) in a 0.25L beaker, adding a proper amount of distilled water and stirring uniformly, if the undissolved ultrasonic waves exist until the ultrasonic waves are completely dissolved, adjusting the pH value to about 8 by using a saturated sodium hydroxide (NaOH) solution, moving the beaker to a 1L volumetric flask, and adding water to the marked line. After mixing, the mixture was transferred to six 0.25L Erlenmeyer flasks and sealed, and sterilized in a sterilizer.
The trace element solution: precisely weigh 0.5mg of beta-glycerol, 0.5mg of folic acid, 2.5mg of pyridoxine hydrochloride (octyl), 1.25mg of thiamine hydrochloride, 1.25mg of riboflavin, 1.25mg of nicotinic acid (nicotinic acid), 1.25mg of 1.25 mgD-calcium pantothenate, and 0.025mg of vitamin B121.25mg p-aminobenzoic acid and 1.25mg zinc sulfate in a 100mL beaker, add appropriate amount of distilled water and stir well, if there is undissolved ultrasound until all is dissolved, move to a 0.25L volumetric flask and add water to the marked line. After mixing, the mixture was transferred to two 0.25L Erlenmeyer flasks and sealed, and sterilized in a sterilizer.
The formula of the catholyte is as follows: 223.5mg of potassium chloride (KCl) and 984mg of potassium ferricyanide (K) were precisely weighed3[Fe(CN)6]) In a 100mL beaker, add 60mL of distilled water and stir well, sonicate if undissolved until all dissolves.
The formula of the anolyte is as follows: 80mg of anhydrous sodium acetate (CH) was precisely weighed3COONa) in a 100mL beaker, 60mL of LPBS solution was added and 200. mu.L of mineral and 500. mu.L of trace elements were pipetted using a pipette gun(sterilizing the gun head with alcohol burner), stirring well, and performing ultrasonic treatment if there is undissolved until all the liquid is dissolved.
The following tests are adopted to verify the effect of the invention:
measurement of COD and CE
When the voltage is reduced to below 50mV, taking out about 4mL of water, then pouring out the water until about 20mL of solution remains in the anode measuring container, then adding 40mL of anolyte, taking out about 2mL of inlet water after water exchange, marking and putting into a refrigerator for freezing. When COD is to be measured, the sample is taken out of the refrigerator and thawed, and then filtered by a 0.45-micron microporous filter membrane. Diluting 3mL of filtered effluent to 6mL, diluting 1.5mL of filtered influent to 6mL, and mixing uniformly. 2mL of the mixed water sample was taken and added to a 10mL digestion tube, 40mg of mercuric sulfate for masking chloride ions in water was further added, and 1mL of a potassium dichromate standard solution and 3mLH were pipetted using a 1mL pipette gun2SO4-Ag2SO4The solution is placed in a digestion tube, shaken to be uniformly mixed and then reacted in an oven at 150 ℃ for 120 min. After the temperature was reduced to room temperature, the mixture was shaken well and transferred to a 0.1L Erlenmeyer flask, the digestion tube was rinsed twice with 10mL of distilled water, and the rinsed solution was also transferred to the Erlenmeyer flask. After cooling, 3 drops of ferron indicator liquid are added and shaken evenly, ferrous sulfate is used for titration according to a standard solution, the end point is that when the yellow channel reaches reddish brown from blue green, the volume of the ammonium ferrous sulfate standard solution consumed by titration is recorded.
The formula of the potassium dichromate standard solution comprises the following components: firstly, a certain amount of high-quality potassium dichromate is put on a watch glass and is put in a drying oven to be dried for 120min at 120 ℃, 3064.5mg of dried high-quality potassium dichromate is precisely weighed and is added with 60mL of distilled water in a 0.1L beaker to be uniformly stirred, and if the potassium dichromate is not dissolved, ultrasonic waves are carried out until the potassium dichromate is completely dissolved. Transfer to a 0.25L brown flask, add water to the mark, mix well and store in a brown jar. (concentration 0.2500mol/L)
The formula of the ferrosofil indicating liquid comprises the following components: precisely weigh 742.5mg of phenanthroline (C)12H8N2·H2O) and 347.5mg of ferrous sulfate (FeSO)4·7H2O), put into a 50mL beaker and add 20mL of distilled water to stirHomogeneous, if any, ultrasound without dissolution until all is dissolved. Transfer to a 50mL brown flask, add water to the mark, mix well and store in a brown jar.
The formula of the ammonium ferrous sulfate standard solution comprises the following components: 1975mg of ferrous ammonium sulfate ((NH) were precisely weighed4)2Fe(SO4)2·6H2O), add 80mL of distilled water to a 100mL beaker and stir well, add 10mL of concentrated sulfuric acid (stir) if there is undissolved sonication until all is dissolved. After cooling to room temperature, the mixture was transferred to a 0.5L brown flask and water was added to the marked line, and the mixture was stored in a brown jar. (concentration is 0.01mol/L, ready for use, if ready for use before calibration with potassium dichromate standard solution)
Sulfuric acid-silver sulfate (H)2SO4-Ag2SO4) The solution formula is as follows: 5g of silver sulfate was precisely weighed into a 0.5L brown bottle, 0.5L of concentrated sulfuric acid was added thereto, and the brown bottle was shaken every several hours for two days thereafter to dissolve white silver sulfate.
The percentage of the portion of the organic matter converted into the electric energy to the total electric energy is called Coulomb Efficiency (CE), and may also be called electron recovery rate, so it can be said that the percentage of the recovered electrons to the electrons provided by the organic matter, and the calculation formula is shown in formula 4-4:
Figure BDA0003135202400000061
wherein CE is coulombic efficiency; qEXIs the actual coulomb quantity in units of C; qTHIs the theoretical coulomb quantity in units of C.
For an intermittent flow microbial fuel cell, QEXThe current of a single battery is a constant integral value between 0 and t in one period, as shown in the formula 4-5:
Figure BDA0003135202400000071
in the formula QEXIs the actual coulomb quantity in units of C; i is a battery with unit of A; u isVoltage in units of U; rexIs the load resistance in Ω.
Calculating the theoretical coulomb quantity of the microbial fuel cell by using Chemical Oxygen Demand (COD), wherein the calculation formula is shown as formula 4-6:
Figure BDA0003135202400000072
in the formula QTHIs the theoretical coulomb quantity and has the unit of C; delta COD is COD removal amount, and the unit is g/L; vAIs volume of anolyte, unit is m3；
Figure BDA0003135202400000073
The molar mass of the organic matter is 32g/mol with oxygen as a standard; b is the number of electrons transferred by oxidation of 1mol of organic substance based on oxygen, 4mole-Per mol; f is a Faraday constant of 96485C/mol.
The new formula for CE is obtained by substituting formulae 4-6 and 4-5 for formula 4-4, as shown in formulae 4-7:
Figure BDA0003135202400000074
the calculation method of COD is shown in the formula 4-8:
Figure BDA0003135202400000075
wherein COD is chemical oxygen demand and the unit is mg/L; c is the concentration of the ammonium ferrous sulfate solution, and the unit is mol/L; v0The volume of the ferrous ammonium sulfate solution consumed by titrating distilled water is mL; v1The volume of the ferrous ammonium sulfate solution consumed in the process of titrating the sample is mL; v is the volume of the water sample in mL.
The calculation method of delta COD is shown in the formula 4-9:
ΔCOD＝CODi-CODo (4-9)
wherein the delta COD is the removal amount of COD in the unit ofg/L；CODiIs COD of inlet water, and the unit is g/L; CODoThe COD of the effluent is in g/L. Calculated, the COD removal rate reaches 88.5427% +/-3.4766%, and the coulombic efficiency reaches 9.5531% +/-0.5416%. It can be shown that the present invention has excellent performance in energy conversion for converting energy in organic matter into electric energy.
WO3SEM pictures of the nanoparticles are shown in FIG. 1, and it can be seen from FIG. 1 that WO3The nano particles are in a cubic block structure, the width of the nano particles is about 200nm, and the thickness of the nano particles is about 80 nm.
WO3XRD patterns of nanoparticles are shown in FIG. 2. from FIG. 2, it can be seen that the material obtained by the preparation method of the present invention and WO3The standard card is in compliance.
The time-voltage diagram is shown in FIG. 3. from the graph of FIG. 3 we can see WO3-maximum voltage of 0.524V for a microbial fuel cell with rGO anode, single cycle period up to 5 days and still in steady state for 140 days.
The power density and polarization curves are shown in FIG. 4. from FIG. 4, it can be seen that the maximum power density is 1651.4mW/m2。
SEM image of bacterial attachment after 140 days of culture is shown in FIG. 5, and it can be seen from FIG. 5 that the bacteria are attached to the electrode surface after the periodic cycle, demonstrating that WO prepared by the present invention3The rGO nano-particles have good biocompatibility as anode materials of MFCs.

Claims (10)

1. WO for microbial fuel cells3-a process for the preparation of rGO nanoparticles, characterized in that said process is carried out according to the following steps:
step one, mixing tartaric acid solution and sodium tungstate solution with equal volumes, adjusting the pH value of the solution to 0.8-1.1, stirring for 1h, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the reaction temperature of 110-130 ℃ for 22-24 h to obtain a turquoise solution after the reaction is finished, centrifuging and cleaning the turquoise solution for 3-5 times by using water, centrifuging and cleaning the turquoise solution for 1 time by using ethanol, and drying the turquoise solution in vacuum to obtain WO3Nanoparticles.
Step three, obtaining WO to step two3Adding isopropanol, Nafion solution and rGO, and carrying out ultrasonic treatment until the mixture is completely and uniformly dispersed.
Step four, coating the mixture on two sides of the pretreated carbon cloth, and naturally drying the mixture; to obtain WO3-rGO nanoparticles.
2. WO for microbial fuel cell according to claim 13The preparation method of the-rGO nano particles is characterized in that in the step one, the concentration of the tartaric acid solution is 0.4-0.6 mol/L, the concentration of the sodium tungstate solution is 0.4-0.6 mol/L, and hydrochloric acid is used for adjusting the pH value of the solution to 0.8-1.1.
3. WO for microbial fuel cell according to claim 13The preparation method of the-rGO nano particles is characterized in that the speed of magnetic stirring in the first step is controlled to be 300 r/min-800 r/min; the centrifugal rate is 9000 r/min-11000 r/min; the process conditions of vacuum drying are as follows: the temperature is 40-60 ℃, the vacuum degree is-25 kpa-30 kpa, and the time is 9-12 h.
4. WO for microbial fuel cell according to claim 13-rGO nano-particles preparation method, characterized by step three WO3The volume ratio of the mass of the rGO compound to the isopropanol is (2-2.5) mg to (20-50) mu L; step three WO3The volume ratio of the mass of the-rGO compound to the Nafion solution is (2-2.5) mg to (16-25) mu L.
5. WO for microbial fuel cell according to claim 13-a method for preparing rGO nanoparticles, characterized in that the pretreatment method of the carbon cloth in step four is as follows: placing carbon cloth in a container, adding dilute hydrochloric acid, soaking, pouring out dilute hydrochloric acid, washing with distilled water, pouring out distilled water, adding acetone, soaking, pouring out acetone, sealing with sealing film, pricking multiple holes on the sealing film, vacuum drying, and sealing with sealing film.
6. WO obtained by the production method according to any one of claims 1 to 53-MFCs built with rGO nanoparticles, characterized in that the microbial fuel cell built is an H-type two-compartment MEC, separated in the middle by a pre-treated Nafion membrane, the anode electrode made by the manufacturing method according to any one of claims 1-5 is used as the anode material in the anode compartment, the pre-treated carbon brush is used as the cathode material in the cathode compartment, the anolyte made of PBS, sodium acetate, vitamin solution and mineral solution is passed into the anode compartment, the catholyte made of potassium chloride and potassium ferricyanide is passed into the cathode compartment, and the cathode and the anode are connected together by means of an external resistance; completing construction to obtain the microbial fuel cell;
the carbon brush pretreatment method comprises the following steps: soaking the carbon cloth fiber side of the carbon brush in acetone for 30min, taking out the carbon cloth fiber side, putting the carbon cloth fiber side into a tubular furnace, sintering the carbon cloth fiber side at the temperature of 200-400 ℃ for 20-35 min, and naturally cooling the carbon cloth fiber side to room temperature to finish the pretreatment of the carbon brush;
the Nafion membrane pretreatment is completed by the following steps: soaking Nafion membrane in 3% H2O2Placing the mixture in a drying oven, treating the mixture for 20 to 35min at the temperature of between 70 and 85 ℃, and pouring out 3 percent of H2O2Adding distilled water, placing in a drying oven, treating at 70-85 ℃ for 20-35 min, pouring out the distilled water, and then adding H with the concentration of 0.5moL/L2SO4Putting the mixture into an oven, treating the mixture for 20 to 35min at the temperature of between 70 and 85 ℃, and pouring off H2SO4Adding distilled water, placing in a baking oven, treating at 70-85 ℃ for 20-35 min, and pouring off liquid to finish the pretreatment of the Nafion membrane.
7. The MFCs of claim 6, wherein the anolyte is disposed as follows: adding 35 mL-70 mL of sodium acetate anhydrous of 50 mg-85 mg, adding 100 mu L-500 mu L of mineral solution and 500 mu L-650 mu L of trace element solution, and fully dissolving.
8. The MFCs of claim 7, wherein said solution of mineral elements is formulated by the steps of: mixing 1.0-2.0 g of nitrilotriacetic acid, 80-100 mg of zinc sulfate, 2-5 mg of magnesium sulfate, 5-15 mg of copper sulfate, 200-700 mg of molybdenum sulfate, 5-15 mg of aluminum potassium sulfate, 80-150 mg of sodium chloride, 10-30 mg of boric acid, 60-100 mg of ferrous sulfate, 100-150 mg of cobalt chloride, 100-120 mg of calcium chloride and 5-25 mg of sodium molybdate, adding a proper amount of distilled water, fully dissolving, adjusting the pH to 6-8 by using a saturated sodium hydroxide solution, adding the distilled water to a constant volume of 1L, uniformly mixing, sealing and sterilizing.
9. The MFCs of claim 7, wherein said trace element solution is formulated by the steps of: 0.5mg to 1mg of beta-glycerol, 0.5mg to 1mg of folic acid, 1mg to 3mg of pyridoxine hydrochloride (octyl), 1mg to 5mg of thiamine hydrochloride, 1mg to 5mg of riboflavin, 1mg to 5mg of nicotinic acid, 1mg to 5 mgD-calcium pantothenate and 0.02mg to 0.03mg of vitamin B12Mixing 1-5 mg of p-aminobenzoic acid and 1-5 mg of sulfuric acid, adding a proper amount of distilled water, fully dissolving, adding distilled water to a constant volume of 0.25L, uniformly mixing, sealing and sterilizing.
10. The MFCs of claim 6, wherein said catholyte is configured as follows: mixing 200-300 mg of potassium chloride and 800-1000 mg of potassium ferricyanide, and adding 50-60 ml of distilled water for full dissolution.
CN202110716591.2A 2021-06-28 2021-06-28 WO3-rGO nano particle synthesis method and microbial fuel cell constructed by same Pending CN113437313A (en)

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